Derek Nelson Brett Michalk Aziz Daabash Amanda Mogollon

Introduction Molecular Rotors Catalyst Nanofibers Drug carriers Questions

atc.atccu.chula.ac.th/research_matsci.htm&usg=__

What is a MOF?
Porous crystalline compounds forming 1,2 or 3 dimensional structures with the use of metal ions Consist of a metal ion and a an organic molecule, often called a ligand.

atc.atccu.chula.ac.th/research_matsci.htm&usg=__
&tbnh=125&tbnw=131&prev=/images%3Fq%3DMetal%2Borganic%2Bframework%26um%3D1%26hl%3Den%26sa%3DX%26tbs%3Disch:1

x6BkSuEgRdYhQHOQJpVldt61WLQ=&h=488&w=512&sz=34&hl=en&start=3&um=1&itbs=1&tbnid=34sU9HfWWdTkfM:

http://www.cup.unimuenchen.de/ac/klausmb/mitarbeit/muellerbuschbaum/bilder/mof-bild1.gif

MOFs were born from zeolites, porous crystalline structures both found in nature and man made

MOFs are the next generation

Sigma-Aldrich, with BASF, have developed a MOF with the surface area of a football field in 1 gram

Zeolites are made from aluminosilicate materials Named from Greek when a Swedish man observed water boiling out of the rock Used in Chem-E industry as catalyst and adsobant

www.lenntech.com/images/zeolite3.jpg

mf.mpg.de


http://imghost.indiamart .com/data/X/8/MY424310/mortar-andpestleporcelain_10732033_250 x250.jpg

MOFs have been synthesized in 2 ways

http://images2.opticsplan et.com/136180/opplanet-vwrdisposable-pellet-mixersand-cordless-motorv7338-901-0-5-mlpestle.gif

solvothermal techniques, crystals are grown from a hot solution of metal precursor, such as a metal nitrate solution mechanochemical methods, grinding, to produce, however these are none porous mechanochemical methods with the addition of isonicotinate (ISA) created porous 3D crystals

MOFs have limitless potential in many fields

Porous
MOFs large surface area to volume makes them perfect to replace zeolites at every level when they are available for mass production

http://www.cat-litter-critic.com/images/freshstep-cat-litter.jpg

Solid
As solid structures produced by mechochemical synthesis, MOFs have very unique electrical properties being explored

http://www.reflectscientific.com/im ages/prod-graphitefabrication.jpg

Currently at the University of Colorado, Boulder researchers are investigating the use of MOFs to replace liquid crystals for optoelectronic applications
Rotating or twisting molecules under an electric field is the principle behind liquid crystals. MOF crystals could lead to sturdier materials to be used in the data communications industry Currently tested MOFs do not yet reach the barrier to rotation to replace liquid crystals

http://www.rsc.org/images/b808104b350-FOR-TRIDION_tcm18-128604.jpg

Structural and Catalytic Performance of a Polyoxometalate-Based MetalOrganic Framework Having a Lanthanide Nanocage as a Secondary Building Block
Dongbin Dang,, Yan Bai, Cheng He, Jian Wang, Chunying Duan,*, and Jingyang Niu

MOFs have characteristics that lend themselves to being excellent heterogeneous catalysts Zeolites are currently holding the market for acidic catalysts MOFs require strong Lewis acid properties in order to replace zeolites for the cleaving of certain compounds

http://www.chem.fsu.edu/~alabugin/Photos/dna_Cleavage_Cartoon.jpg

Strong Lewis acid

Polyoxometalates (POMs)

accepts a pair of electrons from another species Used in the nano cleavage of different http://upload.wikimedia.org/wikipedia molecules /commons/6/6e/Dangclass8.png
Inorganic oxo clusters that contain transition metals Have many properties that can be used to induce Lewis acid properties into MOFs For the purpose of this experiment hetero catalyst has a higher conversion than homo Properties used to see if experiment was a success

Heterogeneous Catalyst

http://wwwback.jacobsuniversity.de/imperia/md/images/schools/ ses/facultypages/ukortz/image71_350x39 6.jpg

Compound {[Ho4(dpdo)8(H2O)16BW12O40] 3 2H2O}, compound 1, was thermally crystallized from the solution
HoCl3 36H2O, 4,40-bipyridine-N,N0-dioxide hydrate (dpdo),HoH2BW12O403 nH2O, and hexahydropyrazine (pz)

Compound 1 crystallizes as shown below

Dongbin Dang,, Yan Bai, Cheng He

Synthesize a MOF with Lewis acid properties, to create a very effective heterogeneous catalyst. Use the synthesized catalist to cleave a BNPP molecule as shown Use P NMR to monitor the reaction kinetics

Dongbin Dang,, Yan Bai, Cheng He

Dongbin Dang,, Yan Bai, Cheng He

UV absorbance was used to determine if the experiment was a success The compound 1 MOF demonstrated heterogeneous catalyst properties with a high yield

Life cycle
How long will the catalyst last Can it be regenerated?

Other MOFs
Can it be mechanochemically synthesized? Are there more efficient compounds?

Inhar Imaz, Marta Rubio-Martnez, Wojciech J. Saletra, David B. Amabilino, and Daniel Maspoch

Creation of 1-dimensional infinite coordination polymer particles (ICPs) via conventional coordination chemistry ICPs offer
Promising functionalities
Magnetism Porosity Ion exchange Optical properties
http://www.rsc.org/ejga/CE/2006/b600447d-ga.gif

Encapsulating matricies

Martin et al. (2004)

Lin et al.
Oh et al.

First discrete metal-organic nanotubes by layer-by-layer growth. Created Gd(III) based nanorods used as contrast agents by waterin-oil microemulsion based technique Porous In(III) based hexagonal nanorods by hydrothermal synthesis Creation of coordination polymer based gels and nanofibers. Efficient in light harvesting due to 1-D structure.

You and Lohs research groups

http://www.aist.go.jp/aist_e/latest_research/2008/20081203_2/fig1.png

Purpose: Formation of long chiral coordination polymer nanofibers Conditions:

Technique based on previous work involving Aspartic acid reacted with transition metal ions to create biorelated coordination polymers.

Ambient conditions Use of aqueous/organic interfacial coordinative polymerization

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta Rubio-Martnez

1) Aspartic acid and NaOH dissolved in EtOH/H2O mixture (5:1) 2) Cu(NO3)2*6H2O dissolved in water. 3) Careful transference of both mixtures to a test tube. 4) After 3 days, fibers form at the interface of the layers. 5) During the next 2 weeks, the ethanol layer diffuses into the aqueous phase, and causes formation of the fibers oriented along the direction of diffusion.

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta Rubio-Martnez

Photomicrograph image of fiber bundles shows: Transmission electron microscopy (TEM) depicts
Length High orientation

Field-emission scanning electron microscopy (FESEM) confirms the uniformity of the sample as well as the narrow diameter distribution.

Homogeneity of fibers Diameter

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta Rubio-Martnez

Confirmation of 1-D structure

Proposed formula [Cu(Asp)(H2O)x]n Energy dispersive x-ray confirmed presence of copper, oxygen, nitrogen, and carbon IR spectra showed bands at wavelengths that suggest the presence of carboxylate groups of aspartic acid functional groups, and they are coordinating to the Cu(II) ions. Elemental analysis confirms 1:1 ratio of Cu(II) ions and Aspartic acid

http://en.wikipedia.org/wiki/File:L-aspartic-acid-3D-balls.png

When the aqueous and organic layers are mixed after addition to the test tube, an opaque blue gel is created. Upon further examination (FESEM) it is observed that the gel is made up of homogeneous shortlength nanofibers. This result indicates that the length of the nanofibers is dependent on the method of synthesis.

Amino Acid Based Metal-Organic Nanofibers Inhar Imaz, Marta Rubio-Martnez

Long chiral nanofibers can be grown using traditional coordination chemistry and biologically derived components by utilizing diffusion controlled growth procedures. Simple changes in the experimental procedure can have large effects on the end product (nanofiber length and orientation) Highly flexible composition of coordination polymers can have a huge impact on future applications.
http://www.mpip-mainz.mpg.de/groups/landfester/projects/dc_sem_fig1

Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Metal-organic frameworks (MOFs) present a new way to introduce drugs to the body. Offer high drug loadings, biodegradability, and versatile functionality. Reduction to nano-scale will increase viability of MOFs to act as drug delivery vehicles.
http://www.dcfe.unimi.it/sezion3.jpg

Lots of progress in the understanding of diseases, but not nearly as much progress in the treatment of those diseases. MOFs can help to target specific distribution areas (tumors for example) and will:

Lower the required doses Extend the time the medication is in the body Optimize pharmacokinetics Reduce side-effects

http://img.thebody.com/legacyAssets/08/76/cover.jpg

Important properties for MOFs used as drug transporters:

Size Drug loading Surface properties Drug release kinetics Improved pharmacokinetics Biocompatibility Tissue specificity Multiple agent engineering

http://2.bp.blogspot.com/_lfgsdvQ8GyY/SlOavkX6KUI/AAAAAAAAKUc/sx4FZPfhmg/s1600-h/metal-organic-carbon-capture_1.jpg

Major goal is to design a carrier that both the ligand and transition metal used exhibit little toxicity to the human body. Iron, copper, manganese, nickel, and zinc are all found in the human body, however little is known about possible biological downfalls to each of these metals.

http://houseofhackers.ning.com/photo/toxic-1

Materials of Institut Lavoisier (MIL) Trivalent metal centers with carboxylic bridging ligands Large pores (25-34 ) Large surface area (3100-5900 m2/g) Functional group incorporation Two MOFs studied, MIL-100 and MIL101

Metalorganic frameworks as potential drug carriers Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Both MIL-100 and MIL-101 are chromium based and are tested with the storage and release of ibuprofen. Drug loading

Drug release

MIL-100 0.347g ibuprofen/g MOF MIL-101 1.376g ibuprofen/g MOF Difference attributed to pore size of MIL-101 at 12700 and 20600 (8200 and 12700 for MIL-100)

Tested using simulated body fluid at 37 C MIL-100 Initial release within two hours with full release after three days MIL-101 Steady release for eight hours with full release after six days

http://www.itg.uiuc.edu/technology/reconstruction/scaffold-cells.jpg

The chromium used is highly toxic in the human body, so an iron analog, MIL-101(Fe) should be used as a more suitable drug carrier. MIL-53 is another MOF in the MIL family that has properties that make it desirable for long release (3 weeks) medications. MIL family has the highest drug loading capabilities of any material previously studied.
http://struktur.kemi.dtu.dk/kenny/MIL_53_b.JPG

MIL family have hydrophobic pores, but what about MOFs that use hydrophilic pores? The hydrophilic pores will hold a positive or negative charge, and the drug used will contain opposite charges to the MOFs. The Rosi group created a MOF consisting of zinc(II) ions, adenine, and para-biphenyldicarboxylic acid. This MOF can be cationically triggered to release the drug contained inside.

Storage
0.22 g drug/g MOF Loaded with a hydrochloride salt of procainamide

Release
Previously this drug is generally limited by its rapid exit from the body, and requires re-dosing every three to four hours Use of MOF extended release time to 72 hours.

Metalorganic frameworks as potential drug carriers Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Gaseous therapeutic carriers Nitric Oxide

MOF made from cobalt or nickel and 2,5dihydroxyterephthalic acid.

Can absorb seven times amount of NO as any other MOF Has little background release
Metalorganic frameworks as potential drug carriers Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Antibacterial Antithrombotic Wound healing applications

NO loaded MOF tested on pig coronary arteries induced vessel relaxation Nickel and Cobalt are too toxic for biological applications, but this work shows the ability of MOFs to carry and release gaseous cargo.

http://pubs.acs.org/cen/img/83/i34/8334cov1aopening.gif

Previously discussed MOFs cannot work because of large size. A reduction to the nano scale (nMOFs) will allow systemic circulation through the body while retaining the properties of bulk MOFs Big Picture: Pharmacokinetic improvements!
http://www.sciencedaily.com/images/2007/06/070627084654-large.jpg

Lin group fabricated nMOF designated NCP-1

Once the MOF reaches the cancer cell, the drug is reduced to a more toxic form to kill the cancer cell.

Tb3+ ions and disuccinatocisplatin (DSCP) ~58.3 nm in diameter Encapsulated in silica to enhance stability Functionalized with c(RGDfk) to target an integrin over expressed in many cancers

Metalorganic frameworks as potential drug carriers Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Lin group also loaded a nano form of MIL-101 with a cancer prodrug and imaging agent. Addition of imaging agent suggests possible future of real time monitoring of the therapeutic response to the drug.

http://healthinfoispower.files.wordpress.com/2009/10/ec20rev.jpg

Drug carriers can be formed from a vast amount of metal centers and connecting ligands to find desirable characteristics for the specific application. Many different drugs can be incorporated into the MOF. Therapeutic drugs in conjunction with imaging agents offer new ways to study the real time effects of medications.

Metalorganic frameworks as potential drug carriers Rachel C Huxford, Joseph Della Rocca and Wenbin Lin

Investigate the toxic effects of metals already found in the body for use in nMOFs Explore additional slow release mechanisms for prolonged exposure to the drug. Design nMOFs for large surface area/volume ratio to maximize drug loading capabilities. Research coatings that will increase the stability of the nMOFs and possibly help contain the drug inside until the desired location is reached.

http://www.granitegrok.com/pix/question%20mark.jpg

Rebuttal Group from U4

Oral Presentation and Slides

We agree that their should have been an introduction slide, instead of just assuming the audience realized the entire front matter before the three papers were the introduction. We agree that the Catalyst Paper slide title was inappropriate and should have matched the other two papers by using the title of the paper for the title of the slided. We agree that we should have stuck on one naming convention for metal organic frameworks, either saying its full description the whole time, or by condensing it to MOF every time after defining it in the introduction. We apologize for any distraction that this may have caused. We agree that some slides should have contained larger pictures, but for the most part we think that we filled the slides in nicely with ample text/figures.

Technical
We agree that our introduction was lacking in technical information to provide the audience with a complete background for the papers. We also agree that in the first paper the heterogeneous/homogeneous catalyst properties should have been better explained. We agree the second paper was very well structured and presented, however we also agree that we should have done more to explain how this research will further research in the field. The third paper was not very descriptive on how the drugs target certain areas of the body. We should have done more in depth research to inform the audience that the ligand can be an amino acid that helps the MOF move to a targeted area. Overall we agree that we should have had a technical summary and additional research and benefits of our presentation

U1 review of U4 Metal Organic Framework

Definition;
consisting of metal ions or clusters coordinated to often rigid organic molecules to form one-, two-, or threedimensional structures that can be porous

Importance;
Have potential to replace zeolite Have unique electrical properties that will be very useful in future electronics and computing

http://medgadget.com/archives/2008/02/organic_me tal_hybrids_promise_materials_of_the_future.html

About the presentation

Overall presentation
Well presented, well organized, clear slides and great research work. Thank you for the superb presentation.

Time length
It was little off the time limit of 30 minutes but it wasnt a boring presentation. They did well to engage the audiences and it was a very good stuff to learn

Food
Provided (thank you)

Impact
We have an opportunity about the MOF and about the research going on this topic It is very helpful for some of us who is considering nano-research as their career

http://www.aps.anl.gov/Science/Highlights/ Images/APS_SCIENCE_20080729-1.jpg

Final thoughts
Such presentation will help in developing the research and presentation skills for undergraduate students like us.

Review of Group U4s Presentation-

By Group U2:
-Kyle Demel -Keaton Hamm -Bryan Holekamp -Rachael Houk

http://www.rsc.org/images/MOF%20image_tcm18-150592.jpg

The presenters did really well at:

Food This group by far brought the best food to class. Ice cream sandwiches, cookies, cupcakes how could we not give you an A just for that?
Figures The graphics used throughout the presentation were pertinent to the topics being presented. The use of graphics was very important to help demonstrate the material being discussed. The group did a good job of incorporating graphics onto every slide. Structure The group followed a clear presentation and structure order. They provided an outline and stuck with it. The outline could have been done better. The topics in the outline were vague and did not properly summarize each section. Articles The presenters chose appropriate articles for this presentation. A total of three articles were used. This is very impressive considering that most groups chose to only report on one pertinent article during their presentation. The speakers discussed metal organic frameworks with respect to catalysts (very important considering the reaction engineering that many students have learned), amino acid nanofibers (incorporating biology with our nanotechnology discussion), and potential drug carriers (which builds off of previous groups presentations.
http://pubs.acs.org/cen/images/8003/8003notw1sphere.gif

The group could improve at:

Timing The group needs to do a better job coordinating the speaking parts and for how long each group member will talk. Only two of the group members presented, which is fine, but of these two members, one spoke for five minutes, and the other spoke for twenty-five minutes. That is clearly malproportioned. The speakers should practice together ahead of time to smooth out transitions and even out the amount of speaking parts.
Background The background was very brief, and predictably, not very informative. The speakers rushed through the introduction in about two or three minutes. More time should be committed to communicating the basic material.

Slide Format The group clearly went with a template formatting and meshed all the sections together. This led to striking inconsistencies in formatting. The text and heading size varied between the slides. Most slides also had too many words on them. These should be short bullet points, not paragraphs! The figures also need to be bigger. There is too much blank space on the slides. Space the text out more if you have to, but do not leave half a slide blank without reason.
Stronger Beginning & End The opening was kind of weak; the intro slide was bland and the outline was not very well done. Also, the conclusion was sort of abrupt. You need to summarize what was discussed during the presentation.
http://www.matternews.com/Images/metal-organic-frameworks.jpg

Undergrad 2nd Review for Group U4 Metal Organic Frameworks

Group U3: Krista Melish James Kancewick Phillip Keller Mike Jones

Presentation Review: Ugrad #4

Presentation Review

Introduction

Paper 2: Amino acid based metal organic nanofibers

The introduction contained good information to describe what MOFs are, but we would have liked to see more information on their history. The papers covered after the introduction should have been mentioned even if each paper has its own intro slides. This would help the audience to see where the presentation is going. Intro slide communicated all necessary information to understand the problem and experiemnt. The theory slide could have been more effective. The last bullet about heterogenous catalystdoesnt seem to be correctly integrated. Heterogenous catalysts simply are ones that have reaction sites within them. Zeolites and

Paper 1: Catalyst

Effective introduction to the topic, and especially liked the history which put it in perspective. The experiemnt and results where both explained well, and in a way that was easy to understand. The only thing that should have been better clarified are the specific positive properties this ICP yielded. The intro mentioned some areas where the might ne useful, but there wasnt much on how this experiment might affect future things. It seemed like it didnt have an end goal in mind in advancing the field. It is not apparent how MOFs can help target specific distribution areas in the body as mentioned in the intro. The rest of the information is correct, but MOFs cant distinguish between different areas of the body. Good job explaining how high surface area of MOF can lend istelf to storage and release of medications, as well as why this fact is important.

Paper 3: MOFs as potential drug carriers

 Review Of Group U4 by

Group U5

 Oral skills and preparation very

good. First speakers seemed to have practiced and knew their information but later speakers needed more work. Great slide quality and sequence. A lot of pictures, figures, and graphics that were helpful for understanding

http://www.rsc.org/images/b808104b-350FOR-TRIDION_tcm18-128604.jpg

 Very good introduction.

Liked how they described what MOFs were, but would have liked to learn more about their history and past work more. Choice of papers were relevant and interesting Did not like how they nicknamed the first paper Catalyst Paper. Would have preferred for them to use the actual title of the paper

Dongbin Dang,, Yan Bai, Cheng He

Dongbin Dang,, Yan Bai, Cheng He

 Jaynesh Shah Greg Pudewell Edwin L. Youmsi Pete

John Pack

http://www.sciencedaily.com/images/2007/06/070627084654large.jpg

 Both speakers were loud,

clear, audible and maintained eye-contact They were confident and sounded knowledgeable on the subject The slides were visually appealing and consistent All the graphics in the slides were appropriately cited and were relevant to the topic

http://news.softpedia.com/images/news2/HowDangerous-Are-Nanoparticles-2.jpg

 Speakers made good use

of technical jargon The papers discussed were relevant and interesting Could and should have discussed further research a little bit more
http://www.rsc.org/images/b808104b-350FOR-TRIDION_tcm18-128604.jpg

Metal Organic Framework

Presented by: Group U4 Critiqued by: Group U6 Pavitra Timbalia + Michael Trevathan

http://www.scientificamerican.com/media/inline/metal-organic-carbon-capture_1.jpg

Critique: Oral Presentation & Slides

Slide Background made the font easy to read and the

http://www.how-tostudy.com/images/oth er-helpfularticles/making-anoral-presentationspeaking.gif

pictures easy to see The Overview slide did a good job summarizing the topics ahead Should have had a slide which said Introduction Instead of saying Catalyst Paper could have just placed paper title The group did a good job in having graphics on each of the slides however, one or two slides did not have any graphics
All of the graphics were referenced good job

We did not like the way the slides end maybe need an

overall conclusion slide to tie things together The group presented well the other two members presented for this presentation Both presenters kept good eye contact with the audience and good posture (Both were also dressed in business clothes)

http://www.beatsworking.tv/greatrex/eyecontact.jp

Critique Technical Content

Introduction was a bit rushed because of pace of speaker It was, however, concise and gave a good overview of metal

http://www.bioinfo.mpg.de/euclis/General/images/clockReferences.jpg

organic frameworks Choice of research papers seemed relevant to topic discussed Three papers discussed which gave a good range of information on current research The second and third papers were more in-depth with the analysis The paper on drug carriers was the most interesting since to us the research could assist advanced in the medical field Each of the papers covered recent research in the field The motivation for each paper given at the beginning something we really liked Further research was incorporated at the end of the slides for each paper would have liked to see the impact of this research in the future Like we said before, the presentation ended abruptly would have liked to see a conclusions/summary slide or an overall further research slide We feel that there should have been a Works Cited slide to let
http://www.medgadget.com/archi ves/img/54747por.jpg

Review for U4
Jung Hwan Woo

 Overall, the presentation and the slides were great. The presentation contained several different applications. It was a good approach as it could introduce more applications of MOFs to the audience. However, this approach resulted in the lack of depth in some of the research topics introduced. Some of the slides were a bit crowded with text but it was ok. I liked the option 1, option 2, etc. approach.