In this investigation, female hair samples (before and after dyed) were spiked externally with two different antipsychotic drugs, Clozapine and Haloperidol and their respective effect at different PH ranges (PH: 2.0, 7.0, 9.0) on the structure of the hair samples was observed.

We have recently observed surface enhancement in molecules adsorbed on semiconductor quantum dot surfaces. We have observed these in MBE grown InAs and CdSe quantum dots, as well as colloidal quantum dots such as ZnS, ZnO and CeTe. Enhancement factors of up to four orders of magnitude are observed. It is impossible to explain these observations using plasmon resonance, which for semiconductors are in the infrared. We explore the possible application of the charge-transfer theory to semiconductor dots. Application of the Herzberg-Teller theory to such systems implicates polaron (electron-phonon) coupling in the suggested mechanism.

Conventional lectures have been replaced by student-centered sessions that rely heavily upon CPS clickers. Each student now attends an 80 minute workshop session. A Chemistry Learning Center has been created for walk-in office hours. An army of undergraduate TAs has joined a smaller number of graduate TAs to cover our many workshops and to staff the Learning Center. Examinations have been modified to allow for efficient and uniform hand grading combined with computerized analysis of the results. Personalized web pages are used for communication of examination results to each student. Some of our changes have worked better than others. This presentation will discuss the high-lights. The low-lights are best forgotten.

The development of scientific literacy, the main goal of the National Science Education Standards can be enhanced through learning environments that incorporate physical experience in the form of direct interaction with natural phenomena, since these have been shown to be more effective in promoting learning than those that don't (Lawson, 1986; Druyan, 1997).

The availability of powerful means of data collection and analysis can transform the traditional role of the laboratory from one of being confirmatory of concepts previously studied and presumably learned, to becoming an exploratory inquiry-based setting. A study of high school students using microcomputer-based chemistry and physical science laboratory activities to predict and observe experimental outcomes provided the means to link process skills, and content retention. Two significantly positive correlations were found: 1) That between the use of two different modes of prediction and the ability to correctly predict an experimental outcome, consistent with previous findings of the performance of high school teachers in the use of the technology in life science and physical science tasks (Espinoza, 2006); 2) That between successful experimental outcomes and a gain in students' performance on content-related tasks.

Jennifer's presentation highlights the ins and outs of the technology consulting world (explaining what a technology consultant actually does), giving examples of client projects (emphasizing science and engineering applications), and how recent graduates can navigate and direct their own career paths. Technical, professional, and personal benefits of the consulting career will also be covered. Additionally, the presentation will provide insight and tips for how to succeed in any consulting environment.

Kuwait Petroleum Corporation, KPC has financed a project to construct new headquarters, Oil Sector Complex, (OSC) that has been completed recently at an old salt-chlorine industrial location. This site has reminiscence history of Salt-Chlorine Plant using large number of mercury cells for electrolysis of brine to produce caustic soda and chlorine gas resulted into mercury pollution in marine waters and silt sediment. The present study focuses on mercury measurements in air, water and sediments around this building and assessment of air quality and comfort levels in KPC building consisting of 22 floors, and adjacent building, Ministry of Oil of 14 floors facing Kuwait Bay.

A detailed investigation to decode the origin of these unique properties has been undertaken by study of its composition, adsorption isotherm, particle size by various instrumental techniques including Scanning Electron Microscopy. The results will be discussed in our presentation.

The intellectual path that led to the potent compounds will be described, and the evidence on their mode of action and the results of animal and human trials. The importance of only medium strength of binding to the receptor protein in this series will be discussed. The kinetic principles involved may be applicable to many other medicinal series.

Paul A. Marks, Ronald Breslow, �Dimethylsulphoxide to vorinostat: development of this histone deacetylase inhibitor as an anticancer drug,� Nature Biotech. 2007, 25, 84-90.

M. Tanaka, J. Levy, M. Terada, R. Breslow, R.A. Rifkind, P.A. Marks, "Induction of Erythroid Differentiation in Murine Virus Infected Erythroleukemia Cells by Highly Polar Compounds", Proc. Nat. Acad. Sci. USA, 72, 1003-1006 (1975).

References:

1. Z. W. Zhu, M. E. Tuckerman, S. O. Samuelson and

G. J. Martyna, Phys. Rev. Lett. 88:100201 (2002).

2. P. Minary, M. E. Tuckerman and G. J. Martyna,

SIAM J. Sci. Comput. (in press).

3. L. Rosso, P. Minary, Z. W. Zhu and M. E. Tuckerman,

J. Chem. Phys. 116:4389 (2002).

4. J. B. Abrams, L. Rosso and M. E. Tuckerman,

J. Chem. Phys. 125:074115 (2006).

Details of the process of depositing reflective layers on an ionic liquid by PVD are discussed, and consideration is given to the potential scale-up process for in-situ coating of a 100 meter ionic liquid mirror telescope on the Moon.

When ionic liquids replace aqueous chemistries for electroplating, energy efficiency of the plating process typically increases from 20% to 90%; hydrogen gas production is significantly reduced. The non-volatile nature of ionic liquids reduces the need for air pollution controls. Electroplating Chromium using ionic liquids is especially advantageous in that hexavalent Chromium, which is highly toxic and carcinogenic, can be replaced by the trivalent form, which is much less toxic. While most metals that can be electroplated from aqueous solution can also be electroplated from ionic liquids, two examples are presented where the reverse is not true. The results are presented of electroplating Aluminum and Molybdenum using an ionic liquid composed of Urea and Choline Chloride.

Electropolishing is a complimentary process to electroplating in that microprojections (peaks) on a metal surface are preferentially electrochemically etched, while microdepressions (valleys) are minimally etched. This produces a surface that is mirror-like and smooth on an atomic scale. Ionic liquids composed of choline chloride and propylene glycol have been used to replace the toxic and hazardous electropolish baths using concentrated sulfuric and phosphoric acids. Greater electrical current efficiency, reduced Hydrogen production, reduced generation of acid mists, and room temperature operation are additional benefits. Results of ionic liquid electropolishing of Stainless Steel are presented.

A spectroscopic study of paints removed from a 15th century sculpture depicting Saint Wolfgang, which is housed in Ball State Museum of Art, was performed. Infrared spectra on minute paint samples were obtained, and the spectra were compared to reference spectra of known art pigments and materials. In addition, energy dispersive x-ray spectra were obtained using a scanning electron microscope. The x-ray spectra were used to support the infrared results and, in some cases, allowed for the identification of materials which have infrared absorptions below the detector range or which are infrared inactive. The combined spectral data on the paints, which were layered in several places on the sculpture, allow us to obtain a detailed description of Saint Wolfgang's different appearances throughout the past three hundred years. Although many of the pigments found are relatively modern, the first application of paint is composed of materials consistent with the sculpture's medieval date.

In this talk selectivities obtained in photoreactions conducted in aqueous medium using a water soluble deep cavity cavitand (octa acid) as host (shown below) will be presented. Photochemistry and photophysics of aromatics, alkenes and carbonyl compounds included in the above host system are distinctly different from that in isotropic solvent medium. Photofragmentation of dibenzyl ketones, geometric isomerization of stilbenes, singlet oxygen mediated oxidation of cyclic olefins would be used as examples to illustrate the power of a confined space and weak C�H---π interaction in controlling chemistry.

Art is treasured everywhere: science increasingly is not. Nevertheless we can teach non-scientists how the scientific examination of art increases their understanding of art. They witness science in action and what a scientific approach can achieve. Scientists, too, studying chemistry and art, see how science benefits art, as they themselves are introduced to art.

Art provides the lure to teach scientific reasoning. Our society faces a crisis in values. We must insist on honest reasoning and teach it widely. How else are we to evaluate global warming?

ChromSwordAuto method development software integrated with LC, LC-MS and SFC instruments enables a rapid and unattended separation of complex mixtures in the reversed phase, normal phase, and chiral separation mode. In the off-line mode a chromatographer can start from structural formulae and properties of reversed-phase columns or from data of two runs. In the on-line mode the software controls HPLC amd SFC instruments and searches for optimal isocratic or(and) gradient conditions fully automatically.

One set of product analogues is based on an experimentally observed class of potent inhibitors consisting of adenine bound to hydroxamic acid through various flexible linkers. The dissociation of the proton from the hydroxamate to produce a potent metal binder within the active site suggests analogous groups such as a sulfonamide can reach the enzyme as a neutral molecule but bind ionically as a product analogue within the active site.

My teaching started as how I had been taught. Why did student results not match my results? What did I do that students did not?

Organic chemistry has two (or three) major focal points. One is the description and terms associated with chemistry. The second are reaction mechanisms. They present a special challenge to students because they are dynamic. The objective is not what you have, but what it can become. My experience suggests they are the greatest challenge for students and the most important variable responsible for individual scores on the ACS exam. Of many methods, which ones were the most successful?

The percentile ranking on the ACS organic chemistry exams were recorded for all classes and the results of teaching changes will be discussed.

As scientists we need to remember that we have choices beyond traditional academic and industry careers. Indeed, in the past several years many scientists have begun to consider the non-profit world as a way to create a more meaningful career. This has been occurring as more people realize that access to potentially life-saving drugs ought to be a human right, like access to food, shelter and education.

This paresentation will focus on ways of controlling photoreactivity of coumarin derivatives within cucurbit[8]uril (CB[8]) nano-cavities. Substituted coumarin derivatives that are either neutral (7-alkyl, 6-alkyl, 7-hyxoxy or 6-hydroxy) or cationic (7-ammonium or 6-amnonium) form 1:2 host-guest complex with CB[8], that are completely soluble in water and are characterized by NMR spectroscopy. Direct irradiation of these coumarin�CB [8] complexes in water gives anti-head-to-tail (anti-HT) adduct as the major product, which is again characterized by NMR spectroscopy. Preferential formation of anti-HT adduct within cucurbiturils, not generally observed upon direct irradiation in isotropic media, highlights the role of CBs in altering photoreactivity of coumarin derivatives. Selective formation of coumarin adducts (4-diffenent adducts are possible) in different organized assemblies is generally unpredictable. Based on reported crystal structure parameters and optimized structures for various coumarin adducts, it is speculated that the available free space within CB[8] nanocavity facilitates formation of the anti-HT 5. Employing CBs as a template is a powerful tool to control photoreactivity of various substituted coumarin derivatives leading to selective formation of anti-HT adduct, which is not generally observed in other isotropic media.

Serum albumins (SA) possess inherently chiral binding sites for endogenous and exogenous organic compounds, which can be exploited for supramolecular photochirogenesis. In this study, we chose 2-anthracenecarboxylate (AC) as guest substrate, and first examined spectroscopically the binding behavior of AC toward various mammalian SA in aqueous buffer solution at pH 7 to characterize the available binding sites for AC. Then, the enantiodifferentiating photocyclodimerization of AC was performed in the presence of SA to give four stereoisomeric [4+4]-cyclodimers. We found that (1) mammalian SA possess 3-5 binding sites for AC of different affinities, stoichiometries, and chiral environment for the photoreaction, (2) the head-to-tail/head-to-head ratio critically depends on the SA used, and (3) SA-mediated photodimerization of AC affords optically active cyclodimers in excellent ee's.

In conclusion, the supramolecular photochirogenesis with SA is a promising strategy for asymmetric synthesis that is not only an attractive alternative to the thermal counterpart but also a unique methodology for obtaining chiral compounds through the electronically excited state in chiral low-entropy environment.

HOCH₂CH₂OO• → •OCH₂CH₂OOH (1)

HOCHRCH₂O• →•OCHRCH₂OH (2)

These types of reactions may play an important role in both the atmosphere and in combustion systems. We have used density functional theory and composite electronic structure methods determine that Reaction (1) has a barrier of 23.6 kcal/mol, and that Reaction (2) has a barrier of 22.7 kcal/mol. We used RRKM/master equation simulations to model the kinetics of chemically activated HOCH₂CH₂OO• formed in the reaction HOCH₂CH₂• + O₂; our calculations suggest that a majority of chemically activated HOCH₂CH₂OO• undergoes a prompt hydrogen shift reaction across the at pressures up to 10 Torr. This low pressure is relevant to many experiments.

Variational transition state theory (TST) calculations were carried out using the POLYRATE program. For Reaction 1 at 298 K, the variational TST rate constant is ~30% lower than the conventional TST result, and the μOMT method predicts that tunneling accelerates the reaction by a factor of 3. TST calculations on Reaction (2) reveal no variational effect. Tunneling is very important in Reaction (2); the 298 K μOMT transmission coefficient is 10⁵.

Analyses of the mixtures were performed on the Agilent 1200 LS Rapid Resolution LC system. The mobile phase was made of two components; A: 25 mM KH2PO4 buffer at pH = 2.5 and B: Methanol. The analytes were separated on Zorbax Eclipse Plus C18 (4.6 x 150 mm, 5 �m), (4.6 x 100 mm, 3.5 �m), and (4.6 x 50 mm, 1.8 �m) columns. As the column particle size decreased; the phase interaction, equilibrium, and separation became faster and more efficient. Identification of the vitamins in the standard mixture, supplements and vitamin drinks was confirmed using the Diode Array Detector with high-speed full spectral UV-Vis detection. This separation was completed in under 3.5 minutes under the conditions stated.

The Oxygen Radical Absorbance Capacity (ORAC) method to quantify the antioxidant property, as promulgated by USDA scientists, has been used to rank (ORAC units/100 g) common foods: Prunes (5,770), and blueberries (2,400) top the list, trailed by such health food industry favourites as kale (1,770), spinach (1,260). ORAC values of various sugarcane products, as reported by Dr. Saska (Saska and Chou, 2002) of Louisiana State University, range from some 5000 (ORAC units/100g dried solid) to over 35,000, and antioxidants in concentrated sugarcane extracts obtained from cane juice was found to contain over one million ORAC unit (�mole TE/100 g dry solids).

According to USDA research (Bank, 2005), ORAC value of an average serving of vegetables equals approximately 900 �moles TE, and that of fruit is approximately 3400 �moles TE. The estimated ORAC intake of the daily recommended nine servings of fruits and vegetables equals about 20,000 �moles TE.

This paper presents the physical chemical aspect of the antioxidants extraction methods from sugarcane products in a pilot plant operation.

We have developed different modular routes for incorporation of electron-deficient boron centers into the main chain and side chain of thiophene-based polymers. The direct attachment of boron to the thiophene moieties provides for strong electronic coupling of the boryl groups and the organic polymer main chain. The photophysical properties, relative Lewis acidity, and environmental stability can all be fine-tuned by introducing suitable pendant aryl groups to the boron centers. The new polymers will be discussed in the context of potential applications as optoelectronic materials and as sensors for nucleophiles.

We have introduced several new methods for the preparation of well-defined organoboron-functionalized styrene polymers. Especially interesting are block copolymers that are capable of forming self assembled nanostructures in solution and in the solid state, and hence are expected to provide exciting new opportunities in the above-mentioned areas. We describe here the preparation and assembly properties of three new classes of organoboron block copolymers containing anionic organoborate, cationic organoboronium, and pH sensitive boronic acid moieties, respectively. The solution self-assembly properties of these novel polymers will be discussed.

The lecture will mainly deal with the structures of the new chromophores contained in the Chl catabolites and with the result of preliminary studies of their photochemical properties.

Further reading

Kr�utler, B., H�rtensteiner, S. (2006). Chlorophyll Catabolites and the Biochemistry of Chlorophyll Breakdown, in �Chlorophylls and Bacteriochlorophylls', (B.Grimm, R.J.Porra, W. R�diger, H.Scheer, Eds.), Adv. Photosynthesis & Respiration, vol. 25 (Govindjee, Series Ed.), Springer, Dordrecht, The Netherlands, p. 237-260.

Support by the Austrian National Science Foundation (FWF) is gratefully acknowledged.

Footnote: * For research use only.

Cellulose can be hydrolysed to glucose which can be oxidized to glucaric acid. Elimination of water and cyclization yields 2,5-furan dicarboxylic acid (2,5-FDA). We have mostly used interfacial polycondensation of the acid chlorides of the various isomers of FDA (2,5; 2,4; 2,4; 3,4) as a route to polyesters and polyamides. Polymers with intrinsic viscosities in the range of 0.1 � 0.7 dl/g could be prepared. Nonactin, a macrocyclic tetraester acts by binding potassium ions and disrupting synaptic signal transmission.A casual examination of this molecule led us to try to generate a helical polymeric analog? We tested the general idea by making reduced derivatives of 2,5-FDA We also made polymers derived from the lactone and the analogous lactam from tetrahydro-2-hydroxymethyl-5 furoic acid and they exhibit varying degrees of ion binding ability.

The major hydrolytic degradation product of cellulose is levulinic acid which can be condensed with phenol to yield a bis-phenol called diphenolic acid which can be protected as a t-butyl ester The ester allowed us to prepare a variety of homo- and copolycarbonates in which, after selective removal of the t-butyl group, the carboxyl group can be used as a site for further modification.

In the spring of 2008, this experiment was implemented into a second semester environmentally focused general chemistry lab. The experiment was modified to allow students to change one component of their reactions and to predict about how the change would influence the success of the reaction.

Abstract:� The electrowetting behavior of ionic liquids as well as electrolyte solutions can manifest itself in a shape change of a droplet on a surface or translational movement across that surface.� The magnitude of the response depends on the strength of the electric field, the nature of the surface being wetted (surface energy, roughness) by the droplet and on the chemical nature of the ionic liquid itself (composition, structure, conductivity, surface tension, viscosity).� In the work to be presented we focus on an ionic liquid monomer � liquid polymer system based on an acrylamidopropane sulfonic acid � oxyethylene amine base (depicted below) and describe comparative electrowetting measurements.� The contact angle dependence on electric field and polarity as well as translational droplet motion will be illustrated.� The issues of interest are comparison of a monoionic with a polyionic liquid system, the molecular weight effect of polyionic system and volume fraction effect of the oxyethylene ammonium counter ion.

[1] Berry, B.C., Bosse, A., Douglas, J.F., Jones, R.L., Karim, A., Nanoletters, 2007, 7(9), 2789.

[2] Bosse, A.W., Douglas, J.F., Berry, B.C., Jones, R.L., Karim, A., Phys. Rev. Lett., 99, 216101, 2007.

A set of XIAP inhibitors has been designed and synthesized in order to mimic Smac interaction with the BIR3 domain of XIAP.

Multi Component Reaction Chemistry (MCR) was adopted as synthetic strategy: diversified reaction products were obtained starting from the combination of three or four building blocks in a one pot operation. Based on the binding fragment Ala-Val novel potent scaffolds have been discovered also showing cell based activity.

X-ray studies of the synthesized inhibitors with the XIAP binding site compared to the Smac-XIAP complex showed that the H bounds of the Ala-Val portion are retained and can therefore contribute to the selectivity for the target. Instead, the high variability of the heterocyclic moiety leads to new additive interactions with XIAP.

Biological evaluations performed showed promising results, suggesting that a further expansion of the chemical diversity of the heterocyclic moiety may increase the interaction with XIAP.

Vibrio cholerae, the causative agent of the human disease cholera, uses cell-to-cell communication to control pathogenicity and biofilm formation. This process, known as quorum sensing, relies on the secretion and detection of signalling molecules called autoinducers. At low cell density V. cholerae activates the expression of virulence factors and forms biofilms. At high cell density the accumulation of two quorum-sensing autoinducers represses these traits. These two autoinducers, cholerae autoinducer-1 (CAI-1) and autoinducer-2 (AI-2), function synergistically to control gene regulation, although CAI-1 is the stronger of the two signals. V. cholerae AI-2 is a furanosyl borate diester, which was identified and fully characterized in Vibrio harveyi.    CAI-1 is (S)-3- hydroxytridecan-4-one, a new type of bacterial signal.  The structure elucidation, synthesis, mechanism of action,  and structure-activity relations for both AI-2 and CAI-1 will be discussed.   CAI-1 represses production of the canonical virulence factor TCP (toxin co-regulated pilus) which suggests that CAI-1 could be used as a therapy to prevent cholera infection and, furthermore, that strategies to manipulate bacterial quorum sensing hold promise in the clinical arena.

The aim of this presentation is to introduce the major areas of silicone chemistry used in the cosmetic and hair care fields, while providing a hands-on experience of touching the ingredients and products containing these ingredients. This presentation is based on the one given annually by the author at Fairleigh Dickenson University to chemists training for a masters degree in chemistry and science related to cosmetics and the greater personal care industries.

He has a broad corporate background having previously held new technology positions at Uniqema, Mona Industries, National Starch, Unilever, and Abex Corp. He has contributed to a number of successful commercial projects, some replacing older materials with safer and greener options.as well as being a proponent of businesses working closely with regulatory agencies to develop realistic solutions to on-going issues.

Another type of biomimetic catalyst is based on hydrophilic polymers with hydrophobic cores. This class is able to imitate the ability of enzymes to use the advantages of water for hydrophobic binding but use the non-aqueous interior of the protein to promote rapid catalytic reactions, producing �a drop of DMSO suspended in water.� The result is an acceleration of the synthesis of tryptophan by transamination with an acceleration of 240,000-fold caused by the polymer. Recently the system has been improved by using non-covalent complexes of coenzyme mimics to accelerate tryptophan synthesis by 725,000-fold.

We thank the National Science Foundation for financial support.

Vitamin C is found in many vegetables and fruit. Its deficiency in the diet causes survy, a fact known very early in history. Various fruits and vegetables can give the daily recommended dose of vitamin C. In this experiment vitamin C is extracted from different fruits and vegetables. These juices are analyzed with

via High Pressure Liquid Chromatography (HPLC). The reverse phase C-18 column is used. UV absorption is used to monitor the Vitamin C content. Since ascorbic acid is stable in acidic pH range a buffer prepared from disodium hydrogen phosphate is used.

Vitamin "C" is one of the essential nutrients whose daily

recommended dose by World Health organization (WHO) is 20-30 mg. Several commercial juices indicate in their label �100% vitamin C". Do they really mean 100% of the recommended dose by WHO? In this experiment the juices are filtered and samples are injected into High Pressure Liquid Chromatography (HPLC). The amount of vitamin "C" is calculated from the standard graph obtained that uses standard ascorbic acid. The amount of vitamin C in different brands of various juices are compared using the standard graph.

The column evaluation process involved screening of a series of 20 columns varying in bonding chemistry using four sets of mobile phases composed of water, acetonitrile and/or methanol at three different pHs. The screening process resulted in identifying two promising columns: XBridge Shield RP18 and SunFire C18. The effects of organic modifiers and separation temperatures were then evaluated to narrow down the chromatographic separation parameters. DryLab� was used to predict optimized gradient profile and separation temperature. Finally, the DryLab� predictions were verified experimentally.

The study demonstrates that factors such as stationary phase composition, organic modifiers, pH and separation temperature have profound and oftentimes complex effects on chromatographic conditions. Therefore, it is critical to adopt a rational strategy as demonstrated here to evaluate the interplay of these factors, there by greatly enhancing method development efficiency.

The photo-Fries rearrangements of o-cresyl acetate (1) and 2-benzylphenyl acetate (2) have been investigated in two unstretched and stretched polyethylene (PE) films and in isotropic solutions. For example, irradiation of 1 yields principally o-cresol, o-xylene, 3-methyl-2-hydroxyacetophenone (2-PF) and 3-methyl-4-hydroxyacetophenone (4-PF) in isotropic solvents, but 2-PF dominates in PE films, especially in stretched PE films. The influence of variables, such as the degree of film crystallinity, film free volume, and the unstretched/stretched state of the films, on the rearrangements has been explored. The selectivity of the photo-Fries rearrangements of 1 is higher in PE films than in isotropic solutions, and increases with degree of crystallinity of the films and upon film stretching. o-Cresol, a product from cage-escape of the initially generated aryloxy and acyl radical pairs, and o-xylene, a product from concerted decarboxylation, are formed in yields that depend upon the nature of the films. These and other results will be discussed.

We thank the U.S. National Science Foundation and the China Scholarship Council for their support of the research.

Novel near-infrared (NIR) fluorescence dye incorporated polymers were synthesized for applications in in vivo imaging. The polymers have glucose side chains to improve water solubility and pendant NIR dyes acting as imaging agents with an azide / biotin chain-ends which serve as reactive handles for the attachment of the polymers to proteins. The polymers were synthesized via Atom Transfer Radical Polymerization (ATRP) using a novel azide initiator. Biotin alkyne was attached to the azide chain-end via �click� chemistry. The polymers were characterized using NMR spectroscopy, GPC and FPLC. Protein hybrids with streptavidin were prepared. The conjugates were characterized and potential biological applications for non-invasive imaging in mice and in 96 well plate assays were explored.

Recently, our laboratory has been developing new strategies for the generation of catalytically active metal nanoparticles.^{1, 2, 3} We have been able to generate and stabilize a fair number of late transition metal nanoparticles via this strategy. In this presentation, we will present catalytic utility of nanoparticles to tailor olefins to silicon molecules via hydrosilylation reactions. We will demonstrate that a fair number of electronically and sterically varied olefins were quantitatively and regioselectively grafted to Si-H containing silicone molecules and oligomers. Furthermore, hybrid nanoarchitectures were generated by selective incorporation of olefin based polymers on predefined nanostructures, such as Octakis(dimethylsiloxy)-T8-silsesquioxane (Q8M8H) and 1,3,5,7 Tetramethylcyclo-tetrasiloxane (D4H).

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[1]Chauhan, B. P. S.; Rathore, J. S., Chauhan, M. and Krawicz, A. J. Am. Chem. Soc. 2003, 125, 2876.[2] Chauhan, B. P. S.; Rathore, J. S. J. Am. Chem. Soc. 2005, 127, 5790-5791.[3]Chauhan, B.P.S.; Balagam, B. Macromolecules 2006, 39, 2010-2012.

Biological molecules like proteins, DNA and lipids have strong ionic components in their molecular structures and electrostatic interactions between such biological molecules play important roles in functional binding processes. Immunosensors have been developed based on monitoring pH changes during the metabolic activities. Such potentiometric measurements follow potential changes evolved from ion activity during the binding with no electric current applied. The selectivity for the specific ion detection can be optimized using special membranes on electrode surfaces for the ion differentiation. We've developed another option for selectivity with surface imprinting; the analyte is �molded� on the electrode surface, washed out and the empty cavity of molecular parameters provides the antibody mimicking selective binding.

Antibody-antigen binding or in general protein-protein interactions cannot be diagnosed with metaloxides/electrodes as the electric double layer of less than 1nm allows protein adsorption studies but not interactions on protein surfaces. Organic electronics, electrically conducting polymers, are organic material with 3D composition of ions and electrons, and do have the electric double layer to limit the binding dimensions. We present how polyaniline electrodes can be used for the monitoring protein-protein interactions and also DNA hybridization. Protein studies include determination of the binding conditions for antibody-antigen reactions, and binding studies using lectins and heptapeptides selective for exosporium protein binding. DNA hybridization studies present our efforts on SNP detection, and hybridization with genomic target.

Here we present an extension of the AFED method that circumvents such transformations. In this approach, additional degrees of freedom, s_i, are used to drive the collective variables of interest, s_i(r) via a harmonic potential coupling. The driving variables are given temperature sufficient to cross any significant barriers and mass sufficient to maintain adiabatic decoupling. The free energy surface along the collective variables is then constructed using the adiabatic probability distribution of the variables, s_i. This driven AFED approach (d-AFED) is employed to compare the conformational preferences of small peptides for three force fields. The results show that d-AFED accurately and efficiently computes the free energy surfaces of interest using radius of gyration, R_G, and number of hydrogen bonds, N_H, as collective variables.

This work involves a fundamental and quantitative investigation of the factors influencing the reaction yield and the transient isotachophoretic stacking of the Jaffe product. The effect of the background electrolyte on the reaction was principally investigated, with borate, glycine, AMPSO, and CAPSO buffers used in the experimentation. The background electrolytes seem to primarily affect the flow rate within the capillary, but they also have a minimal effect on the Jaffe reaction product. Additionally, the timing of the applied voltage used to overlap the reactant zones was studied. Addition of chloride to the creatinine zone is found to yield a significant improvement in stacking behavior, presumably due to minimized electrodispersion of the product.

F = (k.Q⁺ .Q^-)/R²

where F is force of attraction between two oppositely charged species (Qs), k is a proportionality constant and R is the distance between the charged particles.

The sizes of atoms and ions are dependent on the force of attraction between the valence electrons and the nucleus. None of the popular textbooks presents an explanation of trends in sizes based on Coulomb's law. A life experience that parallels the law and a simple application Coulomb's law to explain trends in sizes among members of periodic groups and rows will be presented.

We report in vitro fluorescence spectroscopic studies of PAP-eIFiso4G binding revealing a binary interaction with a Kd of approximately 100 nM. This interaction enhances PAP's binding to the cap analog m⁷GTP 3.6-fold. Our measurements place PAP's affinity for cap between that of the wheat germ cap binding proteins eIFiso4E and eIFiso4F. ATP and GTP compete with cap for PAP binding; both nucleotides and the cap analog show little salt dependence in binding, suggesting that the interactions are specific for these nucleotides. The biological significance of the cap binding remains unclear, however this may serve as a means to target RNA or, since ATP binds to the same site, this may be a protective mechanism for host cell capped RNA. The interaction with eIFiso4G suggests that additional proteins may aid PAP in accessing particular RNA and distinguish structural elements of the RNA. These results support a model where PAP's interaction with initiation factors may play a regulatory role in its enzymatic activity. PAP's binding to the SRL oligonucleotide sequence was measured; it is weaker than for cap analog and is described.

Eight metal objects of the Moche IV period, excavated by Donnan and Mackey in 1978, have been chemically and structurally analyzed to understand their construction and possible ritual uses. The gold content of several objects indicates a deliberate addition of gold to the alloy, however in amounts insufficient to alter the surface color of the objects. Lead-isotope analysis shows that local copper ore sources were used in the object production.

Two unique objects, a metal staff and tumi (ritual knife) have been subject to detailed structural characterization. The fact that these artifacts are constructed in unique ways and intact increases the likelihood that these objects were ritually important. It was also determined that this particular tumi could not have been used as an actual cutting tool, indicating its ritual importance over practical use. Overall, these objects increase our understanding of Moche metallurgy in their terminal period.

We thank the National Science Foundation for its support of this research.

I will describe the Chemical Synthesis and analysis of nanoparticle conjugated 4-HPR and other derivatives of 4-HPR compound libraries, Screening of nanoparticle libraries to test their effect on rhabdoid cell lines. The in vitro and in vivo studies of lead nanoparticles to assess their biodistribution, efficacy and use of microPET for diagnosis using genetically engineered rhabdoid tumor models.

Copper-based ATRP (atom transfer radical polymerization) catalytic systems with polydentate nitrogen ligands such as bpy and aliphatic polyamines is among most efficient controlled/living radical polymerization systems (CRP).^1,2 New ATRP initiating systems allow to decrease level of Cu-catalyst to a few ppm with preserved control.³ ATRP of (meth)acrylates, styrenes, acrylamides, acrylonitrile and other vinyl monomers provides polymers with low polydispersities and molecular weights in a range 200>Mn>20,000,000. Polymers can be formed quantitatively in bulk, in solution and in emulsions. Block, graft, star, hyperbranched, gradient and periodic copolymers as well as molecular brushes have been prepared.² The (co)polymers made by ATRP have many potential applications as components of coatings, elastomers, adhesives, surfactants, dispersants, lubricants, additives, but also as specialty materials in biomedical and electronic areas and will affect the market of ~$20 billion/year.⁴ Examples of design, synthesis, characterization and applications of nanostructured multicomponent polymeric materials enabled by various CRPs will be presented.

(1) Matyjaszewski, K., Davis, T. P., Eds. Handbook of Radical Polymerization; Wiley, Hoboken 2002;

(2) Wang, J. S., Matyjaszewski, K. J. Am. Chem. Soc. 1995, 117, 5614; Matyjaszewski, K., Xia, J. Chem. Rev. 2001, 101, 2921; Matyjaszewski, K. et al. US 5,763,548; US 5,789,487; US 5,807,937; US 5,945,491; (3) Matyjaszewski, K. et al. Proc. Nat. Acad. Sci. 2006, 103, 15309; Angew. Chem. 2006, 45, 4482; J. Am. Chem. Soc. 2006, 128, 10521; (4) Matyjaszewski, K.; Spanswick, J., Materials Today 2005, 8, 26; Matyjaszewski, K.; Gnanou, Y.; Leibler, L., Macromolecular Engineering, Wiley-VCH, Weinheim 2007

Two case studies will be presented. The first case will describe the development of a process to remove residual Pd from a pharmaceutical product utilizing adsorbent kit screening. The second case will describe the rapid development of a process to remove blue color from a pharmaceutical intermediate.

We thank the US National Science Foundation for its support of this research and the Fulbright Foundation for a Visiting Researcher Fellowship to A. A. S.

[1] J. L. Jamison, L. Davenport, B. W. Williams, Chem. Phys. Lett. 422 (2006) 30-35.

We herein describe a novel fragment-based approach that is based on the interplay of structural target information, docking and very efficient multicomponent reaction chemistry (MCR). Potential advantages are the following:

� public available structural target data (pdb) can be used - thus there is no need for expensive and/or advanced techniques & instrumentations;

� a very large chemical space based on hundreds of relevant scaffolds is screened � thus the chances of discovery of expandable hits is greatly enhanced;

� due to the efficient chemistry used (MCR), there is a high ratio of success to effort;

� the discovery of multiple target interacting compound classes allows for their parallel optimization, thus greatly enhancing the chance to develop compounds with excellent PKPD properties.

As a validation of our new drug discovery approach we present the parallel discovery of several potent scaffold classes of selective and dual active p53/mdm2/mdm4 antagonists with potential applications in cancer.

This lecture deals with the synthesis and purification of [-fcB(Mes)-]_n and [-fcB(bipy)-]_nⁿ⁺ and with an investigation of their physical properties ((spectro)electrochemistry, femtosecond laser spectroscopy).

More specifically, the data generated was used to characterize the effects of a polymeric substance that varied in molecular weight and degree of ethoxylation. Examination of concentration dependence and comparison to appropriate controls in the experimental design enabled selection of the appropriate polymeric substance to be incorporated into a sunscreen emulsion composition that provided the highest SPF value. The ethoxylated polymeric materials had no inherent UV absorbing capability and had no affect on particle size at the low concentration levels in this investigation. Yet, not only did these ethoxylated polymeric substances increase the efficiency of the sunscreen filter system, one of the polymeric substances behaved in a synergistic manner causing a significant increase in the In-Vitro SPF.

Our primary goals in this investigation are two fold, to measure the relative abundance of multiple PAH: CD inclusion complexes retained during the ESI process and generate an index of PAH inclusion complexes. This will provide comparative information about PAH inclusion processes. Our secondary goal is to determine the binding energies between the PAH:CD complex via ESI-MS titration and molecular modeling to gain a more comprehensive understanding of how PAHs bind to particulate matter in the gaseous phase.

The PAHs examined include Pyrene, Chrysene, Benzo(alpha) Pyrene, Phenanthracene and Antracene. In addition Alpha, Beta and Gamma cyclocodextrin will all be tested as potential complexing hosts for the PAHs. The instrumentation utilized is a Thermo LTQ Obitrap with nano esi capability and system optimization preformed using PAH.

Conjugated molecules investigated here are polyfluorenes, polythiophenes and oligomers of platinum-acetylides. In some cases the molecules incorporate traps for electrons or holes, usually positioned at the ends of the chains.

These are remarkable materials have properties we are only beginning to understand and potential we are only beginning to tap.

A new method has been developed utilizing Carona Charged Aerosol (CAD-PLUS) detection, whereby molecules with and without chromophores can be assessed and tracked in both synthetic and animal-derived lung surfactants via charged nebulization of the sample with nitrogen flow, capable of assessing four actives and related impurities in Lucinactant (SURFAXIN�; Discovery Laboratories, Inc., Warrington PA), a precision-engineered synthetic lung surfactant.

Method

Analytics utilizing HPLC-CAD (Charged Aerosol Detection) has been developed to assess product impurity profiles in various pulmonary surfactant formulations, both synthetic and animal-derived.

Results

Employ of HPLC-CAD analysis provides a means for impurity profiling and analytic assessment, with concomitant laboratory efficacy benefits, of a new synthetic pulmonary surfactant (Surfaxin�) versus currently marketed animal-derived surfactants. This analytical platform allows for all lipid-related impurities to be tracked and targeted with respect to their active parent compounds. One method of analysis was able to be developed using CAD detection, whereas prior several methods had to be employed, as some compounds lacked chromophores. Increased specificity and sensitivity was achieved using HPLC-CAD. Mass Spectrometry was conducted to support compound identification and method specificity.

Conclusion

The application of HPLC-CAD analytics allowed for the development of one method capable of monitoring four actives (R2 ≥ 0.99) and six known impurities (R2 ≥ 0.98) within SURFAXIN� drug product. Use of this new method also provides a means of assessing and comparing impurity profiles between synthetic surfactant drug product versus that exhibited by current marketed animal-derived surfactant drug product.

In general, baseload coal-fired units, many of which lack adequate NOx control technology are ramped up as load increases. Also as load increases, intermittently used residual oil-burning load-following boilers are deployed. As electric supply must always equal demand, intraday hourly peaks are generally met by generation from high NOx -emitting quick starting combustion turbines.

These phenomena are illustrated through comparison of operating profiles on an average day in June 2005 and the then record demand day of July 26, 2005, which also saw numerous ozone standard violations throughout the region. While peak hourly generation on the PJM power grid mid-Atlantic sector on the two days was 31,162 MW and 58,509 MW, respectively, NOx emissions from �peaking� EGUs in the 6-state Maryland-Connecticut region increased 145% from 492 to 1,202 tons, with a rate increase of 41% from 1.50 lbs NOx / MWh to 2.11 NOx / MWh.

Many of these high-emitting units have been in service since the 1970's and even earlier. While lower emitting units of more modern vintage also are deployed in response to rising demand, their contributions to elevated NOx emissions are miniscule.

We conclude that sensitive structural and dynamic probes such as resonance Raman (RR) spectroscopy guided by calculations could become an essential tool for understanding lead poisoning mechanisms. Simulations of RR spectra of cysteine-rich lead domains indicate that a specific structure and coordination mode of lead might be detectable by RR spectroscopy. We predict that when the excitation wavelength is in resonance with UV lead bands, the enhancement of vibrational modes is found for Pb-S stretching and bending modes and also for characteristic C-S stretching and CH2 bending modes of cysteine. More importantly, computed RR intensities for lead domains show unique patterns and might be successfully applied to identify and/or monitor structure and coordination of lead in poisoned proteins.

Abstract:

A case study is presented illustrating how preparative chromatography is used in support of preclinical development projects. Delivery of preclinical candidates in multikilogram quantities is expedited through the implementation of flash chromatography, HPLC, and SFC for chiral and achiral intermediates and preclinical candidates.

Examples of approaches to method development, column loading studies and injection techniques in conjunction with separation and synthesis strategies will be presented.

We applied ODP2 HP column for drug molecule analysis in BSA and control serum by column-switching experiment in a LCMS system. We obtained good recovery rate of 88 to 112% with a wide variety of small molecules.

The packing material is polyhydroxymethacrylate gel with controlled surface hydrophilicity and pore distribution. The operational pH range is 3 to 10, and the temperature range is 5 to 70 oC. Water soluble organic solvents such as methanol, acetonitrile and DMF can be used.

SB400 series are available with 4 different exclusion limits ranging from 1,000, to 1,000,000. Specifically, the SB401-4E column with the lowest exclusion limit (1,000) is completely new, and not available in the SB-800 series.

We will introduce basic features of SB400 series and their applications in cationic, anionic, and non-ionic polymers.

Here we report the synthesis of new Arene-Ru-Chloroquine complexes and their characterization by NMR techniques and DFT calculations. The new complexes are heme aggregation inhibitors, and intercalate in DNA. Preliminary results indicate antimalarial activity and the main mechanism of action is most likely related to the heme aggregation inhibition activity and the lipophilicity of the metal complexes.

Nanorobotics is a key area of application. PX DNA has been used to produce a robust 2-state sequence-dependent device that changes states by varied hybridization topology. We have used this device to make a translational device that prototypes the simplest features of the ribosome. A protein-activated device that can be used to measure the ability of the protein to do work, and a bipedal walker have both been built. We have also built a robust 3-state device.

A central goal of DNA nanotechnology is the self-assembly of periodic matter. We have constructed 2-dimensional DNA arrays from many different motifs. We can produce specific designed patterns visible in the AFM. We can change the patterns by changing the components, and by modification after assembly. Recently, we have used DNA scaffolding to organize active DNA components, as well as other materials. Active DNA components include DNAzymes and DNA nanomechanical devices; both are active when incorporated in 2D DNA lattices.

We thank the National Science Foundation for its support of this research and Prof. Dan Blair for the use of his rheometer.

This study, designed to assess natural sources of perchlorate, considered collecting samples from a remote area, with no exposure to manufactured perchlorate. High Arctic ice caps receive contaminants solely from atmospheric sources, which allow determining the annual flux of perchlorate received through precipitation. Depth samples, dating between 1996 and 2005, were collected from Devon Island, Nunavut, Canada, in the spring of 2006. A direct injection, optimized ion chromatography-tandem mass spectrometry (IC-MSMS) method allowed detection of perchlorate in all samples. Concentrations were in low ng/L range and showed seasonality. This represents the first temporal trend reported for perchlorate in precipitation. The same samples were previously analyzed for perfluorinated acids, evidencing their atmospheric formation [1].

[1]. CI Young, VI Furdui, J Franklin, RM Koerner, DCG Muir, SA Mabury Perfluorinated Acids in Arctic Snow: New Evidence for Atmospheric Formation, 2007, Environ Sci Technol, 41, 3455-3461.

However, we found that only in-situ polymerized conducting polymers were able to effectively interlink the SWNTs to form a highly conductive network. The pre-formed conducting polymer dramatically decreased the conductivity and increased the percolation threshold of the SWNT networks. Surprisingly, the conducting polymer formed by in-situ polymerization with pre-oxidized SWNTs (�seed� method) did not assemble the nanotubes into a conductive network either. Instead, the polymer induced severe aggregation of the nanotubes into large particles. Consequently, the percolation threshold of the composite formed by the seed approach is much higher and the conductance after the percolation threshold is three orders of magnitude lower than the network formed by SWNTs alone. Various techniques were applied to understand the mechanism for the different enhancement in nano and molecular scales.

We have developed a new class of inorganic-organic hybrid nanostructured semiconductors that possess broad band gap tunability and high absorption coefficients desirable for opto-electronic applications, such as photovoltaics and solid state lighting. They exhibit both enhanced semiconductor properties and strong quantum confinement effect similar to the smallest NCs. Here we present a unique approach of generating direct white light from a single semiconductor bulk material, 2D-Cd2S2(ba)](ba=butylamine) based double layer structure. Luminescence properties of this hybrid semiconductor can be tuned systematically by changing its composition and doping level.

[1] Solid state Lighting http://lighting.sandia.gov/

[2] A.H. Mueller et al., Nano Lett., 5, 1039 (2005)

Herein, we explore the use of an oligomeric peptoid as a scaffold for the incorporation of chiral side chains and an achiral nitroxyl moiety for applications in biooganic chemistry.

In another effort, modification of sodium montmorillonite a cationic clay, has been carried out with pyridinium and imidazolium-based ionic liquids. Our data show an overall increase in interlamellar spacing and improved thermal stability as compared to commercial nanoclays modified with long chain quaternary ammonium salts. This is due to Na+ exchange with cations of the ionic liquids. Utility of the modified montmorillonites has been tested in the preparation of polypropylene nanocomposites. This approach is effective in preparation of biomaterials for the delivery of important therapeutics, illustrated here with representative examples.

Acknowledgment:

Funded by NCI Contract N01-CO-12400

We also present a novel process employing a uniform electric field to control the morphology of polymer synthesized at the interface between an organic liquid and an immiscible IL. SEM and SANS data showed the morphology and microstructure of polymer varied with the intensity and the angle of the external field, which induced excess ions, changed the molecular orientations and thermal fluctuations at the interface, and affected the coarsening and aggregation of the polymeric precipitates. From a general perspective, this work imparted a new concept that may be applicable to non-charge transfer liquid-ionic liquid processes enhanced by external electric fields.

Some general traits of mass spectrometric phosphopeptide ion behavior are already characterized, but this investigation aims for a more detailed and sequence-specific understanding of these behaviors. For example, it is known that serine/threonine-phosphorylated, and some tyrosine-phosphorylated) peptide ions often undergo the neutral loss of the elements H3PO4 upon collisionally induced dissociation (CID) MS2. While this neutral loss can be diagnostic of the presence of a phosphorylated species, it can (if it dominates the spectrum) result in the absence of other structural data. The degree to which neutral loss occurs likely depends on chemistry that occurs proximal to the phosphate group. Results have been obtained thus far on a series of serine-phosphorylated tripeptides with the N-terminal residue varied. Differences in energy required for fragmentation are correlated with the chemical nature of the side chain of the N-terminal amino acid.

Controlled architectures (e.g. block copolymers) are available through living polymerization processes, including a remarkable recently developed photocontrolled method. This talk will focus on recent efforts to use these metallopolymers to create, for example, photonic devices, and self-assembled supramolecular structures, which can be used in nanolithographic applications and catalysis.

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Rider and I. Manners: Nature Materials 2006, 5, 467.

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