Physical Sciences and Mathematics Commons^™

Electrochemistry Of Glucose Oxidase Modified On Porin-Phospholipid Biomimic Membrane, Kun-Qi Wang, Zuo-Ming Zhang, Wei Xing, Chang-Peng Liu, Xing Zhou

Journal of Electrochemistry

Biomimic membrane with nano-channels, which is made up of porin MspA and 1,2-Dimyristoyl-sn-glycero-3-phosphocholine (DMPC) is constructed on glassy carbon substrate, and glucose oxidase (GOD) is modified on it. The direct electrochemical reaction and electrocatalytic behavior to oxygen and glucose of GOD on the GOD/MspA-DMPC/GC electreode are expounded by the cyclic voltammetric method. The study shows that GOD immobilized on porin MspA and DMPC biomimic membrane displays direct and surface-controlled electrochemical reaction nearby formal potential (E0′) of the flavoprotein active centre (FAD/FADH), and the electrochemical reaction contains two electrons and two protons exchange in 0.1 mmol?L^-1 phosphate buffer solution (PBS) …

Thermoelectric Performance Of N-Type (Pbte)0.75(Pbs)0.15(Pbse)0.1 Composites, Sima Aminorroaya Yamini, Heng Wang, Dianta Ginting, David R. G Mitchell, S X. Dou, G. Jeffrey Snyder

Shi Xue Dou

Lead chalcogenides (PbQ, Q = Te, Se, S) have proved to possess high thermoelectric efficiency for both n-type and p-type compounds. Recent success in tuning of electronic band structure, including manipulating the band gap, multiple bands, or introducing resonant states, has led to a significant improvement in the thermoelectric performance of p-type lead chalcogenides compared to the n-type ones. Here, the n-type quaternary composites of (PbTe)0.75(PbS)0.15(PbSe)0.1 are studied to evaluate the effects of nanostructuring on lattice thermal conductivity, carrier mobility, and effective mass variation. The results are compared with the similar ternary systems of (PbTe)1-x(PbSe)x, (PbSe) 1-x(PbS)x, and (PbS)1-x(PbTe)x. The …

Crystal Structure Of 4,5-Bis-(3,4,5-Trimethoxyphenyl)-2H-1,2,3-Triazole Methanol Monosolvate, Nikhil Reddy Madadi, Narsimha Reddy Penthala, Shobanbabu Bommagani, Sean Parkin, Peter A. Crooks

Chemistry Faculty Publications

The title compound, C₂₀H₂₃N₃O₆·CH₃OH, was synthesized by [3 + 2] cyclo­addition of (Z)-2,3-bis­(3,4,5-tri­meth­oxy­phen­yl)acrylo­nitrile with sodium azide and ammonium chloride in DMF/water. The central nitro­gen of the triazole ring is protonated. The dihedral angles between the triazole ring and the 3,4,5-tri­meth­oxy­phenyl ring planes are 34.31 (4) and 45.03 (5)°, while that between the 3,4,5-tri­meth­oxy­phenyl rings is 51.87 (5)°. In the crystal, the mol­ecules, along with two methanol solvent mol­ecules are linked into an R ⁴ ₄(10) centrosymmetric dimer by N—H⋯O and O—H⋯N hydrogen bonds.

Functionalizing Carbon Nanotube Forests, Ben Pound, F. Shen

Ben Pound

A carbon nanotube forest is an array of carbon nanotubes vertically aligned and entangled. Because the aspect ratio of each tube can be more than 1000, the forest will greatly increase the number of potential binding sites on the surface for chemical and biological detector applications, if each bundle of tubes can be functionalized with specific molecules. The 1,5-diaminoaphthalene can be a versatile linker molecule for proteins. In this study, we characterize the concentration of 1,5-diaminoaphthalene in solvent by fluorescence spectroscopy. It appears, however, that the solvent collapses the carbon nanotube forest, resulting in no detectable fluorescence emission. Lithographically defined …

Investigation Of The Crystallization Of Dnl-6 And Ft-Raman Spectroscopic Investigation Of Guest Molecules In Mofs, Maxwell Goldman

Electronic Thesis and Dissertation Repository

Microporous solids are a widely used material in adsorption, storage and catalysis. In this thesis, the crystallization of the silcoaluminaphosphate DNL-6 was characterized using powder X-ray diffraction and solid state nuclear magnetic resonance. Two crystallization routes of the SAPO DNL-6 were studied, which are the hydrothermal method and the dry-gel conversion method. Both methods followed the same crystallization pathway and showed a layered intermediate that is then transformed into DNL-6. The reaction requires two templating agents to create the RHO topology and silicon substitutes into the framework by replacing single phosphorous atoms.

This thesis contains the conformational analysis of halocarbons …

Inhibition Of The Thioesterase Activity Of Human Fatty Acid Synthase By 1,4- And 9,10-Diones, Herman H. Odens

Faculty Works

Fatty acid synthase (FASN) is the enzyme that synthesizes fatty acids de novo in human cells. Although FASN is generally expressed at low levels in most normal tissues, its expression is highly upregulated in many cancers. Consistent with this notion, inhibition of FASN activity has demonstrated potential to halt proliferation and induce cell death in vitro and to block tumor growth in vivo. Consequently, FASN is widely recognized as a valuable therapeutic target. In this report, we describe a variety of 1,4-quinones and 9,10- anthraquinones, including several natural compounds and some newly synthesized compounds, that potently inhibit the thioesterase (TE) …

Effects Of Ether Vs. Ester Linkage On Lipid Bilayer Structure And Water Permeability., S. Deren Guler, D. Dipon Ghosh, Jianjun Pan, John Mathai, Mark Zeidel, John Nagle, Stephanie Tristram-Nagle

Prof. Stephanie Tristram-Nagle Ph.D.

The structure and water permeability of bilayers composed of the ether-linked lipid, dihexadecylphosphatidylcholine (DHPC), were studied and compared with the ester-linked lipid, dipalmitoylphosphaditdylcholine (DPPC). Wide angle X-ray scattering on oriented bilayers in the fluid phase indicate that the area per lipid A is slightly larger for DHPC than for DPPC. Low angle X-ray scattering yields A=65.1A(2) for DHPC at 48 degrees C. LAXS data provide the bending modulus, K(C)=4.2x10(-13)erg, and the Hamaker parameter H=7.2x10(-14)erg for the van der Waals attractive interaction between neighboring bilayers. For the low temperature phases with ordered hydrocarbon chains, we confirm the transition from a tilted …

Structure Of Lipid Bilayers, John Nagle, Stephanie Tristram-Nagle

Prof. Stephanie Tristram-Nagle Ph.D.

The quantitative experimental uncertainty in the structure of fully hydrated, biologically relevant, fluid (L(alpha)) phase lipid bilayers has been too large to provide a firm base for applications or for comparison with simulations. Many structural methods are reviewed including modern liquid crystallography of lipid bilayers that deals with the fully developed undulation fluctuations that occur in the L(alpha) phase. These fluctuations degrade the higher order diffraction data in a way that, if unrecognized, leads to erroneous conclusions regarding bilayer structure. Diffraction measurements at high instrumental resolution provide a measure of these fluctuations. In addition to providing better structural determination, this …

Orientation Of Tie-Lines In The Phase Diagram Of Dopc/Dppc/Cholesterol Model Biomembranes., Pradeep Uppamoochikkal, Stephanie Tristram-Nagle, John Nagle

Prof. Stephanie Tristram-Nagle Ph.D.

We report the direction of tie-lines of coexisting phases in a ternary diagram of DOPC/DPPC/cholesterol lipid bilayers, which has been a system of interest in the discussion of biological rafts. For coexisting Ld and Lo phases, we find that the orientation angle α of the tie-lines increases as the cholesterol concentration increases and it also increases as temperature increases from T = 15 °C to T = 30 °C. Results at lower cholesterol concentrations support the existence of a different two-phase coexistence region of Ld and So phases and the existence of a three-phase region separating the two two-phase regions. …

Volumetric Stability Of Lipid Bilayers., Kelsey Hallinen, Stephanie Tristram-Nagle, John Nagle

Prof. Stephanie Tristram-Nagle Ph.D.

In agreement with recent reports, a commercial densimeter has yielded a gradual decrease in lipid molecular volume of DPPC multilamellar vesicle dispersions in the gel phase upon repeated thermal cycling between 10 °C and 50 °C. The considerable size of this decrease would have significant implications for the physical chemistry of biomembranes. In contrast, neutral buoyancy measurements performed with similar thermal cycling indicate no gradual change in lipid volume in the gel phase at 20 °C. Remixing the lipid in the densimeter shows that the apparent volume decrease is an artifact. We conclude that gel phase DPPC bilayers exist in …

Anaerobic And Aerobic Biodegradation Of The Oil Dispersant Components 1,2-Propanediol And 2-Butoxyethanol In Seawater, Benjamin Rhiner

All Theses

Oil spills are a recurring issue associated with fossil fuel consumption. The largest accidental oil spill in the history of the petroleum industry was the Deepwater Horizon explosion and seafloor well blowout, where the Deepwater Horizon oil rig exploded and sank, allowing the well to gush uncontrolled from April 20, 2010, until it was capped on July 15, 2010, releasing an estimated 210,000,000 gallons of oil. Oil dispersants were used in unprecedented quantities during the cleanup response to the spill with a total of 1,840,000 gallons of the dispersant COREXIT being applied. The goal of this research was to evaluate …

Studies On The Synthesis Of Orthogonally Protected Azalanthionines, And Of Routes Towards B-Methyl Azalanthionines, By Ring-Opening Of N-Activated Aziridine-2-Crboxylates, Keith O'Brien, Keith Ó Proinsias, Fintan Kelleher

Articles

Orthogonally protected azalanthionines were successfully synthesised by the ring-opening of N-activated aziridine-2-carboxylates with protected diaminopropanoic acids (DAPs). The required DAPs were also prepared by ring-opening of N-activated aziridine-2-carboxylates with para-methoxybenzylamine, but it was found that the choice of aziridine protecting groups dictated both the success of the reaction as well as the regioselectivity of the isolated products. Attempts to extend the methodology to the preparation of the more sterically demanding b-methyl azalanthionines have, so far, been unsuccessful.

Conformational Dynamics Associated With Ligand Binding To Vertebrate Hexa-Coordinate Hemoglobins, Luisana Astudillo

FIU Electronic Theses and Dissertations

Neuroglobin (Ngb) and cytoglobin (Cygb) are two new additions to the globin family, exhibiting heme iron hexa-coordination, a disulfide bond and large internal cavities. These proteins are implicated in cytoprotection under hypoxic-ischemic conditions, but the molecular basis of their cytoprotective function is unclear.

Herein, a photothermal and spectroscopic study of the interactions of diatomic ligands with Ngb, Cygb, myoglobin and hemoglobin is presented. The impact of the disulfide bond in Ngb and Cygb and role of conserved residues in Ngb His64, Val68, Cys55, Cys120 and Tyr44 on conformational dynamics associated with ligand binding/dissociation were investigated. Transient absorption and photoacoustic calorimetry …

Convenient Synthesis Of 1,3-Dithiolane-2-Thiones: Cyclic Trithiocarbonates As Conformational Locks, Irina A. Dotsenko, Qinliang Zhao, Andreas H. Franz, Patrick Batoon, Nataliya M. Samoshina, Vyacheslav V. Samoshin

College of the Pacific Faculty Articles

A series of novel 1,3-dithiolane-2-thiones, or cyclic trithiocarbonates, has been prepared by a new simple procedure: a treatment of the corresponding epoxides with the commercially available potassium ethyl xanthogenate, KSC(S)OEt. The stereochemistry of the products was determined by 1 H NMR and in some cases by single-crystal X-ray data. Cyclohexane-based 1,3- dithiolane-2-thiones revealed a trans-fusion of the carbo- and hetero-cycles. The products obtained from the mono-substituted cyclohexene oxides demonstrated an axial position of the substituents. Thus the epoxide transformation into trithiocarbonate can be used as a method for locking cyclic compounds in unstable conformations.

Hydrostatic Piezoelectric Properties Of [011] Poled Pb(Mg 1/3nb2/3)O3-Pbtio3 Single Crystals And 2-2 Lamellar Composites, Lili Li, Shujun Zhang, Zhuo Xu, Xuecang Geng, Fei Wen, Jun Luo, Thomas R. Shrout

Australian Institute for Innovative Materials - Papers

The hydrostatic piezoelectric properties of [011] poled Pb(Mg 1/3Nb2/3)O3-PbTiO3 (PMN-PT) crystals and corresponding 2-2 crystal/epoxy composites were investigated. The crystal volume ratio and compositional dependencies of the hydrostatic charge and voltage coefficients (dh and gh) and hydrostatic figure of merit (FOM) dh x gh were determined, where large FOM value of 3.2 pm2/N with high stability as a function of hydrostatic pressure was achieved for rhombohedral crystal composites. In addition, the stress amplification effects of the face-plate and different epoxy matrixes were investigated, with maximum FOM value being on the order of 92 pm2/N, indicating that 2-2 crystal/epoxy composites are …

Thermoelectric Performance Of N-Type (Pbte)0.75(Pbs)0.15(Pbse)0.1 Composites, Sima Aminorroaya Yamini, Heng Wang, Dianta Ginting, David R. G Mitchell, S X. Dou, G. Jeffrey Snyder

Australian Institute for Innovative Materials - Papers

Lead chalcogenides (PbQ, Q = Te, Se, S) have proved to possess high thermoelectric efficiency for both n-type and p-type compounds. Recent success in tuning of electronic band structure, including manipulating the band gap, multiple bands, or introducing resonant states, has led to a significant improvement in the thermoelectric performance of p-type lead chalcogenides compared to the n-type ones. Here, the n-type quaternary composites of (PbTe)0.75(PbS)0.15(PbSe)0.1 are studied to evaluate the effects of nanostructuring on lattice thermal conductivity, carrier mobility, and effective mass variation. The results are compared with the similar ternary systems of (PbTe)1-x(PbSe)x, (PbSe) 1-x(PbS)x, and (PbS)1-x(PbTe)x. The …

Synthesis And Characterization Of A Novel 3-Amino-1,2,4-Triazole Lead(Ii) Coordination Polymer, Şebnem Esen Sözerli̇, Arzu Özen, İbrahi̇m Kani̇, Deni̇z Demi̇r

Turkish Journal of Chemistry

A novel [Pb_2(\mu-atrz)_2(\mu-CH_3COO)(CH_3COO)]_n (atrz = 3-amino-1,2,4-triazole) complex was synthesized and characterized by IR spectroscopy, thermogravimetric analysis, and single crystal X-ray diffraction. The molecular structure shows that the complex is a coordination polymer in which there are 2 different lead(II) ions with coordination number of 5, Pb(2), and, with a coordination number of 4, Pb(1). Each atrz acts as a bridging ligand between 2 Pb(II) ions through the 2 adjacent nitrogen atoms of the triazole ring. The acetate anions show different types of coordination mode: one acts as a bridge by coordination of the same oxygen atom with Pb(II) ions and …

Spectrophotometric Determination Of Molybdenum Using Surfactant-Mediated Liquid--Liquid Extraction, Rameshwar Dass, Jitander Kumar Kapoor, Sunita Gambhir

Turkish Journal of Chemistry

A new spectrophotometric method has been developed for determination of molybdenum using surfactant-mediated liquid--liquid extraction. Molybdenum(V) obtained by ascorbic acid reduction in 2.5 M H_2SO_4 reacted spontaneously with thiocyanate and cetyl trimethyl ammonium bromide (CTAB), forming an intense orange yellow complex that was extracted quantitatively into 1,2-dichloroethane and absorbed at 460 nm. The absorbance of the extract was found to be stable for more than 24 h. Beer's law was obeyed over the concentration range 0.1--4.2 \mu g Mo mL^{-1} of the extract. The linear range for an accurate determination was found to be 1.2--2.6 \mu g Mo mL^{-1}. The …

Synthesis And Phase Transition Studies Of New Dimer Compounds Connected To A 1,3-Dimethylbarbituric Acid Core, Abdulkarim-Talaq Mohammad, Guan-Yeow Yeap, Hasnah Osman

Turkish Journal of Chemistry

A series of dimeric unsymmetrical liquid crystals derived from heterocyclic 1,3-dimethylbarbituric acid exhibiting smectic A and nematic phase are reported. All compounds were prepared by the condensation of 4'-(R-(4-formylphenoxy)butoxy)biphenyl-4-carboxylate with 1,3-dimethylbarbituric acid in ethanol. The mesomorphic properties were investigated by DSC and POM, where the type of phase depends on the length of spacer alkoxy chains and the length of the terminal chain. While the SmA phase was observed upon the heating and cooling run when the spacer alkoxy chains carbon numbers increased (n = 6), the N phase was observed when the length of spacer alkoxy chains increased (n …

Magnetic Transitions And The Magnetocaloric Effect In The Pr 1-Xyxmn2ge2 System, Jianli Wang, S J. Campbell, M F. Md Din, S J. Kennedy, M Hofmann

Australian Institute for Innovative Materials - Papers

Layered rare earth compounds in the RMn2X2 series (R = rare-earth; X = Ge, Si) are of interest for potential cooling applications at lower temperatures as they enable the structural and magnetic behavior to be controlled via substitution of R, Mn, and X atoms on the 2a, 4d, and 4e sites respectively. We continue investigations of the Pr1−xYxMn2Ge2 magnetic phase diagram as functions of both composition and Mn-Mn spacing using X-ray and neutron diffraction, magnetization and differential scanning calorimetry measurements. Pr1−xYxMn2Ge2 exhibits an extended region of re-entrant ferromagnetism around x ∼ 0.5 with re-entrant ferromagnetism at inline image for Pr0.5Y0.5Mn2Ge2. …

Pd0-Catalyzed Formal 1,3-Diaza-Claisen Rearrangement. Design And Development Of Cationic 1,3-Diaza-Claisen Rearrangement., Yanbo Yang

Graduate College Dissertations and Theses

The dissertation describes Pd⁰-catalyzed formal 1,3-diaza-Claisen rearrangement and the design and development of cationic 1,3-diaza-Claisen rearrangement.

Our previous work has shown that isocyanates react with azanorbornenes and azabicyclo[2.2.2]octenes under thermal conditions to afford zwitterionic intermediates that undergo a thermal 1,3-diaza-Claisen rearrangement to give both ureas and isoureas. However, some azanorbornenes and azabicyclooctenes failed to rearrange or proceeded in low yields. To address these challenging substrates for the thermal 1,3-diaza-Claisen rearrangement, we have developed a Pd⁰-catalyzed formal 1,3-diaza-Claisen rearrangement. Interestingly, under Pd⁰-catalyzed condition, both isocyanates with electron-withdrawing groups and isocyanates without electron-withdrawing groups react with …

Magnetic Properties And Magnetocaloric Effect In Layered Ndmn 1.9v0.1si2, M F. Md Din, Jianli Wang, R Zeng, Shane Kennedy, S J. Campbell, S X. Dou

Australian Institute for Innovative Materials - Papers

The structural and magnetic properties of the compounds NdMn2-xVxSi2 have been studied by x-ray and high resolution neutron powder diffraction, specific heat, dc magnetization, and differential scanning calorimetry measurements over the temperature range 3-450 K. The Curie temperature and Néel temperature of layered NdMn1.9V0.1Si2 are been indicate at TC ~ 24 K and TN ~ 376 K respectively. The giant magnetocaloric effect (GMCE) around TC is found in layered NdMn1.9V0.1Si2 associated with first order magnetic transition from antiferromagnetic [AFil-type] to ferromagnetic [F(Nd)+Fmc]. This behaviorhas been confirmed as contribution of the magnetostructural coupling by using neutron powder diffraction. The magnetic entropy …

Te(Ii)-Induced Heterocyclization Of 1,2-Alkadienephosphonates, Dobromir Dimitrov Enchev

Turkish Journal of Chemistry

The reactivity of some 1,2-alkadienephosphonates towards phenyltelluryl halides was investigated. A plausible mechanism of the reaction is discussed.

Synthesis Of Novel Imidazo[1,2-A]Pyridines And Evaluation Of Their Antifungal Activities, Füsun Göktaş, Nesri̇n Cesur, Di̇lek Şatana, Meltem Uzun

Turkish Journal of Chemistry

New 2-(imidazo[1,2-a]pyridin-2-ylcarbonyl)-N-substituted hydrazinecarbothioamides (4a--j), N'-(3-substituted-4-oxo-1,3-thiazolidin-2-ylidene)imidazo[1,2-a]pyridine-2-carbohydrazides (5a--f), and N-(nonsubstituted/4-substituted phenyl)-5-(imidazo[1,2-a]pyridine-2-yl)-1,3,4-oxadiazole-2-amines (6a--d) were synthesized from imidazo[1,2-a]pyridine-2-carbohydrazide (3) and evaluated for antifungal activity against Microsporum gypseum NCPF 580, M. canis, Trichophyton tonsurans NCPF 245, T. rubrum, Candida albicans ATCC 10231, and C. parapsilosis ATCC 22019 using amphotericin B as the standard. The chemical structures of the compounds were confirmed by elemental analysis, IR, ^1H NMR, ^{13}C NMR, HMBC (^{13}C, ^1H), and mass spectra. Most of the tested compounds showed moderate antifungal activity. Hydrazinecarbothioamide derivatives 4h and 4f exhibited the highest activity against M. canis (MIC: 2 \mu g mL^{-1} and 4 \mu g …

Synthesis Of Novel Triazoles Bearing 1,2,4-Oxadiazole And Phenylsulfonyl Groups By 1,3-Dipolar Cycloaddition Of Some Organic Azides And Their Biological Activities, Yaşar Dürüst, Hamza Karakuş, Muhsi̇ne Zeynep Yavuz, Ali̇ Akçahan Gepdi̇remen

Turkish Journal of Chemistry

1,3-Dipolar cycloaddition of 5-azidomethyl-3-p-substituted phenyl-1,2,4-oxadiazoles to phenyl vinyl sulfone and bismaleimide gives rise straightforwardly to 1-((3-(p-substituted) phenyl-1,2,4-oxadiazol-5-yl)methyl)-4-(phenylsul\-fonyl)-4,5-dihydro-1H-1,2,3-triazoles and bisdihydropyrrolo[3,4-d][1,2,3]triazole-4,6(3aH,5H)-diones. The structures of the new cycloadducts were elucidated by means of IR, NMR (^1H, ^{13}C, 2D), mass spectra, and physical characteristics (mp and R_f values). In addition, anticancer activities of the cycloadducts against MCF-7 cells were also investigated.