Drugs by Ir

DETERMINATION OF NARCOTIC AND PSYCHOTROPIC SUBSTANCES
BY USING INFRARED SPECTROSCOPY
A THESIS SUBMITTED TO
THE GRADUATE OF NATURAL AND APPLIED SCIENCES
OF
MIDDLE EAST TECHNICAL UNIVERSITY
BY
ÖZLEM BARAN
IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

FOR
THE DEGREE OF MASTER OF SCIENCE
IN
CHEMISTRY
JULY 2005
Approval of the Graduate School of Natural and Applied Sciences
Prof. Dr. Canan Özgen

Director
I certify that this thesis satisfies all the requirements as a thesis for the degree of
Master of Science.
Prof. Dr. Hüseyin İşçi

Head of Department
This is to certify that we have read this thesis and that in our opinion it is fully
adequate, in scope and quality, as a thesis for the degree of Master of Science.
Prof. Dr. O.Yavuz Ataman

Supervisor
Examining Committee Members
Prof. Dr. Şefik Süzer (Bilkent Unv.)
Prof. Dr. O. Yavuz Ataman (METU, CHEM)
Prof. Dr. Teoman Tinçer (METU, CHEM)
Prof. Dr. Mürvet Volkan (METU, CHEM)
Faik Öztop (M.S., Jandarma Gn.K.lığı)

I hereby declare that all information in this document has been obtained and
presented in accordance with academic rules and ethical conduct. I also
declare that, as required by these rules and conduct, I have fully cited and
referenced all material and results that are not original to this work.
Name, Last name :
Signature :
iii
ABSTRACT
DETERMINATION OF NARCOTIC AND PSYCHOTROPIC SUBSTANCES BY

USING INFRARED SPECTROSCOPY
Baran, Özlem
M.S. Department of Chemistry
Supervisor: Prof. Dr. O.Yavuz Ataman
July 2005, 139 pages
Narcotic and psychotropic substances are all chemicals that affect a person’s
mental activities, perceptual abilities, behavior and level of consciousness; they
may cause physical and/or psychological dependence. For determination of
narcotic and psychotropic substances, chromatographic techniques are usually
preferred which are aimed to identify the target chemicals and require several
extraction steps. In this study, an Infrared Spectrometric method has been
developed for qualitative determination of most widely encountered substances
(morphine, heroin, cocaine, MDMA (3,4-methylenedioxymethamhetamine) and
amphetamine) and additives (caffeine, paracetamol and lactose). Standard
reference materials and illicit samples have been analyzed in powdered form by
using Fourier Transform Infrared-Attenuated Total Reflectance (FTIR-ATR)
technique. In the first part, a spectral FTIR database was constituted from the
standard references. Illicit samples containing drugs and additives in varying
percentages were analyzed using the same method and their database forecast
results were compared with results from Gas Chromatography and High Pressure
Liquid Chromatography. In the second part of the study, the possibility of finding a
iv
similarity between two samples just by comparing their spectra was investigated.
For this purpose, all illicit sample spectra were collected in a new database, and
then randomly selected samples were searched using this database. Most of the
search attempts resulted in a correct match. Consequently, it has been observed
that FTIR-ATR can be used as a priory detection step for classification studies;
moreover with this technique pre-determination of narcotic and psychotropic
substances can be done simply and rapidly.
Keywords: Narcotic and psychotropic substances, FTIR, drug, forensic chemistry.
v
ÖZ
NARKOTİK VE PSİKOTROPİK MADDELERİN İNFRARED SPEKTROSKOPİ

YÖNTEMİ İLE TAYİNİ
Baran, Özlem
Yüksek Lisans. Kimya Bölümü
Tez Yöneticisi: Prof. Dr. O.Yavuz Ataman
Temmuz 2005, 139 sayfa
Narkotik ve psikotropik maddeler, kişilerin ruhsal durumunu, fiziksel ve düşünsel

güçlerini etkileyen ve fiziksel ya da psikolojik bağımlılığa yol açan maddelerdir.
Narkotik ve psikotropik maddelerin analizlerinde genellikle hedef bileşenlerin
tayinlerine yönelik olarak, ekstraksiyon işlemleri ve uzun analiz süresi gerektiren
kromatografik yöntemler kullanılmaktadır. Bu çalışmada, ülkemizde en sık
rastlanan narkotik ve psikotropik maddeler (morfin, eroin, kokain, MDMA (3,4-
metilendioksimetamfetamin) ve amfetamin) ve bu maddelerin bileşimlerinde
bulunabilecek çeşitli katkı maddelerinin (kafein, parasetamol, laktoz) nitel tayinleri
için Infrared Spektrometri yöntemi geliştirildi. Standart maddeler ve yasadışı
yollarla üretilmiş örnekler toz halinde Fourier Transform Infrared-Attenuated Total
Reflectance (FTIR-ATR) tekniği ile analiz edildi. Çalışmanın ilk aşamasında
standart maddelerden sanal bilgisayar FTIR Kütüphanesi oluşturuldu ve kullanıldı.
Bu yöntemle değişik oranlarda etken ve katkı maddeleri içeren yasadışı örnekler
tanımlandı ve sonuçlar Gaz Kromatografi ve Yüksek Basınçlı Sıvı Kromatografi
analizleri ile doğrulandı. İkinci aşamada ise, iki örnek arasındaki benzerliğin
sadece spektrumlarının karşılaştırılması ile mümkün olup olmadığı araştırıldı. Bu
vi
amaçla, yasadışı yollarla üretilen örneklerin spektrumları yeni bir kütüphane
altında toplandı ve rasgele seçilen örneklerin spektrumları alınarak bu
kütüphanede tarandı. Çalışma sonucunda, örneklerin büyük bölümünün
kütüphanede bulunan kendi spektrumu ile eşleştiği görülmüştür. Sonuç olarak,
FTIR-ATR tekniğinin narkotik ve psikotropik maddelerin sınıflandırma
çalışmalarında bir ön eleme basamağı olarak kullanılabileceği; ayrıca bu
maddeler için basit ve hızlı bir ön belirleme yöntemi olduğu belirlenmiştir.
Anahtar Kelimeler: Narkotik ve psikotropik maddeler, FTIR, drog, adli kimya.
vii
ACKNOWLEDMENTS
I am deeply grateful to my supervisor Prof. Dr. O. Yavuz Ataman for his guidance,
encouragement, advice and criticism throughout the study.
I would like to thank to Mr. Faik Öztop, Director of Chemistry Branch, Gendarme
Criminal Laboratory for his support during the study.
I also thanks to my colleague Mr. Koray Çakır for his helps and discussions about
the study.
I thank to the examining committee members for their contribution to my thesis.
Finally, I would like to deeply thank to my daughter Ceren, my husband Haluk and
my mother for their endless patient and support during my studies.
viii
TABLE OF CONTENTS
PLAGIARISM.................................................................................................. ..... iii

ABSTRACT .......................................................................................................... iv
ÖZ......................................................................................................................... vi
ACKNOWLEDGMENTS ...................................................................................... viii
TABLE OF CONTENTS ....................................................................................... ix
LIST OF TABLES ................................................................................................. xii
LIST OF FIGURES .............................................................................................. xiii
CHAPTER
1. INTRODUCTION ............................................................................................ 1
1.1 Definitions of Narcotic and Psychotropic Substances ............................ 1
1.2 History of Drugs ...................................................................................... 1
1.3 Drug Trafficking and Control Mechanisms.............................................. 2
1.4 Terminology of Drugs ............................................................................. 3
1.4.1 Drug Abuse .................................................................................... 3
1.4.2 Drug Dependence.......................................................................... 3
1.4.2.1 Psychological Dependence................................................ 3
1.4.2.2 Physical Dependence ........................................................ 3
1.4.3 Tolerance ....................................................................................... 4
1.5 Classification of Drugs ............................................................................ 4
1.5.1 Central Nervous System Depressants........................................... 4
1.5.1.1 Narcotics ............................................................................ 4
1.5.1.2 Hypnotic Sedatives ............................................................ 7
1.5.2 Central Nervous System Stimulants .............................................. 8
1.5.2.1 Cocaine .............................................................................. 8
1.5.2.2 Amphetamine and Amphetamine Related Drugs............... 9
1.5.3 Hallucinogens ............................................................................... 11
1.5.3.1 Lysergic Acid Diethylamide ............................................... 11
1.5.3.2 Cannabis ........................................................................... 12
1.6 Theory of the Method Used in the Study ............................................... 13
1.6.1 Infrared Spectrometry ................................................................... 13
1.6.2 Fourier Transform Infrared Spectrometry ..................................... 15
ix
1.6.3 Attenuated Total Reflectance Technique...................................... 16
1.7 Literature Survey ................................................................................... 18
1.8 Aim of the Study .................................................................................... 19
2. EXPERIMENTAL ........................................................................................... 21
2.1 Chemical and Reagents ........................................................................ 21
2.1.1 Standards...................................................................................... 21
2.1.2 Samples ........................................................................................ 22
2.2 Instrumentation and Apparatus.............................................................. 22
2.2.1 FTIR .............................................................................................. 22
2.2.2 GC-MSD .......................................................................................24
2.2.3 HPLC ............................................................................................ 25
2.2.4 GC-FID.......................................................................................... 26
2.3 Procedures ............................................................................................ 26
2.3.1 FTIR .............................................................................................. 26
3. RESULTS AND DISCUSSIONS.................................................................... 28
3.1 Optimization of FTIR Parameters .......................................................... 28
3.1.1 Scan Number and Holding Time................................................... 28
3.1.2 Particle Size .................................................................................. 31
3.1.3 Effect of Humidity on Spectra ....................................................... 32
3.2 Constitution of Spectral ATR Database for Drug Standards.................. 33
3.2.1 Relation Between Percent Concentration and Band Intensity ...... 33
3.2.2 FTIR Spectral Database Content.................................................. 35
3.3 Interpretation of the Spectra .................................................................. 37
3.3.1 Heroin Spectrum ........................................................................... 37
3.3.2 Cocaine Spectrum ........................................................................ 37
3.3.3 Amphetamine Spectrum ............................................................... 38
3.3.4 MDMA Spectrum........................................................................... 38
3.3.5 Morphine Spectrum....................................................................... 38
3.3.6 Caffeine Spectrum ........................................................................ 38
3.3.7 Paracetamol Spectrum ................................................................. 38
3.3.8 Lactose Spectrum ......................................................................... 38
3.4 Investigating the Effects of Additives on Drug Spectra .......................... 39
3.5 Comparison of the IR Forecasts with HPLC and GC Results................ 43
3.5.1 Evaluation of the comparison........................................................ 45
3.6 FTIR Spectral Database for Illicit Samples ............................................ 47
x
3.6.1 Blind Study.................................................................................... 48
3.6.2 Evaluation of Blind Study .............................................................. 50
4. CONCLUSIONS ............................................................................................ 51
REFERENCES ..................................................................................................... 52
APPENDICES
A CHEMICAL AND PHYSICAL PROPERTIES OF DRUGS........................... 55
B IR-ATR SPECTRA OF DRUG STANDARDS .............................................. 58
C IR-ATR SPECTRA OF ILLICIT SAMPLES ................................................102
xi
LIST OF TABLES
TABLES
1.1 Properties of Commonly Used ATR Crystal Materials ................................. 18

2.1 Specifications of Reference Standards........................................................ 21
2.2 Parameters of FTIR ..................................................................................... 23
2.3 Parameters of GC-MSD Method.................................................................. 24
2.4 Parameters of HPLC Method....................................................................... 25
2.5 Parameters of GC-FID Method .................................................................... 26
3.1 Variation of % T with Number of Scans ....................................................... 28
3.2 Variation of % T with Holding Time.............................................................. 29
3.3 Statistical Evaluation of the Results.............................................................31
3.4 Database Content........................................................................................ 35
3.5 Comparison of the IR Forecast with HPLC and GC Results ....................... 43
3.6 Results of Blind Study.................................................................................. 48
A.1 Chemical and Physical Properties of Drugs ................................................ 55
xii
LIST OF FIGURES
FIGURES
2.1 Schematic Representation of ATR Technique......................................... 23

3.1 Effect of Humidity on IR Spectrum of Heroin ........................................... 33
3.2 Effect of Heroin Concentration on the Appearance of Carbonyl Peaks ... 34
3.3 IR-ATR Spectrum of Heroin with Caffeine ............................................... 39
3.4 IR-ATR Spectrum of Amphetamine with Caffeine.................................... 40
3.5 R-ATR Spectrum of MDMA with Caffeine................................................ 40
3.6 IR-ATR Spectrum of Heroin with Paracetamol ........................................ 41
3.7 IR-ATR Spectrum of Heroin Containing Caffeine and Paracetamol ........ 42
3.8 IR-ATR Spectrum of MDMA Containing Lactose..................................... 42
B-1 Effect of Humidity on IR Spectrum........................................................... 58
B-2 Effect of Heroin Concentration on the Appearance of Carbonyl Peaks ... 59
B-3 IR-ATR Spectrum of Heroin HCl (R1) ...................................................... 60
B-4 IR-ATR Spectrum of Acetyl Codeine (R2) ............................................... 61
B-5 IR-ATR Spectrum of Caffeine (R3) .......................................................... 62
B-6 IR-ATR Spectrum of Cocaine HCl (R4) ................................................... 63
B-7 IR-ATR Spectrum of Codeine (R5) .......................................................... 64
B-8 IR-ATR Spectrum of d,l-amphetamine SO4 (R6) ..................................... 65
B-9 IR-ATR Spectrum of d,l-MDMA HCl (R7)................................................. 66
B-10 IR-ATR Spectrum of d,l-methamphetamine HCl (R8).............................. 67
B-11 IR-ATR Spectrum of Morphine (R9)......................................................... 68
B-12 IR-ATR Spectrum of Narcotine HCl ......................................................... 69
B-13 IR-ATR Spectrum of Papaverine HCl (R11) ............................................ 70
B-14 IR-ATR Spectrum of Paracetamol (R12) ................................................. 71
B-15 IR-ATR Spectrum of Morphine HCl (R13)................................................ 72
B-16 IR-ATR Spectrum of Morphine SO4 (R14) ............................................... 73
B-17 IR-ATR Spectrum of Heroin Containing Caffeine (P1)............................. 74
xiii
B-26 IR-ATR Spectrum of MDMA Containing Caffeine (P10) .......................... 83
B-27 IR-ATR Spectrum of MDMA Containing Paracetamol (P11) ................... 84
B-28 IR-ATR Spectrum of MDMA Containing Lactose (P12) ........................... 85
B-29 IR-ATR Spectrum of MDMA Containing Caffeine and Paracetamol (P13) ................. 86
B-30 IR-ATR Spectrum of MDMA Containing Caffeine and Lactose (P14)...... 87
B-31 IR-ATR Spectrum of Amphetamine Containing Caffeine (P15) ............... 88
B-32 IR-ATR Spectrum of Amphetamine Containing Paracetamol (P16) ........ 89
B-33 IR-ATR Spectrum of Amphetamine Containing Lactose (P17)................ 90
B-34 IR-ATR Spectrum of Amphetamine Containing Caffeine and Paracetamol (P18) .......... 91
B-35 IR-ATR Spectrum of Amphetamine Containing Caffeine, Paracetamol and Lactose (P19)92
B-36 IR-ATR Spectrum of Amphetamine Containing Caffeine and Lactose (P20)..........................93
B-37 IR-ATR Spectrum of Heroin Containing Caffeine and Paracetamol(P21) 94
B-38 IR-ATR Spectrum of Heroin Containing Caffeine and Paracetamol(P22) 95
B-39 IR-ATR Spectrum of Heroin Base (P23) .................................................. 96
B-40 IR-ATR Spectrum of Heroin Base (P24) .................................................. 97
B-41 IR-ATR Spectrum of Caffeine with Paracetamol (P25)............................ 98
B-42 IR-ATR Spectrum of Caffeine with Griseofulvin (P26) ............................. 99
B-43 IR-ATR Spectrum of Morphine (P27)...................................................... 100
B-44 IR-ATR Spectrum of Lactose Standard .................................................. 101
C-1 IR-ATR Spectrum of S1 .......................................................................... 102
C-10 IR-ATR Spectrum of S10 ........................................................................ 106
xiv
xv
xvi
CHAPTER I
INTRODUCTION
1.1 DEFINITIONS OF NARCOTIC AND PSYCHOTROPIC SUBSTANCES
Narcotic and Psychotropic substances are all chemicals that has an affect upon
the body and mind. Their use may lead to physical and/or psychological
dependence [1].
In scientific publications, narcotics are usually distinguished from psychotropic

substances as they are referred to opium alkaloids but for forensic purposes the
term “DRUG” can be used to define all of the substances that have a risk of being
abused.
1.2 HISTORY OF DRUGS
The history of drugs can be attributed to the beginning of the human race. Natural
drugs were used by ancient medicine men to heal some diseases without
considering any side effects. Today, it is known that there is no drug that is not
harmful or even poisonous at high doses, and much of the scientific work on
drugs has attempted to widen the gap between effective and toxic doses.
Ancient drugs, prepared from plants, were used for treatment of diseases as well
as having power on the community. Sumerians had known opium and used it as a
painkiller. Pre-Columbian Mexicans used many substances from tobacco to mind-
expanding hallucinogenic plants in their medicinal treatments and religious
ceremonies. Cocaine’s potential for addiction was known and used with evil intent
by South American Indian chiefs hundred years ago. Tobacco, Cannabis, Opium
Poppy, Coca bush, Khat and other drug containing plants has been chewed or
smoked in many regions of the world as a traditional habit since those times [2].
1
Morphine has been used during World War I as a painkiller and anesthetics;
cocaine has been used for a long time as a local anesthetic for eye and nose
surgeries until they were replaced by less toxic synthetic counterparts.
After the developments in technology and drug industry, it became possible to

produce the synthetic counterparts of these natural drugs. Especially, after 1930
several numbers of drugs had been synthesised for medicinal use. However, in all
cultures there have always been a few individuals who have tendency to misuse
drugs. Thus, both the non-medical use of drugs and problem of drug abuse are as
old as civilization itself.
1.3 DRUG TRAFFICKING AND CONTROL MECHANISMS
It is important to realize that almost all drugs have been and should be isolated or
synthesized for the benefit of human; however, for some of them, just during the
research studies, or after using for a time, it has been understood that they have
the potential of developing dependency and are liable to be abused. Therefore, it
has been a necessity for the governments to constitute some national and
international control systems in order to regulate the production, selling and use of
these drugs.
Three important international conventions, under the United Nations provision,

have been accepted by a large number of participant governments;
“Single Convention on Narcotic Drugs (1961)” [3]
“Convention on Psychotropic Substances (1971)” [4]
“UN Conventions Against Illicit Traffic in Narcotic Drugs and Psychotropic

Substances (1988)” [5]
On the other hand, limitations of legal production resulted in an increase of the

demand for illicit drugs, thus led to the growing problem of illicit productions.
Today, illicit manufacture, trafficking and abuse of clandestinely produced drugs
are serious global problems.
Illicit trafficking of drugs is a many-sided problem that creates a risk for public
health because drugs produced in clandestine laboratories are usually not
2
hygienic and may contain several harmful impurities due to the lack of quality
control steps. Another important aspect is the diversion of money, owned from
drug trafficking, into several terrorist activities.
Illicit trafficking of drugs has a general distribution tendency that opiates are
usually originated from Asia and dispersed through Europe and America, whereas
cocaine and amphetamines are usually produced in European and American
countries and dispersed through Asia and Africa. Along with this dispersion,
Turkey covers a very important geographical location through which all trafficking
ways pass over.
In this crucial location, Turkey has to take responsibility of struggling against illicit
trafficking which will be successful only with the full collaboration of national and
international law enforcement teams, governments, community and forensic
laboratories.
1.4 TERMINOLOGY OF DRUGS
1.4.1 Drug Abuse
Drug abuse is the misuse of medicinal preparations without prescription and

usually with increased doses or usage of illicitly produced drugs.
1.4.2 Drug Dependence
Drug dependence is the tendency to take drug with repeatedly and in increasing
doses. There are two forms of dependence, namely Psychological and Physical.
1.4.2.1 Psychological Dependence
Psychological dependence on the effects of the drug related to a subjective and

individual appreciation of those effects. It means there is a tendency to take the
drug regularly or continuously either to obtain the specific effects it produces or to
nullify certain unpleasant sensation.
1.4.2.2 Physical Dependence
Physical dependence on the drug is resulting from the adaptation of the body to
the substance and leading to the appearance of severe physical and/or
3
psychological disorders when the person concerned stops taking the drug. These
disorders constitute the withdrawal or abstinence syndromes. The complex of
syndrome varies according to the type of drug.
1.4.3 Tolerance
In addition to one or both forms of dependence, the drug user may develop a
tolerance to a particular drug. This means that he has to take larger doses to
obtain the same result since the effect of a given quantity of the drug becomes
progressively less [6].
1.5. CLASSIFICATION OF DRUGS
An effective classification of drugs can be done according to their effects on the

human body; namely depressants, stimulants and hallucinogens. However, many
substances have not strictly defined boundaries in that their effects may change
according to the dose. Usually, the first impression is the sense of well being and
large doses make the dominant effects become observable.
1.5.1 CNS (Central Nervous System) Depressants
CNS depressants slow down the central nervous system so that they create
sedation. The popular drugs in this group are Narcotics and Hypnotic sedatives.
1.5.1.1 Narcotics
The term narcotic come from the Greek word for stupor, refers to induce sleep. In
a legal context, narcotic refers to opium, opium alkaloids (morphine and codeine),
opium alkaloid derivatives (heroin) and totally synthetic substituents with
morphine-like effects (meperidine, methadone, and fentanyl).
Aside from their clinical use in the treatment of pain, cough suppression and acute
diarrhea, narcotics produce a general sense of well being by reducing tension,
anxiety and aggression. These effects are helpful in a therapeutic setting but
contribute to their abuse. With repeated use of narcotics, tolerance and
dependence develop quickly.
4
Opium
Opium is a natural product obtained from the Papaver Somniferum L. The plant
was grown in the Mediterranean region as early as 3000 BC and opium was
known and used as a painkiller until that times [7].
Opium is obtained by incision of the unripe poppy capsules. The milky latex that
oozes from the incisions is scraped by hand and air-dried to produce the opium
gum, which is known as raw opium. The major constituents of raw opium are plant
fragments, resins, sterols, triterpenoid alcohols, fatty acids, polysaccharides and
more than thirty alkaloids. These alkaloids are divided into two chemical classes;
phenanthrene alkaloids (morphine, codeine and thebaine) and isoquinoline
alkaloids (papaverine and narcotine). Papaverine and narcotine have no
significant effect on Central Nervous System but they are found in the final
morphine product as impurities.
The relative amounts of the different alkaloids can vary greatly depending on such
factors as the climate, the altitude, the fertility of the soil, the moisture, age of the
plant, the time of lancing and the variety of Papaver Somniferum L.
Morphine
Morphine is the principal alkaloid of opium, ranging in concentration of 4-21 %.It is

one of the most effective drugs known for relief of pain but clinically it is used in
only absolutely necessary cases due to rapid development of tolerance and
dependency.
The crude morphine in illicit market can be of very high or very low quality,
depending upon the purification procedures, the intended purpose of the material,
habits, knowledge and professional skill of the illicit producer.
Final morphine product diverted into the illicit market contains codeine, thebaine,
narcotine and papaverine as impurities.
Codeine
Codeine, which has effects similar to morphine, naturally founds in opium in

concentrations ranging from 0.7-3 %. Its presence in crude morphine results in
5
the formation of acetyl codeine during the conversion of morphine to heroin.
Codeine is prescribed as an analgesic, cough suppressant and hypnotic.
Papaverine
Papaverine is a non-addictive opium derivative, present at the 0.5-1.3 % level,

used medicinally to relieve spasms of smooth muscle.
Narcotine
Narcotine is the second most abundant alkaloid, usually present in 2-8 % and
sometimes is present in crude morphine as an impurity.
Heroin (Diacetylmorphine)
Heroin is derived from morphine by acetylating with acetic anhydride via a batch
process. Pure heroin is a white powder with a bitter taste. Most illicit heroin is in
powder form and may vary in color from white to dark brown due to the impurities
(acetyl codeine, monoacetylmorphine, narcotine and papaverine) left from the
manufacturing process or the presence of additives (caffeine, paracetamol,
griseofulvin) and diluting agents like sugars, starch, powdered milk and quinine.
Heroin was first synthesized in 1874 as a safe, non-addictive substitute for

morphine [7]. However, it was soon realized that severe dependency develops
very quickly. Heroin is a highly addictive substance and can produce dependence
within only a few days of regular use.
Heroin is a sedative and induces a euphoric, drowsy, warm and content feeling. It
also relieves stress and discomfort by creating a relaxed detachment from pain,
desires and activity.
As well as killing pain, moderate doses of pure opiates produce a range of mild
effects. They depress the activity of the nervous system, including such reflexes
as coughing, breathing and heart rate. At a higher dose sedation can be extreme
and an overdose can result in unconsciousness, coma and often death from
respiratory failure.
6
Synthetic Narcotics
Synthetic narcotics were marketed in order to replace with morphine and to treat
heroin addictives. Most common drugs in this group are Meperidine, Methadone
and Fentanyl. Although these drugs are used clinically, they have the potential of
developing dependence, suffer from illicit production and abuse [6-8].
1.5.1.2 Hypnotic Sedatives
These groups of drugs are used to induce sleep, relieve stress and reduce
anxiety by depressing central nervous system. Unlike most other classes of drugs
of abuse, depressants are rarely produced in clandestine laboratories. Instead,
legitimate pharmaceutical products are diverted into the illicit market.
Two major groups of depressants have dominated the licit and illicit market for
near a century, first barbiturates and now benzodiazepines.
Barbiturates
Barbiturates are derivatives of barbituric acid and were first introduced for
medicinal use in the early 1900s [6]. Barbiturates produce a wide spectrum of
CNS depression, from mild sedation to coma, and have been used as sedatives,
hypnotics, anesthetics and anticonvulsants. Barbiturates are classified according
to how fast they produce an effect and how long those effects last, as ultra short
(methohexital, thiamylal, thiopental), short and intermediate acting (pentobarbital,
secobarbital, amobarbital) and long-acting (phenobarbital, mephobarbital). Ultra
short-acting barbiturates produce anesthesia within about one minute after
intravenous administration. Short and intermediate-acting barbiturates are used
for sedation or to induce sleep, while long-acting barbiturates are used primarily
for daytime sedation and the treatment of seizure disorders or mild anxiety.
Depending on the dose, frequency and duration of use one can rapidly develop
tolerance, physical dependence and psychological dependence on barbiturates.
Barbiturates are only legal if prescribed and supervised by a doctor.
Abuse of barbiturates is very widespread but there is no indication of clandestine

production, in that barbiturates in illicit market result from the diversion of
legitimate sources [6, 8, 9].
7
Benzodiazepines
Benzodiazepines were first marketed in the 1960s [6]. It was claimed that they
were much safer depressants with far less addiction potential than barbiturates. It
has been recently realized that benzodiazepines share many of the undesirable
side effects of the barbiturates. A number of toxic CNS effects are seen with
chronic high dose benzodiazepine therapy.
The benzodiazepine family of depressants is used therapeutically to produce

sedation, induce sleep, relieve anxiety and muscle spasms and to prevent
seizures. In general, benzodiazepines act as hypnotics in high doses, anxiolytics
in moderate doses and sedatives in low doses. Benzodiazepines differ from one
another in how fast they take effect and how long the effects last. Shorter acting
benzodiazepines (estazolam, flurazepam, quazepam, temazepam, triazolam)
used to manage insomnia; longer duration benzodiazepines (alprazolam,
chlordiazepoxide, clorazepate, diazepam, and oxazepam) are primarily used for
the treatment of general anxiety.
Prolonged use can lead to physical dependence and even at recommended

dosages withdrawal syndrome may be resulted [6, 8, 10].
1.5.2 CNS Stimulants
Stimulants have a long history of misuse. The well known less potent stimulants,
which are nicotine and caffeine, relieve fatigue and increase alertness. More
potent stimulant drugs are used medically and on prescription whilst others are
made clandestinely and distributed on the illicit market.
The most popular drugs in this group are Cocaine and Amphetamines. They are
used therapeutically only when it is necessary to stimulate mental or muscular
activity or to treat obesity by reducing the appetite.
1.5.2.1. Cocaine
Cocaine is a unique chemical in that it is both a central nervous system stimulant

and an anesthetic. It is obtained from the leaves of the Erthroxylum coca plant
that is native to the mountains of South America. The traditional method of coca
use is to chew the leaves. On the other hand, in illicit market cocaine is served as
8
powder cocaine or free-base (chemically purified cocaine) and produces much
stronger effect than chewing the leaves.
While as early as 3000 BC, there is evidence of coca use in South America, pure
cocaine was first isolated in the 1880’s and used as a local anesthetics in eye,
nose and throat surgery because of its ability to provide anesthesia as well as to
constrict blood vessel and limit bleeding. In 1914 cocaine was banned in the U.S.
under the Harrison Act, which controlled the sale of opium, opium derivatives and
cocaine [6].
Cocaine increases alertness, wakefulness, elevates the mood, induces a high

degree of euphoria, decreases fatigue, improves thinking, and increases
concentration and energy. In large doses, users often display symptoms of
psychosis with confused and disorganized behavior, irritability, fear and paranoia.
Cocaine is a highly addictive substance developing a strong tolerance and

psychological dependence and moderate physical dependence.
Illicit Cocaine is usually distributed as a white crystalline powder in hydrochloride

salt form or as an off white chunky material which is cocaine free base and
commonly named as crack. Cocaine powder is often diluted with sugars and local
anesthetics like lidocaine [6, 8, 11].
1.5.2.2 Amphetamine and Amphetamine Related Drugs
Amphetamine, dextroamphetamine and methamphetamine, are collectively

referred to as amphetamines, while other members of the group, namely MDMA
(3,4-methylenedioxy-N-methamphetamine), MDA (3,4-methylenedioxy-
amphetamine), DOM (2,5-dimethoxy-4-methylamphetamine ) and DOB (4-bromo-
2,5-dimethoxyamphetamine) are the ring-substituted amphetamines.
Amphetamine
Amphetamine was first marketed in the 1930s as Benzedrine in an over-the-

counter inhaler to treat nasal congestion. By 1937 amphetamine was available by
prescription in tablet form and was used in the treatment of the narcolepsy
(sudden sleep disorder) and Attention Deficit Hyperactivity Disorder [6].
9
During World War II, amphetamine was widely used to keep the fighting men
going; both dextroamphetamine (Dexedrine) and methamphetamine (Methedrine)
became readily available. As use of amphetamines spread, so did their abuse.
Amphetamines became a cure-all for helping truckers to complete their long
routes without falling asleep, for weight control, for helping athletes to perform
better and train longer, and for treating mild depression. But with experience, it
became evident that the dangers of abuse of these drugs outweighed most of
their therapeutic uses. After 1965, limitations for amphetamines were initiated.
Today, amphetamines have found a very limited therapeutical value whereas
increasing demand of abusers lead to a huge number of illicit productions.
Methamphetamine
Methamphetamine is a central nervous system stimulant from the amphetamine

family. It produces alertness, and elation, along with a variety of adverse
reactions. First Synthesized in 1887, in the 1930s it was sold in the U.S. as a
nasal spray for treatment of inflammation of nasal passages and as treatment for
narcolepsy. During World War II, both sides used it to improve soldiers’
performance. This became a major problem in Japan after World War II as they
experienced the first known epidemic of methamphetamine abuse. In 1970, the
Controlled Substances Act regulated the production of methamphetamine [6].
Today much of the methamphetamine available on the street is illicit and

produced in clandestine laboratories.
Methamphetamine’s effects include euphoria, hyper-excitability, extreme

nervousness, accelerated heartbeat, sweating, restlessness, insomnia, tooth
grinding and incessant talking. Users of large amount of methamphetamine over a
long period can develop an amphetamine psychosis, which is a mental disorder
similar to paranoid schizophrenia. Methamphetamine abuse develops moderate
physical and psychological dependence as well as a strong tolerance. Withdrawal
symptoms can occur when use of any amphetamines is stopped abruptly.
10
MDMA (3, 4-methylenedioxy-N-methamphetamine)
MDMA can be extracted from an essential oil of the sassafras tree. Its effects
include euphoria, an increase in emotional openness and mild to moderate
stimulant effect.
MDMA is commonly known as Ecstasy and was first patented in Germany in 1912
as a potential appetite suppressant though it was used as a psychotherapeutic
tool in the late '70s and started to become available on the street. It gained wider
popularity and at the time, it was banned by the DEA (Drug Enforcement Agency)
in 1985 [6].
Mild to moderate doses of ecstasy produces a euphoric sense of well-being and a

feeling of connectedness with and empathy for other people, an enhanced sense
of pleasure and self-confidence and increased energy. In overdoses or misuses
though, users can experience confusion, disorientation, anxiety, panic attacks,
depression, insomnia, perceptual disorders and hallucinations, paranoia and
psychosis. MDMA usage develops moderate psychological dependence and
tolerance [6, 8, 12, 13].
1.5.3 Hallucinogens
Hallucinogen substances can be natural or synthetic origin and have no medicinal

use because they have a violent effect on a person’s mental activity, perceptual
abilities and level of consciousness. The name is due to fact that they cause
hallucinations, visions and on impression of depersonalization.
1.5.3.1 LSD (Lysergic Acid Diethylamide)
LSD is one of the potent hallucinogenic substances known. It was first discovered
in 1938 while researching blood stimulants [6]. Because of its structural similarity
to a chemical present in the brain and the similarity of its effects to certain aspects
of psychosis, LSD was used for a time as a research tool to study mental illness.
There has been no licit use for LSD in over 20 years and LSD products
encountered today on the illicit market are produced only in clandestine
laboratories.
11
In its base form, LSD is a liquid and it is frequently served by dropping the liquid
on to a small absorber like paper, sugar cubes or pharmacologically inert
powders.
During the first hour after LSD ingestion, the user may experience visual changes
with extreme changes in mood. In the hallucinatory state, the user may suffer
impaired depth and time perception accompanied by distorted perception of the
size and shape of objects, movements, color, sound, touch and user’s own body
image. Flashbacks have been reported days or even months after taking the last
dose.
LSD creates no physical but moderate psychological dependence and tolerance

[6, 8, 14].
1.5.3.2 Cannabis
Cannabis Sativa L., the hemp plant grows wild or cultivated in many areas of the
world, with records dating back to at least the 9th century BC [6]. It’s flowering or
fruiting tops contain the psychoactive components delta-9-tetrahydrocannabinol
(THC), cannabinol (CBN) and cannabidiol (CBD). Delta-9-tetrahydrocannabinol
owns the most characteristic of psychoactive effects of the plant.
Cannabis is a very versatile plant; a strong fiber produced from the stem has been
used to make rope, paper and cloth; the dried leaves and flowers are used as
marijuana for their psychoactive or medicinal properties; the roots of the plant
have been used medicinally; and the seeds are used for oil and animal feed.
In illicit market, cannabis is usually used as an herbal product (commonly known

as marijuana), cannabis resin and liquid cannabis. Cannabis resin is formed by
collecting the resin containing parts via some special methods to increase the
THC content of the final product. On the other hand, liquid cannabis is produced
by the extraction of THC from the plant by using chemical solvents.
Cannabis usage leads to time, color, and spatial perception distortions, a dreamy
euphoria, excitement, laughter and increased appetite. Panic attacks and
paranoia sometimes occur, particularly in new users. It develops no physical
dependence but moderate psychological dependence and tolerance.
12
Marijuana has shown promise in many areas of medicine including as an anti-
epileptic, as a treatment for nausea and other side effects of chemotherapy and
AIDS drugs, as one of the only known treatments for glaucoma and as a
treatment for asthma. Recently, the drug has also been used as an experimental
treatment for anorexia nervosa [6, 8, 15].
1.6 THEORY OF THE METHOD USED IN THE STUDY
1.6.1 Infrared Spectrometry
The infrared spectrometry deals with the interaction of infrared (IR) radiation with
matter. The infrared region of the electromagnetic spectrum covers the
wavenumbers from 12800 cm-1 to 10 cm-1 and is further subdivided into near, mid
and far-infrared regions in terms of applications and instrumental designs. The
mid-infrared region extends from 4000 cm-1 to 200 cm-1 and covers most of the
applications.
Absorption of infrared radiation causes transitions between vibrational energy

levels of a molecule, which are also accompanied by several rotational motions.
Vibrational energy corresponds to the vibrations of atoms about the mean center
of their chemical bonds, whereas rotational energy changes occur due to tumbling
motion of a molecule.
In order to absorb IR radiation, a molecule must undergo a net change in dipole

moment as a consequence of its vibration. Homonuclear diatomic molecules do
not absorb IR radiation. On the other hand, complex mixtures give rise to very
crowded spectra in which assigning of bands to specific functional groups is very
difficult. Therefore, IR Spectrometry is mostly useful for pure substances.
Absorption spectrum is a graph of wavelength (λ) vs. absorbance (A), but for IR
region usually it is represented as wavenumber (in cm-1) vs. percent transmittance
(%T). Transmittance is the ratio of the radiant power (P) transmitted by a sample
to the radiant power incident on the sample (P0), i.e.
P
T=
Po
13
Transmittance is related with absorbance as;
A = − log T .
There are two types of molecular vibrations, stretching and bending. Stretching
vibration is the movement along the bond axis and it causes the interatomic
distance become increase or decrease. Bending motion, on the other hand, is the
changing of bond angles.
When an IR spectrum is examined, three properties are considered. These are

the number, the positions and the intensity of absorption bands resulted from a
molecule.
The theoretical number of bands, i.e. fundamental vibrations, present for a

molecule can be calculated from the formulas 3N-6 and 3N-5 for non-linear and
linear molecules, respectively. The formulas are derived from the statement that,
a molecule has three degrees of freedom on the x, y and z coordinates and
molecules with N atoms have 3N degrees of freedom. However, in a non-linear
molecule three of these motions translate the whole molecule on the x, y and z
axes, while another three rotate the molecule on these axes, leaving 3N-6
motions for vibrational changes. On the other hand, for a linear molecule rotation
around one of these axes does not affect the molecule and it has 3N-5 degrees of
freedom for vibrations.
The spectrum of a molecule may contain fewer or more bands than expected. The
reason for having fewer bands is due to the degenerate vibrations, resulted from
the absorptions of common groups at the same wavenumber. In addition, some of
the fundamental bands can be too weak to be observed or so close that they
coalesce.
A greater number of bands can be present also when overtones, multiples of a

given frequency, and combination bands, differences or sums of two other
vibrations, are accompanied to the spectrum.
14
The position of absorption bands depends on the relative masses of the atoms;
the force constants of the bonds and the geometry of the atom and it can be
calculated from the Hooke’s law.
For a diatomic molecule A-B, the wavenumber (in cm-1) of the absorption is:
1 K K
ν= = 5.3 x10 −12 [16]
2πc µ µ
ν : wavenumber (cm-1)
c: the velocity of light (cm/s)
K: force constant of the bond (N/m)
MaMb
µ: the reduced atomic mass of the atoms A and B (kg) ( µ = )
Ma + Mb
In practice, however, specific groups do not absorb at a definite wavenumber due
to the effects of local environment of the group, but their band positions are given
over a range of wavenumbers.
There are two useful regions in the IR spectrum. The group frequency region
encompasses 3600 to 1200 cm-1 region, where the identical functional groups
absorbs in a defined range of wavenumbers. Other important part is called
fingerprint region from 1200 to 700 cm-1 and it reflects the absorptions from the
skeletal structure of the molecule. Small differences in the structure result in
significant changes in fingerprint region so it leads to great evidence for the
identity of the compounds yielding the spectra. Only stereoisomers absorb exactly
in the same way in this region [16-18].
1.6.2 Fourier Transform Infrared (FTIR) Spectrometry
There are several instrumental designs for IR absorption measurements.

Dispersive instruments employ monochromator; nondispersive instruments
employ filters for wavelength selection. Another design is the multiplex type,
which employs an interferometer and uses Fourier Transform for signal encoding.
In multiplex designs, many sets of information are transported simultaneously
through a single channel.
15
An interferometer splits a beam of radiation into two and causes them to travel
different distances, which is called optical path difference. Thereafter, two beams
are combined in destructive and nondestructive means; by changing the optical
path difference an interferogram is measured. Therefore interferogram is a plot of
detector response versus optical path difference that is then Fourier transformed
to give infrared spectra.
FTIR has several advantages over other IR designs. The first one is the Fellgett
or multiplex advantage that is based on the fact that in FTIR instruments all
wavelengths reach to the detector simultaneously. Therefore multiple scans of the
sample can be done in a very short time and signal to noise ratio is improved. In
addition, FTIR has high resolution, wavelength accuracy and precision so that
signal averaging from multiple scans are possible and the result is the improved
signal to noise ratio.
The second advantage is the Jaquinot or throughput advantage; FTIR systems

have no limitations of entrance slit to reduce the radiation; as a result, the power
of radiation reaching to the detector is much greater and hence the signal to noise
ratio is improved.
The final advantage is the lack of interference from stray radiation since each IR
frequency is modulated at a different frequency in an interferometer.
On the other hand, FTIR has a disadvantage. Since it is a single beam

instrumental system, background measurement is done at a different time from
the sample measurement; therefore a change in the environment can affect the
final spectrum [16, 19].
1.6.3 Attenuated Total Reflectance Technique
FTIR spectra can be obtained from the transmission or reflection of IR radiation

from the sample. In transmission measurements, the IR beam passes through the
sample and it is applicable to solids, liquids, gases and polymers that allow
transmission of source light. Reflectance measurements are based on the
reflection of IR radiation on the sample. Reflectance techniques are classified as
diffuse reflectance and Attenuated Total Reflectance (ATR).
16
ATR is especially useful for opaque solid samples regardless of thickness with a
minimum time of preparation. Thin films, pastes, powders, suspensions, paper,
coatings, and fibers can easily be analyzed with ATR technique.
The technique depends on the fact that when a beam of radiation passes from a
denser medium to a less dense medium, reflection occurs. The fraction of the
incident beam that is reflected increases as the angle of incidence becomes
larger and beyond a critical angle, total radiation is internally reflected. However,
the radiation penetrates somehow into the less dense medium before being totally
reflected at the interface. The extent to which the radiation penetrates to less
dense medium is called as depth of penetration and it is given by the following
equation:
1
DP = [19]
2π W N C (sin 2 θ − N 2 sc )1 / 2
DP: Depth of penetration, cm

W : Wavenumber of the radiation, cm-1
Nc : Refractive index of crystal
Θ : Angle of incidence at the interface
N sc : Ratio of refractive indices of sample and crystal (N sample / N crystal)
The penetrating radiation is named as evanescent radiation. If the less dense

medium absorbs the evanescent radiation, attenuation of the beam occurs at
wavelength of absorption bands, which is so called Attenuated Total Reflection.
According to above phenomenon, in ATR measurements sample is pressed

against an internal reflection element with a high refractive index and the
absorption of evanescent radiation occurs.
In order to obtain ATR effect, the refractive index of the internal reflection element
should be greater than that of sample. Commonly used materials with high
refractive indices are thallium bromide/iodide (KRS-5), zinc selenide, germanium
and diamond crystals; their properties are shown in Table 1.1.
17
Table 1.1 Properties of Commonly Used ATR Crystal Materials. [17]
IR Transmission Refractive Index

ATR Crystal Material
Range (cm-1) at 2000 cm-1
KRS-5 (Thallium Bromide/Iodide) 5000-250 2.38
Ge 5000-600 4.01
ZnSe 5000-500 2.40
Diamond 5000-10 2.40
When ATR spectrum of a sample is compared with its transmission spectrum, it is

seen that bands in high wavenumbers (shorter wavelengths) are less intense.
This occurs because depth of penetration is directly proportional with wavelength
and at shorter wavelengths penetration decreases. Therefore, ATR spectrum is
usually corrected when it is necessary to compare it with a transmission spectrum
[16-19].
1.7 LITERATURE SURVEY
Levy et al. (1996) studied illicit heroin samples by FTIR with KBr pellet technique.
Among the 2977 samples, they have distinguished five major groups according to
having different additives. They also grouped the samples into the five districts of
the country where each area has a different distribution of additives [20].
Koulis et al. (2000) collected spectra of 455 controlled and non-controlled drug
standards with FTIR–ATR technique and they constituted a spectral library [21].
Ravbery (1987) proposed method for the quantitative determination of heroin and
cocaine samples by using FTIR-ATR technique. Standard samples and prepared
synthetic mixtures were quantitatively studied as KBr pellets.
For cocaine, two strong carbonyl absorption bands at 1730.9 cm–1 and 1712.8
cm-1 were selected and the effects of base and salt form and additives like
procaine, mannitol, and lactose on the shape of the peaks were investigated. For
heroin, on the other hand, the carbonyl peaks at 1763.0 cm-1 and 1736.0 cm-1
were selected and same variables were studied [22].
18
Ryder (2002) studied 85 solid samples containing illegal drugs by using Near
Infrared and Raman Spectroscopy. Samples were prepared from the standard
materials to reflect the real illicit drugs. The results were evaluated with
chemometric methods and classification had been done according to type of the
drug [23].
Ryder et al. (1999) studied cocaine, MDMA and heroin samples by near-IR and
Raman Spectroscopy in order to make a discrimination between them. In addition,
effect of various diluents and additives on Raman Spectra was investigated and
the results were evaluated with Partial Least Square algorithm [24].
Beckstead and Neville (1988) investigated the ethyl acetate complex formation of
O6-acetylmorphine during the basic extraction of heroin samples. By examining
the IR spectra of extracts, it is concluded that complex formation lead to the
additional peaks that are closely similar to that of heroin and may lead to
misidentification of the samples [25].
Heagy (1970) proved that infrared spectra could be used as an easy and rapid
method to differentiate the optical isomers of amphetamine. It is observed that in
the 800-600 cm-1 region of the spectrum d-, dl- and l- forms of amphetamine
shows distinguishable absorbance characteristics [26].
Sondermann and Kovar (1999) studied ecstasy tablets with near infrared
spectroscopy and applied partial least square regression models to differentiate
main ingredients (MDMA or MDA), diluents and additives [27].
1.8 AIM OF THE STUDY
From the forensic science point of view, drug analysis is referred as the
identification of contents and determination of percent amounts of active
ingredients. In addition, sophisticated works on additives, diluents, specific
impurities and some physical properties give very valuable information about
drugs. It is known that chemical processes applied in clandestine production show
close similarity around the same geographical regions, besides similar precursors
and additives are usually used. Thus, identification of specific characteristics of
drugs can help for making correlations between separate seizures, thereafter drug
19
trafficking ways can be followed, and furthermore the origin of drugs may be
identified.
There are so many articles in the literature about drugs. Although, TLC and GC-
MS for qualitative analysis and GLC and HPLC for quantification are commonly
used ones, new drugs and the increasing number of samples have forced the
scientist to employ powerful hyphenated and fast techniques like LC-MS, LC-MS-
MS, GC-FTIR and Capillary Electrophoresis.
When working with chromatographic methods, specific extraction methods should

be used for the identification of active ingredient and for each of other substances.
In addition, chromatography is usually limited with the solubility of target
compounds. Moreover, it is relatively time consuming and expensive.
In this study, the advances of FTIR technique have been exploited for the
identification of drugs as for being a fast method and requiring almost no
preparation work. It has been aimed to form an IR spectral database that could be
used in differentiating various drugs and their additives by means of a simple
method. Another scope of the study was to create another spectral database for
illicit drugs seized in recent years; thus by comparing a newly handled drug with
this database might indicate a correlation between them.
The drugs covered in this study have been the ones that most widely encountered
in Turkey, namely morphine, heroin, amphetamine, MDMA and cocaine. Despite,
cannabis is the most commonly cultivated drug; it has not been included because
it can be simply identified by the detection of specific microscopic characters. In
addition, the commercially available depressant drugs like benzodiazepines and
barbiturates were not included because they are not produced illicitly.
20
CHAPTER II
EXPERIMENTAL
2.1 Chemicals and Reagents
2.1.1 Standards
Standards were supplied from Lipomed and Sigma-Aldrich and their catalog
numbers are indicated in the Table 2.1.
Table 2.1 Specifications of Reference Standards

Reference Standard Producer Catalog Number
Heroin Lipomed (Certificated HPLC M-29-HC
(C21H23NO5.HCl.H2O) Purity 89.33 %)
Cocaine Lipomed (Certificated HPLC COC-156-HC
(C17H21NO4.HCl) Purity 99.89 %)
d,l-amphetamine Sigma-Aldrich A 1263
(C18H26N2.H2SO4)
d,l-MDMA Lipomed (Certificated HPLC MDM-94-HC
(C11H15NO2.HCl) Purity 99.66 %)
d,l-methamphetamine Lipomed (Certificated HPLC AMP-301-HC
(C10H15N.HCl) Purity 99.44 %)
Morphine Base TMO (Toprak Mahsülleri Ofisi) > 95 % (Private
(C17H19NO3) Bolvadin Plant Alkaloid Factory discussion)
Morphine Sulfate Sigma-Aldrich M 8777
(C34H40N2O10S.5H2O)
Morphine Hydrochloride Lipomed M 35-HC
(C17H19NO3.HCl.H2O)
Narcotine Sigma-Aldrich N 9007
(C22H23NO7.HCl)
Papaverine Sigma-Aldrich P 3510
(C20H21NO4.HCl)
Paracetamol Sigma-Aldrich A 7085
(C8H9NO2)
Caffeine Sigma-Aldrich C-7731
(C8H10N4O2)
Lactose Sigma-Aldrich L-3625
(C12H22O11.H2O)
21
2.1.2 Samples
During the study, a total of 76 illicit drug samples, containing several additives and
active drugs in varying percent amounts, were analyzed. Illicit samples were
obtained from the Gendarme Criminal Laboratory Chemistry Branch. They were
selected in order to reflect a wide range of variety in terms of their compositions.
However, as for the active drugs only heroin, morphine, cocaine, amphetamine
and MDMA were studied because they are the most commonly encountered
drugs in Turkey. On the other hand, although these drugs can contain many other
additives, only the presence of caffeine, paracetamol and lactose were examined,
again due to the same reason of having a wide usage.
2.2 Instrumentation and Apparatus
All drug standards and samples were analyzed with FTIR-ATR System.
Quantitative analyses of the samples were done by HPLC (High Pressure Liquid
Chromatography) and GC-FID (Gas Chromatography-Flame Ionization Detector).
Qualitative analyses of the samples were done by GC-MSD (Gas
Chromatography-Mass Selective Detector).
2.2.1 FTIR
Perkin Elmer FTIR Spectrometer, Model Spectrum One was used to collect the
spectra of drug standards and illicit drug samples. Method parameters are shown
in Table 2.2.
22
Table 2.2 Parameters of FTIR
Detector MIR-TGS (Mid Infrared- Triglycerine Sulphate)
Source Silicon Carbide (Globar)
IR Accessory Universal ATR
Resolution 4 cm-1
Scan Range 4000-650 cm-1
Scan Number 32
145-150 Newton
Force applied onto
samples
(Corresponding pressure is 5.13x106 – 5.31x106 N/m2)
Diameter of pressure 6.0 mm

arm
All spectra were obtained by using an ATR accessory. A schematic

representation of the ATR used in the study is shown in Figure 2.1.
Figure 2.1 Schematic representation of ATR technique [28].
23
The ATR accessory composed of a single reflection Diamond crystal with a
refractive index of 2.40 and reflection angle of 450. A composite of ZnSe is
covered at the bottom of crystal to prevent the radiation loss. [29].
2.2.2 GC-MSD
Qualitative analyses of the samples were done with Agilent Technologies 6890 N
GC-MSD System. Method parameters are shown in Table 2.3.
Table 2.3 Parameters of GC-MSD Method.
Column Cross-linked %5 phenyl %95 dimethylpolysiloxane

(Hewlett-Packard HP-5MS) 0,25 mm in internal
diameter, 30 m in length and 0.25 µm in film thickness
Carrier Gas Helium with 1.0 mL/min constant flow rate
Injection Port T 265 0C
MSD transfer line T 280 0C
MS Quad T 150 0C
MS Source T 230 0C
Solvent Delay 4.00 min.
Column T Initial T:100 , initial time:1 min., ramp 20 0C /min , final

T:280 0C, hold time:20 min
Injection volume 1.0 µL
Split Ratio 70:1
Mass Range 40.0-550.0 amu
24
2.2.3 HPLC
Quantitative analyses of Morphine, Heroin, Amphetamine and MDMA were done

with Agilent 1100 Series Reverse phase HPLC system. Parameters of the method
are shown in Table 2.4.
Table 2.4 Parameters of HPLC Method
Column Waters bondapak C-18, 30 cm in length, 3.9 internal

diameter
Detector UV Diode Array Detector
Wavelength 218 nm (selected for best absorbance)
Flow rate 1 ml / min.
Mobile phase A: Phosphate buffer (pH 2.26),
B: Methanol
Gradient conditions Time % Methanol % Buffer

(for morphine and heroin) 0 5 95
20 40 60
27 40 60
32 60 40
37 60 40
42 5 95
Gradient conditions Time % Methanol % Buffer
(for amphetamine and 0 5 95
MDMA) 20 40 60
25 5 95
30 5 95
Injection solution Water, Acetonitrile, Acetic Acid (89:10:1) pH:3,71
Injection volume 20 µL
25
2.2.4 GC-FID
Quantitative analyses of cocaine samples were done with Agilent 5890 GC

System. Parameters of the method are shown in Table 2.5
Table 2.5 Parameters of GC-FID Method
Detector Flame Ionization detector (FID)
Carrier Gas Helium
Column 5% Phenyl 95% dimethylpolysiloxane (HP-5), 30 m in

length, 0.32 mm internal diameter, 0.25 µm film
thickness
Injection port T 265 0C
Column T Initial T: 100 0C, Initial Time : 1.0 min., ramp: 20 0C /

min, final T:280 0C, hold time 20.0 min.
Detector T 280 0C
Internal Standard n-octacosane
Injection volume 1.0 µL
2.3. Procedures
2.3.1 FTIR
In IR spectrometry; solid samples are usually sampled as KBr disc or Nujol mull
techniques, which give good spectra and compensate inhomogeneity problems.
However, both techniques require time for preparation and do not practical as
compared to ATR sampling.
26
In the study, powdered samples were directly applied onto ATR crystal. During
ATR sampling one of the most important parameters is the particle size of the
sample. Samples should be finely powdered to get the best contact with the
crystal and obtain the best homogeneity.
All standards and samples were ground by using an agate mortar and pestle for
about 2 minutes that was an adequate time for obtaining a fine powder.
With the help of the pressure arm on the ATR accessory, 145-150 N force was
applied onto samples to get a good contact with the crystal surface. The
application of force leads to a thin film that the final thickness of the samples was
not greater than 1.0 mm.
IR spectra were obtained in % transmission mode, however when the comparison

of band intensities were needed then they were transformed to absorbance mode
by using the software.
Background spectra were collected for every 5 samples.
The crystal surface was cleaned with isopropyl alcohol by using a piece of cotton.
IR searches of spectra were done by using an Euclidian search, which is one of

the possible searching tool in the software and it is based on the comparison of
spectra shapes. The best spectrum shape match appears on the top of the hit list.
Hit lists can also be generated in other criterions like Possible Structural Unit
score and Peak match score [30].
However, the best results were obtained by using Euclidian search.
27
CHAPTER III
RESULTS AND DISCUSSIONS
3.1 Optimization of FTIR Parameters
3.1.1 Scan Number and Holding Time
In order to optimize the scan number, standard Heroin Hydrochloride salt in

powder form was studied by applying different scan numbers and for each of
them four replicate measurements were done. Results are shown in Table 3.1
Table 3.1 Variation of %T with Number of Scans

Scan % T at % T at
Evaluation of Results Evaluation of Results
Number 1759 cm-1 1735 cm-1
8 (1) 71.66 54.06
Mean: 70.82 Mean: 53.74
8 (2) 71.72 56.73
Standard Deviation:1.22 Standard Deviation:2.22
8 (3) 70.79 52.42
8 (4) 69.10 51.75
16 (1) 69.02 51.58
Mean: 71.54 Mean: 54.96
16 (2) 73.11 57.94
16 (3) 70.43 52.85
16 (4) 73.62 57.47
32 (1) 71.65 54.21
Mean: 70.28 Mean: 51.88
32 (2) 70.28 51.70
32 (3) 71.18 53.54
32 (4) 68.01 48.05
64 (1) 68.17 51.06
Mean: 71.46 Mean: 54.39
64 (2) 71.07 53.10
64 (3) 69.32 51.06
64 (4) 77.30 62.35
124 (1) 75.91 60.45
Mean: 72.94 Mean: 56.00
124 (2) 69.32 50.86
124 (3) 72.74 55.38
124 (4) 73.80 57.33
28
Another parameter in relation with the percent transmittance value is the time
elapsing under pressure; this parameter will be called as holding time. As the time
is prolonged under pressure, particles come closer and a better contact with the
crystal is obtained. To investigate the time needed to obtain the best intensities,
the spectra of standard Heroin Hydrochloride salt in powder form were collected
at every 5 minutes up to 20 minutes using the same scan number and with four
replicate measurements. Results are shown in Table 3.2.
Table 3.2 Variation of % T with Holding Time, Number of Scans is 32.
Holding % T at % T at 1735
Evaluation of results Evaluation of results
time 1759 cm-1 cm-1
5 min (1) 73.19 57.25

Mean: 72.82 Mean: 55.92
5 min (2) 72.19 54.91
Standard deviation:1.49 Standard deviation:2.39
5 min (3) 71.21 53.08
5 min (4) 74.70 58.42
10 min (1) 73.18 57.23

Mean: 72.80 Mean: 55.90
10 min (2) 72.17 54.93
10 min (3) 71.14 52.96
10 min (4) 74.70 58.51
15 min (1) 73.15 57.23

Mean: 72.79 Mean: 55.86
15 min (2) 72.17 54.87
15 min (3) 71.13 52.92
15 min (4) 74.71 58.40
20 min (1) 73.17 57.34

Mean: 72.79 Mean: 55.89
20 min (2) 72.17 54.90
20 min (3) 71.11 52.90
20 min (4) 74.71 58.41
29
In order to see the differences between the data sets for various scan numbers
and holding time statistical evaluation was applied according to the following
relation;
N1 + N 2
X1 − X 2 < ± t s pooled [31]
N1 N 2
X 1 and X 2 are the mean values of two sets to be compared, N1 and N2 are
respective number of measurements.
If the difference between the mean values of two experimental data sets is
smaller than the calculated value on the right side of the equation, then there is no
significant difference between the two mean values.
spooled is the combined standard deviation for two data sets and can be calculated
from the formula;
N1 N2
∑ (X ) + ∑ (X )
2 2
i − X1 j − X2
i =1 j =1
s pooled = [31]
N1 + N 2 − 2
Comparison of the scan numbers of 32 and 124 and holding time of 5 and 20
minutes are shown in the Table 3.3. These were selected as the sets with lowest
and highest mean values.
30
Table 3.3 Statistical Evaluations of the Results.
For scan numbers of For holding time of
32 and 124 5 min and 20 min.
At 1759 cm-1 At 1735 cm-1 At 1759 cm-1 At 1735 cm-1
t (for 95% confidence

level and 6 degree of 2.45 2.45 2.45 2.45
freedom)
Spooled 2.26 4.21 1.51 2.41
N1 + N 2
t s pooled 3.91 7.29 2.62 4.18
N1 N 2
X1 − X 2 2.66 4.12 0.03 0.03
As it can be seen in the table, all mean value differences are smaller than the
calculated values which indicates variations in scan number and holding time do
not result in any improvement in band transmittances. Therefore, it was decided
to use an average scan number of 32 with zero holding time.
On the other hand, during the preliminary studies it was observed that the regime
of tightening has a notable effect on the band intensities; i.e. increasing the
applied force slowly up to 150 Newton, and then immediately relaxing the
pressure arm till 100 Newton and thereafter rapidly rising the applied force again
to 150 Newton gave the best results. It can be suggested that during the
relaxation process, air between the particles is forced to come out further and
subsequent force application ensures that the particles get together closer leading
to a better contact with the crystal surface.
All IR spectra were obtained so that minimum transmittance was not less than 25
% to ensure a healthy signal to noise ratio.
3.1.2 Particle Size
It was observed that particle size has a great effect on FTIR-ATR spectra.
Naturally, smaller particle sizes result in better contact with ATR crystal; sensitivity
is better.
31
It could be suggested to sift the samples in order to decrease the particle size,
however these drug samples consist of several components with their respective
particle size distributions; consequently a sifting procedure would result in a
mixture that may not be representative of the original sample. In other words, the
component with the smallest particle size would be present in the final sample
with an enriched concentration; the final sample will not be representative.
The most convenient way to decrease the particle size was grinding the samples
until a fine powder is obtained using a minimal period that is 2 minutes for this
study. A grinding procedure that is excessively long would result in several
undesired effects. It has been reported that grinding may alter the composition of
the sample and may result in a phase transformation from crystalline to
amorphous state due to pressure applied or direct frictional heating [32]. Besides,
extensive grinding would make the procedure longer that is in contrast with the
general purpose of the study.
3.1.3 Effect of Humidity on Spectra
Water contributes to the spectra with O-H stretching bands in 3600-3200 cm-1
region. The effect of humidity and crystal water on the spectra of drugs in
accordance with IR search results was examined with several samples by
collecting the spectrum before and after drying (2 hours at 100 0C in oven) the
sample. It was observed that although water causes an obvious change in
spectrum regarding visual examination, its presence does not cause any
significant influence on the computer search results. Therefore, it was decided
that there is no need to dry the samples before collecting the spectra. Effect of
humidity on heroin spectrum is shown in Figure 3.1. The searching software
decided both spectra as Heroin base.
32
0 .26 0 S31 dried.sp / drug.dlb Euclidean Search Hit List
1758.26 1738.96 1192.37
0 .24 0.986 PP023 P P23 HEROIN BASE
1229.39
S31.sp / drug.dlb Euclidean Search Hit List

0 .22
0.965 PP024 P P24 HEROIN BASE
0 .20
1447.28
0 .18 3366.66
1366.90
1052.90
0 .16
1620.00
0 .14
A
0 .12
0 .10
0 .08
0 .06
0 .04
0 .02 0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure 3.1 Effect of humidity on IR spectrum of Heroin (Black: IR-ATR Spectrum of S31
before drying, Red: IR-ATR Spectrum of S31 after drying)
3.2. Constitution of Spectral ATR Database for Drug Standards
In the first part of the study, an FTIR-ATR spectral database was constituted to
identify the compositions of illicit samples.
Illicit samples contain active drug and additives in varying percent amounts.
Therefore, a successful IR database should comprise possible alternatives of
different compositions as well as the pure standards.
In order to constitute the database for standards, pure standards and secondary
standards with known percent concentrations were used. The mixtures of
standards were prepared to simulate the illicit samples.
3.2.1 Relation Between Percent Concentration and Band Intensity
In order to find a correlation between percent concentration of the drug in the

sample and its characteristic absorption bands, several sets of samples with
varying percent amounts of drugs were examined. It was expected that increasing
the percent amount of the drug should enhance its absorption, and it was thought
33
that identification of the samples in known concentration ranges might be
possible, but the results were not as expected.
The first set contained three heroin samples with different heroin percent
amounts, i.e., 0.4 %, 19.9 % and 63.7 %, shown in Figure 3.2.
1758.83 1738.27
1230.29
1448.00 1366.96 1192.80
S14 (63.7 % Heroin)
1751.57
1271.42 1258.11
1497.59 1477.02
A S16 (19.9 % Heroin)
1751.57
1271.42 1258.11
1497.59
1477.02
S17 (0.4 % H eroin)
1 81 3.3 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 60 .6
cm-1
Figure 3.2 Effect of Heroin concentration on the appearance of carbonyl peaks.
It was observed that percent amount of heroin in the sample has a direct effect on
the appearance of carbonyl stretching bands; low concentrations (0.4 %) result in
a single peak at 1751 cm-1 as a significant contribution from narcotine only and
spectrum resembles naturally to that of narcotine, which is the second most
abundant component in the sample. On the other hand, when the heroine
concentration is large (63.7 %), both peaks appear as contribution from heroine at
1759 cm-1 and 1738 cm-1. However, for sample 16 (S16) although concentration
of heroin is large enough (19.9 %), carbonyl stretching of narcotine is still very
dominant and it shields the heroin peaks.
34
Consequently, it could not be possible to make a direct correlation between the
percent amount and intensity because other components of the sample have a
great influence on the spectra.
Besides, in another set of samples the effect of percent amount of caffeine was
investigated by successively increasing the caffeine concentration in heroin
sample. It was expected that an increase in caffeine concentration would enhance
its absorbance bands with a direct correlation. However, again no relation
between concentration and characteristic band intensities could be made.
As a result, for the database it was decided to include different percent

combinations of drugs and additives so as to cover all possible alternatives of
illicit samples but their respective percent concentrations were not noted in the
final form of the database. Consequently, it was just aimed to detect whether the
sample contains an additive or not in any amount.
3.2.2 FTIR Spectral Database Content
Final form of the database is shown in Table 3.4 in which Drug standards were
labelled as “R”, prepared mixtures and secondary standards as “P”. All spectra in
the database are shown in the Appendix B from Figures B-3 to B-44.
Compositions of secondary standards below have been determined by HPLC.
Table 3.4 Database Content.

Label Drug Composition (w/w %)
R1 Heroin Hydrochloride 100.0 %
R2 Acetyl Codeine Base 100.0 %
R3 Caffeine 100.0 %
R4 Cocaine Hydrochloride 100.0 %
R5 Codeine Base 100.0 %
R6 d,l-amphetamine Sulfate 100.0 %
R7 d,l- MDMA Hydrochloride 100.0 %
d,l-methamphetamine
R8 100.0 %
Hydrochloride
R9 Morphine Base 100.0 %
R10 Narcotine Hydrochloride 100.0 %
R11 Papaverine Hydrochloride 100.0 %
35
Table 3.4 (Continued)
R12 Paracetamol 100.0 %
R13 Morphine Hydrochloride 100.0 %
R14 Morphine Sulfate 100.0 %
P1 Heroin, Caffeine 52.2 % Heroin, 15.2 % Caffeine
P10* MDMA, Caffeine 30.7 % MDMA, 26.9 % Caffeine
P11* MDMA, Paracetamol 29.5 % MDMA, 29.5 % Paracetamol
P12* MDMA, Lactose 29.2 % MDMA, 30.5 % Lactose
24.0 % MDMA, 23.3 % Caffeine,
P13* MDMA, Caffeine, Paracetamol
19.5 % Paracetamol
23.9 % MDMA, 21.4 % Caffeine,
P14* MDMA, Caffeine, Lactose
21.6 % Lactose
P15 Amphetamine, Caffeine 66.4 % Amphetamine, 33.5 % Caffeine
P16 Amphetamine, Paracetamol 66.8% Amphetamine, 33.1 % Paracetamol
P17 Amphetamine, Lactose 71.4 % Amphetamine, 28.6 % Lactose
Amphetamine, Caffeine, 62.2 % Amphetamine, 17.9 % Caffeine,
P18
Paracetamol 19.7 % Paracetamol
P19
Paracetamol, Lactose 16.4 % Paracetamol, 22.4 % Lactose
P20
Lactose 30.6 % Lactose
43.5 % Heroin, 14.7% Caffeine,
P21 Heroin, Caffeine, Paracetamol
15.0 % Paracetamol
24.7 % Heroin, 18.2 % Caffeine,
P22 Heroin, Caffeine, Paracetamol
13.1 % Paracetamol
P23 a Heroin Base 62.6 % Heroin
P24 b Heroin Base 36.5 % Heroin
P25 Caffeine, Paracetamol 41.4 % Caffeine, 47.6 % Paracetamol
P26 Caffeine, Griseofulvin 12.9 % Caffeine, Griseofulvin
c
P27 Morphine Base 10.8 % Morphine
36
* P10, P11, P12, P13 and P14 were prepared by mixing the powder of an illicit
MDMA tablet, containing 42.0 % MDMA, with respective amounts of caffeine,
paracetamol and lactose standards.
a
P23 is an illicit heroin sample containing 62.6 % Heroin, 1.9 %
Monoacetylmorphine, 5.1 % Acetyl codeine, 2.3 % Papaverine and 20.6 %
Narcotine. It was used to prepare P1, P2, P3, P4, P5 and P21.
b
P24 is an illicit heroin sample containing 36.5 % Heroin, 9.2 %
Monoacetylmorphine, 3.1 % Acetyl codeine, 1.9 % Papaverine and 30.6 %
Narcotine. It was used to prepare P6, P7, P8, P9 and P22.
c
P27 is an illicit morphine sample containing 10.8 % Morphine, 3.5 % Codeine,
1.6 % Papaverine and 7.6 % Narcotine.
3.3 Interpretation of the Spectra
Drug standards have characteristic absorptions, which are very helpful to identify
them.
3.3.1 Heroin Spectrum
The major peaks in heroin base spectrum are 1759 and 1738 cm-1 (carbonyl
stretching), 1447 cm-1, 1366 cm-1, 1230 and 1211 cm-1 (acetate C-O stretching),
1192 cm-1 and 1052 cm-1.
In heroin hydrochloride spectrum small shifts occur in the peak positions as; 1759
cm-1, 1735 cm-1, 1444 cm-1, 1369 cm-1, 1244 cm-1, 1198 cm-1, 1176 cm-1, 1155
cm-1, and hydrochloride salt formation results in N-H band at around 2600 cm-1.
3.3.2 Cocaine Spectrum
Spectrum of cocaine hydrochloride has absorption peaks at 1728 and 1711 cm-1
(carbonyl stretching), 1264 cm-1, 1230 and 1105 cm-1 (acetate C-O stretching),
1071 cm-1, 1025 and 729 cm-1 (mono substituted benzene stretch) and
hydrochloride salt formation is also identical due to the N-H stretching bands
around 2530 cm-1.
37
For cocaine base the major peaks are 1734 cm-1, 1706 cm-1, 1272 cm-1, 1253
cm-1, 1106 cm-1, 1035 and 711 cm-1.
3.3.3 Amphetamine Spectrum
The major peaks in Amphetamine Sulfate spectrum are 1550 cm-1, 1144 cm-1
(ionic SO4 stretch), 1050 cm-1, 729 and 698 cm-1 (mono substituted benzene
stretch) and N-H stretching of amine salt at 2800-3000 cm-1 region.
3.3.4 MDMA Spectrum
In the MDMA Hydrochloride spectrum important peaks are 2710 cm-1 (N-H
stretching of amine salt), 2458 cm-1 (C-H stretching of CH3 group), 1488 cm-1 (C-H
bend), 1244 and 1030 cm-1 (C-O-C stretching of methoxy group), 930 cm-1 (C-O
stretching).
3.3.5 Morphine Spectrum
Morphine has characteristic peaks at around 3200 cm-1 (O-H stretching), 1471
cm-1 (O-H bend), 1442 cm-1 (C-C stretch) 1241 cm-1, 1117 cm-1, 1086 cm-1, 941
cm-1, 800 cm-1 and 757 cm-1.
3.3.6 Caffeine Spectrum
Caffeine has important peaks at 1693 and 1644 cm-1 (carbonyl stretch), 1547
cm-1, 1237 cm-1, 758 cm-1 and 743 cm-1.
However, it was observed that when caffeine exists is heroin, its peak positions
change as 1698 cm-1, 1656 cm-1, 1550 cm-1, 1230 cm-1, 764 cm-1and 745 cm-1.
3.3.7 Paracetamol Spectrum
The major peaks in paracetamol spectrum are 3321 cm-1 (N-H stretching), 3108
cm-1 (O-H stretching), 1650 cm-1 (carbonyl stretching), 1609 cm-1 (N-H bend),
1561 cm-1, 1505 cm-1, 1433 cm-1, 1258 cm-1and 1224 cm-1.
3.3.8 Lactose Spectrum
Lactose has important peaks at 3260 cm-1 (O-H stretching), 1140 cm-1, 1114
cm-1, 1070, 1018 cm-1, 987 cm-1and 875 cm-1.
38
3.4 Investigating the Effects of Additives on Drug Spectra
Caffeine, paracetamol and lactose when exist in the sample can be identified with
the addition of extra bands.
When caffeine exists in the sample its carbonyl absorption bands at 1698 cm-1 (or
1693) and 1656 cm-1 (or 1644) can easily be identified. The spectra of heroin,
amphetamine and MDMA containing caffeine are shown in Figure 3.3, Figure 3.4
and Figure 3.5, respectively.
9 6.7
94
92
90
1656.56
88
1699.82
%T 8 6
84
82
1738.87
80 1758.66
78
7 6.3
1 84 0.0 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 00 8 00 7 00 6 20 .0
cm-1
Figure 3.3 IR-ATR Spectrum of Heroin with Caffeine (additional caffeine peaks at 1699
cm-1 and 1656 cm-1)
39
9 6.8
95
90
85
80
%T
1238.19
758.86
75
1547.39
70
1694.62
65 1645.54 744.14
6 3.2
1 76 3.3 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 00 8 00 7 00 6 10 .0
cm-1
Figure 3.4 IR-ATR Spectrum of Amphetamine with Caffeine (additional caffeine peaks at
1694 cm-1 and 1645 cm-1)
9 8.9
98
96
94
92
%T 9 0 759.30
1547.72
88
86 1244.60
1488.06
744.79
84
1696.05 1646.22
8 2.5
1 77 6.7 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 00 8 00 7 00 6 40 .0
cm-1
Figure 3.5 IR-ATR Spectrum of MDMA with Caffeine (additional caffeine peaks at 1696
cm-1 and 1646 cm-1)
40
Addition of paracetamol into sample also gives identical bands at 1651 cm-1, 1610
cm-1, 1561 cm-1 and 1433 cm-1. This is shown in Figure 3.6.
9 6.7
96
95
94
93
1561.67
92
91
1651.41 1610.00
90
89
%T
88 1433.97
87
86
1366.66
1447.77
85
84
83 1759.12
1739.43 1230.33
82
1192.36
8 0.8
1 85 3.3 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 00 8 00 7 00 6 36 .7
cm-1
Figure 3.6 IR-ATR Spectrum of Heroin with Paracetamol (additional paracetamol peaks at
1651 cm-1, 1610 cm-1, 1561 cm-1 and 1433 cm-1)
However, when the sample contains both caffeine and paracetamol identification
of them separately is impossible due to their close absorption bands in 1700-1650
cm-1 region. This is shown in Figure 3.7. In the spectrum, caffeine peaks at 1699
cm-1, 1657 cm-1 and 1548 cm-1 are evident; on the other hands paracetamol peaks
at 1650 cm-1, 1610 cm-1, 1561 cm-1 and 1432 cm-1 exist as shoulders, hence they
could not be identified by the searching software.
41
9 6.5
94
92
90
1561.46
88
1548.03
86
1610.14
84
82
%T 1432.22
80
1699.10 1650.42 745.72
78 1657.13 1366.76
76 1759.52 1447.32
1739.38
74
72
70
6 7.7
1 82 6.7 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 00 8 00 7 00 6 43 .3
cm-1
Figure 3.7 IR-ATR Spectrum of Heroin containing Caffeine and Paracetamol
Existence of lactose in the amphetamine and MDMA tablets is evident from the
additional peaks at 1140 cm-1, 1114 cm-1, 1070 cm-1 and 1018 cm-1. This is shown
in Figure 3.8.
9 7.9
96
94
92
2458.05
1140.78
90
3262.01
875.14
88 2710.60 1114.82
86
%T 8 4 1488.93
1244.93 1070.69
82
930.82
80 987.63
78
76
74
1037.18
7 2.4 1018.78
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure 3.8 IR-ATR Spectrum of MDMA containing lactose. (additional lactose peaks at
1140 cm-1, 1114 cm-1, 1070 cm-1 and 1018 cm-1)
42
3.5 Comparison of the IR Forecasts with HPLC and GC Results
After constitution of the database of standards, 76 illicit drug samples were

studied with the same method and they were searched against this database by
means of Euclidian search. Only the first search result was taken in account. The
IR forecasts for 76 illicit drugs were compared with their HPLC and GC results
and are shown in Table 3.5
Table 3.5 Comparison of IR Forecasts with HPLC and GC Results.

Sample
IR Forecast HPLC or GC-FID Results
No
S1 Cocaine 89.3 % Cocaine
S4 Cocaine 63.6 %Cocaine
S6 Morphine 11.6 % Morphine
S14 Heroin 63.7 % Heroin, 26.7 % Narcotine
S16 Narcotine 19.9 % Heroin, 49.6 % Narcotine
S20 Heroin, Caffeine 27.8 % Heroin, 13.7 % Caffeine, 35.4 % Narcotine
43
26.7 % Heroin, 0.4 % Caffeine, 1.4 % Paracetamol,
S26 Narcotine
40.9 % Narcotine
S27 Narcotine
42.8 % Narcotine
S28 Narcotine
40.7 % Narcotine
S29 Heroin, Caffeine
12.8 % Paracetamol, 24.3 % Narcotine
S30 Heroin, Caffeine
14.4 % Paracetamol, 23.1 % Narcotine
S42 Paracetamol 90.5 % Paracetamol
S43 Caffeine, Paracetamol 41.4 % Caffeine, 47.6 % Paracetamol
S44 Griseofulvin, Caffeine 16.9 % Caffeine, Griseofulvin
S45 Griseofulvin, Caffeine 12.9 % Caffeine, Griseofulvin
S46 Paracetamol 88.3 % Paracetamol
Amphetamine, caffeine,
S47 3.5 % Amphetamine, 14.2 % Caffeine, Lactose
lactose
S48 Caffeine 1.6 % Amphetamine, 19.5 % Caffeine, Lactose
lactose
S50 Amphetamine, lactose 14.3 % Amphetamine, 0.9 % Caffeine, Lactose
lactose
lactose
S53 Amphetamine, lactose 15.1 % Amphetamine, 0.4 % Caffeine, Lactose
lactose
44
S55 MDMA, lactose 15.0 % MDMA, lactose
S58 MDMA lactose 35.1 % MDMA, lactose
S59 MDMA, lactose 22.6 % MDMA
S60 MDMA, lactose 38.9 % MDMA, 2.1 % Caffeine
lactose
S63 MDMA 31.5 % MDMA
S70 MDMA 26.2 % MDMA, 1.8 % Caffeine
S71 MDMA, lactose 25.6 % MDMA, 0.6 % Caffeine
S74 MDMA 55.9 % MDMA, lactose
3.5.1 Evaluation of the Comparison
The IR forecasts of the samples can be evaluated as satisfactory except for a few
deviating results. There is no completely wrong result, but some of them are
incomplete, which means some of the components in the sample could not be
identified.
For cocaine samples, S1 through S5, there was no problem and all of them were
identified correctly. Illicit cocaine samples are usually served in high purity, usually
greater than 80 %. Some of them may contain sugar or carbonates, but during the
study, additives of cocaine were not examined. In addition, it was observed that
45
base and hydrochloride salt form of the cocaine could easily be differentiated from
the IR spectra due to the shifts in the peak positions. This is true for S5, which is
in base form and shown in the Appendix C-5.
Similarly, for morphine samples, S6 through S13, no problem was encountered

because morphine almost never contains additives. During the conversion of
morphine to heroin, additives are included to increase the total amount.
Illicit heroin samples can be found in many different compositions due to several
impurities coming from the morphine (like meconine, thebaine, narcotine and
papaverine) and conversion steps (like calcium carbonate) and other substances
(such as caffeine, griseofulvin, paracetamol, procaine) included into the final
product. Therefore, it was not easy to predict the influence of each component on
to the spectra.
One criterion for the heroin samples was the percent amount of heroin in the
sample, when the heroin is in low amounts then the second most abundant
component narcotine becomes dominant on the spectra, this was the case for
samples S17 and S19.
Another factor is the significant contribution from narcotine peak at 1751 cm-1,
which is shielding the carbonyl bands of heroin at 1759 and 1738 cm-1 and
resulting the spectra resembles to that of narcotine. For samples S16, S22, S26,
S27 and S28 this can be an explanation for the IR forecasts giving narcotine,
although all samples contained a notable amount of heroin.
On the other hand, when we examine the narcotine concentration in above

samples, it was seen that all have narcotine greater than 40 %, which is very high
and makes the narcotine major ingredient of the sample. Consequently, we can
conclude that IR forecasts are accurate, although the existence of heroin is not
detected. Besides, the presence of narcotine is also an indication of an opium
product.
Existence of caffeine in heroin was identified easily even when it is present in

small amounts, such as in S23, S24, S36 and S37. Caffeine peaks at 1698, 1656,
1550 and 1230 cm-1 are still observable in the spectra.
46
Samples containing both caffeine and paracetamol, S26, S27, S28, S29 and S30,
were not identified correctly. Three of them, S26, S27 and S28, suffer from great
narcotine contribution at 1751 cm-1, consequently, the forecast results were
narcotine only; whereas for other two, S29 and S30, although caffeine peaks at
1698, 1656, 1550 1230, 764 and 745 cm-1 are clear, paracetamol peaks exist in
the shoulders at 1650, 1609, 1561 and 1430 cm-1; consequently IR forecasts
indicated the composition as heroin plus caffeine.
Amphetamine tablets numbered as S47, S49, S51, S52, S54 and S61 were
correctly identified.
In the samples S50 and S53, caffeine concentrations are very low (0.9 % and 0.4
%), therefore caffeine was not detected. On the other hand, in the samples S48
and S56, amphetamine concentrations are low (1.6 % and 5.5 %) and caffeine is
the major component, naturally IR forecasts were caffeine and not amphetamine.
MDMA tablets numbered as S58, S59, S63, S64, S65, S66, S67, S68, S69, S72
and S73 were correctly identified.
Caffeine content in the MDMA tablets (S60, S70 and S71) was not detected
because the concentration of caffeine was low in all of them (2.1 %, 1.8 % and 0.6
%, respectively). However, small absorption band of caffeine at 1694 cm-1 is
visually observable in the spectra.
Finally, for MDMA tablets S57, S74, S75 and S76 the searching software did not
detect lactose, although existence of lactose was visually evident from the IR
spectra.
3.6 FTIR Spectral Database for Illicit Samples
In the first part of the study, the identification of illicit samples was tried by
searching them against a database constituted from drug standards.
In this part, the aim was rather different in that the comparison of illicit sample
spectra were done by searching them against a database constituted from only
real illicit samples, not the synthetically formed ones.
47
As it is known, all components of the sample contribute to the IR spectrum so that
small variations are identical in IR analyses of the samples. Besides, two samples
having identical spectra should be very similar to each other.
Keeping this statement in mind, it was investigated whether it would be possible

to detect presence of samples that was included in database just by comparing
their IR spectra. This is important because in case of success, the procedure will
constitute a simple way of grouping the illicit samples. In other words, some
samples can be differentiated in several defined groups having the same
properties so that this can be used as a pre-selection step in profiling studies
before other detailed analyses are performed.
3.6.1 Blind Study
In order to test the comparison power of the FTIR-ATR method, a blind study was
designed.
All illicit sample spectra were collected in a new database. Then some of the illicit
samples labeled as unknowns were analyzed again and their spectra were
searched against this new database. The aim was to examine whether all blind
samples would match with their own spectrum in the database.
In the blind study, 26 illicit samples were selected randomly from a total of 76;
using some of them two or three times, the total number was raised to 45. The
search results of blind study are presented in Table 3.6.
Table 3.6 Result of Blind Study

Sample No IR Forecast Forecast Result True Sample
1 MDMA, lactose S69 S69
2 Caffeine S62 S62
3 Caffeine, griseofulvin S45 S45
5 Caffeine S48 S48
48
9 Heroin, caffeine S20 S20
10 Caffeine S62 S62
11 Cocaine S1 S1
12 Cocaine S2 S4
14 Narcotine S17 S19
15 Cocaine S2 S4
16 Heroin S14 S14
18 Caffeine, griseofulvin S45 S45
19 MDMA, caffeine, lactose S57 S57
20 Amphetamine, lactose S50 S50
22 MDMA S63 S63
23 Caffeine S56 S56
24 Heroin, Caffeine S24 S24
25 MDMA S60 S60
26 Cocaine S2 S1
27 Heroin S14 S14
28 Amphetamine, caffeine, lactose S53 S54
29 Caffeine S48 S48
31 MDMA S57 S57
32 Heroin S18 S18
33 MDMA S75 S75
35 MDMA S67 S70
37 Morphine S9 S9
44 Caffeine, S49 S49
49
3.6.2 Evaluation of Blind Study
Almost all the blind samples were correctly matched with their counterparts in the
database, which indicates that similar samples can also be found with the same
way.
Blind samples numbered as 12, 14, 15, 21, 28 and 40 were matched with different
samples but examination of the results pointed out that the real sample and the
forecast sample did belong to the same seizure. Therefore, it is highly probable
that they are the same substances in different packages.
Blind samples numbered as 13, 26 and 35 gave totally irrelevant results using IR
spectra. But when their spectra compared visually with that of forecasted spectra,
it was seen that they are identical. Therefore, it may be considered that they have
a great similarity.
In addition, the identification of the sample composition was not a limiting factor in
this blind study. For example, for the samples S62, S60, S59 and S50, the IR
search results did not exactly identifie the true composition; however, in the blind
study these samples were correctly match with their counterparts. In contrast, S1,
S4 and S20 were identified correctly with IR search but they were not matched
with their own spectra in the blind study.
As a consequence of this blind study, it can be concluded that FTIR-ATR is a very

powerful technique for comparison purposes; small variations in sample
compositions can easily be observed and similar samples can be found from the
IR analyses and classification of the drugs can be possible with this simple way.
50
CHAPTER IV
CONCLUSION
The applicability of the FTIR-ATR technique for illicit drugs was investigated.
Unlike KBr and Nujol mull techniques, working with ATR requires no complicated
sample preparation and this makes the technique very advantageous for the
identification of huge numbers of captured material.
Illicit drugs are not pure substances but they contain several chemicals.
Therefore, it is impossible to identify all the components and to prepare a totally
representative working sample in order to include into the IR database. Therefore,
although secondary standards were used, some of the components of the sample
should be still out of control. However, the technique has been applied on the real
samples and can be utilized satisfactorily for the studied group of drugs.
This technique can be used as an alternative to pre-determination techniques

such as color tests, TLC and GC-MS. It can be used conveniently in crucial points
like customs, where a rapid decision is needed about a suspicious material. In
addition, for chemical profiling studies, it can be used as a fast pre-detection step
to determine the similarities between new samples and those from previous
seizures. Correlations between separate seizures may also be detected.
As future aspects of the study, work on larger number of additives and different
compositions should be performed to widen the content of the standard database
to identify more drugs. Number of illicit samples in the sample database should be
increased and multivariate statistical methods can be employed to improve the
power of the technique.
51
REFERENCES
[1] Harney ML, Cross JC, The Narcotic Officer’s Notebook, 2 nd Ed., Charles C
Thomas Publisher, Illionis, USA, 1975, p.328.
[2] Burger A, Understanding Medications; What the Label Doesn’t Tell You,
American Chemical Society, Oxford University Press, New York, 1995, pp.1-50.
[3] Single Convention on Narcotic Drugs, 1961, United Nations.
[4] Convention on Psychotropic Substances, 1971, United Nations.
[5] UN Conventions Against Illicit Traffic in Narcotic Drugs and Psychotropic

Substances, 1988, United Nations.
[6] Drugs of Abuse, U.S. Department of Justice, Washington, 1997, pp.11-39.
[7] Recommended Methods for Testing Opium, Morphine and Heroin, United
Nations, 1998 ST / NAR / 29 / Rev.1, pp. 3-18.
[8] Erowid, The Vaults of Erowid, http://www.erowid.org/psychoactives/

psychoactives.shtml, May 2005, last accessed date May 2005.
[9] Recommended Methods for Testing Barbiturate Derivatives Under

International Control, United Nations, 1989, ST / NAR / 18, pp. 4-10.
[10] Recommended Methods for Testing Benzodiazepine Derivatives Under

International Control, United Nation, 1988, ST / NAR / 16, pp. 4-22.
[11] Recommended Methods for Testing Cocaine, United Nations, 1986, ST /

NAR / 7, pp. 7-9.
[12] Recommended Methods for Testing Amphetamine and Methamphetamine,

United Nations, 1987, ST / NAR / 9, pp. 4-9.
52
[13] Recommended Methods for Testing Illicit Ring-Substituted Amphetamine
Derivatives, United Nations, 1987, ST / NAR / 12, pp. 4-12.
[14] Recommended Methods for Testing Lysergide (LSD), United Nations, 1989,
ST / NAR / 17, pp. 4-7.
[15] Recommended Methods for Testing Cannabis, United Nations, 1987, ST /

NAR / 8, pp. 4-16.
[16] Skoog DA, Leary JJ, Principles of Instrumental Analysis, 4th Ed., Saunders
College Publishing, New York, 1992, pp.252-280.
[17] Osland RCJ, Principals and Practices of Infrared Spectroscopy, Pye Unicam
Ltd., Great Britain, 1985, pp.5-32, 64-69.
[18] Silverstein R, Bassler GC, Morrill TC, Spectrometric Identification of Organic

Compounds, 4 th Ed., John Willey and Sons, New York, 1981, pp. 95-135.
[19] Smith BC, Fundamentals of Fourier Transform Infrared Spectroscopy, CRC

Press, USA, 1996, pp.1-41, 117-125.
[20] Levy R., Ravbery M., Meirovich L., Shapira-Heiman O., A survey and
Comparison of Heroin Seizures in Israel During 1992 by Fourier Transform
Infrared Spectrometry, Journal of Forensic Science, 41 (1), 1996, 6-11.
[21] Koulis CV., Hymes KJ., Rawlins JL., A new Infrared Spectral Library of
Controlled and Noncontrolled Drug Standards Using Internal Reflection
Spectroscopy, Journal of Forensic Science, 45 (4), 2000, 876-881.
[22] Ravbery M., Quantitative Determination of Cocaine and Heroin by Fourier

Transform Infrared Spectrophotometry, Journal of Forensic Science, JFSCA, 32
(1), 1987, 20-37.
[23] Ryder AG. Classification of Narcotics in Solid Mixtures Using Principal

Component Analysis and Raman Spectroscopy, Journal of Forensic Science, 47
(2), 2002, 275-284.
53
[24] Ryder AG, O’Connor GM, Glynn TJ, Identification and Qualitative
Measurements of Narcotics in Solid Mixtures Using Near-IR Raman Spectroscopy
and Multivariate Analysis, Journal of Forensic Science, 44 (5), 1999, 1013-1019.
[25] Beckstead HD., Neville GA., Fourier Transform Infrared Characterization of

the Ethyl Acetate Complex of O6 –Acetylmorphine, Journal Of Forensic Science,
33 (1), 1988, 223-229.
[26] Heagy , Infrared Method for Distinguishing Optical Isomers of Amphetamine,

Analytical Chemistry, 42(12), 1970, 1459.
[27] Sondermann N, Kovar KA, Screening Experiments of Ecstasy Street

Samples Using Near Infrared Spectroscopy, Forensic Science International,
106(3), 1999, 147-156.
[28] Perkin Elmer Spectrum One Multimedia CD-ROM, PerkinElmer Inc., USA.
[29] Perkin Elmer Instruments, Universal ATR Sampling Accessory User’s Guide,
PerkinElmer Inc., USA.
[30] Perkin Elmer, Spectrum One Software Help Tool, PerkinElmer Inc., USA.
[31] Skoog DA, West DM, Holler FJ, Fundamentals of Analytical Chemistry, Sixth
Ed., Saunders College Publishing, New York, 1992, pp.39-52.
[32] De Faubert Maunder MJ, Practical Hints on Infra-red Spectrometry From a

Forensic Analyst, Adam Hilger Ltd., London, 1971, p.67.
[33] The Merck Index, An Encyclopedia of Chemicals, Drugs and Biologicals,

Twelfth Ed., Merck & Co. Inc. USA, 1996.
[34] The NIST Mass Spectral Library, Version 2.0, FairCom Corporation, USA.
* The publications of United Nations can be accessed on the website http://

www.unodc.org under the title “news and publications / publications / scientific
support”.
54
APPENDIX A
CHEMICAL AND PHYSICAL PROPERTIES OF DRUGS
Table A.1 Chemical and Physical Properties of Drugs [33, 34]
Names Molecular Structure & Physical Properties

Molecular Formula
Heroin
Solid
Diacetylmorphine
mol wt. 369.4
(5α,6α)-7,8-Didehydro-
4,5-epoxy-17- mp. 173 0C
methylmorphinan-3,6-diol
diacetate (ester)
C21H23NO5
Morphine Solid
(5α,6α)-7,8-Didehydro- mol wt. 285.3

4,5-epoxy-17-
methylmorphinan-3,6-diol mp. 197 0C
C17H19NO3
Codeine Solid
(5α,6α)-7,8-Didehydro- mol wt.299.4

4,5-epoxy-3-methoxy-17-
methylmorphinan-6-ol mp. 154-156 0C
C18H21NO3
55
Table A.1 (Continued.)
Narcotine
Solid
[S-(R*,S*)]-6,7-
dimethoxy-3-(5,6,7,8-
mol wt. 413.4
tetrahydro-4-methoxy-6-
methyl-1,3-dioxolo[4,5-
mp. 176 0C
g]isoquinolin-5-yl)-1(3H)-
isobenzofuranone
C22H23NO7
Cocaine Solid
[1R-(exo,exo)]-3- mol wt. 303.6

(Benzoyloxy)-8-methyl-
8-azabicyclo[3.2.1]- mp. 98 0C
octane-2-carboxylic acid
methyl ester
C17H21NO4
Amphetamine Mobile liquid
(±)-α-methylbenzene- mol.wt. 135.2

ethanamine
bp760. 200-203 0C
C9H13N
Solid
Methamphetamine
mol wt. 149.2
(S)-N,α-
dimethylbenzene-
C10H15N mp. 170-175 0C
ethanamine
56
Table A.1 (Continued.)
MDMA
Oil
3,4-methylenedioxy-
methamphetamine mol wt. 193.2
N,α-dimethyl-1,3- bp(0.4) 100-110 0C

benzodioxole-5- C11H15NO2
ethanamine
Caffeine Solid
3,7-dihydro-1,3,7- mol wt. 194.2

trimethyl-1H-purine-2,6-
dione mp. 238 0C
C8H10N4O2
Paracetamol Solid
Acetaminophen mol wt. 151.2
N-(4-hydroxyphenyl)- mp. 169 0 C

acetamide
C8H9NO2
Solid
Lactose
mol wt. 342.3
4-(β-D-galactosido)-D-
glucose mp.201-202 0C
C12H22O11
57
0.260 S31 dried.sp / drug.dlb Euclidean Search Hit List
1758.26 1738.96 1192.37
0.24 0.986 PP023 P P23 HEROIN BASE
1229.39
S31.sp / drug.dlb Euclidean Search Hit List

0.22
(R: Reference Standards, P: Prepared Standards)

0.965 PP024 P P24 HEROIN BASE
0.20
1447.28
IR-ATR SPECTRA OF STANDARDS

0.18 3366.66
1366.90
1052.90
0.16
1620.00
APPENDIX B
0.14
A
0.12
58
0.10
0.08
0.06
0.04
0.020
4000.0 3000 2000 1500 1000 650.0
cm-1
Figure B-1 Effect of humidity on IR spectrum ( Black: IR Spectrum of S31before drying,

Red: IR Spectrum of S31 after drying)
1758.83 1738.27
1230.29
1448.00 1366.96 1192.80
S14 (63.7 % Heroin)
1751.57
1271.42 1258.11
1497.59 1477.02
A S16 (19.9 % Heroin)

59
1751.57
1271.42 1258.11
1497.59
1477.02
S17 (0.4 % H eroin)
1 81 3.3 1 70 0 1 60 0 1 50 0 1 40 0 1 30 0 1 20 0 1 10 0 1 00 0 9 60 .6
cm-1
Figure B-2 The effect of Heroin concentration on the appeareance of carbonyl peaks at 1758 cm-1 and 1738 cm-1.
9 6.0
90
85
2606.66
80
%T
75
60
1368.91
1444.01
70 1759.50
1155.46
65
1735.05
1176.21
60 1244.40
5 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-3 IR-ATR Spectrum of Heroin HCl (R1)

9 6.0
90
85
80
2930.70
2811.10
75
%T 7 0
61
1502.43
65
1447.45
1271.52
60
55
1231.44 1050.53
50 1732.31
4 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-4 IR-ATR Spectrum of Acetyl Codeine (R2)

9 8.1
95
90
85
80
75
70
%T 6 5
758.58
62
60
55
1237.34
1547.53
50
45
1693.57
40 743.82
1644.26
3 7.2
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-5 IR-ATR Spectrum of Caffeine (R3)

9 8.0
95
90
85 2537.96
80
75
%T
70
63
65
1230.00 1025.95
60 1728.86
1071.37
55
1711.70
1264.94
50 1105.14
4 7.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-6 IR-ATR Spectrum of Cocaine HCl (R4)

9 7.0
95
90
85
2927.46 2788.15
80
75
%T
64
70
1500.51 1114.17 935.78

65
1274.82
60
795.07
1055.76
5 4.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-7 IR-ATR Spectrum of Codeine (R5)

1 00 .0
90
80
70
1550.82
60
2853.33
50 1144.29
%T 729.39
698.24
65
40
30
20
1050.75
10
0 .0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-8 IR-ATR Spectrum of d,l-Amphetamine SO4 (R6)

9 7.0
95
90
85
80
75
%T 2458.25
66
70
2710.79
65
60
1488.88 1244.20 1030.63
5 4.0 930.35
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-9 IR-ATR Spectrum of d,l-MDMA HCl (R7)

9 7.0
96
94
92
1603.51
90
88
1487.09 1453.33 1059.61
2459.55
86
%T
84
67
2722.94
82
80
78
699.51
76
748.02
7 4.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-10 IR-ATR Spectrum of d,l-methamphetamine HCl (R8)

1 06 .0
1 00
95
90
85
80
%T 7 5
68
70 3181.91
65
60
1471.22
55 1241.34 800.11
1086.49 757.93
1442.29 1117.83 942.56
4 9.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-11 IR-ATR Spectrum of Morphine Base (R9)

9 7.0
94
92
90
88
86
84
%T 8 2
69
80
78
1496.96 1083.22
76 1476.34
74
72
1258.26
1270.66 998.66
1749.95 1032.97
6 9.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-12 IR-ATR Spectrum of Narcotine HCl (R10)

9 7.0
95
90
85
2480.00
%T 8 0
70
75
1406.89
70 1434.56
1506.99
1279.78 1143.94
1263.68 1024.23
6 4.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-13 IR-ATR Spectrum of Papaverine HCl (R11)

9 7.0
95
90
85
80
75
3321.93
70
%T 3108.53
65
71
60
55
1650.70
50 1609.21 1258.08
1561.34
45 1224.66
4 2.0 1505.17 1433.68
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-14 IR-ATR Spectrum of Paracetamol (R12)

9 8.0
96
94
92
90
88
86 1648.42
%T 8 4
3366.66
82
72
1474.04
80
1503.33 1315.72
78
939.56
76
74
1065.23
786.38
72
7 1.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-15 IR-ATR Spectrum of Morphine HCl (R13)

9 4.0
90
85
80
3373.33 1648.60 1332.82
75
1477.45 1269.49
70 1497.13 970.93
%T
73
65
60
1122.79 790.85
55
50 1070.15
4 7.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-16 IR-ATR Spectrum of Morphine H2SO4 (R14)

9 7.0
94 1550.06
92
90
88
86
84
82 764.09
%T 1656.69
80
1698.55 745.68
74
78 1366.36
76 1759.84
1447.57
74 1052.86
1738.64
72
70
1231.13
68
6 6.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-17 IR-ATR Spectrum of Heroin containing Caffeine (P1)
(52.2 % Heroin, 15.2 % Caffeine)
9 6.0
1550.12
90
85
80
1657.04
75 745.25
1698.27 764.99
%T
70
75
1366.73
1447.41
65
1052.28
1759.81
60
1738.66
55 1230.99 1192.26
5 2.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
9 7.0
1550.00
96
94
92
1657.55
90
1698.26
88 765.65 745.68
%T
86
76
1447.13 1366.76
84
1759.90
82
1052.45
1738.58
80
78 1231.46
7 7.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
9 6.0
1550.87
90
85
1655.12
745.55
1698.90
80
765.13
%T
75
77
1366.55
1447.30
70
1052.52
1759.37
65
1738.52
1230.87
1192.05
6 0.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
9 6.0
745.41
94 1657.00
92
1550.19
90
88
1698.48
86
84
82
765.21
%T 8 0
78
78
1447.07 1366.15
76
74 1052.76
1759.45
72
70 1738.34
68 1192.41
6 6.0 1230.68
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 4.5
1656.93
90
1550.56
745.65
85
80 1697.16
764.58
%T
75
79
1366.52
1447.36
70 1052.11
1759.01
65
1738.59
1230.79 1192.45
6 1.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.3
1550.52
90
85
80
745.46
1656.93 764.46
75
%T
1698.26
80
70
1366.72
1447.63
65 1052.42
1759.15
60 1738.90
1231.09
1192.12
5 5.4
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(34.1% Heroin, 5.3 % Caffeine)
9 6.0
94
92
90
88
86
1550.63
84
82 764.22
%T 8 0 745.48
78 1656.73
81
76
1698.53 1366.57
1052.83
74
1447.75
1759.32
72
70
1738.72
68
1231.89
1192.24
6 5.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(32.4 % Heroin, 10.0 Caffeine)
9 6.4
94
92
90
1550.08
88 764.39
86
%T
84
82
1366.78
745.03
82 1759.12 1052.75
1447.23
1738.78
80 1656.78
1697.45
78
1231.23 1192.68
7 5.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 9.0
98
96
94 2458.83
2710.75
92
%T 9 0 758.75
1547.74
83
88 930.88
86 1243.03
1488.74
1038.39
84
1697.17 1644.83 745.26
8 2.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-26 IR-ATR Spectrum of MDMA containing Caffeine (P10)

(35.7 % MDMA, 36.2 % Caffeine)
9 9.0
98
96
94
92 2458.31
3322.77 3108.36
90
2710.23
%T
88
1609.67
84
1562.75 1258.61
86 1651.90
931.10
84
1433.10 1038.16
1505.99
82 1489.83
1228.30
1244.72
8 0.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-27 IR-ATR Spectrum of MDMA containing Paracetamol (P11)

(37.2 % MDMA, 33.5 % Paracetamol)
9 7.9
96
94
92
2458.05
1140.78
90
3262.01
875.14
88 2710.60 1114.82
86
%T 8 4 1488.93
1244.93
85
1070.69
82
930.82
80 987.63
78
76
74
1037.18
7 2.4 1018.78
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-28 IR-ATR Spectrum of MDMA containing Lactose (P12)
(34.2 % MDMA, 38.8 % Lactose)
9 8.0
95
90
3322.01 2458.17
3109.90 1562.44
85 2710.60
1505.67
80
%T 1258.84 930.83
758.53
86
75
1548.77
1038.18
70
1224.72
1697.65 1431.30
1488.37
1230.08
65 1241.47
1656.34
1650.44 744.96
6 2.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-29 IR-ATR Spectrum of MDMA containing Caffeine and Paracetamol (P13)
(33.4 % MDMA, 17.4 % Caffeine, 22.9 % Paracetamol)
9 9.2
98
97
1141.80
3261.41 2458.91
1114.87 875.03
96 2710.87
95
1070.80
987.89
1548.05
%T 9 4 931.06
87
93
1488.91
1243.56
92
1645.44
91 1697.75
90 1038.51
8 9.2
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-30 IR-ATR Spectrum of MDMA containing Caffeine and Lactose (P14)
(35.9 % MDMA, 19.4 % Caffeine, 16.5 % Lactose)
9 7.4
90
85
80
75
70
65
2841.45
%T 6 0 1237.77
729.07
55
88
1144.12
1547.10
50 1696.74
45 1645.92
40 698.00
35
30 1050.47
2 4.9
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-31 IR-ATR Spectrum of Amphetamine containing Caffeine (P15)
(66.4 % Amphetamine, 33.5 % Caffeine)
9 6.0
90
85
80
75 3322.18
70
1258.14
65
%T 1650.96 1433.62
60
89
1609.41 1225.36
55
2840.00 729.15
1505.53
50
1561.47 1144.96
1550.28
45
40
1050.10
35 697.28
3 2.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-32 IR-ATR Spectrum of Amphetamine containing Paracetamol (P16)

(66.8 % Amphetamine, 33.1 % Paracetamol)
9 8.0
95
90
85
80
875.89
75 3260.00
70
65
1550.12
%T 6 0
55 1144.19 729.47
90
2840.93
50
1114.37 987.97
45
40
1018.77
35 1070.78
697.35
30 1050.44
2 5.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-33 IR-ATR Spectrum of Amphetamine containing Lactose (P17)

(71.4 % Amphetamine, 28.6 % Lactose)
9 7.0
95
1609.51
90
3320.33
85
1258.85
80
1237.77
1505.75
75
2841.04 1696.97 1561.84 1432.84
%T
70 1224.56 729.03
91
1652.82
1550.66 1145.17
65
1547.81
1647.50
60
55 1050.22
697.65
5 0.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-34 IR-ATR Spectrum of Amphetamine containing Caffeine and Paracetamol (P18)
(62.2 % Amphetamine, 17.9 % Caffeine, 19.7 % Paracetamol)
9 7.0
90 1609.12
85 1505.77
80
3321.41
875.36
75
1258.39
70 3109.20
%T 6 5
1561.78 1225.46
92
2833.33 729.20
60 1696.97 1144.95
1432.07 987.58
55
1114.45
50 1549.23
1649.63 1070.53
45 1644.53
697.52
1018.08
1050.88
3 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-35 IR-ATR Spectrum of Amphetamine containing Caffeine, Paracetamol and Lactose (P19)
(42.4 % Amphetamine, 18.8 % Caffeine, 16.4 % Paracetamol, 22.4 % Lactose)
9 7.0
95
90
85
3260.00
80
875.06
75
758.99
2840.59 1237.30
%T 7 0
93
1144.08 729.58
65
1547.00
1114.70
1549.57
987.84
60
1696.06
743.76
55 1645.49
1070.62
50 1018.60
698.07
1050.37
4 7.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-36 IR-ATR Spectrum of Amphetamine containing Caffeine and Lactose (P20)
(46.6 % Amphetamine, 22.7 % Caffeine, 30.6 % Lactose)
9 6.5
1561.55
94
92
90
88
1550.30
86
1609.88 764.75
84 1258.97
1505.04
82
%T
80 1650.16 1433.03
94
1698.87
745.28
78 1656.15
1759.61 1366.44
1052.47
1447.04
76
1738.68
74
72
1192.38
70 1230.94
1224.04
6 7.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-37 IR-ATR Spectrum of Heroin containing Caffeine and Paracetamol (P21)
(43.5 % Heroin, 14.7 % Caffeine, 15.0 % Paracetamol)
9 6.3
94
92
90
88
764.94
86
1561.95
84
%T 8 2 1505.00 1258.94
95
80 1759.23 1432.27
1052.98
78 1738.95 1366.09
1447.27
76 1698.39 745.21
1649.14
74 1656.59
1192.76
72
1230.78
1224.12
6 9.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-38 IR-ATR Spectrum of Heroin containing Caffeine and Paracetamol (P22)
(24.7 % Heroin, 18.2 % Caffeine, 13.1 % Paracetamol)
9 6.0
90
85
80
%T
75
96
1447.77
70 1366.76
1052.52
1759.85
65
1738.58
1230.78 1192.05
60
5 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-39 IR-ATR Spectrum of Heroin Base (P23)

(62.6 % Heroin, 1.9 % Monoacetylmorphine, 5.1 % Acetyl Codeine, 2.3 % Papaverine, 20.6 % Narcotine)
9 5.3
94
92
90
88
86
84
82
%T
80
97
78
1366.58
76 1447.91
1052.86
74
1759.01
72
1230.75
70 1738.48
1192.69
6 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-40 IR-ATR Spectrum of Heroin Base (P24)

(36.5 % Heroin, 9.2 % Monoacetylmorphine, 3.1 % Acetyl Codeine, 1.9 % Papaverine, 30.6 % Narcotine)
9 8.0
95
90
85 3321.35
80
3108.73
1505.29
75 1561.34
758.83
%T 7 0
1258.13
98
65
60
1693.83 1609.29
55
1547.73
1237.88
1224.44
50 743.47
1650.59
4 5.0
4 00 0.0 3 00 0 2 00 0 1645.78 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-41 IR-ATR Spectrum of Caffeine with Paracetamol (P25)

(41.4 % Caffeine, 47.6 % Paracetamol)
9 9.2
98
96
94
92
90
88
86 745.02
%T
84 1550.70
99
82
80
78
1656.73 800.03
76
1136.22
1700.77 1583.98
74
1615.12 1221.07 1211.30
7 2.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-42 IR-ATR Spectrum of Caffeine with Griseofulvin (P26)

(12.9 % Caffeine and Griseofulvin)
9 5.0
94
92
90
757.48
88
941.16
86
%T
84
100
800.24
82 1442.06 1117.26
80
1086.93
1241.12
78
7 6.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-43 IR-ATR Spectrum of Morphine (P27)

(10.8 % Morphine, 3.5 % Codeine, 1.6 % Papaverine, 7.6 % Narcotine)
9 8.6
95
90
85
1166.63
875.95
%T 8 0 3260.00
1140.21
101
759.91
75 1114.93
70 987.40
1070.12
1018.42
6 4.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure B-44 IR-ATR Spectrum of Lactose Standard

APPENDIX C
IR-ATR SPECTRA OF ILLICIT SAMPLES
(S: Sample)
9 7.1
95
90
85
80
75
%T 7 0
65
1025.83
60 1230.52
1728.82 1071.32
55
1711.84
50 1105.00
1264.63
4 5.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1
Figure C-1 IR-ATR Spectrum of S1

(89.3 % Cocaine)
9 6.5
90
2537.58
85
80
75
70
%T
65
1025.96
60 1230.18
1071.76
55 1728.51
1711.82
50 1105.64
1264.54
45
4 1.4
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(90.4 % Cocaine)
102
9 6.7
90
85
2537.95
80
75
70
%T 6 5
1025.92
60
1230.15
55
1071.44
1728.45
50
1711.92
45 1105.39
1264.89
40
3 7.8
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(58.1 % Cocaine)
9 7.1
95
90
2537.95
85
80
1025.84
%T
75 1230.78
1071.46
1728.78
70 1711.97
1105.95
1265.69
65
60
5 8.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(63.6 % Cocaine)
103
1 01 .0
90
80
70
60
%T
50
40
1253.09
30
1734.87 1272.96
1035.66 711.70
1 9.0 1706.53 1106.80
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(80.1 % Cocaine)
9 6.0
94
92
90
88 941.47
86
84
%T 8 2
80 3181.75
800.03
78
1117.90
76 1476.00 1442.04
74 1240.00
1086.64
72
1614.44
70
6 9.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(11.6 % Morphine)
104
9 5.0
94
92
90
1476.27 941.33
88
86
%T 3181.30
800.01
84
1116.88
82 1442.11
1086.24
80 1241.69
78
1614.58
7 6.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(10.8 %Morphine)
9 7.0
96
94
92
90
3181.73
%T 8 8
86
84
1471.80 942.40
1241.44
82 1442.18
1117.21
1086.02 801.65
8 0.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(73.3 % Morphine)
105
9 7.0
96
94
92
90
88
3181.01
%T
86
84
82
941.99
1471.94 1241.81
80
1442.43
1117.90
800.99
78 1086.10
7 7.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(27.2 % Morphine)
9 8.0
97
96
95
94
93
92
91 3181.87
%T 9 0
89
88
87
86 1471.90
1241.71 941.98
85
1442.56
1117.02
84
1086.05
8 3.0 800.89
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(42.7 % Morphine)
106
9 6.7
96
95
94
93
92
91
3181.90
90
%T
89
88
87
86
85 1472.48 1241.27
942.51
1442.69
84 1117.87
800.85
8 2.8 1086.66
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(51.2 % Morphine)
9 9.0
98
97
96
95
94
93
92
%T 3181.89
91
90
89
88 1117.47
1472.01 941.90
87
1241.25
86 1442.84 800.90
1086.52
8 5.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(54.3 % Morphine)
107
9 9.0
98
97
96
95
94
93
%T 9 2 3181.93
91
90
89
88 1472.54 941.87
1241.29
87 1442.86 1117.73 801.27
8 6.0 1086.04
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(50.6 % Morphine)
9 6.0
90
85
80
%T
75
1366.52
1447.65
70
1052.72
1759.63
65 1738.54
1192.26
1230.22
6 1.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(63.7 % Heroin, 26.7 % Narcotine)
108
9 7.0
96
94
92
90
88
86
%T
84
1366.52
1447.97
82
1759.10 1052.84
80
1738.39
78 1230.78
76
7 5.0 1192.36
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.0
90
85 1052.41
80
1447.13
%T
75 1738.38 1192.34
1477.77
1223.61
1497.68
70
1759.48
1258.17
1271.04
65
1751.58
1032.25
6 0.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(19.9 % Heroin, 49,6 % Narcotine)
109
9 4.8
90
85 1052.59
80
%T 7 5
1223.63
1477.73
70 1497.42
65
1751.19
1271.24
1258.86
60 1031.07
5 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 4.6
90
85
80
1366.04
%T
75 1052.69
1447.78
1497.47
1477.70
1258.36
70
1738.72 1192.55
1759.91
1230.39 1223.81
65 1751.28
6 1.4
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

110
9 6.4
94
1052.51
92
90
1211.09
88
1622.17
86
84
%T 8 2
1223.67
80
1477.22 1079.14
78 1497.26
76
74
1751.98 1271.45
72 1258.35
1032.37
6 9.2
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 6.7
94
1550.74
92
90
1656.00
88 745.84
1698.79 764.49
%T 8 6
1366.09
84 1447.65
1052.83
82
1738.95
1759.33
80
78 1230.63 1192.34
7 6.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(27.8 % Heroin, 13.7 % Caffeine, 35.4 % Narcotine)
111
9 5.4
1550.47
94
92
90
88
86 1622.24 745.39
84 1656.16
764.28
1698.36
82
1366.01
%T 8 0
1052.17
78 1447.06
1738.26
76
1759.35
74 1192.12
1230.89
72 1751.87
70
6 7.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 6.4
94
92
90
1622.42
88
1052.80
86
84
1366.53
%T 8 2
1447.95
80
1738.31
1477.61 1230.62
78 1497.39
1192.76
76
74 1258.34
1751.41 1271.19
72
1032.38
6 9.2
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

112
9 5.8
94
92
90
1550.55
88
86
84
745.17
82 1656.66
%T 764.53
80
1698.44
1366.16
78
1447.29
76
1052.75
74
1759.33 1738.88
72
70
6 8.2 1230.85 1192.63
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 4.6
1550.38
90
85
745.70
1656.05
80 1698.73
%T 7 5
764.53
70 1366.82
1447.84
65 1759.57 1052.33
60
1192.24
1738.36
5 6.8 1230.07
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

113
9 7.0
96
95
94
1550.57
93
92
1656.72 764.54
%T 9 1
1366.12
745.01
1698.64
90
1497.83 1052.49
1447.80
89
1738.53
1477.55
88
1759.49
87 1192.62
1230.49
86 1032.65
8 5.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(27 % Heroin, 13 % Caffeine, 33.3 % Narcotine)
9 4.1
1550.70
90
85
1650.70
745.66
80 1656.36
1698.35
764.11
75
1505.11 1433.21
%T
1230.84 1052.36
70 1738.82
1477.65
1497.47
1192.97
65
1223.70
60 1271.10 1258.80
1751.94
55
5 3.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(26.7 % Heroin, 0.4 % Caffeine, 1.4 % Paracetamol, 40.9 % Narcotine)
114
9 4.6
1550.64
90
85
1650.35 745.68
1698.86
764.03
80
1366.09
%T
75 1447.04 1052.55
1497.91
1738.43 1477.75 1192.69
70
1223.83
1258.72
1271.39
65 1751.84
1032.58
6 0.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(25.1 % Heroin, 4.6% Caffeine, 0.9 % Paracetamol, 42.8 % Narcotine)
9 5.1
1550.25
92
90
88
86
84 745.30
1650.02
82 1656.40
764.10
80
%T 1698.32 1433.16
78
1052.71
1497.80 1447.88
76
74 1477.72
1738.89 1192.53
72
1223.60
70 1230.67
1271.41
68 1258.52
1751.73
66 1032.96
6 4.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(27 % Heroin, 5.3 % Caffeine, 1.0 % Paracetamol, 40.7 % Narcotine)
115
9 6.5
95
94
1561.27 1550.55
93
92
91
764.13
90
745.08
89
%T 1698.38 1052.84
88
1366.03
87 1656.25
1650.12
86 1433.28
1447.00 1258.51
85
1738.86
1758.10
84
1192.20
83
8 1.8 1230.65 1224.36
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0
1032.80 6 50 .0
cm-1

9 5.3
94
92
1561.95
90
1550.52
88
86
764.19
84 1609.75
745.07
82 1698.26
%T
1052.38
80 1650.00
1656.73
78 1366.01
1497.41
76 1477.67
1738.43 1258.41
74 1447.03
1758.18
72 1192.22
1230.28 1033.35
6 9.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

116
9 4.2
90
85
80
75
%T
1620.14
70
1366.23 1052.59
3360.00 1447.65
65
60
1758.43 1192.19
1738.58 1230.21
5 6.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.2
90
85
80
75
%T
70
1366.33
1447.83
65 1052.86
60
1758.17
1738.71 1230.49
55
5 3.1 1192.87
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

117
9 5.9
90
85
80
%T
75
1366.47
1447.65
70
1052.04
1759.56
65
1738.07
1230.53 1192.69
60
5 8.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.7
90
85
80
%T 7 5
70
1447.28 1366.76
1052.16
65
1759.64
60 1738.62
1192.51
5 6.2 1230.50
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

118
9 6.8
96
94
92
90
88
%T
1366.54
86 1447.38
84
1052.73
1759.35
82 1738.94
1230.11
7 9.4
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.7
90 1550.33
1656.00
85
80
1622.41 745.61
75
1698.68
764.60
%T 7 0
1366.60
1497.64
65 1477.48 1052.80
1447.24
60
1271.22
1738.97
1759.21
55
1751.41
1192.90
1230.12
50 1223.92
1032.57
4 6.8
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

119
9 5.7
1550.86
90
1656.66
85
1621.30 745.93
1698.67 764.15
80
1366.27
%T
75 1497.44 1447.41 1052.63
1477.83
70 1738.83
1271.15
1759.28 1192.61
1230.55
1223.60
65
1751.82
1032.60
5 9.6
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.9
90
85
80
75
%T 1497.33
1477.33
70
1366.00
1447.33 1271.49 1052.41
65
60
1758.54
1738.52
1230.41
55
5 3.1 1192.76
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

120
9 6.5
90
85
80
75
70
%T
65
60
1366.09
1447.11
55
1052.41
50
1758.89
45
1192.27
1738.67
3 9.8 1230.53
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.7
94
92
90
88
86
%T 8 4
82 1366.45
1447.58
80 1052.17
78 1758.99
76 1738.77
1230.67
74 1192.34
7 3.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

121
9 5.3
94
92
90
88
86
84
82
%T
80
1366.24
78
1447.65
76 1052.51
74
1758.93
72
1738.51
70
1230.61 1192.50
6 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 8.0
95
90
85
80 3321.33
3108.00
%T 7 5
70
65
1609.22 1258.73
60
1650.85
1561.78 1433.85
1505.72 1224.64
5 4.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(90.5 % Paracetamol)
122
9 9.1
98
97
96 3321.08
3108.55 1550.79
95
1561.88
94
93
%T
92
1258.90
91 758.85
1609.57
90
1505.56
89 1698.44 1433.23
1230.15
1224.83
88
1656.01
87 745.81
8 6.4
4 00 0.0 3 00 0 2 00 0 1650.17 1 50 0 1 00 0 6 50 .0
cm-1

(41.4 % Caffeine, 47.6 % Paracetamol)
9 9.1
96
94
92
90
88
86 758.88
84
%T 1550.41
82
80
745.36
78
76
74 1136.64 800.26
1583.76
72
1615.88
1698.39 1221.51
70
6 8.7 1656.64
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(16.9 % Caffeine, Griseofulvin)
123
9 9.2
98 758.85
96
94
92
90
88
86 745.41
%T 1550.82
84
82
80
78
1656.95
76 1583.66 1136.41
1698.42 800.42
1615.43
74 1221.30
7 2.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(12.9 % Caffeine, Griseofulvin)
9 7.5
96
94
92
90 3321.61
3108.21
88
%T 8 6
84
82
1650.69
80 1609.30
1258.42
78 1561.57
1505.24 1433.97 1224.69
7 6.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(88.3 % Paracetamol)
124
9 6.8
95
90
85
875.65
698.96
1237.92
80
%T 1144.10 729.23
1140.56 758.58
3260.34
75 1550.26
1547.61
987.84
70 1694.27 1114.56
1644.51
1018.58
65 1070.59 743.92
6 3.2
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(3.5 % Amphetamine, 14.2 % Caffeine, Lactose)
9 4.0
1140.97
90
85
80
3260.83 1114.93
758.34
75
%T 1070.51
70 1237.77
65
1547.30
60
1694.02
1644.95 743.33
5 5.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

125
9 8.0
95
90
875.26
85
698.74
3260.20
1140.52
%T 8 0 729.18
1237.61
987.03
75 1114.15
70 1550.53 1070.43
1547.39
1694.54
65
6 3.0 1644.23
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(8.6 % Amphetamine, 20.2 Caffeine, Lactose)
9 8.0
95
90
85 1550.43
875.98
80
729.47
75 698.79
3260.00 1144.00
%T
70
1114.29
65
60 987.07
1070.25
55
1051.51
4 9.0 1018.81
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

126
9 7.5
95
90
1237.49
1695.60 875.79
85
1550.92 1144.51 698.64

745.57
80 729.75
%T 1644.53
3260.91
75
1114.55
70
987.90
1070.05
65
1018.70
6 3.0 1051.22
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 7.4
96
94
92
90
88 875.17
86
1551.46 758.71
84 698.17
%T
82 1143.92 729.68
3260.00
80 1114.26
78
76
1644.89 1051.25
74
743.58
72
987.30
1018.81
6 9.6 1070.71
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

127
9 8.1
95
90
1694.24
1551.00
85
1644.95 875.03
698.52
80
%T
3260.05 1144.12
729.67
75
1114.70
70
65 1070.58
987.51
1051.54
5 8.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 9.0
98
97
96
95
1547.46 875.57
94
1694.65
93 3260.02
1144.09
%T 9 2 698.89
1644.16 1114.52
91 729.53
90
89 987.68
88 743.31
1070.49
87
1051.43 1018.57
8 6.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

128
9 7.5
95
90
2458.21
1140.78
85 875.48
2710.83
1488.88 1244.88
3260.35
1114.39
%T 8 0
1070.42
75
930.44
70
1030.11 987.61
6 3.8
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1 1018.39

(15.0 % MDMA, Lactose)
9 5.9
90
85
3260.02
80 1140.77
875.65
1114.17
75
758.55
%T
70 1070.14
1237.46
65
1547.40
60
55 1693.30 1018.78
743.12
1644.49
5 0.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

129
9 7.9
96
94
1140.26
92 2458.91 875.64
3260.80 1114.25
90 2710.44
%T 1070.75
88
1488.91
86 930.59
1244.98
84
1018.65
82 1030.90
8 1.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 7.0
94
92
90
2458.52
88 3260.99 1140.94
86 2710.52 875.90
84 1114.57
1488.66
%T 8 2
1244.66
80 1070.62
930.66
78
987.46
76
74
72
1018.56
70 1030.73
6 7.9
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(35.1 % MDMA, LActose)
130
9 8.0
96
94
92 2458.55
90
2710.55
88
1488.69
%T 8 6
1244.89
84
930.00
82
80
78 1030.08
7 6.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(22.6 % MDMA)
9 7.2
96
1694.66
94
1644.60
92 743.94
2458.15
90
88
2710.44
86
%T
1488.97
84
82 1244.89
80 930.48
78
1033.33
76
7 5.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

131
9 8.2
97
96
758.82
95 875.57
3260.59
94 1237.40
93
729.31
92
91 1547.41 1144.37
%T 9 0 698.90
89 1695.39
1644.56 1114.80
88
743.84
87
86
85
1070.77
84
1051.05 1018.85
8 2.4
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 6.7
96
94
92 698.71
3260.00 1144.95
758.72
90
729.26
%T 8 8 1237.57
1114.69
1547.68
86
84
1694.63
82
1051.30
1644.32 743.99
8 0.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

132
9 5.6
90
85
2458.49
80
%T 2710.55
75
70 1488.88
1244.72
930.59
65
1030.44
5 9.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(31.5 % MDMA)
9 7.7
96
94
2458.17
1140.51 875.31
92 3260.23
2710.64
90 1114.29
1488.78
%T 8 8
1070.80
1244.86
930.45
86
987.40
84
82
1030.37 1018.65
7 9.4
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(34.5 MDMA, Lactose)
133
9 7.5
96
94
92 2458.24
1140.87
875.10
90 3260.00
2710.63
1114.77
88
1488.66
%T 8 6 930.74
1244.95
1070.18
84 987.54
82
80
78
1030.91 1018.53
7 6.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 8.0
96
94
92
90
2458.19
88 1140.56 875.82
3260.17
86
1114.79
84 2710.49
82 1488.99
%T
80 1244.94 1070.99 930.26
78 987.57
76
74
72
70
1030.09
68
6 6.0 1018.94
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

134
9 7.8
95
90
85
2458.20
80
2710.49
%T 7 5
70 1488.95
1244.89
930.59
65
60
1030.51
5 4.9
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(41.5 % MDMA)
9 7.4
96
94
92
90 2458.99
88
86 2710.77 875.68
1140.72
3260.66 1488.79
84 1244.71 930.69
%T 8 2 1114.04
80
987.55
78
76 1070.16
74
72
70 1018.52
1030.95
6 8.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

135
9 7.0
96
94
92
2458.11
90 1140.40
3260.52 875.48
88
2710.05 1114.58
86
%T 1488.69
987.35
84
1244.43 1070.33
930.80
82
80
78
1018.69
76
1030.75
7 4.3
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 7.9
96
1694.55 758.79
1644.78
94
2458.03 743.50
92
90 2710.13
%T 8 8
1488.96
86 1244.94
84
82 930.21
80 1030.21
7 9.1
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

136
9 6.5
94
92
90
88
2458.81
86
84
%T 8 2
2710.35
80
78 1488.77
76
1244.82
74
930.80
72
1030.53
6 9.8
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 5.8
94
92
90
88
86
2458.13
84
82
%T
80
2710.63
78
76
74 1488.70
72
930.63
70 1244.90 1030.63
6 8.0
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

(35.9 % MDMA)
137
9 5.7
94
92
90
88
86 3260.91
2458.18 1140.65 875.65
84
82 1114.77
80 2710.31 987.61
%T
78
76
1488.90 1070.88
74
1244.84 930.25
72
70
68
1018.56
66 1030.56
6 3.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 6.0
90
3260.14
2458.28 1140.92 875.90
85
1114.87
2710.53
80
%T 987.73
1070.45
75
1488.84
1244.93
930.74
70
1018.87
65 1030.26
6 3.5
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

138
9 5.3
90 1140.42
85
875.53
80
1114.68
75
%T 1070.21
70
3337.58 1488.86
65
930.21
1244.87
60
1030.14
5 4.7
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

9 6.9
96
1140.54
94
92
875.50
90 1114.85
987.06
88
1070.23
%T
86
84 3337.59
1488.94
82 1018.17 930.30
80
1244.82
1030.75
78
7 6.9
4 00 0.0 3 00 0 2 00 0 1 50 0 1 00 0 6 50 .0
cm-1

139

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DETERMINATION OF NARCOTIC AND PSYCHOTROPIC SUBSTANCES

BY USING INFRARED SPECTROSCOPY

IN PARTIAL FULFILLMENT OF THE REQUIREMENTS

Prof. Dr. Canan Özgen

Prof. Dr. Hüseyin İşçi

Prof. Dr. O.Yavuz Ataman

Examining Committee Members

Prof. Dr. Şefik Süzer (Bilkent Unv.)

Prof. Dr. O. Yavuz Ataman (METU, CHEM)

Prof. Dr. Teoman Tinçer (METU, CHEM)

Prof. Dr. Mürvet Volkan (METU, CHEM)

Faik Öztop (M.S., Jandarma Gn.K.lığı)

Name, Last name :

DETERMINATION OF NARCOTIC AND PSYCHOTROPIC SUBSTANCES BY

July 2005, 139 pages

Keywords: Narcotic and psychotropic substances, FTIR, drug, forensic chemistry.

NARKOTİK VE PSİKOTROPİK MADDELERİN İNFRARED SPEKTROSKOPİ

Temmuz 2005, 139 sayfa

Narkotik ve psikotropik maddeler, kişilerin ruhsal durumunu, fiziksel ve düşünsel

Anahtar Kelimeler: Narkotik ve psikotropik maddeler, FTIR, drog, adli kimya.

encouragement, advice and criticism throughout the study.

Criminal Laboratory for his support during the study.

I thank to the examining committee members for their contribution to my thesis.

my mother for their endless patient and support during my studies.

PLAGIARISM.................................................................................................. ..... iii

1.1 Properties of Commonly Used ATR Crystal Materials ................................. 18

2.1 Schematic Representation of ATR Technique......................................... 23

1.1 DEFINITIONS OF NARCOTIC AND PSYCHOTROPIC SUBSTANCES

In scientific publications, narcotics are usually distinguished from psychotropic

1.2 HISTORY OF DRUGS

After the developments in technology and drug industry, it became possible to

1.3 DRUG TRAFFICKING AND CONTROL MECHANISMS

Three important international conventions, under the United Nations provision,

“Single Convention on Narcotic Drugs (1961)” [3]

“Convention on Psychotropic Substances (1971)” [4]

“UN Conventions Against Illicit Traffic in Narcotic Drugs and Psychotropic

On the other hand, limitations of legal production resulted in an increase of the

1.4 TERMINOLOGY OF DRUGS

1.4.1 Drug Abuse

Drug abuse is the misuse of medicinal preparations without prescription and

1.4.2 Drug Dependence

1.4.2.1 Psychological Dependence

Psychological dependence on the effects of the drug related to a subjective and

1.4.2.2 Physical Dependence

1.5. CLASSIFICATION OF DRUGS

An effective classification of drugs can be done according to their effects on the

1.5.1 CNS (Central Nervous System) Depressants

Morphine is the principal alkaloid of opium, ranging in concentration of 4-21 %.It is

Codeine, which has effects similar to morphine, naturally founds in opium in

Papaverine is a non-addictive opium derivative, present at the 0.5-1.3 % level,

Heroin was first synthesized in 1874 as a safe, non-addictive substitute for

1.5.1.2 Hypnotic Sedatives

Abuse of barbiturates is very widespread but there is no indication of clandestine

The benzodiazepine family of depressants is used therapeutically to produce

Prolonged use can lead to physical dependence and even at recommended

1.5.2 CNS Stimulants

Cocaine is a unique chemical in that it is both a central nervous system stimulant

Cocaine increases alertness, wakefulness, elevates the mood, induces a high

Cocaine is a highly addictive substance developing a strong tolerance and

Illicit Cocaine is usually distributed as a white crystalline powder in hydrochloride

1.5.2.2 Amphetamine and Amphetamine Related Drugs

Amphetamine, dextroamphetamine and methamphetamine, are collectively

Amphetamine was first marketed in the 1930s as Benzedrine in an over-the-