Spectroscopy 1012 2012

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October 2012 Volume 27 Number 10 www.spectroscopyonline.com

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CONTENTS
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Co|umn

12
Classical Least Squares, Part XI: Comparison of Results from the
Two Laboratories Continued, and Then the Light Dawns
ln the lina| inta||ment ol thi erie, the main prob|em i o|ved uing the CLS a|gorithm to lind
that the pectrocopy i enitive to the vo|ume lraction ol the variou component in a miture.
Howard Mark and Jerome Workman, Jr.

18
Making Images at the Speed of Light
Kic|ing oll thi new erie on |ight-baed techno|ogie and app|ication, Spectroscopy
interviewed /ndrea ve|ten about hi wor| deve|oping lemto photography a a
potdoctora| aociate at the Maachuett lntitute ol Techno|ogy Media Lab.
/rtic|e
Label-Free Chemical Detection in Microfabricated Devices 22
Using FT-IR Spectroscopic Imaging
/ ummary ol ome recent ellort to deve|op app|ication ol Fourier tranlorm inlrared
(FT-lF) imaging lor microl|uidic and a dicuion ol dillerent approache (tranmiion and
attenuated tota| rel|ectance mode) to obtain FT-lF image ol microl|uidic device.
K.L. Andrew Chan and Sergei G. Kazarian
Observing Heterogeneous Catalysts While They 32
Are Working Using Operando Raman Spectroscopy
The opportunitie and current progre ol operando Faman pectrocopy are preented
through eamp|e baed on the author wor|.
M. Olga Guerrero-Prez and M.A. Baares
Energize Your Laboratory at the 2012 Eastern 40
Analytical Symposium
The 2012 F/S program chair preent high|ight ol the invited ympoia in pectrocopy and
re|ated lie|d, lrom the perpective ol what the chair ol the invited eion had in mind
when deve|oping the eion and what you can epect to |earn.
Mary Ellen McNally
October 2012
vo| ume 27 Number 10
vO|uvt z; nuvst| io
OcOst| zoiz
Cover image courtey ol
iStoc|photo/Thin|Stoc| lmage.
ON THF WFB
FACSS-SCIX PODCAST SERIES
The lina| podcat in a erie preented in
co||aboration with the Federation ol
/na|ytica| Chemitry and Spectrocopy
Societie (F/CSS), in connection with SciX
2012, the annua| conlerence ol F/CSS:
Expanding the Frontiers of Raman
in Pharmaceutical Discovery and
Development
/n interview with Don Pivon|a, enior prin-
cipa| chemit at lncyte Corporation and the
winner ol the 2012 Char|e Mann /ward lor
app|ied Faman pectrocopy.
spectroscopyonline.com/podcasts
FT-IR SPECTROSCOPY
ln a new roundtab|e, epert dicu
the ana|ytica| capabi|itie lor divere
app|ication ollered by Fourier tranlorm
inlrared (FT-lF) pectrocopy, a we|| a the
chemometric and pectra| interpretation
oltware that are important e|ement ol the
technique.
spectroscopyonline.com/TechForum
Join the
Spectrocopy Croup
on Lin|edln
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Editorial Advisory Board
Ramon M. Barnes University of Massachusetts
Paul N. Bourassa Blue Moon Inc.
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Kenneth L. Busch Wyvern Associates
Ashok L. Cholli Polnox Corporation
David M. Coleman Wayne State University
Bruce Hudson Syracuse University
David Lankin University of Illinois at Chicago,
College of Pharmacy
Barbara S. Larsen DuPont Central Research
and Development
Ian R. Lewis Kaiser Optical Systems
Jeffrey Hirsch Thermo Fisher Scientific
Howard Mark Mark Electronics
R.D. McDowall McDowall Consulting
Gary McGeorge Bristol-Myers Squibb
Linda Baine McGown Rensselaer Polytechnic Institute
Robert G. Messerschmidt Rare Light, Inc.
Francis M. Mirabella Jr. Mirabella Practical Consulting
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John W. Olesik The Ohio State University
Jim Rydzak GlaxoSmithKline
Jerome Workman Jr. Unity Scientific
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David W. Ball Cleveland State University
Kenneth L. Busch Wyvern Associates
Howard Mark Mark Electronics
Volker Thomsen Consultant
Jerome Workman Jr. Unity Scientific
Spectroscopys Editorial Advisory Board is a group of distinguished individuals
assembled to help the publication fulfill its editorial mission to promote the effective
use of spectroscopic technology as a practical research and measurement tool.
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members perform a range of functions, such as reviewing manuscripts, suggesting
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Figure caption Figure caption Figure caption
News Spectrum
Demand for vibrational spectroscopy techniques in the oil
and gas industry is quite strong and is seeing strong growth
as a result of the development of biofuels. Although biofuels
account for a small part of the oil and gas industry, they are
one of the largest factors in driving the growth in demand for
vibrational spectroscopy from the industry.
The biofuels sector is a subset of the
oil and gas industry, and consists of
fuels derived from organic materials.
The most common biofuels are
bioethanol and biodiesel, and while
they still account for only a small
percentage of global fuel production,
growth in this sector has been
rapid. The same vibrational
spectroscopy techniques popular for
analyzing petroleum-based fuels are
just as important, if not more so, for this burgeoning industry.
Vibrational spectroscopy, which includes infrared, near-
infrared (NIR), and Raman spectroscopy, is already widely used
in both laboratory and process analysis applications in the oil
and gas industry. Infrared spectroscopy, which consists mostly
of Fourier transform infrared (FT-IR) instruments, is by far
the most popular, as it is capable of providing quantitation of
key fuel components, especially in monitoring biofuel blends.
Characteristics of NIR and Raman make them particularly
useful in monitoring transesterification reactions, which are
used to produce biodiesel fuels. The global market for laboratory
vibrational spectroscopy in the oil and
gas industry was about $45 million
in 2011, of which biofuel analysis
accounts for only a small percentage.
However, biofuels will unquestionably
continue to be a major driver of
demand for this class of instruments.
The foregoing data were extracted
from SDis market analysis and
perspectives report entitled The Global
Assessment Report, 12th Edition: The
Laboratory Life Science and Analytical Instrument Industry,
October 2012. For more information, contact Stuart Press,
vice president, Strategic Directions International, Inc., 6242
Westchester Parkway, Suite 100, Los Angeles, CA 90045, (310)
641-4982, fax: (310) 641-8851, www.strategic-directions.com.
Market Profile: Vibrational Spectroscopy and Biofuels Analysis
A Model for R&D: The Center for Mid-Infrared
Technologies for Health and the Environment
By Phillip Braun
The Center for Mid-Infrared Technologies for Health and the
Environment (MIRTHE) an NSF engineering research center
headquartered at Princeton University develops mid-infrared
(mid-IR) sources and sensor systems that aim to combine the
sensitivity and reliability of established, expensive spectroscopic
and spectrometric systems with the affordability and portability
of far less sensitive systems, enabling environmental, security,
and health applications. These include readily deployed point
sensors and sensor networks that provide extensive temporal
and spatial data for environmentally relevant trace gases;
inexpensive, widely accessible sensors for remote detection
of hazardous materials, and noninvasive, point-of-care disease
diagnostics and monitoring via breath and tissue analysis.
MIRTHE has employed ultrasensitive sensors for carbon
monoxide, carbon dioxide, nitrous oxide, nitric oxide, nitrogen
dioxide, ozone, ammonia, ethane, methane, isopropanol vapor,
and water vapor isotopes. Future targets include uranium
hexafluoride, formaldehyde, expanded hydrocarbon detection,
and additional compounds relevant to breath analysis. The
versatility of MIRTHE sensors for target gases is enabled by the
inherent usefulness of the mid-IR for sensing. In this spectral
range, many security, environmentally, and medically relevant
compounds have strong characteristic absorption features, from
which presence and concentration can be determined. Sensor
versatility is also enabled by the quantum cascade laser, which
is highly customizable and can be designed to emit at specific
wavelengths corresponding to absorption features throughout
the mid-IR.
MIRTHE takes a comprehensive, integrated approach to
sensor development. Its research relies on strong collaboration
with industry and talented students of Princeton University as
well as the organizations academic partners Johns Hopkins
University, Rice University, Texas A&A University, University of
Maryland Baltimore County, and the City College of New York,
and clinical partner St. Lukes Hospital. As students assist world-
class faculty in sensor research, and through participation in a
core education program, they become highly trained and skilled
in all aspects of mid-IR sensing, from fundamental materials
development to field implementation and data analysis.
Industry affiliates participate closely in the education and sensor
development processes, giving them access to excellent talent
and speeding commercialization.
MIRTHE further expedites the commercialization process
with its Investment Focus Group, which brings the investment
community together with engineers, clinicians, federal
funding agencies, and industry affiliates to formulate
strategies for translating MIRTHE technology from R&D to
commercial production.
MIRTHE is constantly seeking new collaboration partners as
well as novel applications for its affordable, compact, highly
sensitive mid-IR sensors, in addition to those application foci
and structures already in place. For more information or to
become a MIRTHE member, visit www.mirthecenter.org.
Infrared - 64%
Near-Infrared - 27%
Raman - 9%
64%
27%
9%
Vibrational spectroscopy demand from oil and gas
applications in 2011.
Chemometrics in Spectroscopy
Howard Mark and Jerome Workman, Jr.
Finding that the experiments performed in two different laboratories gave substantially the same
results, we redoubled our efforts to determine the cause of the discrepancy between the spectral
and reference concentrations. Serendipity leads to success.
Classical Least Squares, Part XI:
Comparison of Results from the
Two Laboratories Continued, and
Then the Light Dawns
T
his column is the last installment of our discussion of
the classical least squares (CLS) approach to calibration
(110). Our previous column (10) discussed how we ob-
tained results from the second laboratory that had essentially
the same properties as the results from the first laboratory, de-
spite the fact that it was a different laboratory, the experiments
were performed by different scientists, and the mixtures used
contained different materials. In both cases we examined the
results for possible experimental blunders, and for both labo-
ratories we rejected the hypothesis that experimental problems
were the cause of the unexpected results.
This being the case, we are forced to the conclusion that
there is some real, previously unsuspected, physical phenom-
enon affecting the behavior of the samples or the spectroscopic
measurement. At this point, we have no clue as to the nature
of the phenomenon. The only course of action left to us is to
continue the analysis of the data as we had done previously,
keeping an eye out for any other unexpected effects that might
relate to an explanation of the results. The next step in the
analysis of the first set of experimental measurements was
to compute the mole percent values of the various mixture
components, and compare those values with the CLS values
computed from the spectral data. Therefore, we computed the
mole percents for the samples from the second laboratory, and
compared them with the spectral results. Table I presents that
set of comparisons.
We can see that the agreement between the CLS-deter-
mined percents and the mole percents is about the same as
what we found in the comparison with weight percents, with
errors for some samples being as much as 1015%.
Furthermore, from Table IV in part X of this series (10)
(for weight percents from the second laboratory) as well as
from Table V in part VIII (8) (for mole percents from the first
laboratory), we find that the nature and the approximate mag-
nitudes of the discrepancies are roughly the same for all three
sets of comparisons.
This finding was both encouraging and discouraging. It was
encouraging because it demonstrated whatever the effects that
are operative, they are reproducible, and this provides further
confirmation that they represent real physical phenomena,
even though we didnt know which phenomena those were. On
the flip side of the coin, it was discouraging for the same rea-
son: It provided no further insight into the nature of the cause
(or causes) of the errors.
At this point, there seemed to be no
further direction to go in other than
to continue the analysis of the data the
same way we did according to the previ-
ous schema: to compute the percentage
of hydrogen atoms from each compo-
nent of the mixtures, and then compute
the percentage of hydrogen atoms after
correcting for the density of the various
components. It was all a bit depressing,
since there was no real expectation that
we would find some new or different
results that would point us in the proper
direction.
The Light Dawns
Then serendipity struck.
Figure 1 in part V (5) specified the ex-
Table I: Comparisons of spectroscopic values with mole percents for data from the second laboratory
Sample
Mole Percent CLS Percent
Toluene Chloroform Heptane Toluene Chloroform Heptane
1 100 0 0 100 0 0
2 69.22 30.77 0 73.43 22.46 0.11
3 80.53 0 19.46 76.33 0.84 22.95
4 42.84 57.15 0 48.48 47.62 -0.7
5 49.27 32.86 17.86 49.35 24.4 23.57
6 57.96 0 42.03 51.52 1.2 47.49
7 19.99 80 0 23.02 72.78 0.04
8 22.76 60.72 16.5 24.36 49.76 23.87
9 26.42 35.24 38.32 25.22 25.36 48.5
10 31.49 0 68.5 25.96 0.26 73.27
11 0 100 0 0 100 0
12 0 84.65 15.34 0.74 75.83 23.79
13 0 64.78 35.21 0.56 51.55 48.83
14 0 38.01 61.99 0.42 25.86 74.35
15 0 0 100 0 0 100
perimental design, and from that we know that all concentra-
tions have a target value (in their appropriate units) that is one
of the values from the set (0, 25, 50, 75, and 100). One day while
trying to tear out only the white hairs (so as to at least leave the
dark ones in place), attention was drawn to the CLS values in
Table I. We extracted those values and present them in Table II
by themselves.
The realization suddenly struck that the values in Table I
are all within a couple of percent points of one of the values
from the set making up the experimental design. We recalled
that for the second laboratory the experimental design was
implemented by apportioning out the specified volume of the
specified component. This allowed the immediate creation of
the hypothesis that the physical phenomenon involved in the
absorption of light is the volume percent of the corresponding
component, not the weight percent, which is the concentration
unit most commonly used in chemical analysis.
The first test of this hypothesis, of course, was to compare the
various CLS values computed with the target values specified by
the experimental design. We show this comparison in Table III.
From Table III it appears eminently clear that indeed, not
only are the individual readings within the range of values
used in the experimental design, but each one also corresponds
to the actual value specified by the experimental design, within
a moderate experimental error. This leads us to the tentative
hypothesis that the concentrations determined by CLS analysis
of absorbance data correspond to the volume percents of the
components in the mixture corresponding to the various sam-
ples. That is, the spectroscopy is sensitive to the volume per-
cents of the components in a mixture. A hypothesis like this
is, of course, what we have been searching for. Having found a
tenable hypothesis, it raised a number of questions:
1: Why didnt we observe this correspondence in the data
from the first laboratory?
2: Is volume percent a more reasonable unit for spectroscopic
analysis than the other units that are commonly used?
3: When mixing different materials, it is common that there
Table II: CLS values from the second laboratory
Sample Toluene Chloroform Heptane
1 100 0 0
2 73.43 22.46 0.11
3 76.33 0.84 22.95
4 48.48 47.62 -0.7
5 49.35 24.4 23.57
6 51.52 1.2 47.49
7 23.02 72.78 0.04
8 24.36 49.76 23.87
9 25.22 25.36 48.5
10 25.96 0.26 73.27
11 0 100 0
12 0.74 75.83 23.79
13 0.56 51.55 48.83
14 0.42 25.86 74.35
15 0 0 100

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is shrinkage of the total volume, compared to the sum of
the volumes of the components; this is commonly called
the partial molal volume. How do we know that our sam-
ples are not affected by this phenomenon, and if so, can we
gain any insight about it or from it?
4: How can we confirm this hypothesis?
The answers that emerged are as follows.
Response to Question 1: We didnt observe a correspondence
between the CLS values from the first laboratory and the ex-
perimental design because the experimental design was imple-
mented in samples that were made gravimetrically. From Table
I in part X (10) we see that there are large disparities between
the weight percents and volume percents for the constituents in
most of the samples. Thus, a sample specified as having a par-
ticular composition according to weight would not necessarily
have the same, or even nearly the same, value for composition
when expressed as volume. Therefore, if the hypothesis is cor-
rect, then the values obtained from the spectra through the use
of the CLS algorithm would follow the volume percents, which
are likely not to match the weight percents, and thus we do not
observe a correspondence to the experimental design.
Response to Question 2: On reflection, there would seem to not
be any reason for a connection between spectral behavior and
weight percents of the components in a sample. Nor is there any
physical reason to expect the component weight to play a role in
the spectral behavior because the weight of a molecule does not
affect the molecular behavior; on the contrary, the weight is a
result, not a cause, of the underlying molecular structure and be-
havior. On the other hand, it is not clear a priori whether volume
percents are more reasonable than weight percents. As we will
show in a future column, however, it is possible to mathemati-
cally derive the fact that by starting with Beers law, spectra of
mixtures can be shown to exhibit absorbance directly related to
the volume percents of the components of the mixture.
Response to Question 3: The derivation described in the
answer to question 2 describes what happens when Beers law
holds rigorously, which includes the fact that the absorbances
add in strict proportion to their concentrations, and also in
proportion to the absorbance of the pure materials. This is
equivalent to an assumption that no partial molal effects are
operative. It is not yet clear what we should expect to happen if
one, or the other, or both of these conditions do not occur. In a
future column, we will discuss this situation further. For now
we will simply note that in a previous column (1), where the
components are known to interact and mixtures are known
to exhibit shrinkage, the spectrum of the mixture was severely
distorted by the interaction, so that the mixture spectrum
could not be regenerated from the spectra of the components.
Response to Question 4: The answer to our puzzle was found
partially through serendipity. The answer to question 4 can
also be found in another aspect of the serendipity that underlay
the experiment. Question 1, and the answer to it, brought out
the fact that we couldnt find a correspondence between the

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spectroscopic values and the weight per-
cent values, because the spectroscopic
values were not sensitive to the weight
percents.
It follows, therefore, that if we com-
pute the corresponding volume percent-
ages for the components used by the first
laboratory, this will provide evidence
as to whether or not the hypothesis we
formed to explain the results is correct.
In fact, this is a direct example of what
is called the scientific method in action:
Based on the result of one experiment
(in this case the data from the second
laboratory) we were able to form a hy-
pothesis (that volume percents were the
operative characteristic in explaining the
absorbance of the spectra of mixtures).
The serendipity involved here is the fact
that we already had the data we needed
to verify whether our hypothesis is cor-
rect, and all we need to do is carry out
the necessary calculations.
The next step in applying the scientific
method to the problem at hand is to see
if the hypothesis formulated can predict
the results of a different experiment.
Therefore, now we apply this hypothesis
to predict the results of a different experi-
ment (in this case, the results from the
first laboratory). We previously com-
pared the CLS values from the first labo-
ratory only to the weight percent, mole
percent, and values for the concentration
in some other units (for example, see
Table III in part VIII [8] for the compari-
son of CLS values to weight percents).
Now, we will compare the CLS results
from the data from the first laboratory to
the volume percents of the components
in those mixtures. If the CLS results
agree with the volume percents of the
mixture components in that set of sam-
ples, then this constitutes strong evidence
that the hypothesis is correct.
Table I in part X (10) presented the
correspondences between volume
percents and weight percents for the
samples from the second laboratory, and
from this table we were able to compare
results in both of those units to the
spectral results. Similarly, in Table IV
we show the correspondences between
weight percents and volume percents for
the samples from the first laboratory.
We note in Table IV the same phe-
nomenon we observed previously in
Table I in part X (10): the conversion of
concentration values between differ-
ent units is not unique. We note that
toluene, for example, has roughly a 2%
difference between two samples when
expressed as weight percent (76.4% and
74.1%), but an almost 15% difference
Table IV: Conversion from volume percents to weight percents for samples from the first
laboratory (Buchi)
Weight Percent Values Volume Percent Values
Toluene
Dichloro-
methane
n-Heptane Toluene
Dichloro-
methane
n-Heptane
100 0 0 100 0 0
76.40 23.60 0 83.30 16.69 0
74.10 0 25.90 69.29 0 30.70
50.30 49.70 0 60.93 39.06 0
48.90 025.11 25.99 49.82 16.60 33.79
49.94 0 50.06 44.03 0 55.96
25.30 074.77 0 34.27 65.72 0
25.33 49.65 25.02 28.37 36.08 35.53
23.86 26.45 49.68 22.93 16.50 60.56
25.19 0 74.81 20.98 0 79.01
0 100 0 0 100 0
0 75.04 24.96 0 60.60 39.39
0 49.54 50.46 0 33.44 66.55
0 24.34 75.66 0 14.13 85.86
0 0 100 0 0 100
Table III: Comparisons of spectroscopic values from the second laboratory with experimental design target values
Sample
Design Targets CLS Percent
Toluene Chloroform Heptane Toluene Chloroform Heptane
1 100 0 0 100 0 0
2 75 25 0 73.43 22.46 0.11
3 75 0 25 76.33 0.84 22.95
4 50 50 0 48.48 47.62 -0.7
5 50 25 25 49.35 24.4 23.57
6 50 0 50 51.52 1.2 47.49
7 25 75 0 23.02 72.78 0.04
8 25 50 25 24.36 49.76 23.87
9 25 25 50 25.22 25.36 48.5
10 25 0 75 25.96 0.26 73.27
11 0 100 0 0 100 0
12 0 75 25 0.74 75.83 23.79
13 0 50 50 0.56 51.55 48.83
14 0 25 75 0.42 25.86 74.35
15 0 0 100 0 0 100
(83.3% and 69.2%) when expressed as
volume percent. The other constituents
behave similarly. Again, we will defer
further discussion of this point until a
suitable time later.
For now, we return to our main dis-
cussion and point out that above, we ex-
plained why we saw no correspondence
between the weight percent values and
the spectral values in the data from the
first laboratory, and Table IV gives us the
information we need to make the com-
parison with the volume percent values.
All we need to do now is to take those
values of volume percent from Table
IV and use them in place of the weight
percents from Table III in part XIII (8).
Table V shows those results.
A cursory examination of the cor-
responding values in Table IV reveals
excellent agreement between the volu-
metric percentages and the CLS calcu-
lations for the concentrations.
Thus, this application of the scientific
method, albeit in a microcosm, has suc-
ceeded in verifying the hypothesis we
formulated: The operational variable in
optical spectroscopy is the volume per-
centage of the components. Therefore,
we conclude that the volume percentages
of the components is the physical char-
acteristic of materials that the measure-
ment of absorbance is in fact sensitive to.
We have solved our main problem, in
using the CLS algorithm to find that the
spectroscopy is sensitive to the volume
fractions of the various components in
a mixture. Although many questions
are still left open, and this result has
important implications and ramifica-
tions, including explaining the behavior
of the more conventional calibration
algorithms, some of these are briefly de-
scribed in a 2010 publication (11) and the
interested reader may want to inspect
that. However, Chemometrics in Spec-
troscopy is about more than this one
finding, important as it is. Therefore, we
will interrupt this discussion in favor
of other topics related to chemometrics
in spectroscopy, in some cases stepping
back for a less detailed but more encom-
passing perspective, or a view from a
height, to quote Isaac Asimov.
References
(1) H. Mark and J. Workman, Spectroscopy
25(5), 1621 (2010).
25(6), 2025 (2010).
25(10), 2231 (2010).
26(2), 2633 (2011).
26(5), 1222 (2011).
26(6), 2228 (2011).
26(10), 2431 (2011).
27(2), 2234 (2012).
27(5), 1419 (2012).
27(6), 2835 (2012).
(11) H. Mark, R. Rubinovitz, D. Heaps, P. Gem-
perline, D. Dahm, and K. Dahm, Appl.
Spect. 64(9), 9951006 (2010).
Howard Mark
serves on the Edito-
rial Advisory Board of
Spectroscopy and runs
a consulting service,
Mark Electronics
(Suffern, New York).
He can be reached via
e-mail: hlmark@prodigy.net
Jerome Work-
man, Jr. serves on
the Editorial Advisory
Board of Spectros-
copy and is the Ex-
ecutive Vice President
of Engineering at
Unity Scientific, LLC,
(Brookfield, Connecticut). He is also
an adjunct professor at U.S. National
University (La Jolla, California), and
Liberty University (Lynchburg, Vir-
ginia). His email address is
JWorkman04@gsb.columbia.edu
For more information on
this topic, please visit:
www.spectroscopyonline.com
Table V: Volumetric percents and spectrally calculated compositions using the CLS algorithm for all samples from the first laboratory
Sample
Volume Percent Values Spectroscopic Values
Toluene Dichloromethane n-Heptane Toluene Dichloromethane n-Heptane
1 100 0 0 100 -0.00 0.00
2 83.30 16.69 0 83.06 14.39 1.58
3 69.29 0 30.70 70.45 0.72 29.21
4 60.93 39.06 0 61.04 35.35 3.03
5 49.82 16.60 33.79 50.76 15.84 33.79
6 44.03 0 55.96 45.57 0.76 54.33
7 34.27 65.72 0 34.78 62.43 2.68
8 28.37 36.08 35.53 28.82 35.17 36.53
9 22.93 16.50 60.56 23.67 15.54 61.30
10 20.98 0 79.01 21.98 0.47 77.85
11 0 100 0 -0.00 100 0.00
12 0 60.60 39.39 -0.47 61.19 40.87
13 0 33.44 66.55 0.50 34.76 67.21
14 0 14.13 85.86 0.33 14.72 86.47
15 0 0 100 0.00 -0.00 100
THE FUTURE OF LIGHT-BASED TECHNOLOGIES
CHAD BAKER/GETTY IMAGES
Xxxx_xxxxx_xxxx
T
oday, the capabilities of modern
technologies are constantly increas-
ing, and instruments are becoming
smaller, faster, cheaper, more portable, and
more easily interconnected. This is true for
many analytical spectroscopy techniques
as well as for a wide range of other tech-
nologies that have the potential to intersect
with the field of spectroscopy and expand
its boundaries. To explore these develop-
ments, Spectroscopy is launching an ar-
ticle series about new technologies and
new applications of existing technologies
that are based on or related to light. We
kick off the series with this interview with
Andreas Velten about his work as a post-
doctoral associate at the Massachusetts
Institute of Technology (MIT) Media Lab
in Cambridge, Massachusetts. (Velten has
since taken a position as associate scientist
at the Morgridge Institute for Research at
the University of Wisconsin in Madison).
Velten and his colleagues in Professor
Ramesh Raskars Camera Culture group
at the MIT Media Lab, in collaboration
with the spectroscopy laboratory of MIT
Professor Moungi Bawendi, developed a
technique they called femto photography.
The technique uses a titaniumsapphire
laser that emits pulses every ~13 ns, pico-
second-accurate detectors, and complex
mathematical reconstruction techniques.
By combining hundreds of streak im-
ages (one-dimensional movies of a line),
captured with this high-speed camera,
they have created moving pictures (never
perhaps was there a more apt use of the
term) that show the movement of light
(groups of photons). Examples of their
use of the technique include combined
images of light traveling through a soda
bottle and, in a separate application, over
a piece of fruit.
Spectroscopy: How did the femto photog-
raphy project get started?
Velten: About two years ago, I joined Ra-
mesh Raskars group at the MIT Media
Lab to do a post-doc. Ramesh had been
thinking for a long time about combining
ultrafast optics and computational pho-
tography to build an imaging system that
can look around corners. He and his group
had taken some initial steps in implement-
ing the idea. Its kind of an unusual match,
because my background is in ultrafast op-
tics and this group is doing computer vi-
sion and computational photography. But
its very interesting to combine the two
fields. People in ultrafast optics are trying
to push the envelope of the hardware to
see how short we can make the pulses, to
improve ranging. For example, with light
detection and ranging (LIDAR) we send
a laser pulse to a target and wait until the
light comes back, and from the time that
has passed, we can measure the distance to
the target. Its used in traffic control these
days. But I was thinking about imaging
and what could be done with imaging data
in signal processing.
On the other hand, with computa-
tional photography people basically take
consumer cameras and make small
modifications to them, and do amazing
things by processing the data and look-
ing at the data in a new way. Our project
is kind of a combination of the two fields.
We use nonstandard hardware hard-
ware you can set to the time of flight of
the light that you are using it for imaging.
We wanted to develop new capabilities
of this method by further processing the
data. The initial goal was to build a cam-
era that could image around a corner (a
special application).
Spectroscopy: So how did you end up
photographing visible light photons
in other words, doing photography at
the speed of light?
Velten: Once you have the time-of-flight
imaging, you can get a lot more informa-
tion from the light by post-processing the
data. Professor Raskar and our whole
Camera Culture group is very interested
in computational photography and were
inspired by the bullet through an apple
strobe photos by Doc Edgerton. I had
taken some of our streak camera images
and created one-dimensional movies. Pro-
fessor Raskar challenged us to think about
ways to convert the one-dimensional
streak tube to create visually meaningful
ultrafast two-dimensional movies. I real-
ized at some point, from playing with the
camera, that you could actually compose
movies that you could stitch the data
together in a way that would allow you
to reconstruct a complete movie out of
the data that you capture. Making these
movies was really a side project. Our team,
especially Everett Lawson and I, started to
put together a mirror based system. Then
a set of collaborators, Diego Gutierez,
Di Wu, and members of Diegos group,
More Online:
Making Images at
the Speed of Light
To see the moving images produced
at the MIT Media Laboratory, and
more about their work, visit:
http://web.media.mit.edu/~raskar//trillionfps
http://www.mit.edu/~velten/press/content/
http://www.mit.edu/~velten
http://cameraculture.media.mit.edu/
October 2012 Spectroscopy 27(10) 19
Adrian Jarabo, Elisa Amoros Galindo, and
Belen Masia, got excited and worked on
visualizing the results better in the videos
and doing things like generating single
pictures from them.
Spectroscopy: How do you create such
clear moving images from multiple still
images?
Velten: We use a titaniumsapphire laser
that gives very regular pulses, and the
camera is synchronized to that. The cam-
era takes lots of images of the scene, but
because the camera and the laser are very
well synchronized and everything is very
regular, the images all look the same. So
we can just stitch them together to get the
final moving image of the scene.
Spectroscopy: Does it take a lot of time or
work to put them together?
Velten: The image capturing is what
takes hours, actually. To get a movie
that looks really good, you need quite a
few shots. And it takes much longer to
set everything up.
Then theres the post-processing. What
you see is actually a color photo in the
background, and the light is put on top of
that. The raw, straight camera images are
all black and white; the color is added for
visualization. Thats all post-processing.
If you watch the videos, the plain data
the pulsed elimination only, which shows
how the plain black-and-white image
from the laser looks is always there in
the videos.
Spectroscopy: The photons moving
through the soda bottle look like a fluid
in motion; there is more velocity at the
center than at the outside, and then it
seems to bunch up at the spout. What
do you think is going on?
Velten: The view of what you see is a little
distorted, because you dont see an event
when its actually happening; rather, you
see it when the light from the event has
traveled to the camera. I think thats why
it looks like things are moving slower far
away from the pulse than close to the
pulse, because there is a distortion that
comes from the light having to travel to
the camera.
Spectroscopy: What potential ap-
plications do you see for using this
technology?
Velten: One idea is to use this technology
to look into materials, because some of the
light always travels into the material and
some scatters back out. You can see this
very nicely in our images of the tomato:
The tomato actually keeps glowing after it
has been exposed, because light travels in-
side and then slowly comes back out. From
that light, you could actually get informa-
tion about what is going on inside that
material, if you developed a proper way
of probing and analyzing the materials
that you are looking at. There is currently
some interest in this. Many people have
tried to image living tissue, for medical
applications, like doing an ultrasound or
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lot of advantages over the common X-ray,
because it would be practically harmless.
That is one thing people are trying.
For industrial imaging, you could try
to detect cracks inside material, if some
light is actually transmitted through. You
dont need a lot, you just need a little bit
of light coming through and coming back
out. By analyzing how the light scatters off
the materials, we can learn a lot about the
material.
Spectroscopy: For potential applications
like medical imaging, to what level of
detail or size can you see things?
Velten: Thats an open research question,
because really, you are posed with a data
collection and processing problem. The
information that the light gets the
wavelengths, the resolution of the light
is very high, so you should be able to get
quite detailed information out. But the
scattering inside the material destroys a lot
of that information by bouncing the light
around. And then the question is, How
well can you detect the intensity of what is
coming out (not only the time it takes for
the light to come back out) and how well
can you computationally reconstruct what
is inside the material? It depends a lot on
how deep the material is, obviously.
Spectroscopy: Can you envision using
different wavelengths so that you could
actually make vibrational spectroscopy
measurements?
Velten: Our limitation right now is that
we only have one light source at 800 nm.
So the movie, the moving part of it, is ac-
tually in the near infrared. But if we had
three different light sources, red, green,
and blue, or a tunable light source, like
if you used an optical parametric oscil-
lator (OPO) instead of a titaniumsap-
phire laser, then we could scan different
wavelengths or even try to send a broad
spectrum in and learn more about the
spectral properties of the material. That
is something we are looking into.
The vibrational modes in some materi-
als are slow enough that you could actually
see something happening. You wouldnt
just see a spectral signature; I think you
might be able to see the vibration happen-
ing inside, the frequency. That would be
very interesting.
For this camera, or at this point for this
camera, it would need to be something
macroscopic something we could put
in front of the camera and in which we
could excite enough molecules or enough
material simultaneously so we could actu-
ally see something.
Spectroscopy: What do you envision this
high-speed camera technology may be
able to do in terms of measuring and
studying the interaction of light with
various media, such as liquids, powders,
and large and small particles?
Velten: We have done some of that. Its al-
ways an interesting game to put something
in front of the camera to see if the camera
can detect something interesting, because
the amount of information you get in one
of these exposures is actually quite big,
and you may, by chance, discover some-
thing that has been missed before. Visu-
ally analyzing something is an incredibly
powerful technique, compared to looking
at things with a computer or looking at
plots, or just numbers.
Applying this technology to spec-
troscopy techniques is a very interest-
ing direction to take this work. There
are, of course, a lot of interesting effects
that occur when you hit something
with a very powerful laser pulse and
evaporate material. Of course, usu-
ally that is a very small effect, and you
would need a microscope in front of our
camera to see something there. But all
these things are interesting. You could
trace plasmas in the air; light filaments
would also be interesting to look at. At
this stage, we are just brainstorming
about all the things that could be done
by looking at things with this speed.
Right now our limitation is that we need
repeatable events. We have to be able to re-
peat the same thing over and over again
many times to collect enough data to cap-
ture the movie. That limits some of the
applications that you can actually do in
terms of looking at interactions with mat-
ter, because often you destroy your sample
the first time you shoot light at it, and then
youre done.
Spectroscopy: There has been so much
work done using simulations to gener-
ate models for how light interacts with
multiple particles of different sizes, de-
pending on their scattering properties or
absorptive properties. Is that a potential
field of use?
Velten: We have done a little bit of that sort
of thing, such as taking tissue samples or
materials like wax, and trying to analyze
them. So far we have been looking more in
the direction of computer graphics, which
is more about how things look than whats
actually happening. Thats the background
of the group, and thats why we have done
some work in that direction. But the other
direction, of looking at scattering models,
is also very interesting and a worthwhile
direction for this research.
Spectroscopy: This work brings to mind
the dramatic effects of high-speed cam-
eras, such as in The Matrix, when you
see a bullet moving very slowly and inter-
acting with the images of the people and
the scene around it. At the high speed of
your cameras, you could actually do the
same thing with light moving through
a scene, right?
Velten: Its very interesting. Actually, if you
were to capture a bullet with this camera,
that is, if you could shoot the bullet several
times and actually make a movie of the
bullet, it would take about three years to
watch the film of the bullet going from one
side of the scene to the other. Thats true
for almost any piece of matter. So I dont
think you will ever look at solid or atomic
matter with this camera, unless you have
a very violent explosion, because there is
just not enough happening in a time frame
that is interesting to watch.
The other question people ask is, Dont
you capture a lot of data? Well, we capture
512 frames, so its not a lot, about half a
megabyte per frame. If you were actually
capturing a whole second, of course there
would be a lot of data, but it would also
take tens of thousands of years to watch.
So there is no point in capturing a full sec-
onds worth of data.
Spectroscopy: What are your next steps
with this work?
October 2012 Spectroscopy 27(10) 21
Velten: We have a publication that is under
review right now, using an application of
this time-of-flight imaging. We have an-
other one we just submitted that is about
further processing and visualizing the
data visualizing the movies, essentially.
Beyond that, many other things that
have been done in computer vision and
computational photography can also be
done using this system and using this
camera. We would like to go through
those and demonstrate them one by one,
to demonstrate the capabilities, including
some things that were not possible before,
like looking inside materials from a dis-
tance by analyzing the scattering and the
time of flight. We also have received some
interest from people who would like to in-
vestigate scientific phenomena, to lead to
new discoveries. So thats an interesting
direction that will also be explored.
The other thing that comes to mind is
improving the system. Right now, it uses
a lot of high-end equipment that is bulky
and heavy. Its really a laboratory setup.
For many applications, it would be bet-
ter to make it much more compact and
much more portable. So we are working
on building a dedicated compact system.
Spectroscopy: What plans do you have to
partner with other scientists at MIT or
other universities?
Velten: We dont have any thing concrete
yet. We have chatted with a number of
people who are interested, but we are still
exploring what kind of concrete collabora-
tions could come out of it.
Here at MIT, for example, Professor
Moungi Bawendi (of the spectroscopy
laboratory) is providing the equipment
for us, and is also a member of this proj-
ect. He usually works on spectroscopy and
quantum dots, so he is an interesting part-
ner for the spectroscopy and nanocrystal
applications.
We are also interested in working with
the people at the MIT Edgerton Center, be-
cause we see our work as being kind of in
line with the work that Doc Edgerton did
about 50 years ago. I dont know if youve
ever seen those art photography pictures
of a bullet going through an apple. That
was done at MIT. I think it was kind of a
similar situation, that he had this equip-
ment, and wondered if he could just take
still pictures with it, and he came up with
that stunning photography. That is still on
display in the Edgerton Center, and I think
its mentioned on our web page.
Another person is Nils Abramson in
Sweden who did light-in-flight holography
back in the 1970s, also trying to capture
light moving, with holographic film. He
had some very interesting short movies
of moving light and things like that. He
is retired, but we are in contact with him.
Most of these things are in the early
stages of just talking to people and seeing
what can be done.
For more information on this topic,
please visit our homepage at:
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icrofluidic technology is a powerful tool that has a
wide range of applications in chemical and biological
analysis (1). The improved heat and mass transfer in
microfabricated systems in comparison to traditional processes
provides the opportunity to increase control over the yield, the
speed of the turnover of experiments for high-throughput
studies, and reduce the amount of precious reagents used (2).
Knowing the chemical composition at a specific point in the
microfabricated device can aid in the design and optimization
of these devices (3,4).
Detection in microfabricated devices often relies on addi-
tional tracers or tags to visualize the existence and the dis-
tribution of particular components. One of the most widely
used methods is confocal fluorescence microscopy. The ad-
vantage of fluorescence is that it is highly sensitive (5) and can
often achieve sufficient spatial resolution. However, finding a
suitable fluorescence agent and photobleaching are some of
the remaining challenges to overcome. The tracer also has to
be inert enough that it will not decompose or interfere with
the process of interest (for example, chemical reactions and
diffusion). Raman, surface-enhanced Raman spectroscopy
(SERS), and coherent anti-Stokes Raman scattering (CARS)
have been shown as promising label-free detection methods
in microfluidic systems (610). In this article, we discuss some
recent studies that have demonstrated that Fourier transform
infrared (FT-IR) spectroscopic imaging can be a powerful de-
tection tool, as was proposed earlier (11), to extract spatially
resolved rich chemical information from microfluidic devices
in a label-free manner.
FT-IR Spectroscopic Imaging
FT-IR imaging has been used as a highly versatile analytical
method, providing spatially resolved, chemically specific in-
formation for studying multicomponent systems (12). Recently,
conventional FT-IR microscopy using a single-element detec-
tor was applied to analyze fast reactions in microfluidic flows
where spectral information from a specific location in a channel
was obtained (13). FT-IR spectroscopic imaging combines the
benefits of imaging and spectroscopy providing chemical maps
of studied samples. The chemical specificity comes from the
intrinsic molecular vibrations, revealed by spectral bands, while
spatial information is collected from the focal plane array (FPA)
detectors. An FPA detector comprises thousands of detector
pixels, each collecting an infrared spectrum so that thousands
of infrared spectra are collected simultaneously in a single im-
aging measurement. This approach reduces the time required
to collect all the spectral data when compared to point-to-point
mapping using a single element detector with apertures (14).
Characteristic spectral bands can then be used as markers
for specific components, which allows their distribution within
the imaged area to be revealed. Multivariate methods are also
available to separate components with similar spectral fea-
tures to generate representative maps for each component. A
full mid-IR spectrum (4000900 cm
-1
) is collected from each
K.L. Andrew Chan and Sergei G. Kazarian
Fourier transform infrared (FT-IR) spectroscopic imaging is a highly versatile technique that can be
applied to a wide range of systems. This article summarizes some of the recent efforts developing
applications of FT-IR imaging for microfluidics. The main advantage of FT-IR imaging compared to
traditional imaging methods is that it is a label-free imaging technique. There is no need to develop
tags or labels, multiple components are simultaneously traced, and images can be taken without
disturbing the sample. All of these advantages are accompanied with a near-video frame rate acquisi-
tion speed. Different approaches to obtain FT-IR images (transmission and attenuated total reflection
mode) of microfluidic devices are discussed including novel ways to create microfluidic devices.
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detector pixel, and multiple components
can be simultaneously tracked in one
single imaging measurement either using
univariate or multivariate approaches.
This multicomponent imaging feature
is a significant advantage compared to
ordinary fluorescence measurements in
which only one component is traced at a
time. The absorbance of a spectral band
is directly correlated to the concentration
of the component so that results obtained
can be quantified.
Because all spectra are collected si-
multaneously, FT-IR imaging using FPA
detectors is suitable for studying dynamic
systems such as diffusion and dissolution
(1520) and has great potential for high-
throughput applications, especially when
combined with the attenuated total re-
flection (ATR) sampling method (11,21).
ATR Imaging
In the ATR approach, the infrared light
is totally internally reflected at the inter-
face between the high refractive index
infrared-transparent element and the
lower refractive index medium (the
sample). Common elements used for
ATR measurement are diamond (n
2.4), ZnSe (n 2.4), Si (n 3.4), or Ge
(n 4). In this measurement mode, the
infrared light probes into the sample as
an evanescence wave, the field strength
of which decays exponentially into the
sample. The depth of penetration is on
the order of a few micrometers and the
resultant pathlength (the equivalent
pathlength) is also in the order of several
micrometers depending on the refractive
indices of the sample, the ATR element,
and the incident angle. The ATR element
is selected such that it will provide a rela-
tively small, but known, pathlength that
will produce an appropriate on-scale ab-
sorbance. Other considerations include
the physical and chemical properties of
the ATR element for specific applica-
tions. The generally small pathlength
from ATR mode measurement offers
the opportunity to measure materials
that have strong mid-IR bands such as
water and reduces sample preparation
because no microtoming or polishing of
the sample is required. The possibility of
acquiring spectra using ATR mode in-
creases the applicability to study samples
in situ and to monitor processes on line.
The simplicity of measurement allows
rapid analysis of an array of deposited
samples in the imaging area (11,2123).
Combined FT-IR Imaging
and Microfluidics
ATR Mode
Because the evanescent wave probes a rel-
atively shallow layer, the sample must be
in close contact with the ATR element to
be exposed to and interact with this eva-
nescent wave. This sampling requirement
for ATR measurement is automatically
satisfied when the sample being mea-
sured is a fluid. FT-IR imaging in ATR
mode is therefore suitable to study mi-
crofluidic systems. Microfluidic devices
are often made of polydimethylsiloxane
(PDMS) using templates in which chan-
nels are created when the PDMS stamp
is bonded to a flat surface such as glass.
With ATR FT-IR imaging, instead of
bonding the PDMS device to glass, the
PDMS device is bonded to the imaging
surface of the ATR element so that the
measuring surface forms one of the walls
of the microfluidic channel. The fluid
flowing inside the channel that comes to
close proximity with the surface of the
ATR element is measured.
ATR elements are often expensive
and cannot be used as disposable units;
therefore, the bonding of PDMS onto
the ATR surface must be reversible.
PDMS will bond weakly with a clean,
oil-free surface. However, most micro-
fluidic experiments cannot rely on this
weak bonding as the seal for the chan-
nels because pressure from the fluid will
cause liquid to escape by overcoming
this weak adhesion force. Fortunately,
this issue can be easily rectified. A rigid
poly(methyl methacrylate) (PMMA)
sheet (or any rigid, ideally transparent
material for visible inspection) can be
used as a press to provide a stronger
bonding between the PDMS and the
ATR element. One of the inherent ad-
vantages of ATR imaging measurements
is that the presence of foreign particles
(dust) that may affect contact quality
between the PDMS chip and the ATR
surface can be easily detected (24). Leak-
age of fluids through the gap between
the ATR surface and the PDMS chip can
also be detected from the image as the
escaped fluid will be in contact with the
ATR element. Figure 1 shows the typi-
1 mm
Figure 1: Top left: The Y-junction PDMS microfluidic device. Middle: The PDMS microfluidic
device on the ATR imaging surface. Imaging area is indicated by the red rectangle. Bottom right:
RGB imaging of a Y-junction microfluidic device with water entering from the right and PEG 200
entering from the left measured with macro ATR FT-IR imaging. Red, blue, and green represent the
presence of PDMS, water, and PEG 200, respectively. The imaging area is 2.56 mm 3.58 mm.
cal Y-junction PDMS microfluidic device that we have used
as the first test of the principle (25). An image of the device
can be generated based on the band specific to PDMS. When
two different fluids are injected from the two entrances of
the microfluidic device, the mixing between the two fluids
can be studied. As an illustration, we injected water (75 L/h)
through the right entrance and PEG 200 (25 L/h) through
the left channel. Because both fluids are transparent in visible
range, it was not possible to visualize the flow pattern using
visible light without adding dye to the solution. Using ATR
FT-IR imaging, the two fluids are easily distinguished. Water
can be traced using the (O-H) band at 37003100 cm
-1
, and
PEG 200 can be traced using the characteristic (C-H) bands
at 30002800 cm
-1
. A red-green-blue (RGB) figure (Figure 1)
has been created to show the distribution of PDMS (red), water
(blue), and PEG (green). The image allows us to immediately
identify the effect of viscosity to the flow pattern. The water
stream, despite having a higher flow rate, was constrained to
the right while most of the channel was occupied by the PEG
200 because of the difference between their viscosities.
Transmission Mode
There are both advantages and disadvantages to working in
transmission mode. One of the main advantages is that the
whole volume of the fluid is analyzed as compared to the first
few micrometers from the surface in ATR mode. However, for
the same reason, one of the main disadvantages is that the fluid
thickness is often limited to ~10 m to ensure that most of the
spectral bands are within the linear detection limit (around
0.8 absorbance units). For the stronger spectral bands such as
the band from water (O-H) mode, the thickness may need
to be further reduced to 23 m. In general, therefore, certain
parts of the spectral region will not be accessible in transmis-
sion with a workable pathlength when the fluid studied has
strong spectral bands.
1 mm
Figure 2: A picture of the wax-printed microfluidic device before being
sandwiched between the two CaF
2
windows for imaging in transmission.
Rigaku Corporation and its Global Subsidiaries
website: www.Rigaku.com | email: info@Rigaku.com
To study in transmission mode, the
top and bottom layer of the microflu-
idic device has to be transparent in the
infrared region. Common infrared-
transparent materials used for making
spectroscopic windows include BaF
2
,
CaF
2
, and ZnSe. Hygroscopic materials
such as NaCl and KBr are not suitable for
this purpose because water will dissolve
the window. Silicon is also transparent in
the mid-IR region and has great potential
for use as a material to construct micro-
fluidic devices for FT-IR imaging because
etching techniques for silicon wafers are
well established and its surface properties
can be tuned with self-assembled mono-
layers. Other infrared transparent win-
dows are often not malleable and specific
etching techniques may first need to be
developed (26). Furthermore, these crys-
tals are often too expensive to be used as
a one-off device (a pair of large windows
would cost as much as $320). The ability
to create reusable microfluidic devices on
these windows would be an important
step forward for the wider application of
this approach.
Wax-Printed Microfluidic Devices
One of the possibilities for producing
microfludic devices is direct wax print-
ing. Machines that can print molten wax
droplets at precise locations are com-
mercially available. Previous studies used
wax printers in one of two ways, either to
create the master, which was then used to
cast PDMS devices to obtain the nega-
tive design of the printed features (27,28),
or printing the device on paper to cre-
ate paper microfluidics (29,30). Our wax
printing approach manufactures micro-
fluidic devices with free-flowing chan-
nels directly without the need for casting
PDMS over the print. We have applied
this method to create various microflu-
idic devices on a CaF
2
substrate. The
procedure is relatively straightforward.
Microfluidic devices are first designed
and programmed into the computer
that operates the microdrop machine.
Molten wax droplets, each of which has
a controllable diameter of 3070 m, are
printed directly onto the CaF
2
window.
The CaF
2
window can be precoated with
a thin layer of polymer to create a hydro-
phobic surface when necessary. The ad-
jacent molten wax droplets join together
and solidify to form a wax wall. Figure
2 shows a photograph of a T-junction
microfluidic device created by the wax
printing method.
A spacer is added that determines the
depth of the channel, which is also the
pathlength of the measurement. The
microf ludic channel is created when
another CaF
2
window is pressed on
top and held together by screws, for ex-
ample. Experiments can be conducted
immediately after the printing process,
and the infrared-transparent windows
can be reused because the wax channels
can be removed easily. Depending on the
complexity of the design, the printing
time is typically less than 10 min. New
microf luidic devices can be modified
and created in a matter of minutes. The
size of the wax droplet is on the order of
50 m and the machine has an accuracy
of 40 m, which defines the resolution of
the microfluidic device. So far, we have
only experimented using wax that is vul-
nerable to many organic solvents and oil.
However, waxes that are highly chemi-
cally resistant are also available; we plan
to test these and present the results in
the future.
Transflection mode
In transf lection mode, the sample is
placed on an infrared-ref lective sub-
strate surface where the IR radiation
passes through the sample, is reflected
off the surface of the substrate, and
passes through the sample again before
being collected with the sample objective.
For microfluidic applications, the advan-
tage of this approach is that only the top
surface needs to be infrared transparent.
When an open channel is used (that is,
when the top surface is not covered and is
open to air), there is no need to construct
1 mm
PDMS
10
5
0
-5
Oil
ATR element
IR light
Oil
Water
A
b
s
o
r
b
a
n
c
e
Wavenumber (cm
-1
)
0.3
0.25
0.2
0.15
1000 1100 1200 1300 1400 1500 1600 1700 1800
Water droplet
Figure 3: Top figure: ATR FT-IR image of oil with water droplets flowing inside microfluidic channels
taken with a snapshot at less than 50 ms scanning time with a frame rate of approximately 18 Hz.
Imaging area to right of the FT-IR image: schematic diagram showing the side view of the moving
water droplet in oil in the microfluidic device on the ATR element. Bottom figure: The blue line
represents the extracted averaged ATR spectrum from the moving water droplet region and the
red line represents the extracted averaged ATR spectrum from the oil region.
the microfluidic device in an infrared-
transparent material. The main require-
ment is that the bottom of the channel
is infrared reflective, which can be easily
achieved. However, the thickness con-
straint that applies in transmission mode
measurement is more severe because the
pathlength is twice the thickness of the
fluid. Nevertheless, such an approach
was used in the study of biofilms and
live cells in an open channel setting (31).
Two-Phase Segmented Flow
In comparison to laminar f low, seg-
mented flow and droplet flow offer the
possibility to perform high-throughput
studies without increasing the size or
complexity of the microfluidic device
(32). Although each droplet or segment
is compartmentalized by the immiscible
inert phase, each segment can be consid-
ered as individual experiments.
FT-IR imaging of droplets or segments
can be captured easily when they are sta-
tionary. The applications of segmented
flows include protein crystallization, live
cells in droplets, and other slow processes.
Many of these research ideas are yet to be
realized in combination with FT-IR imag-
ing. One of the main challenges in imag-
ing segmented flows is when one wants
to capture the droplet or segments while
they are moving. The acquisition time for
a typical FT-IR imaging measurement is
on the order of seconds. Although this
imaging speed is already a great improve-
ment from the early FT-IR imaging sys-
tems; it is often not fast enough to capture
the moving droplets. Fortunately, through
optimization of the data acquisition pro-
cess, FT-IR imaging of moving segments
or droplets in microfluidic channels has
been demonstrated (33). Traditionally,
the acquired data in an FT-IR imaging
measurement are the average of several
scans to improve on the signal-to-noise
ratio. (In theory, the signal-to-noise
ratio is improved by the square root of
the number of scans taken.) However, to
capture droplet flow, only one scan can
be collected. The time taken for one scan
is governed by the spectral range and
spectral resolution set in the experiment
as well as the number of detector pixels
used. For an imaging experiment with
a 64 64 pixel array, 8 cm
-1
spectral
resolution, and 4000900 cm
-1
spectral
range, the scanning time is approximately
600700 ms. With current technology,
one needs to reduce the amount of data
collected to improve this speed. For ex-
ample, most of the spectral information
is contained in the so-called fingerprint
region of the infrared spectrum (between
1800 and 500 cm
-1
). Because the detec-
tion limit for the FPA detector is around
900 cm
-1
or ~1000 cm
-1
when CaF
2
is
used as the substrate material, there is
an opportunity to reduce the amount of
data collected without losing significant
chemical information by reducing the
spectral range to 18001000 cm
-1
. This
can increase the speed of the scan four-
fold. By reducing the spectral resolution
from 8 cm
-1
to 16 cm
-1
, 32 cm
-1
, or even
64 cm
-1
, the signal-to-noise ratio will be
improved and the spectral bands will be
broader while the speed of the scan can
be doubled, quadrupled, or even octupled.
Together, this brought the scanning time
down to well below 100 ms (33).
First, we attempted imaging of droplet
flow using the ATR approach. A micro-
fluidic chip with a T-junction design
was mounted on the measuring surface
of the ATR element (Si was used in this
case). The surface of the Si was pre-
treated to increase the hydrophobicity.
The oil (FC-40) and water were intro-
duced at flow rates of 2 L/min and 1
L/min, respectively. The result is shown
in Figure 3. The images of oil have
shown that the water droplets flowing
in the oil have been captured. In the re-
gion in which a water droplet is present,
the oil absorbance is lowered. However,
spectra extracted from the water droplet
region have shown a high absorbance of
oil while the water absorbance was very
low (see spectra in Figure 3). The reason
for this observation is that when water
droplets are moving at high speed inside
the channel, there is a thin layer of oil in
between the water droplet and the ATR
element (see Figure 3). Because in ATR
measurements only the layer of several
micrometers from the surface of the
ATR element is detected, the resultant
spectral bands were contributed mostly
by the oil layer on the surface of the ATR
element. On the other hand, the spec-
trum of pure water can be obtained from
the imaging data when the water droplet
is stationary. Comparing the absorbance
of the oil in the water droplet region to
the bulk oil, the thickness of this oil layer
can be calculated using the following
equation (34,35):
In 1
A(t)
A( )
2t
d
p
[1]
where A(t) is the absorbance of the oil at
the water droplet region, t is the oil film
thickness, A() is the absorbance of the
oil at the region without the water drop-
let, and d
p
is the depth of penetration.
The thickness of the oil layer is calculated
as 790 nm.
To capture the spectrum of water more
clearly in the segment, imaging in trans-
mission mode needs to be used. Figure
4 shows the image, the schematic dia-
gram, and the extracted spectra of a water
droplet flowing in oil in a wax-printed
microfluidic device with a pathlength of
25 m. The absorbance of water is far
more pronounced compared to the spec-
trum extracted from the ATR measure-
ment shown in Figure 3. However, as dis-
cussed in the transmission mode section,
the large pathlength could lead to some
parts of the spectral region becoming
inaccessible. In this case, the spectral re-
gion in which oil absorbs IR light strongly
(11001350 cm
-1
) is not accessible in the
oil-rich region of the image. This is in
contrast to the spectra extracted from the
ATR imaging measurement, in which the
absorbance of all spectral bands was less
than 0.8, the value below which analysis
can be quantitative. On the other hand,
a large amount of the spectral range
remains accessible in the water droplet
region (16001000 cm
-1
). We have dem-
onstrated previously that, despite the use
of only one scan per image, the presence
of protein can be detected at the ~1 mM
level in the water segment in transmission
mode by observing the amide II band at
1560 cm
-1
(36).
Reactions
One of the potential benefits of combin-
ing FT-IR imaging with microfluidics is
the in situ study of chemical reactions
inside the channel. This allows for op-
timization of reaction conditions to ob-
tain better yields, or understanding the
diffusion and reaction kinetics inside
the microfliudic device. This technique
can be developed into a tool for chemical
detection in microreactors for studying
the effect of changing parameters to the
overall efficiency. One of the examples
(25) that demonstrated this potential
was the observation of isotopic exchange
between water and D
2
O forming HDO
(semiheavy water). The spectral bands of
H
2
O, D
2
O, and HDO are readily distin-
guishable. Because FT-IR measurements
can be quantified, the concentrations of
reactants and products at different points
of the devices can be obtained. Another
1 mm
Oil
CaF
2
CaF
2
IR light
Water droplet
1.5
A
b
s
o
r
b
a
n
c
e Oil
Water
1
0.5
0
Wavenumber (cm
-1
)
1100 1200 1300 1400 1500 1600 1700 1800
Figure 4: Top figure: Transmission FT-IR image of water droplets in oil flowing inside microfluidic
channels taken with a snapshot at less than 50 ms scanning time with a frame rate of approximately
18 Hz. Right of the FT-IR image: schematic diagram showing the side view of the moving water
droplet in oil in the CaF
2
sandwiched wax-printed microfluidic device. Bottom figure: The blue
line represents the extracted transmission spectrum from the moving water droplet region and
the red line represents the extracted transmission spectrum from the oil region.
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possible experiment is a reaction in a
two-phase system in which one of the re-
actants is dissolved in the oil phase while
the other reactant is dissolved in aqueous
phase (37). The resultant effect is that the
reaction can only happen at the interface
between the two fluids. Diffusion profiles
and the formation of product in such sys-
tems can be monitored simultaneously
using the FT-IR imaging approach (37).
This detection approach is set to benefit
automation of reactions and other pro-
cesses in microreactors (38).
Conclusions
In this article, we have discussed a meth-
odology that permits the in situ chemical
imaging of flows in microfluidic chan-
nels using FT-IR spectroscopic imaging
that does not require added labels or
dyes. This inherent chemical specific-
ity of FT-IR imaging significantly adds
to the detection capabilities of flows in
microfluidic devices because it obtains
quantitative chemical information as a
function of space and time. This chemi-
cal imaging methodology has wide appli-
cability to the study of dynamic systems
ranging from the analysis and modeling
of mixing in laminar flows to studies of
reactions in segmented flows and sepa-
rating live cells in moving droplets. We
hope that this article can stimulate fur-
ther applications of FT-IR spectroscopic
imaging to study processes and reactions
in microfabricated devices and micro-
reactors because this methodology has
great potential for in situ fast chemical
analysis of microfluidic flows.
Acknowledgment
SGK acknowledges research funding from
the European Research Council under the
European Communitys Seventh Frame-
work Programme (FP7/2007-2013)/ERC
advanced grant agreement no. [227950].
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C. Elvira, J. San Roman, P.S. Wray, and
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Dr. Ka Lung Andrew Chan is a
Research Associate and Sergei G.
Kazarian is a Professor of Physical
Chemistry with the Department of
Chemical Engineering at Imperial College
London in London, UK. Please direct
correspondence to: s.kazarian@
imperial.ac.uk.
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CHEM
& BI
POWERING
INNOVATIONS IN
T
he synthesis of most chemicals requires a cata-
l yt ic process. As a result , cat al yst s are of ten
studied with the goal of improving their prop-
erties and catalytic behavior. Spectroscopy is a valu-
able tool to characteri ze t he surface of sol id (het-
erogeneous) catalysts and also can be usef ul for the
determi nat ion of react ion i ntermediates and ot her
adsorbed species. Raman spect roscopy i s part icu-
l arly usef ul for st udyi ng catalysts because Raman
spectra can be obtai ned under a wide range of con-
ditions (at high pressures and at temperatures above
1000 C, by the use of the appropriate excitation wave-
length), which makes it possible to use Raman spec-
troscopy to characterize catalysts during a reaction.
Determining catalyst performance (such as conversion
or selectivity) during a reaction, at the same time that
the catalyst is characterized, is the concept of the ope-
rando Raman methodology (16).
Over the last decade, operando Raman spectroscopy
has been applied successfully to the study of several cat-
alytic systems, in both liquid- and gas-phase processes.
Such studies have provided a better understanding, and
subsequent improvement, of various catalytic processes.
The aim of this article is not to provide a detailed re-
view of the method, but rather to present brief ly the
opportunities and current progress of operando Raman
spectroscopy through some examples based on the au-
thors work.
Look, But . . . How?
One of the critical issues in performing operando ex-
periments is to correctly design the Raman cell, because
it has to perform like a catalytic reactor and meet the
optical requirements for spectroscopy. The Raman cell
and the reaction conditions must prevent any mass or
heat transfer limitations and the contribution of non-
catalytic reactions such as gas-phase reactions. Thus,
conventional cells cannot be used to perform catalytic
tests. Traditional cells are good for in situ studies, be-
cause the sample is fully aware of the presence of the
gas, but most in situ Raman cells are designed in such
a way that not all the gas f lowing through it interacts
with the sample (catalyst). Figure 1 shows the home-
made operando reactor designed by our group that was
used to perform the operando experiments discussed
in this article. Essential ly, it is a f i xed-bed catalytic
M. Olga Guerrero-Prez and M.A. Baares
Operando means working, thus, this technique refers to the combination of a characteriza-
tion study of the surface of a catalyst at the same time that the activity is being monitored.
This approach, which permits the simultaneous characterization of both parameters in a single
experiment, facilitates uncovering the relationships between structure and activity. Such infor-
mation is critical to improving the performance and formulation of catalysts. We illustrate the
possibilities of operando Raman spectroscopy with four examples.
Observing Heterogeneous
Catalysts While They Are
Working Using Operando
Raman Spectroscopy
reactor with walls that are optically
appropriate for Raman spect ros-
copy. To prevent the participation
of homogeneous reactions, the re-
actor was designed to minimize gas-
phase activation of reactants (by not
having any void volume). Thus, the
operando reactor makes it possible
to obtain Raman spectra of catalysts
and genuine catalytic data. Figure 2
shows the results obtained for sev-
eral catalysts at different tempera-
tures i n t he operando reactor and
al so i n a convent ional f i xed-bed
catalytic reactor; t he activit y and
selectivit y obtai ned i n bot h reac-
tors i s essent ial ly t he same, t hus
proving the validity of the catalytic
tests performed during the operando
Raman experiments in this home-
made reactor cell.
When the Active Phases Are
Sensitive to the Environment
There are many cases in which the
active phases of a catalyst form, or,
at least change, duri ng react ion.
Such phases may not be present
before or af ter catalysis, but only
during catalysis. The following ex-
amples il lustrate two cases, one in
which the reaction conditions shape
the working catalyst structure, and
one i n whi ch we moni tored t he
preparation of the active phase.
Case I: VSbO
4
Active Phase
During the Propane
Ammoxidation Reaction
Activating al kanes to obtain com-
modi t y chemi cal s i s one of t he
major chal lenges the chemical in-
dust r y must sol ve i n t he comi ng
years. The i nt eract i on bet ween
surface antimony oxide, with very
weak Raman bands, and surface va-
nadium oxide species, with Raman
bands at 1020 and 900 cm
-1
(Figure
3, spectrum of dehydrated sample),
takes place under reducing or non
net-oxidizing environments (such
as ammoxidation reaction condi-
tions) leadi ng to the formation of
the trirutile VSbO
4
phase, charac-
terized by a broad Raman band at
840 cm
-1
and segregated -Sb
2
O
4
,
as shown by the spectra taken dur-
ing ammoxidation (Figure 3). The
cat al yst i s sel ect i ve to acr yl oni-
tri le (yield close to 30%) when the
trirutile band is intense, indicative
that VSbO
4
is present on the surface
of the catalysts. The interaction be-
tween Sb and V is partially reversed
upon reoxidat ion, where reduced
vanadium oxide species segregate
as surface V
5+
species, characterized
by a band near 1024 cm
-1
(Figure 1,
reoxidized sample). Thus, operando
Raman spectroscopy uncovers the
redox cycl e t aki ng pl ace on t he
VSbO
4
active phase during propane
ammoxidation (Figure 4) (79).
Case II: Ni-Mo
Hydrotreatment Catalysts
Ni-Mobased catalysts are promising
for hydrodesulfurization reactions,
which are i mportant processes i n
the oil refining industry. Hydrode-
sulfurization eliminates sulfur and
other contaminants from fossil fuels
and intermediate petroleum distil-

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Multiple laser excitation 532, 785, 1064 or custom
High light throughput with optimized VPG grating
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BaySpec ultimate research grade bench top Raman spectrometer is ideally
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H
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so
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tio
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1
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4
R
a
m
a
n
lates. Figure 5 shows representative
Raman spect ra obt ai ned duri ng
sul f idation of Ni-Mooxide based
catalysts (10). At the initial sulfida-
tion stages, below 300 C, oxysul-
fides and less-reduced molybdenum
sul f ide phases (MoS
3
) are appar-
ent. The lack of Raman features at
300 C during the sulfidation process
is probably a result of a very broad
distribution of states, because Raman
bands of nanocrystalline MoS
2
be-
come apparent at 400 C. Thus, the
spectra show that there is a partial
sulfidation process at temperatures
up to 300 C, and that an important
rearrangement happens before the
formation of an incipient and defec-
tive MoS
2
structure that is beneficial
to hydrodesulfurization activity.
Understanding
Deactivation Processes
Given t hat react ions may lead to
progressive deact ivat ion of cata-
lysts, the simultaneous determina-
tion of structure and activity offers
the opportunity to understand the
deactivation phenomena and infer
t he nature of t he act ive site. The
examples presented below illustrate
this possibility.
Case III: Ce-V-OBased
Catalysts During Ethane
Oxidative Dehydrogenation
Understanding the mechanism and
act i ve phases of Ce-V- Obased
catalysts is very important, because
both vanadia and ceria are used for
many catalytic applications. It has
been reported that ceria-supported
vanadia catalysts form CeVO
4
at
lower temperatures than upon calci-
nation in air (11). This is because of
the redox cycle during the reaction.
The redox cycle periodically reduces
ceria sites, promoting the solid-state
reaction to form CeVO
4
(an irrevers-
ible reaction), with the subsequent
deactivation of the catalysts. Mar-
t i nez-Huerta and col leagues (11)
monitored t he t ransformat ion of
surface vanadium oxide species on
ceria into CeVO
4
during an ethane
oxidative dehydrogenation reaction.
That study detected how the cata-
lysts deactivated at reaction temper-
atures above 500 C; the operando
Ramangas chromatography (GC)
study shows an incipient formation
of CeVO
4
on the surface of catalysts
with no appreciable deactivation at
Catalyst
Operando reactor
Operando system
Thermocouple well
Inert packing
On-line gas chromatograph
Raman system
Gas feed system
Vent
Heat screen
Heating element
NH3
O2
C3H8
He
Temperature controller
Figure 1: An operando Ramangas chromatography setup. Adapted from reference 9 (with permission).
50
P
r
o
p
a
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e

c
o
n
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e
r
s
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n

(
%
)
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e

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(
%
)
40
30
70
60
50
50
40
40
30
30
20
20
10
10
20
25
20
15
10
5
0
10
0
350
4Mo5V4Nb0.5Te0.5 Operando
4Mo5V4Nb0.5Te0.5 Fixed-Bed
4Mo5V4Nb1 Operando
8Mo5V4Nb1 Operando
12Mo5V4Nb1 Operando
4Mo5V4Nb1 Fixed-Bed
8Mo5V4Nb1 Fixed-Bed
12Mo5V4Nb1 Fixed-Bed
4Mo5V4Nb1 Operando
8Mo5V4Nb1 Operando
12Mo5V4Nb1 Operando
4Mo5V4Nb1 Fixed-Bed
8Mo5V4Nb1 Fixed-Bed
12Mo5V4Nb1 Fixed-Bed
375 400 425 450 350 375 400 425 450
Temperature (
o
C) Temperature (
o
C)
Propane conversion (%) Propane conversion (%)
0
0 50 40 30 20 10 0
Figure 2: Propane conversion vs. temperature and selectivity to acrylic acid for several catalysts
obtained in a conventional fixed-bed reactor and in an operando reactor. Propane partial
oxidation conditions: C
3
H
8
/O
2
/H
2
O/He = 12.5/20.4/15.9/51.2; 4800 h
1
; 0.2 g of catalyst. Adapted
from reference 13 (with permission).
460 C. The operando study (Figure
6) shows that the Raman bands of
CeVO
4
become sharper during reac-
tions at temperatures greater than
500 C. Thi s t rend i s consi stent
with a decrease in the exposure of
the active sites rather than with a
change in the structure of the active
phase. The Arrhenius plots of activ-
ity data measured in the operando
Raman cell (Figure 6) show that the
apparent activation energy does not
change signi f icant ly as t he sol id-
st ate react ion t ransforms ceri a-
supported vanadium oxide species
i nto CeVO
4
. The Arrhenius plots
underline a decrease in the number
of active sites but not a change in
the nature of the active sites. These
dat a l ead to t he conclusion t hat
V-O-Ce bonds present in both the
fresh (ceria-supported vanadia) and
aged (CeVO
4
) catalysts are directly
related to the active sites, and that
the redox cycle is related to the ce-
rium ions at the interface with vana-
dia. Figure 6 (right) illustrates how
the progressive interaction between
ceri a suppor t and surf ace vana-
dium oxide species stabi lizes Ce
3+

ions at the vanadiaceria interface.
Af ter shari ng t hese data, Sauers
and Freunds groups performed a
detai led experimental and density
f unctional t heory (DFT) study of
t his i nteract ion t hat showed t hat
t he preferred i nter f ace bet ween
dispersed vanadia and ceria sup-
port involves reduced Ce
3+
ions in
the V-O-Ce bonds and conf irmed
t hat t he preferred oxidation state
for vanadium is V
5+
, which is nearly
impossible to reduce (12).
Case IV:
Multioxide Mo-V-Nb-Te-O
Catalysts for the Partial Oxida-
tion of Propane into Acrylic Acid
The selective oxidation of propane
i nto acryl ic acid is an i nteresti ng
route for al kane valorization. The
Mo-V-Nb-Te-O catalytic system is
active in partial oxidation reactions
of propane. Tel lurium is a critical
component, t he role of which re-
cent ly has been uncovered usi ng
operando RamanGC (13). Oper-
ando RamanGC shows t hat t he
shape of the spectra changes dras-
tical ly when the temperature reac-
tion is increased to 375 C (Figure
7). Below that temperature, Raman
bands near 815 and 380 cm
1
as-
signed to MoVO structures and
bands near 1000 cm
1
assigned to
MoOx or VOx dominate the spec-
t r a. I n addi t i on, Raman bands
near 760 and 230 cm
1
, assigned
to Al VMoO
7
st r uct ures, can be
det ect ed al ong wi t h t he Raman
band near 880 cm
1
, assigned to an
Mo
5
O
14
-type structure. Conversely,
Raman bands near 960, 780, and
237 cm
1
dominate the spectra when
t he react ion temperature reaches
375 C; such Raman bands are in-
dicative of a distorted MoO
3
oxide
wit h some mi nor amounts of va-
nadium species (14). The amount
of such an MoO
3
structure is not
very l arge, because no X-ray di f-
fraction (XRD) pattern for a simi-
lar structure was detected, but its
alpha300 AR
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bands dominate the Raman spectra because this phase
possesses a very high Raman cross-section and Raman
spectra uncover important changes at the nanometer
scale during the reaction. In addition to monitoring
SbVO4
Sb2O4
V=O
Reoxidised
Ammoxidation
Dehydrated
480
o
C
480
o
C
f
d
c
b
a
e
420
o
C
420
o
C
400
o
C
400
o
C
200
o
C
200
o
C
30 20 10
Acrylonitrile
Acetonitrile
Propylene
CO2
CO
Yield (%)
4,6
4,9
1,4
5,2
8,1
4,3
2,6
1,0
4,1
4,9
2,4
10,9
18,1
22,0
29,2
Raman shift (cm
-1
)
0 900 1100 700 500 300 100
Figure 3: Raman spectra of SbVO/Al
2
O
3
catalyst during a propane
ammoxidation reaction: (a) dehydration at 200 C; (b) ammoxidation
at 200 C; (c) 400 C; (d) 420 C; (e) 480 C; (f) reoxidation at 440 C.
The corresponding yield values are presented in the left panel. Reaction
conditions: 200 mg of catalyst, total flow 20 mL/min; feed composition
(% volume); C
3
H
8
/O
2
/NH
3
/H
2
O/He (9.8/25/8.6/56.5). Adapted from
reference 7 (with permission).
VSbO
4
VOx
Sb
2
O
4
VSbO
4
Sb
5+
V
5+
Sb
5+
V
3+
Structural
cycle
Redox
cycle
Figure 4: Possible catalytic redox cycle of vanadium and migration
cycle of antimony during propane ammoxidation in V-Sb-O catalysts.
Adapted from reference 9 (with permission).
NiMo/50ASA
MoS
2
MoS
3
4
0
4
4
3
5
3
2
0
5
4
0
4
5
0
3
4
8
3
2
5
2
1
3
3
7
7
2
8
0
2
2
0
10 min, 300
o
C, H
2
S
Raman shift, cm
-1
10 min, 200
o
C, H
2
S
10 min, 100
o
C, H
2
S
4h, 400
o
C, H
2
S
700 600 500 400 300 200
(g578)
Oxysuldes
Figure 5: In situ Raman spectra at different sulfidation stages of
NiMo50ASA. Adapted from reference 10 (with permission).
l
o
g

C
o
n
v
e
r
s
i
o
n
1.5
O
O V
5+ O
O
O
O
O OO
O V V O
O
1
3
4
5
2
O
O O
n
O
V
V
O
O O O
OO
O
CeO2
CeVO4
CeO2
CeO2
CeO2
CeO2 CeO2
Ce
3+
Ce
3+
Ce
3+
First run
Second run
1.1
0.7
0.3
-0.1
-0.5
0.0012 0.0013 0.0014 0.0015
1/T (K)
Figure 6: Left: Arrhenius plot of ethane conversion vs. reaction temperature
in the operando fixed-bed reaction cell. Right: Qualitative illustration of
dynamic states of the V
5
+/CeO
2
system during the incipient and extensive
formation of CeVO
4
. Adapted from reference 11 (with permission).
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changes occurring in the NbMo
VO st r uct ures duri ng propane
oxidat ion, operando RamanGC
experiments show the formation of
coke because bands appeari ng i n
the 12001650 cm
1
region are at-
tributed to carbon deposits with sp
2

hybridization.
A si mi lar operando RamanGC
experiment was performed with a
catalyst doped with tel lurium. As
Figure 8 shows, t he addition of a
small amount of Te to the Mo-V-Nb
oxide system inhibits the deactiva-
tion of the catalyst by its rearrange-
ment into distorted MoO
3
structures
and t he bui ldup of carbonaceous
deposits. In this case, Raman bands
i n t he 9001020 cm
1
range and
the Raman bands near 820 and 370
cm
1
of di spersed oxides are ap-
parent during a reaction at 350 C.
Such di spersed oxide st ruct ures
blend into distorted rutile structure
phases as the reaction temperature
increases (to 375450 C) and are
characterized by a broad Raman sig-
nal near 800 cm
1
. Thus, the study
demonstrated that tel lurium dop-
ing generates highly distorted rutile
structures during the reaction that
are capable of inhibiting the forma-
tion of MoO
3
crystallites under re-
action conditions and improves the
performance of t hese catalysts to
achieve sufficient performance.
Conclusions
The operando Raman methodology
combines structural and catalytic
measurements i n a si ngle experi-
ment. Because the molecular struc-
ture of a catalyst depends on its spe-
cific environmental conditions, this
combination is critical to be able to
rel iably assess st ructureact ivit y
relationships at the molecular level.
The examples presented here illus-
trate that this methodology can fol-
low the dynamic states of catalysts,
which are determined by the reac-
tion. The formation of active phases
during the reaction and their even-
tual deactivation are directly linked
to kinetic data. In addition, it has
been shown that Raman spectros-
copy uncovers i mportant changes
at the nanometer scale during reac-
tions, even t hough t hose changes
are not revealed by XRD. In sum-
mary, the state of a catalyst is de-
termined by the reaction conditions.
This could be expressed borrowing
450
o
C
1
6
9
5
1
6
1
0
1
5
2
0
1
3
9
0
1
0
6
4
1
0
0
4
8
8
9
8
2
1
7
6
2
5
0
6
4
6
5
3
7
8 2
2
9
9
6
9
7
8
7
2
3
7
425
o
C
450
T
e
m
p
e
r
a
t
u
r
e

(
o
C
)
425
400
375
350
200
0 10 20 30 40 50 60
400
o
C
375
o
C
350
o
C
200
o
C
25
o
C
2000 1600 1200 800 400
Raman shift (cm
-1
) % Conversion/Selectivity
Figure 7: Operando RamanGC spectra during the selective oxidation of propane on 12Mo
5
V
4
Nb
1
;
Left: Raman spectra obtained during reaction at the temperature indicated; right: simultaneous
activity and selectivity data obtained during Raman spectra acquisition. C
3
H
8
/O
2
/NH
3
/H
2
O/He
= 12.5/20.4/15.9/51.2; 4800 h
1
; 0.2 g of catalyst. Adapted from reference 13 (with permission).
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the expression by the Spanish phi-
losopher Ortega y Gasset , I am
I pl us my ci rcumst ances . The
exampl es present ed here t el l us
t hat t he cat al yst i s it sel f and it s
circumstances.
References
(1) B.M. Weckhuysen, Chem. Commun.
97110 (2002).
(2) M.A. Baares, M.O. Guerrero-Prez,
J.L.G. Fierro, and G.G. Cortz, J. Mater.
Chem. 12(11) 33373342 (2002).
(3) M.O. Guerrero-Prez and M.A.
Baares, Catal. Today 113, 4857
(2006).
(4) V. Calvino-Casilda and M.A. Baares,
Catalysis 24, 147 (2012).
(5) M.A. Baares, Adv. Mater. 23, 5293
(2011).
(6) I.E. Wachs and C.A. Roberts, Chem.
Soc. Rev. 39, 5002 (2010).
(7) M.O. Guerrero-Prez and M. A. Ba-
ares, Chem. Commun. 12921239
(2002).
(8) M.O. Guerrero-Prez and M. A.
Baares, J. Phys. Chem. C 111, 1315
(2007).
(9) M.O. Guerrero-Prez and M. A.
Baares, Catal. Today 96, 265
(2004).
(10) M.O. Guerrero-Prez, E. Rojas, A.
Gutirrez-Alejandre, J. Ramrez,
F. Snchez-Minero, C. Fernndez
Vargas, and M. A. Baares,
Phys. Chem. Chem. Phys. 13,
9260 (2011).
(11) M.V. Martnez-Huerta, G. Deo, J.L.G.
Fierro, and M.A. Baares, J. Phys.
Chem. C 112, 11441 (2008).
(12) M. Baron, H. Abbott, O. Bondar-
chuk, D. Stacchiola, A. Uh, S. Shai-
khutdinov, H.-J. Freund, C. Popa,
M.V. Ganduglia-Pirovano, and J.
Sauer, Angew. Chem. Int. Ed. 48,
8006 (2009).
(13) R. Lpez-Medina, J.L.G. Fierro,
M.O. Guerrero-Prez, and M. A.
Baares, Appl. Catal. A 406, 34
(2011).
(14) M.A. Baares and S.J. Khatib, Catal.
Today 96, 251 (2004).
M. Olga Guerrero-Prez is with
the Department of Chemical Engineering
at the University of Malaga in Malaga,
Spain. Please direct correspondence to:
oguerrero@uma.es.
M.A. Baares is with the Catalysis
and Petrochemical Institute of the
Consejo Superior de Investigaciones
Cientficas (CSIC), in Madrid, Spain.
450
o
C
425
o
C
400
o
C
375
o
C
350
o
C
25
o
C
450
T
e
m
p
e
r
a
t
u
r
e

(
o
C
)
425
400
375
350
200
0 10 20 30 40 50 60
% Conversion/Selectivity
2000 1600 1200 800 400
Raman shift (cm
-1
)
Figure 8: Operando RamanGC spectra obtained during the selective oxidation of propane on
12Mo
5
V
4
Nb
0.5
Te
0.5
. Left: Raman spectra during the reaction at the temperature indicated. Right:
Simultaneous activity and selectivity data obtained during Raman spectra acquisition. Reaction
conditions: C
3
H
8
/O
2
/H
2
O/He = 12.5/20.4/15.9/51.2; 4800 h
1
; 0.2 g of catalyst. Adapted from
reference 13 (with permission).
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Spectroscopy continues to recognize the global scale of
the issues faced by spectroscopists in labs worldwide.
EVENT OVERVIEW:
Fiscal targets placed on laboratories make it critical that todays
chemical analysis instrumentation works as hard as the people
that use them. This presentation will outline how Agilents pre-
mium 700 series ICP-OES instruments can help you achieve
your productivity goals more cost-eectively than ever before.
A base metal CRM and orchard leaf CRM were analyzed to
demonstrate the new productivity gains achievable with
Agilent 720/725 ICP-OES instruments. Join us to hear how you
can experience a higher level of ICP-OES performance with
faster run times, lower operational costs, and proven reliability.
Key Learning Objectives:
n
Please provide 3 learning objectives for this webcast
n
Learn how to accelerate run times and increase ICP-OES
sample throughput
n
Learn how to optimize ICP-OES method parameters in order
to lower operational costs

For questions, contact Kristen Farrell at kfarrell@advanstar.com
PRESENTERS
Ross Ashdown
Product Manager for ICP-OES
and MP-AES
Agilent Technologies
MODERATOR
Laura Bush
Editorial Director
Spectroscopy
Who Should Attend:
n
Atomic Spectroscopists
looking to enhance the
analysis of geological and
nutrient/food samples.
n
ICP-OES users looking to
increase productivity and
lower running costs.
n
ICP-OES analyzing
geochemical and food/
nutrient samples.
Presented by Sponsored by
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Boosting the Productivity of Geological
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Boosting the Productivity of Geological
and Nutrient/Food analysis using ICP-OES
REMARKABLY BETTER ATOMI C SPECTROSCOPY
S
ummer is long gone now and as our minds focus on the
luscious fall foliage and long, cold winter months ahead, we
should also turn to the positive feelings that come from hav-
ing new problems to solve and the ability to productively contrib-
ute to their solutions. This years Eastern Analytical Symposium
(EAS), being held November 1215 in Somerset, New Jersey, will
offer those positive feelings and a wealth of knowledge to help you
find the solutions you need. To highlight the invited symposia in
spectroscopy and related fields we have asked some of the chairs
of the invited sessions to briefly describe their intentions as they
pulled together well-known and well-respected speakers for their
chosen topics. My hope, as the 2012 EAS program chair, is that
this synopsis will encourage you to come, see, hear, and enjoy the
directions that spectroscopy has taken over the past year. This is
with the goal that once you return from EAS in November, you can
use your new-found knowledge to energize your own laboratory
and solve problems.
Mass Spectrometry
This year, Fred McLafferty, of Cornell University, is being recog-
nized for his many transformative innovations over the last half
century with the Award for Outstanding Achievements in Mass
Spectrometry, to be given at a symposium in his honor. From de-
veloping electron-capture dissociation to offering fundamental
understanding of gas-phase-rearrangement phenomena, McLaf-
ferty has been a towering figure in the field. Beyond his more than
500 publications on all aspects of the technique, the hundreds of
colleagues McLafferty has trained over seven decades, many of
whom have themselves made major contributions in mass spec-
trometry (MS), make his impact on the field almost unparalleled.
Several former students will present in this symposium, including
Neil Kelleher of Northwestern University, Gary Valaskovic of New
Objective, Inc., and Edward Chair of Life Sciences Consulting, Inc.
Among the topics to be discussed are the latest technologies for
electrospray MS of whole proteins in the gas phase (the so-called
top down proteomics), and recent advances in application of this
technology to the area of expression genomics.
A two-session mini symposium titled Mass Spectrometry of
Large and Biomolecules will feature leaders and emerging sci-
entists from academia, industry, and instrument manufacturing.
A wide array of recent developments that overcome challenges
faced when using MS for the study of large and biomolecules will
be discussed, including method development and applications
for proteomics and metabolomics, as well as the analysis of oligo-
nucleotides, polymers, and supramacromolecules. For example,
Martin Gilar of Waters Corporation will discuss liquid chroma-
tography (LC) separations for complex mixtures of oligonucle-
otides, peptides, and glycopeptides. Kimberly Ralston-Hooper of
Duke University will present proteomic applications in environ-
mental toxicology. Jiong Yang of Merck will speak on modified
oligonucleotide sequencing for identity confirmation of phospho-
rothioate-containing siRNAs. Chrys Wesdemiotis of the Univer-
sity of Akron will discuss method development for MS analysis
of synthetic polymers and supramacromolecules. The effect of
peptide structure on matrix-assisted laser desorptionionization
time-of-flight mass spectrometry (MALDI TOF-MS) signal inten-
sity will be presented by Kevin Owens of Drexel University. Sarah
Trimpin of Wayne State University will put forth new ionization
approaches, Gary Kruppa of Bruker Daltonics, Inc., will touch on
applications using MALDI-TOF for biopharmaceutical quality
control, and Mark Cancilla of Merck will acquaint the audience
with MS-based assays for the characterization of oligonucleotides.
NMR
Jeffrey A. Reimer of the University of California at Berkeley is the
2012 recipient of the EAS Award for Achievements in Magnetic
Resonance. This award recognizes his contributions to solid-state
nuclear magnetic resonance (NMR) and magnetic resonance im-
aging (MRI), in catalysis, electrochemistry, polymer science, and
semiconductor physics. Joining Reimer are three distinguished
Mary Ellen McNally
From November 12 to 15, 2012, as in the preceding 50 years, the Eastern Analytical
Symposium will bring a rich assortment of potential solutions and collaborations to its
attendees and contributors.
Energize Your Laboratory at
the 2012 Eastern Analytical
Symposium
LIVE WEBCAST:
Tuesday, October 23, 2012 at 11:00 am EDT

Register Free at http://www.spectroscopyonline.com/FTIR
EVENT OVERVIEW:
FTIR Microscopy is among the most powerful tools in the identica-
tion of unknown materials. This can range from the examination of
raw materials, failure analysis, or research and development. Each
molecule has a unique infrared signature providing great specic-
ity in the identication process. The distribution of these compo-
nents in mixtures can also be determined by collecting infrared area
images of the product in question. Examples will be shown that
demonstrate the eectiveness of FTIR Microscopy for identication,
quantication and distribution of materials on a microscopic level.
These examples will be collected with a simple to use and fully auto-
mated FTIR microscope.

n
Demonstration of the simplicity of FTIR Microscopy for routine
and advanced applications
n
Specic examples of mapping for specic molecular distribution
n
Ease-of-use software for simple to advanced measurements
For questions, contact Kristen Farrell at kfarrell@advanstar.com
PRESENTERS
Fred Morris
Business Development Manager
for Industrial and Routine Products
Bruker Optics, Inc.

MODERATOR
Laura Bush
Editorial Director
Spectroscopy
WHO SHOULD ATTEND:
n
Lab Managers
n
QA/QC Scientists
n
Analytical Chemists
n
Forensic Scientists
n
Art Conservation Scientists
n
Current FTIR Microscopy
Users
FTIR Microscopy:
A Powerful Tool for Sample Analysis
Applications of Raman Spectroscopy
in Biomedical Diagnostics
n
The importance of Raman
spectroscopy in biomedical research.
n
How Raman spectroscopy is being
used for cancer detection.
n
The advantage of using SERSbased
immunoassays.
Who Should Attend:
n
Spectroscopists, analytical chemists,
biochemists, or anyone interested in
learning more about spectroscopic
biomedical diagnostics.
LIVE WEBCAST: Wednesday, October 17, 2012 at 1:00 pm EST

Register Free at http://www.spectroscopyonline.com/diagnostics

EVENT OVERVIEW
In recent years, Raman spectroscopy has gained widespread
recognition in biomedical research as a principal diagnostic
and screening tool. This presentation will begin with an over-
view of the uses of Raman in a variety of biomedical applica-
tions, and then discuss one of the most active research areas
for Raman biospectroscopy: cancer detection, focusing on
research at the University of Utah on the development of a
surface enhanced Raman scattering (SERS)based immuno-
assay array for pancreatic cancer marker screening.

Pancreatic adenocarcinoma is the fourth most common
cause of cancer deaths in the US with a 5-year survival rate
of 4%, the lowest of any cancer. Early diagnosis of pancre-
atic adenocarcinoma remains elusive due to the asymptom-
atic development of the disease and the advanced disease
state required for radiological and histopathologic determi-
nation. However, a proof-of-principle immunoassay panel
using SERS has been developed. The SERS assay uses gold
nanoparticles conjugated with both a secondary antibody
and a Raman reporter molecule as the assay label. Matrix
metallopeptidase 7 (MMP-7), a relevant and well-estab-
lished marker for pancreatic adenocarcinoma, was used to
develop the proof-of-concept marker panel. We will discuss
the design and implementation of this rst generation SERS
array for pancreatic adenocarcinoma and its comparison to
current clinical diagnostics.
For questions, contact Kristen Farrell
at kfarrell@advanstar.com
Presenters:
Dr. Jennifer Granger
Research Scientist
Nano Institute of Utah

Dr. Michael Kayat
Vice President
B&W Tek

Moderator:
Meg Evans
Managing Editor
Spectroscopy
colleagues who will reflect on the connec-
tion between basic knowledge and appli-
cations of magnetic resonance. Anant K.
Paravastu of Florida State University will
speak on multidimensional NMR and
13
C-
13
C nuclear dipolar couplings for the
structural characterization of designer self-
assembling proteins that form biomedi-
cally important nanofiber matrices. Alexej
Jerschow of New York University will dis-
cuss newly discovered long-lived magnetic
resonance signals in solids, which may en-
able new approaches for the analysis and
imaging of hard tissues (such as bone) as
well as battery materials. Cecil Dybowski
of the University of Delaware will report
on NMR of heavy metals with enormous
chemical shift ranges, and how measure-
ments can be applied to problems such as
elucidating the properties of formulations
of artists paints or the nature of semicon-
ducting materials.
Advances in NMR hardware and tech-
niques are allowing increasingly rapid
identification of metabolites. Two areas
are key: first, the development of hyphen-
ated techniques such as LCMSNMR,
and second, the introduction of cryogenic
probes. Dr. Steve Cheatham of DuPont
Crop Protection has assembled a session
entitled NMR Techniques for Metabolite
ID. The session focus is on applications of
these tools toward metabolite identifica-
tion. The first two talks in the session will
focus on the use of hyphenated techniques,
as representatives from both Bruker and
Agilent provide perspective and results of
the latest technology in the field.
The second two speakers in this session
are representatives of the pharmaceutical
industry and will provide insight into the
practical aspects of metabolite identifica-
tion using NMR techniques. While focus-
ing on metabolite identification, the struc-
ture elucidation techniques to be discussed
in the session should prove relevant to a
variety of areas including natural product
chemistry, food chemistry, and mixture
analysis.
Surface Science
Dan Strongin of Temple University has
organized a session titled Environmen-
tal Surface Chemistry that will highlight
recent research on redox transformations
in the environment. Redox chemistry
that occurs between mineral surfaces and
aqueous organic and inorganic species con-
tributes to geochemical cycling of metals,
to remediation of toxic aqueous environ-
mental pollutants, and to processes such
as the sequestration of CO
2
. One talk will
focus on the reactivity of ferrous iron with
aluminum oxide and montmorillonite clay
and the reactivity of these systems toward
redox-active species such as hexavalent Cr
and U. Another will concentrate on the
redox chemistry of Cr(VI) as it applies to
the photochemistry of the mineral phases
of the small-band-gap semiconductor
FeOOH. A further talk will spotlight how
mixtures of binary metal oxides drive
redox chemistry relevant to the removal of
pollutants from wastewaters. Research on
potential redox chemistry involving min-
eral phases will highlight the potential of
metal carbonation that is relevant to CO
2

sequestration.
Surface Spectroscopy, organized by
Lars Gundlach of the University of Dela-
ware, will turn attention to the interaction
of molecular adsorbates and solid surfaces.
Piotr Piotrowiak of Rutgers University will
show the sensitivity of spectroscopy of a titanate cluster to every
atom, although other properties like the density of states show
bulk-like characteristics. Graphene, a hybrid between a molecular
and a solid state material (being atomically thin in one dimen-
sion), is the focus of X-ray photoelectron spectroscopy (XPS) and
reflected electron energy loss spectroscopy (REELS) investiga-
tions by Brian Strohmeier of Thermo Fisher Scientific. With these
techniques, he addresses chemical surface modification, surface
impurities, and substrate interaction. Hsuan Kung of the Univer-
sity of Delaware will report on a novel, highly controlled route for
depositing metal nanoparticles on zinc oxide particles that allows
precise control of the surface morphology. Eric Borguet of Temple
University will present time-resolved infrared measurements on
the watersilica interface to allow for the study of these important
materials. Laurel Kegel of the University of Delaware, in discuss-
ing studies of plasmonic nanostructures, will emphasize the im-
portance of penetration depth and resonance wavelength for the
sensitivity of surface plasmon resonance sensors.
Vibrational Spectroscopy
As a workhorse analytical technique in so many industries for
such a long time, vibrational spectroscopy might possibly be in
danger of being taken for granted. In the session Bringing Home
the Bacon Vibrational Spectroscopy Gets the Job Done, or-
ganized by Linda Kidder of Malvern Instruments, presentations
about out-of-the-box applications of mid-infrared, near-infrared,
and Raman spectroscopy will show that there are many new ways
to analyze materials with vibrational spectroscopy. Nancy Jestel of
Sabic Innovative Plastics will provide an industrial perspective for
using vibrational spectroscopys unique capabilities to solve critical
analytical problems. The proliferation of multivariate algorithms
and their increasingly routine application to spectroscopic data
has been critical in enabling development of vibrational spectros-
copy. Katherine Bakeev of Camo Software will explore data vi-
sualization and analysis. Cutting-edge vibrational spectroscopic
tools and their applications to chiral drugs and biotherapeutics
will be the topic of a presentation by Rina Dukor of BioTools. As
Raman spectroscopy has become more mobile, it has assumed
a new dimension, as will be seen in the presentation focusing on
Raman five-component identification from Edita Botonjic-Sehic
of Morpho Detection.
A Coblentz Societysponsored session entitled Spectroscopy in
the Palm of your Hand, organized by Heinz Siesler of the Univer-
sity of Duisburg-Essen (Germany), will provide a new perspective
on spectroscopic control of drug-product production and analysis.
For example, Benoit Igne of Duquesne University will present a
case study in which specific algorithms and analyses of on-line
blend data were evaluated to determine their ability to provide
quality control of tablets. Douglas Both of Bristol-Myers Squibb
(BMS) will describe an approach to designing real-time-release
(RTR) testingbased control strategies for commercial manufac-
turing and how it relates to and evolves from the quality-by-design
(QbD) work performed during development, where the funda-
mental understanding of the products critical quality attributes
were established. Like BMS, Pfizer has also received regulatory
approval for RTR-based control strategies, and Steve Hammond
will demonstrate why it is beneficial to measure ones process in
real-time. Martin Warman of Vertex will describe a systematic
approach to defining the critical steps in making an acceptable
product, defining the process space within which we should op-
erate to ensuring the process stays within that defined space. His
talk will provide a wide range of examples in which spectroscopic
techniques have supported QbD and RTR.
Conclusion
Spectroscopy is a vast field with diverse uses and results both
fundamental and applied. EAS 2012 offers a full range of spectros-
copy sessions, both theoretical and applied. A trip to EAS 2012 will
be rewarded with ideas, understanding, and learning, but more
importantly with the atmosphere to make connections to others
who work at the cutting edge of these spectroscopic technologies.
The EAS 2012 full technical program, list of short courses, and
registration is available at the following website: www.eas.org
For more information on this topic, please visit our
homepage at: www.spectroscopyonline.com
Mary Ellen McNally is the Program Chair of EAS 2012
and a Technical Fellow at Dupont Crop Protection in Newark,
Delaware. Please direct correspondence to: Mary-Ellen.
McNally@USA.dupont.com.
www.piketech.com
sales@piketech.com
tel: 608-274-2721
Accessories for analysis of
gas, solid, and liquid samples.
Contact us with your
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Complete list of products
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Spectroscopy
Sampling Solutions
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ON-DEMAND WEBCAST

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For questions, please contact Kristen Farrell at kfarrell@advanstar.com
Combined Spectroscopy
Methods for General
Analytical Services
EVENT OVERVIEW
FT-IR spectroscopy is relied upon in analytical support and
research laboratories for identication of a variety of unknown
materials or characterization analysis. Within these analyses,
however, there are many dicult questions you are probably
being challenged with such as:
n
Why didnt this material pass our quality standards?
n
What is the source of the contamination?
n
What is the best formulation for this new product?
n
Why are these two materials performing dierently?

During this webinar, we will show you how you can combine mul-
tiple sampling and spectroscopic techniques in a single, easy to
use, and compact platform. We will also show you how you can
solve your challenges faster and more eciently, with the trust
and condence you need on your most critical analysis tools.
Key Learning Objectives
n
Identify materials using FT-IR, FT-Raman and NIR
n
Isolate dierences between materials quickly and easily
n
Investigate product failures and competitive analyses
n
Perform deformulation to check compositional and
processing operations
Who Should Attend
n
Analysts working in
- Pharmaceuticals
- Polymer/plastics
- Forensics
- Art conservation
- Inks/paints/coatings
- Foods/avors/oils
n
Analytical services/
contract labs/academics
Presenters
Mike Bradley, Ph. D.
Product Manager for FT-IR
Thermo Fisher Scientic

Laura Bush
Editorial Director
Spectroscopy
Product resources
Fluorescence and UVvis system
Horibas Dual-FL system
reportedly combines a
CCD-based benchtop
fluorometer with a built-in
UVvis spectrophotometer.
According to the company,
the instrument provides
spectral rates as fast as
80,000 nm/s and a signal-
to-noise ratio of greater
than 20,000:1 RMS.
Horiba Scientific,
Edison, NJ;
www.horiba.com
IMS analyzer
An ion mobility spectrom-
etry (IMS) analyzer from
Photonis is designed for
simple integration with
most mass spectrometers.
the compact system can
be scaled or customized
to interface with a variety
of instruments to provide
simple IMS analysis that can be performed at
room temperature.
Photonis, Sturbridge, MA;
www.photonis.com
Microwave digestion
Milestones UltraWAVE micro-
wave digestion system uses
the companys single reaction
chamber technology for use in
metals digestions. According to
the company, the system uses
a single pressurized vessel for
all samples, allowing for simul-
taneous digestion of up to 22
samples. The system reportedly
can accommodate a maximum
temperature of 300 C and
pressure of 199 bar. Milestone, Inc., Shelton, CT;
www.milestonesci.com/ultrawave.
ICP-MS system
Thermo Fisher Scien-
tifics iCAP Q ICP-MS sys-
tem is designed to provide
increased throughput to
enable laboratories to cut
analysis times by up to 50%.
the system features an inter-
face that enables one-click
setup and allows users to
go from standby to perfor-
mance-qualified analysis with the push of a button.
Thermo Fisher Scientific, Inc., San Jose, CA;
www.thermoscientific.com
Analysis of sulfur in gypsum
An application note from Rigaku
describes the use of the companys
NEX QC energy dispersive X-ray
fluorescence spectrometer in the
monitoring of gypsum for quality
control during the cement production
process. According to the publication,
other elements in the gypsum, includ-
ing calcium, can also be measured.
Applied Rigaku Technologies,
Austin, TX;
www.rigakuedxrf.com
USP 232 standards
SPEX CertiPreps con-
sumer safety compliance
standards now include
USP 232 elemental impu-
rities standards. Accord-
ing to the company, the
standards can be used
as a calibration or check
standard to verify oral
daily dose PDE, parenteral
component limit, or parenteral daily dose PDE.
SPEX CertiPrep,
Metuchen, NJ;
www.spexcertiprep.com
Silicon drift detector
EDAXs thermoelectrically
cooled 50-mm
2
silicon drift
detector is designed for
use in its Orbis micro-XRF
elemental analyzer system
for high-resolution spectral
acquisition. According to the
company, the system can be
useful for those who make
measurements on small frag-
ments, coatings and deposits
on thin substrates (such as ink on paper). biological samples, and
trace element analysis using heavy filters to improve sensitivity.
EDAX, Mahwah, NJ; www.edax.com
UV polarizers
Moxteks UV wire-grid
polarizers are designed
for use at wavelengths
as low as 250 nm with
high transmission, extinc-
tion, and angular aper-
ture. According to the
company, the products
materials are metal and
glass, making it suitable for harsh environments and
demanding applications.
Moxtek, Orem, UT;
www.moxtek.com
Getting the Most From
Your ICP-MS Instrument
LIVE WEBCAST: Thursday, October 18, 2012 at 8:00 am PST, 11:00 am EST, 15:00 GMT

Register Free at www.spectroscopyonline.com/icpms-software
For questions, please contact Kristen Farrell at kfarrell@advanstar.com
EVENT OVERVIEW
Sample analysis is not all about having just good technology. Software
is the most user-interactive feature of an instrument package and as
such greatly inuences sta morale, performance, and throughput
capabilities. This complimentary webinar will demonstrate how new
software for ICP-MS can improve laboratory performance by enabling
simple operation and fast start up, full workow solutions via seam-
less integration with dierent inlet systems, rapid evaluation of results
from clear and exible presentation of the analytical data, and reduced
operational costs.

Learn how to:
n
Achieve rapid start up and intuitive method development
n
Simplify workow control and analytical reporting for all levels of
users
n
Integrate control of dierent inlet systems and peripherals,
including laser ablation and chromatographic systems
n
Build an approval workow for compliance with regulations such
as 21CFR11

There will also be a 15 minute Q&A session where our Thermo Scientic
ICP-MS and software experts will answer your questions and queries.
Who Should Attend?
n
Managers of contract,
government or
manufacturing
laboratories
n
Those performing
environmental,
pharmaceutical or food
safety analyses
n
Analysts using peripherals,
such as autodilutors,
autosamplers,
chromatographic
techniques, laser ablation
coupled with ICP-MS
instrumentation
Presenters
Lothar Rottmann
ICP-MS Product Manager.
Thermo Fisher Scientic,
Bremen

Julian Wills
Applications Specialist.
Thermo Fisher Scientic,
Bremen

Moderator:
Steve Brown
Technical Editor.
Spectroscopy
ICP-MS system
The Agilent 8800 triple-
quadrupole ICP-MS system is
designed to provide improved
performance compared with
single-quadrupole ICP-MS
and to provide MS-MS opera-
tion for interference removal
in reaction mode. According
to the company, the system
can be used to analyze elements in
life-science, soil, rock, and plant materials. The system
reportedly also can be set up to operate like a
single-quadrupole ICP-MS system.
Agilent Technologies,
Santa Clara, CA; www.agilent.com
Long-path gas cells
PIKEs long-path IR gas cells are
designed for analysis of air contami-
nants, pure gases, and gas mixtures.
According to the company, the fixed-
path cells range from 2.4 m to
20 m, and the variable model can be
adjusted from 1 m to 16 m. All of the
cells reportedly mount rigidly to the
baseplate of an FT-IR spectrometer.
PIKE Technologies,
Madison, WI;
www.piketech.com
Microvolume UV spectrophotometer
Shimadzus BioSpec-nano spectro-
photometer is designed for fast,
reproducible concentration determi-
nation of nucleic acids and proteins.
The instrument reportedly requires
a sample volume of 1 L (0.2-mm
pathlength) or 2 L (0.7-mm path-
length), which is pipetted onto its
measurement plate. No standard
rectangular cell is needed, although
a rectangular cell adapter is available. According to the company,
sample mounting, measurement, and cleaning are performed
automatically by the instrument, and measurement time is 3 s.
Shimadzu Scientific Instruments, Columbia, MD;
www.ssi.shimadzu.com
FT-IR microscope
The Lumos stand-alone FT-IR micro-
scope from Bruker Optics is designed
for visible inspection and infrared
spectral analysis. According to the
company, all internal moveable
components are motorized and the
instruments software guides operate
stepwise through the process of
data acquisition.
Bruker Optics,
Billerica, MA;
www.brukeroptics.com/lumos.html
STATEMENT OF OWNERSHIP, MANAGEMENT, AND CIRCULATION
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St. Louis County, Minnesota 55802-2065
Contact Person: Peggy Olson
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8. Complete Mailing Address of Headquarters or General Business Office of Publisher:
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9. Full Names and Complete Mailing Addresses of
Publisher: Michael J. Tessalone, 485F US Highway 1 S., Ste. 100, Iselin, NJ 08830-3009
Editorial Director: Laura Bush, 485F US Highway 1 S, Ste. 100, Iselin, NJ 08830-3009
Managing Editor: Megan Evans, 485F US Highway 1 S., Ste. 100, Iselin, NJ 08830-3009
10. This publication is owned by: Advanstar Communications Inc., 2501 Colorado Avenue, Suite 280,
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Inc., whose mailing address is 2501 Colorado Avenue, Suite 280, Santa Monica,
CA 90404.
11. Advanstar Communications Inc. is a borrower under Credit Agreements dated May 31, 2007,
with various lenders as named therein from time to time. As of June 12, 2012, the agent for the
lenders is: Credit Suisse, Administrative Agent, 11 Madison Avenue, New York, NY 10010.
12. Does Not Apply
13. Publication Title: Spectroscopy
14. Issue Date for Circulation Data Below: August 2012
15. Extent and Nature of Circulation
Average
No. Copies No. Copies of
Each Issue Single Issue
During Published
Preceding Nearest to
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Mail Subscriptions Stated on PS Form 3541 20,698 18,196
2. In County Paid/Requested Mail Subscriptions
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3. Sales Through Dealers and Carriers,
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Paid or Requested Distribution Outside USPS 20 18
4. Requested Copies Distributed by
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C. Total Paid and/or Requested Circulation
(Sum of 15b (1), (2), (3), and (4) 20,718 18,214
D. Non-requested Distribution
1. Outside County Non-requested Copies
Stated on PS Form 3541 1,068 3,534
2. In-County Non-requested Copies
Stated on PS Form 3451 0 0
3. Non-requested Copies Distributed
Through the USPS by Other Classes of Mail 0 0
4. Non-requested Copies Distributed
Outside the Mail 337 686
E. Total Non-requested Distribution
(Sum of 15d (1), (2), (3) and (4)) 1,405 4,220
F. Total Distribution (Sum of 15c and e) 22,124 22,434
G. Copies not Distributed 330 281
H. Total (Sum of 15f and g) 22,453 22,715
I. Percent Paid and/or Requested Circulation 93.65% 81.19%
16. Publication of Statement of Ownership for a Requester Publication is required and will be
printed in the October issue of this publication.
17. Name and Title of Editor, Publisher,
Business Manager, or Owner: Anne Brugman, Audience Development Director
Date: 9/28/2012
I certify that the statements made by me above are correct and complete.
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Print Magazine Universe.................................... 54,605
eNewsletter Universe ........................................ 82,966
Total Print Magazine and eNewsletter Universe .... 99,598*
Pharmaceutical Science Conference Attendees.... 40,000
Pharmaceutical Science Webinar Attendees ......... 41,581
Total Pharmaceutical Science Conference and
Webinar Attendees ............................................ 72,988*
Total Unduplicated Print Magazine, eNewsletter,
Conference and Webinar ...................................165,578**
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Showcase
Ad Index Ad Index
ADVERTISER PG# ADVERTISER PG#
ABB, Inc. 29
Agilent Technologies 9, 39
Amptek 10
B&W Tek, Inc. 7, 42
BaySpec, Inc. 33
Bruker Optics 3, 41
CVI Melles Griot 21
Cetac Technologies, Inc. 43
EDAX, Inc. 37
Enwave Optronics, Inc. 50
Hamamatsu Corp. 23
Horiba Scientific CV4
Mightex Systems 36
MIRTHE 2012 CV3
Moxtek, Inc. 19, 50
New Era Enterprises, Inc. 50
PerkinElmer Corp. 5
Photonis 13
PIKE Technologies 14, 15, 44
Pittcon 31
Renishaw, Inc. 6
Rigaku 25
Shimadzu Scientific Instruments CV TIP
Stellar Net, Inc. 27
Thermo Fisher Scientific CV Tip, CV2, 4, 45, 47
WITec GmbH 35
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October 2012 Volume 27 Number 10 www.spectroscopyonline.com

Raman Microscope combines many novel and patented features such as

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