Chemistry Commons^™

Synthesis Of Orthogonally Protected Azalanthionines (Lanazanines) By Sequential Ring-Opening Of N-Substituted Aziridine 2-Carboxylates, Keith O'Brien, Keith Ó Proinsias, Fintan Kelleher

Articles

Orthogonally protected azalanthionines (lanazanines, 4-azadiaminopimelic acids or b-aminoalaninoalanines) have been synthesised in good yields by the ring-opening of N-protected aziridine 2-carboxylates with suitably protected diaminopropanoic acids (DAPs). The required DAPs were also synthesised by ring-opening of N-protected aziridine 2-carboxylates with para-methoxybenzylamine.

Chemical Analysis Of Ophthalmic Solutions, Pagagiotis Tavlarakis

Seton Hall University Dissertations and Theses (ETDs)

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Probing The Bifunctional Catalytic Activity Of Ceria Nanorods Towards The Cyanosilylation Reaction, Gonghua Wang, Lu Wang, Xiang Fei, Yunyun Zhou, Renat F. Sabirianov, Wai-Ning Mei, Chin Li Cheung

Department of Chemistry: Faculty Publications

Ceria nanorods were demonstrated to be an active, bifunctional catalyst for the cyanosilylation of aldehydes. The catalytic activity of ceria was shown to be positively correlated with a decrease in the coordination numbers of neighbouring oxygen atoms around cerium atoms in the catalyst. Chemisorption and density functional theory studies suggested that the coordinatively unsaturated cerium sites exposed by the surface oxygen vacancy defects functioned as Lewis acid sites and the neighbouring oxygen atoms behaved as Lewis base sites in the catalytic cycle.

An Expanded Genetic Code In Mammalian Cells With A Functional Quadruplet Codon, Wei Niu, Peter G. Schultz, Jiantao Guo

Department of Chemistry: Faculty Publications

We have utilized in vitro evolution to identify tRNA variants with significantly enhanced activity for the incorporation of unnatural amino acids into proteins in response to a quadruplet codon in both bacterial and mammalian cells. This approach will facilitate the creation of an optimized and standardized system for the genetic incorporation of unnatural amino acids using quadruplet codons, which will allow the biosynthesis of biopolymers that contain multiple unnatural building blocks.

Porous Polymer Coatings As Substrates For The Formation Of High-Fidelity Micropatterns By Quill-Like Pens, Michael Hirtz, Marcus Lyon, Wenqian Feng, Andrea E. Holmes, Harald Fuchs, Pavel A. Levkin

Department of Chemistry: Faculty Publications

We explored the potentials of microarray printing using quill-like microcantilevers onto solid supports that are typically used in microspot printing, including paper, polymeric nitrocellulose and nylon membranes. We compared these membranes with a novel porous poly(2-hydroxyethyl methacrylate-co-ethylene dimethacrylate) support (HEMA) with narrow pore size distribution in the 150 nm range, which demonstrated advantages in pattern definition, spot homogeneity, and consistent spot delivery of different dyes (phloxine B and bromophenol blue) with diameters of several micrometres. The bromophenol blue arrays on HEMA support were used to detect the presence of bovine serum albumin (BSA). In the presence of BSA, …

Single Transcriptional And Translational Preq1 Riboswitches Adopt Similar Pre-Folded Ensembles That Follow Distinct Folding Pathways Into The Same Ligand-Bound Structure, Krishna C. Suddala, Arlie J. Rinaldi, Jun Feng, Anthony M. Mustoe, Catherine D. Eichhorn, Joseph A. Liberman, Joseph E. Wedekind, Hashim M. Al-Hashimi, Charles L. Brooks Iii, Nils G. Walter

Department of Chemistry: Faculty Publications

Riboswitches are structural elements in the 50 untranslated regions of many bacterial messenger RNAs that regulate gene expression in response to changing metabolite concentrations by inhibition of either transcription or translation initiation. The preQ₁ (7-aminomethyl-7-deazaguanine) riboswitch family comprises some of the smallest metabolite sensing RNAs found in nature. Once ligand-bound, the transcriptional Bacillus subtilis and translational Thermoanaerobacter tengcongensis preQ₁ riboswitch aptamers are structurally similar RNA pseudoknots; yet, prior structural studies have characterized their ligand-free conformations as largely unfolded and folded, respectively. In contrast, through single molecule observation, we now show that, at nearphysiological Mg²⁺ concentration and pH, …

Iodonium Cyclophanes For Secure Arene Functionalization, Stephen Dimagno

Department of Chemistry: Faculty Publications

This disclosure relates to compounds, reagents, and methods useful in the synthesis of aryl fluorides, for example, in the preparation of 18F labeled radiotracers. For example, this disclosure provides universal “locked” aryl substituents that result in StereoElectronic Control of Unidirectional Reductive Elimination (SECURE) from diaryliodonium salts. The reagents and methods provided herein may be used to access a broad range of compounds, including aromatic compounds, heteroaromatic compounds, amino acids, nucleotides, and synthetic compounds.

Development Of Affinity Microcolumns For Drug–Protein Binding Studies In Personalized Medicine: Interactions Of Sulfonylurea Drugs With In Vivo Glycated Human Serum Albumin, Jeanethe Anguizola, K. S. Joseph, Omar S. Barnaby, Ryan Matsuda, Guadalupe Alvarado, William Clarke, Ronald Cerny, David S. Hage

David Hage Publications

This report used high-performance affinity microcolumns to examine the changes in binding by sulfonylurea drugs to in vivo glycated HSA that had been isolated from individual patients with diabetes. An immunoextraction approach was developed to isolate HSA and glycated HSA from clinical samples, using only 20 μL of plasma or serum and 6–12 nmol of protein to prepare each affinity microcolumn. It was found that the affinity microcolumns could be used in either frontal analysis or zonal elution studies, which typically required only 4–8 min per run. The microcolumns had good stability and allowed data to be obtained for multiple …

Aqueous Red-Emitting Silicon Nanoparticles For Cellular Imaging: Consequences Of Protecting Against Surface Passivation By Hydroxide And Water For Stable Red Emission, Sheng-Kuei Chiu, Beth Ann Manhat, William J.I. Debenedetti, Anna L. Brown, Katye Fichter, Tania Vu, Micah Eastman, Jun Jiao, Andrea Mitchell Goforth

Chemistry Faculty Publications and Presentations

Stable, aqueous, red-to-near infrared emission is critical for the use of silicon nanoparticles (Si NPs) in biological fluorescence assays, but such Si NPs have been difficult to attain. We report a synthesis and surface modification strategy that protects Si NPs and preserves red photoluminescence (PL) in water for more than 6 mo. The Si NPs were synthesized via high temperature reaction, liberated from an oxide matrix, and functionalized via hydrosilylation to yield hydrophobic particles. The hydrophobic Si NPs were phase transferred to water using the surfactant cetyltrimethylammonium bromide (CTAB) with retention of red PL. CTAB apparently serves a double role …

Frozen Rotor Approximation In The Mixed Quantum/Classical Theory For Collisional Energy Transfer: Application To Ozone Stabilization, Alexander Teplukhin, Mikhail V. Ivanov, Dmitri Babikov

Chemistry Faculty Research and Publications

A frozen-rotor approximation is formulated for the mixed quantum/classical theory of collisional energy transfer and ro-vibrational energy flow [M. Ivanov and D. Babikov, J. Chem. Phys.134, 144107 (Year: 2011)]. Numerical tests are conducted to assess its efficiency and accuracy, compared to the original version of the method, where rotation of the molecule in space is treated explicitly and adiabatically. New approach is considerably faster and helps blocking the artificial ro-vibrational transitions at the pre- and post-collisional stages of the process. Although molecular orientation in space is fixed, the energy exchange between rotational, vibrational, and translational digresses of freedom still occurs, …

Molecular-Level Investigations Combining Nanoscale Lithography And Atomic Force Microscopy, Chamarra Karmelia Saner

LSU Doctoral Dissertations

In this dissertation, nanostructures of octadecyltrichlorosilane (OTS) and were prepared using particle lithography and evaluated using characterizations with atomic force microscopy (AFM). The nanostructures of OTS were used as a resist for patterning fibronectin, an extracellular matrix protein. Particle lithography provides a practical and reproducible approach to generate billions of nanostructures comprised of organic thin films or nanomaterials. A film of mesospheres can be applied as a surface mask to define the periodicity and size of nanopatterns using processes of self-assembly. A close-packed arrangement of mesospheres is produced spontaneously when monodisperse solutions of latex or silica are dried on a …

Molecular Docking And Nmr Binding Studies To Identify Novel Inhibitors Of Human Phosphomevalonate Kinase, Pornthip Boonsri, Terrence S. Neumann, Andrew Lawrence Olson, Sheng Cai, Timothy J. Herdendorf, Henry M. Miziorko, Supa Hannongbua, Daniel S. Sem

Chemistry Faculty Research and Publications

Phosphomevalonate kinase (PMK) phosphorylates mevalonate-5-phosphate (M5P) in the mevalonate pathway, which is the sole source of isoprenoids and steroids in humans. We have identified new PMK inhibitors with virtual screening, using autodock. Promising hits were verified and their affinity measured using NMR-based ¹H–¹⁵N heteronuclear single quantum coherence (HSQC) chemical shift perturbation and fluorescence titrations. Chemical shift changes were monitored, plotted, and fitted to obtain dissociation constants (K_d). Tight binding compounds with K_d’s ranging from 6–60 μM were identified. These compounds tended to have significant polarity and negative charge, similar to the natural …

Study Of The Reaction Of Nitriles With Dialkyl Phosphites For Synthesis Of A-Amino-Bis-Phosphonates, Prasanna Vanja

Master's Theses and Doctoral Dissertations

Amino bisphosphonate compounds are found in a vast array of products from water chelators to flame retardants to pharmaceuticals. Previous methods to synthesize these compounds involved the use of protic acids, which don’t provide ideal conditions for the starting materials containing acid labile functional groups in pharmaceutical compounds. The present study adopts a new synthetic route in which diethyl phosphite addition to the nitrile would be effected in the presence of a Lewis acid catalyst. This study utilized lanthanum trifluoromethane sulfonate as the Lewis acid catalyst, facilitating the addition of the P-H bond across the nitrile triple bond. Product purification …

Periplasmic Binding Proteins In Thermophiles: Characterization And Potential Application Of An Arginine-Binding Protein From Thermotoga Maritima: A Brief Thermo-Story, Alessio Ausili, Maria Staiano, Jonathan D. Dattelbaum, Antonio Varriale, Alessandro Capo, Sabato D'Auria

Chemistry Faculty Publications

Arginine-binding protein from the extremophile Thermotoga maritima is a 27.7 kDa protein possessing the typical two-domain structure of the periplasmic binding proteins family. The protein is characterized by a very high specificity and affinity to bind to arginine, also at high temperatures. Due to its features, this protein could be taken into account as a potential candidate for the design of a biosensor for arginine. It is important to investigate the stability of proteins when they are used for biotechnological applications. In this article, we review the structural and functional features of an arginine-binding protein from the extremophile Thermotoga maritima …

Structurally Diverse Hamigerans From The New Zealand Marine Sponge Hamigera Tarangaensis: Nmr-Directed Isolation, Structure Elucidation And Antifungal Activity, A. Jonathan Singh, Jonathan D. Dattelbaum, Jessica J. Field, Zlatka Smart, Ethan F. Woolly, Jacqueline M. Barber, Rosemary Heathcott, John H. Miller, Peter T. Northcote

Chemistry Faculty Publications

The NMR-directed investigation of the New Zealand marine sponge Hamigera tarangaensis has afforded ten new compounds of the hamigeran family, and a new 13-epi-verrucosane congener. Notably, hamigeran F (6) possesses an unusual carbon–carbon bond between C-12 and C-13, creating an unprecedented skeleton within this class. In particular, the structural features of 6, hamigeran H (10) and hamigeran J (12) imply a diterpenoid origin, which has allowed the putative biogenesis of three hamigeran carbon skeletons to be proposed based on geranyl geranyl pyrophosphate. All new hamigerans exhibited micromolar activity towards the HL-60 …

Theoretical Design Of Stable Small Aluminium-Magnesium Binary Clusters, Edison Osorio, Alejandro Vasquez, Elizabeth Florez, Fanor Mondragon, Kelling J. Donald, William Tiznado

Chemistry Faculty Publications

We explore in detail the potential energy surfaces of the Al_xMg_y (x, y = 1–4) systems as case studies to test the utility and limitations of simple rules based on electron counts and the phenomenological shell model (PSM) for bimetallic clusters. We find that it is feasible to design stable structures that are members of this set of small Al–Mg binary clusters, using simple electron count rules, including the classical 4n + 2 Hückel model, and the most recently proposed PSM. The thermodynamic stability of the title compounds has been evaluated using several different descriptors, including …

Evaluation Of Single Electron Transfer Reduction Products Of 3-Oxoindoles As Antibacterial Agents, Debasish Bandyopadhyay, Irani Biswas, Subrata Laskar, Bidyut Basak

School of Integrative Biological & Chemical Sciences (Formerly Dept. of Chemistry)

Objective: The objective of the present study is to assess the antibacterial properties of six indole derivatives viz, 3-(Naphth-1-y - methyl) –indole (II), 3-(1-Naphthylcarbonyl – indole (III), 3,3' –diformyl-2,2' –bis indole (IV), 1,4- (3,3' –di indolyl) – 1,4-dioxobutane (V), 3-benzoyl indole (VI) and 1,1 – bis – (3-indolyl)- ethane (VII) synthesized by single electron transfer reduction of 3-formylindole (I) against two Gram +ve and two Gram –ve bacteria which usually cause human infections.

Methods: Synthesis of 3-formyl indole from which the indole derivatives were prepared were further characterized by IR and NMR analysis. The six synthesized compounds were screened for …

Isocyanate-Derived Organic Aerogels: Polyurethanes, Polyureas, Polyamides And Polyimides, Chakkaravarthy Chidambareswarapattar

Doctoral Dissertations

"Aerogels are 3D assemblies of nanoparticles with high open porosity and high surface area, and are pursued for their low density, low thermal conductivity, low dielectric constant and high acoustic attenuation. The foundation for those exceptional properties is their complex hierarchical solid framework (agglomerates of porous, fractal secondary nanoparticles). On the down side, however, aerogels are also fragile materials. The mechanical strength of silica aerogels has been improved by crosslinking the framework with organic polymers. The crosslinking polymer has been assumed to form a conformal coating on the surface of the skeletal framework bridging covalently the elementary building blocks. However, …

Intercalation And Delamination Of Layered Carbides And Carbonitrides, Olha Mashtalir, Michael Naguib, Vadym Mochalin, Yohan Dall'agnese, Min Heon, Michel W. Barsoum, Yury G. Gogotsi

Chemistry Faculty Research & Creative Works

Intercalation and delamination of two-dimensional solids in many cases is a requisite step for exploiting their unique properties. Herein we report on the intercalation of two-dimensional Ti₃C₂, Ti₃ CN and TiNbC - so called MXenes. Intercalation of hydrazine, and its co-intercalation with N,N-dimethylformamide, resulted in increases of the c-lattice parameters of surface functionalized f-Ti₃C₂, from 19.5 to 25.48 and 26.8 Å, respectively. Urea is also intercalated into f-Ti₃C₂. Molecular dynamics simulations suggest that a hydrazine monolayer intercalates between f-Ti₃C₂ layers. Hydrazine is also intercalated …

Luminescent Laf₃:Ce-Doped Organically Modified Nanoporous Silica Xerogels, Mingzhen Yao, Ryan Hall, Wei Chen, Dhairyashil Mohite, Nicholas Leventis, N. Lu, J. Wang, M. J. Kim, H. Luo, Hongbing Lu

Chemistry Faculty Research & Creative Works

Organically modified silica compounds (ORMOSILs) were synthesized by a sol-gel method from amine-functionalized 3-aminopropyl triethoxylsilane and tetramethylorthosilicate and were doped in situ with LaF₃:Ce nanoparticles, which in turn were prepared either in water or in ethanol. Doped ORMOSILs display strong photoluminescence either by UV or X-ray excitation and maintain good transparency up to a loading level of 15.66% w/w. The TEM observations demonstrate that ORMOSILs remain nanoporous with pore diameters in the 5-10 nm range. LaF₃:Ce nanoparticles doped into the ORMOSILs are rod-like, 5 nm in diameter and 10-15 nm in length. Compression testing indicates that …

The Cloning And Expression Of Histone Genes From The Archaeal Organisms Pyrococcus Furiosus And Methanobrevibacter Smithii In The Polycistronic Vector Pst44., Doha Abdullah Alqurashi

Electronic Theses & Dissertations

The Euryarcheota branch of the Archaea contains histone proteins that are highly homologous to eukaryotic histones. Virtually all species within this group have two histone proteins (designated H1A and H2B). These proteins contain a canonical histone fold motif that stabilizes homo- and perhaps hetero-dimeric interactions. Molecular modeling calculations previously carried out in our laboratory revealed that both homo and hetero-dimers of histones from two euryarchaeal organisms are equally plausible. We have also shown through molecular modeling that inter-species hetero-dimers are structurally identical to existing solution structures archaeal histones. An interesting question that needs to be addressed is whether homo- and …

Air-Sea Dimethylsulfide (Dms) Gas Transfer In The North Atlantic: Evidence For Limited Interfacial Gas Exchange At High Wind Speed, T. G. Bell, Warren J. De Bruyn, S. D. Miller, B. Ward, K. Christensen, E. S. Saltzman

Biology, Chemistry, and Environmental Sciences Faculty Articles and Research

Shipboard measurements of eddy covariance dimethylsulfide (DMS) air-sea fluxes and seawater concentration were carried out in the North Atlantic bloom region in June/July 2011. Gas transfer coefficients (k(660)) show a linear dependence on mean horizontal wind speed at wind speeds up to 11 m s(-1). At higher wind speeds the relationship between k(660) and wind speed weakens. At high winds, measured DMS fluxes were lower than predicted based on the linear relationship between wind speed and interfacial stress extrapolated from low to intermediate wind speeds. In contrast, the transfer coefficient for sensible heat did not exhibit this effect. The apparent …

Liquid Sorption Properties And Structural Changes Of Metal-Organic Frameworks Of Cobalt Nitrate And 4,4'-Bipyridine, Kathryn Mauger-Sonnek

Dissertations and Theses @ UNI

Metal-organic frameworks consist of metal ions connected by organic ligands. When the metal ions and organic ligands link together in the right geometry, polymeric and infinite 1D chains or 2D and 3D networks are formed. Porous metal-organic frameworks were synthesized from the organic ligand 4,4′-bipyridine (bpy) and cobalt(II) nitrate. The metal-organic frameworks synthesized in this study grew into both a previously known 2D bilayer structure, [Co2(bpy)3(NO3)4]n, and a new, orange 1D chain structure, [Co(bpy)NO3)2(H2O)2]n, within ethanol. It was found that the presence of water was the main factor of causing formation of the orange 1D chain crystals. Drying the orange …

Decoration Of Graphene With Metal Nanoparticles And Its Application For Bioanalysis, Keun Soo Kwon

Theses, Dissertations and Culminating Projects

Graphene is a two-dimensional monolayer of tightly packed sp² hybridized Carbon atoms. Formed from graphite, the theoretical surface area of the monolayer is about 2630 m²/g, and the initial formation of graphene oxide from graphite oxide introduces a variety o f functional groups, such as -COOH, -C=0, and -OH, on its surface. The high surface area and the rich presence of functional groups, along with the potential formation o f sp² bonding networks within graphene oxide, all serve as critical factors allowing for additional chemical modifications. There are extensive research attempts being performed to explore and …

Analysis And Simulation Of Kinetic Model For Active Suspensions, Panon Phuworawong

Mathematics & Statistics Theses & Dissertations

In this research, we study the recently proposed kinetic model for active suspensions, where the active particles are assumed to be rigid rod and are driven in the suspension either by their own biological/chemical forces or external electric/magnetic fields. We first study the stability of the isotropic suspension in quiescent flow. Then we investigate the weak shear perturbation of the isotropic state and study some rheological properties of the suspension by explicit analytic formulas derived directly from the model. For imposed shear, we give some bifurcation diagrams of the stable states in some parametric spaces through numerical simulations. Some rheological …

Interaction Of Ceo2 And Zno Nanoparticles Towards The Symbiotic Association Of Alfalfa (Medicago Sativa) And Sinorhizobium Meliloti In Soil, Susmita Bandyopadhyay

Open Access Theses & Dissertations

The production of engineered nanoparticles (ENPs) has rapidly increased due to their wide range of applications in the field of electronics, medicine, chemistry and biology. Consequently, concerns have risen about the environmental release and potential negative impact of NPs. A few reports have described the effects of TiO2 NPs and quantum dots upon nitrogen fixing bacteria. However, the understanding of the interaction of NPs in plant-microbe interface (symbiotic association), like alfalfa (Medicago sativa L.)-Sinorhizobium meliloti, is still in its infancy. Alfalfa is the world's most important forage crop. It grows in association with S. meliloti, which is very important in …

Preparation Of Cobalt/Nickel Molybdenum Sulfide Catalysts Supported By Aqueous Media Soluble Multi-Wall Carbon Nanotubes., Hassan Ahmad Bleibel

Open Access Theses & Dissertations

Multi-walled carbon nanotubes (MWCNTs) have been subjected to chemical treatment in order to introduce hydrophilic functional groups on their surfaces. These covalently bonded groups did enhance the solubility of MWCNTs in aqueous media as expected. Functionalized MWCNTs were characterized using FTIR, Raman spectroscopy, TGA, X-ray diffraction, dispersion test and TEM. Then, functionalized MWCNTs were incorporated in the hydrothermal synthesis method of transition metal sulfide catalysts (CoMo, NiMo, and Ethylenediamine-CoMo Sulfides). Catalysts were characterized using X-ray diffraction, TEM, SEM, N2 Gas adsorption-desorption, elemental analysis, and Hydrodesulfurization (HDS) reaction of dibenzothiophene (DBT). The objective was to study the functionalized MWCNTs' effect; being …

Method Development For A Chemical And Biological Analysis Of Glucocorticoids In Wastewater, Maria Carmen Lozano

Open Access Theses & Dissertations

Glucocorticoids are a class of steroid hormones that can either be produced synthetically or naturally by the adrenal glands. The synthetic glucocorticoids are highly prescribed in the United States for their anti-inflammatory and immunosuppressive properties to treat a variety of ailments and diseases; however, these have been implicated in a number of adverse human conditions such as obesity, metabolic syndrome, immune-suppression, delayed puberty, adrenal insufficiency and Cushing Syndrome, among others. Ongoing research has shown that synthetic and natural hormones are transported to aquatic environments via mammalian excretion or wastewater effluent, and as a result, the release of glucocorticoids into the …

Purification Of Sodium Sulfate By Crystallization, Perla Teresita Torres

Open Access Theses & Dissertations

Sodium sulfate can be recovered from a dilute solution by concentrating it by conventional water treatment techniques like reverse osmosis and electrodialysis; however, those processes also concentrate impurities like arsenic. The sodium sulfate would have commercial use if it can be recovered in an arsenic-free form. This study demonstrated that sodium sulfate could be separated from impurities using slow cooling crystallization in a novel apparatus developed and designed during the experimentation. This device is called a heat exchanger crystallizer and allows slow cooling crystallization in order to grow pure crystals of sodium sulfate decahydrate. Crystals grown in the heat exchanger …

Complexity-Driven Properties Of The Intermetallic Compounds Gd₁₁₇Co₅₆Sn₁₁₂ And Ln₃₀Ru₄Sn₃₁ (Ln = Gd And Tb), Devin Charles Schmitt

LSU Doctoral Dissertations

Understanding the relationships between the structure of materials and their properties in extended solid systems is a necessity when intuitively designing functional materials. One of the most fundamental properties of a material is its ability to transport heat, which is linked to the lattice complexity of the material. Here, the single crystalline materials Gd117Co56Sn112 and Tb30Ru4Sn31 are grown to study the pronounced effect of a complexity-driven reduction of lattice thermal conductivity. The transport and magnetic properties of Gd117Co56Sn112 and Ln30Ru4Sn31 (Ln = Gd and Tb) are also presented and related to other systems. Tb30Ru4Sn31 is found to be a large …