Chemistry Commons^™

Stable Isotope Compositions Of Sedimentary Organic Matter Off Zanzibar Town, Ann Muzuka

Tanzania Journal of Science

Stable isotope compositions of sedimentary organic carbon for sediments collected off the Zanzibar Town averaged -17.9%. Low isotope values of organic carbon, which were associated with high C/N ratios, were observed within Zanzibar harbour suggesting a significant contribution of terrestrial organic matter to the harbour. Sediments collected outside the Zanzibar harbour were richer in ¹³C than those collected within the harbour area. This 13 enrichment in ¹³C can be attributed to a decrease in the influence of terrestrial organic matter (0M) and high contribution of' sea grasses. A decrease in the influence of terrestrial OM is further supported …

A Simple Method For Indexing Powder Diffraction Patterns Of Cubic Materials (11): Using The D-Values Of Reference, Me Kamwaya

Tanzania Journal of Science

From the d-values (in decreasing order) taken from powder diffraction patterns of the cubic material a variable constant, KQ, which is a multiple of Ʃh₁² where Q = l/d² can be determined. The smallest values of Q give rise to multiples of ones, twos and threes, which correspond to the smallest values of Ʃh₁² for the primitive, bcc, and fcc/diamond Type structures, respectively. Cognance of the lattice types is best accomplished by the ΔQ-criterion, where ΔQ denotes the difference between successive values of Q. Indexing is greatly simplified and the use of rigorous tables is …

Bis(4-Carboxylato-5-Methyl-Oxazolidine) Nickel(Ii)Dihydrate, Its Preparation And Crystal Structure, Me Kamwaya

Tanzania Journal of Science

An aqueous solution of nickel (Il) acetate tetrahydrate was added to warm solution of L-threonine and sodium bicarbonate. The mixture was subsequently treated with aqueous solution of formaldehyde and stirred until the blue solution turned green. The reaction consists in a base catalysed condensation of formaldehyde with L-threonine-nickel (Il) – complex followed by formation of an oxazolidine ring. A single crystal X-ray investigation was carried out at 120(1) ^oC. The X-ray structure analysis showed an octahedral nickel comp/ex containing two water molecules. The oxazolidine rings were connected to the Ni by nitrogen and one of the carboxylato oxygen atoms. …

Synthesis Of Bis-(3-Carbethoxy-6-Methoxy-4-Methyl-2-Quinolyl) Selenide, Rr Malisa, G L. Mhehe, Sjm Mdachi

Tanzania Journal of Science

In the execution of a synthetic strategy aiming at 3-acetyl-2,4-dichloro-6-methoxyquinoline, a precursor to a 4-methoyselenolo[2,3-b]quinolone, we have instead obtained 2-chloro-3-carbethoxy-6-methoxy-4-methylquinoline. These results strongly suggest that the compound claimed to be 3-acetyl-2,4-dihydroxy-6-methoxyquinoline in the literature and a precursor to 3-actyl-2,4-dichloro-6-methoxyquinoline, is 3-carbethoxy-2-hydroxy-6-methoxy-4-methylquinoline, a precursor to 2-chlo-3-carbethoy-6-methoxy-4-methylquinoline. The reaction of the latter compound with sodium hydrogen selenide in ethanol yielded bis-(3-carbethoxy-6-methoxy-4-methyl-2-quinolyl) selenide.

Probing The Mechanisms Of Enantioselective Hydrogenation Of Simple Olefins With Chiral Rhodium Catalysts In The Presence Of Anions, Jillian M. Buriak, Jason C. Klein, Deborah Herrington, John A. Osborn

Peer Reviewed Articles

The strong influence of various anions upon the hydrogenation of 2-phenyl-1-butene, catalyzed by chiral rhodium catalysts was investigated. Both sulfonates and halides exert large increases in the enantioselectivity when [Rh{(−)-bdpp}(NBD)]ClO4 (bdpp=2,4-bis(diphenylphosphino)pentane, NBD=2,5-norbornadiene) is used as the catalyst precursor at high pressures (70 atm) of dihydrogen in nonpolar solvents. A dihydride mechanism similar to that for Wilkinson's catalyst [RhCl(PPh3)3] was shown to be operating at both high- and low-pressure conditions through a combination of catalytic studies, 31P, 1H and parahydrogen-induced polarization (PHIP) NMR experiments. With sulfonate and in neat methanol, however, a mechanistic switch takes place from a dihydride route (dihydrogen …

Cu(Ii) Potentiation Of Alzheimer A Neurotoxicity, Xudong Huang, Math P. Cuajungco, Craig S. Atwood, Mariana A. Hartshorn, Joel D. A. Tyndall, Graeme R. Hanson, Karen C. Stokes, Michael C. Leopold, Et Al.

Chemistry Faculty Publications

Oxidative stress markers as well as high concentrations of copper are found in the vicinity of Aβ amyloid deposits in Alzheimer's disease. The neurotoxicity of Aβ in cell culture has been linked to H2O2generation by an unknown mechanism. We now report that Cu(II) markedly potentiates the neurotoxicity exhibited by Aβ in cell culture. The potentiation of toxicity is greatest for Aβ1–42 > Aβ1–40 ≫ mouse/rat Aβ1–40, corresponding to their relative capacities to reduce Cu(II) to Cu(I), form H2O2 in cell-free assays and to exhibit amyloid pathology. The copper complex of Aβ1–42 has a highly positive formal reduction potential (≈+500–550 mV versus …

Emissions Of Formaldehyde, Acetic Acid, Methanol, And Other Trace Gases From Biomass Fires In North Carolina Measured By Airborne Fourier Transform Infrared Spectroscopy, Robert J. Yokelson, Jon G. Goode, Darold E. Ward, Ronald A. Susott, Ronald E. Babbitt, D. D. Wade, Issac T. Bertschi, David W. T. Griffith, Wei Min Hao

Chemistry and Biochemistry Faculty Publications

Biomass burning is an important source of many trace gases in the global troposphere. We have constructed an airborne trace gas measurement system consisting of a Fourier transform infrared spectrometer (FTIR) coupled to a “flow-through” multipass cell (AFTIR) and installed it on a U.S. Department of Agriculture Forest Service King Air B-90. The first measurements with the new system were conducted in North Carolina during April 1997 on large, isolated biomass fire plumes. Simultaneous measurements included Global Positioning System (GPS); airborne sonde; particle light scattering, CO, and CO₂; and integrated filter and canister samples. AFTIR spectra acquired within …

Synthesis And Reactivity Of Acyclic (Pentadienyl)Iron(1+) Cations: Model Studies For The Preparation Of The 8E,10Z,16E,18E-Tetraene Segment Of Macrolactin A, Abdel-Aziz S. El-Ahl, Young Yun, William A. Donaldson

Chemistry Faculty Research and Publications

The dicarbonyl(1,2-dimethylpentadienyl)triphenylphosphineiron(1+) cation (11) has been prepared from methyl 4-methyl-2E,4E-hexadienoate in four steps. The cation (11) reacts with hydride and carbon nucleophiles in a regiospecific fashion to afford (3-methyl-2E,4Z-diene)iron complexes. Dicarbonyl(3-methyl-7-nitro-2E,4Z-heptadiene)triphenylphosphineiron (15), the product from the reaction of 11 with nitromethane anion, has been utilized as a precursor for nitrile oxide–olefin cyclocondensations.

A Patching Model For Surface Tension Of Spherical Droplet And Tolman Length. Ii, T.V. Bykov, Xiao Cheng Zeng

Xiao Cheng Zeng Publications

In the framework of density functional theory (DFT), two patching models for the density profile of spherical liquid droplet are developed. The patching is based on analytical expressions of the asymptote of the density profiles. The first model leads to analytic expressions of the Tolman length and the effective rigidity constant, from which the temperature dependence of the Tolman length and effective rigidity constant can be determined. The second model is developed particularly for small spherical droplets, from which the dependence of chemical potential and the surface tension of the droplet on the radius are obtained. The results are compared …

Langmuir Monolayers As Disordered Solids: Disorder And Elastic Fluctuations In Mesophases , Tadeusz Luty, Craig J. Eckhardt, Jacques Lefebvre

Craig J. Eckhardt Publications

Ordering in Langmuir monolayer mesophases is examined using an approach based on the elastic theory of crystals. Molecular tails are modeled as ‘‘defects’’ grafted onto a two-dimensional elastic medium and are characterized by elastic dipoles. It is assumed that disorder in the parent, LS, phase is due to competition between local (within a domain) and global (hexagonal arrangement of domains) structure. By treating the LS phase as a mixture of rectangular and/or oblique domains (rectangular and/or oblique defects within the two-dimensional elastic medium), density fluctuations due to elastic interactions between domains are analyzed. The correlation function for the elastic dipoles …

Enantioseparation Of Alkylaryl Sulfoxides Using Capillary Zone Electrophoresis, Chad Snyder

Masters Theses & Specialist Projects

Alkylaryl sulfoxides possess a chiral sulfur atom easily identifiable by capillary zone electrophoresis (CZE). Separation of chiral alkylaryl sulfoxides has already been accomplished by modified method of CZE known as micellar electrokinetic chromatography (MEKC). However, no articles have been published on the enantioseparation of alkylaryl sulfoxides using capillary zone electrophoresis.

A series of sulfoxides were synthesized, purified and identified via NMR. Enantioseparation was performed using CZE employing a 10 mmol. Phosphate buffer (pH 4.0, 25% acetonitrile, 2% sulfated-β-cyclodextrin). Synthesis of these sulfoxides will be presented along with the results of the procedure’s optimization. Separation of the sulfoxide enanitomers relies on …

A Study Of The Thermal Properties Of Peti-5/Im7, Yan Tang

Masters Theses & Specialist Projects

PETI-5 (Phenylethynyl-terminated polyimide) is a substance that shows a great deal of potential in the high-speed aircraft and the aerospace industry. PETI-5 has been used for the High Speed Civil Transport (HSCT), a supersonic passenger aircraft in development at NASA. In this project, four staging samples, one fresh sample, one fully cured sample and one partially cured sample were analyzed and compared using thermal analytical techniques. The sample staged at 450°F with full vacuum showed the highest thermal properties among four staging samples. The results indicated that vacuum is helpful in improving the thermal stability of PETI-5. The mechanism of …

Further Studies On Fire Retardant Polystyrene By Friedel–Crafts Chemistry, Zhitao Wang, David D. Jiang, Charles Wilkie, Jeffery W. Gilman

Chemistry Faculty Research and Publications

The combination of a copolymer of 4-vinylbenzyl alcohol and styrene with 2-ethylhexyldiphenylphosphate (DPP) and with metal chlorides has been studied by TGA, radiative gasification, Cone Calorimetry, and oxygen index measurements. Evidence is presented in support of a cross-linking reaction with the additives and the copolymer, which proceeds through a Friedel–Crafts mechanism. This approach reduces the peak heat release rate (HRR) by 60% as measured in the Cone Calorimeter. There is a significant reduction in the mass loss rate during the thermal degradation, and evidence of char formation is observed in the radiative gasification experiments.

Molecular-Dynamics Study Of Phase Transitions In Alkali Azides, M. M. Ossowski, John R. Hardy, Robert W. Smith

Physics Faculty Publications

An account is presented of our studies of the order-disorder phase transitions in KN₃, RbN₃, and CsN₃. These are based on parameter-free interionic potentials based on the Gordon-Kim modified electron-gas formalism extended to molecular ions. We performed static structural relaxations and supercell molecular dynamics and predicted with reasonable accuracy the temperatures for the onset of the transitions. In particular, we address the question of how the N₃^- ions reorient to yield the transitions. We found the existence of NaCl-type high-temperature phases in disordered KN₃ and RbN₃ and argue that this …

Alkyl Nitrates During The Prophet ’98 Summer Intensive, Kristi A. Ostling

Masters Theses

As part of the PROPHET intensive held at the University of Michigan Biological Station in northern Michigan, a gas chromatography system for making fast-turnaround measurements of C1 to C5 alkyl nitrates was developed and deployed from July 19 to August 21, 1998. Every 30 minutes, samples were automatically acquired on a small Tenax trap made from silicosteel column and injected on a GC column by thermal desorption prior to ECD detection. Tests performed to measure breakthrough and on-trap destruction indicated no breakthrough for C3, C4, and C5 nitrates and excellent stability for these compounds on the trap. Chromatographic resolution of …

Bulletin 4385 - Control Of Mediterranean Fruit Fly (Medfly) In Commercial Orchards, Sonya Broughton, Francis De Lima

Bulletins 4000 -

The Mediterranean fruit fly (Medfly) is thought to originate from tropical Africa. It is a pest in many areas of the world including Western Australia. It was first detected at Claremont in 1895 and is now found as far south as Esperance and as far north as Derby. The main area of infestation extends from Carnarvon to Bunbury.

Medfly is known to infest over 200 fruit and vegetable species. In Western Australia, stone fruit, pome fruit, citrus, guavas, figs and loquats are particularly susceptible.

Tga/Ftir: An Extremely Useful Technique For Studying Polymer Degradation, Charles A. Wilkie

Chemistry Faculty Research and Publications

Thermogravimetric analysis coupled to Fourier transform infrared spectroscopy, TGA/FTIR, has been used to probe the degradation of several polymeric systems. These include poly(methyl methacrylate) in the presence of various additives, graft copolymers of acrylonitrile-butadiene-styrene and styrene-butadiene with sodium methacrylate and styrene with acrylonitrile, blends of styrene-butadiene block copolymers with poly(vinylphosphonic acid) and poly(vinylsulfonic acid), and cross-linked polystyrenes. Additives may interact with poly(methyl methacrylate) by coordination to the carbonyl oxygen to a Lewis acid and the subsequent transfer of an electron from the polymer chain to the metal atom or by the formation of a radical which can trap the degrading …

On-Road Remote Sensing Of Automobile Emissions In The Denver Area: Year 1, Peter J. Popp, Sajal S. Pokharel, Gary A. Bishop, Donald H. Stedman

Fuel Efficiency Automobile Test Publications

No abstract provided.

Thermal Degradation Of Blends Of Polystyrene And Poly(Sodium 4-Styrenesulfonate) And The Copolymer, Poly(Styrene-Co-Sodium 4-Styrenesulfonate), Qiang Yao, Charles Wilkie

Chemistry Faculty Research and Publications

The thermal degradation of blends and copolymers of styrene with styrenesulfonic acid has been studied using thermogravimetric analysis, TGA/FTIR, and cone calorimetry. The blends have enhanced thermal stability relative to virgin polystyrene but there is no enhancement in thermal stability for the copolymers. Apparently, it is necessary to have adjacent sulfonic acid groups in order to permit the formation of a graphite-like char which can provide thermal protection to the polymer. It is necessary to have a good match in degradation temperatures of the two components if one is to have significantly enhanced thermal stability.

Surface Enhanced Raman Spectroscopic Study Of Scn- Adsorbed At The Copper And Gold Nanowire Arrays, Jian-Lin Yao, Guo-Ping Pan, Kuan-Hong Xue, Yong Xie, Jing Tang, Bin Ren, Dong-Mei Sun, Bing-Wei Mao, Zhong-Qun Tian

Journal of Electrochemistry

Two-dimensional arrays of Cu and Au nanowires have been fabricated by template synthesis method, using the anodic aluminum oxidation films as the template. The morphology of the nanowire array was monitored by atomic force microscope (AFM) in the dissolution processes of the alumina film. Based on the probe molecule strategy, the spectral feature of SCN^- adsorbed at the Cu and Au nanowires with different diameters has been investigated by surface enhanced Raman spectroscopy (SERS). The results reveal that the intensity of the SERS bands depends on the length of the exposed nanowires. The C≡N stretching vibration frequency (ν_{CN …}

The Electrochemical Behaviors Of Superoxide Dismutase At Promoter Modified Gold Electrode, Xia-Qin Wu, Xiao-Yun Meng, Zhe-Su Wang, Zong-Rang Zhang

Journal of Electrochemistry

The electron-transfer process of superoxide dismutase was investigated by cyclic voltammetry at the 4,4'-dithiodipyridine, L-cysteine, histidine and arginine modified gold wire electrodes repectively. The quasi-reversible behavior was observed at L-cysteine modified gold electrode. An irreversible electrochemical behavior has been observed at hisdinine modified gold wire electrode.

Aes Multi-Layer Structural Analysis Of Si Based Anodic Porous Alumina Films And Studies On Its Formation Mechanism, Jun-Hui Wu, Jian-Ping Zou, Qing Zhu, Xi-Mao Bao

Journal of Electrochemistry

400 nm aluminum films were deposited onto a p-type, 0.5 Ω·cm,〈100〉oriented silicon wafers using electron beam evaporation technique. Then, the wafers was immersed in 15 wt% H₂SO₄ for porous-type over-anodization under a constant voltage of DC 60V. During the anodization,the temperature of the electrolyte was maintained at 0 ℃. The obtained samples were investigated by means of transmission electron microscopy, scanning electron microscopy, and AES depth profile for multi-layer structural information. In addition, the basic anodic formation mechanism of the Si-based aluminum films was brielfly discussed.

Study On Electrochemical Reduction Properties Of Nitrobenzene, Chu-Na Ma, Wen-Kui Zhang, Hui Huang, Yong-Ping Gan

Journal of Electrochemistry

The electrochemical reduction characteristics of nitrobenzene was extensively investigated by using the techniques such as quasi-steady-state polarization, cyclic voltammetry, fast linear potential sweep method and chronoamperometry in this paper. The electroanalytic properties of Cu, Cu-Hg and Cu-Ni electrodes were evaluated. Based on the study of the transient steping behaviour of nitrobenzene to PAP, the reduction mechanism was discussed. The results showed that the transition steps existed on the electrochemical reduction of nitrobenzene in acidic solution, the reactant is also absorbed on electrodes surface. The control step in the reduction of nitrobenzene was ascribed to the diffusion of nitrobenzene and its …

A Gas Analysis Method For Determining The Perchlorate Current Efficiency And Other Applications, Zhi-Gang Shao, Bao-Lian Yi

Journal of Electrochemistry

A method for determining the current efficiency by means of measuring the flow capacity of the cell gas in a perchlorate cell has been proposed. The perchlorate cell system was equipped with an oxygen cathode or a Na⁺ ion exchange membrane. This method is simple and convenient as well as accurate in the evaluation of the perchlorate current efficiency in the perchlorate cell as compared with the traditional methods of analysis. It is useful in the investigation of electrochemical problems with high perchlorate concentration, as well as for the assessment of electrocatalytic performance of anode materials.With an oxygen cathode …

High Performance Proton Exchange Membrane Fuel Cells, Jing-Rong Yu, Bao-Lian Yi, Ming Han, Xiao-Liang Cheng, Zhi-Gang Shao, Jing-Xin Zhang

Journal of Electrochemistry

Proton-exchange membrane fuel cells(PEMFC) using a perfluorosulfonic acid proton exchange membrane as an electrolyte can simplify water and electrolyte management. In this paper, the effects of thickness of PEM on the performance of PEMFC were studied. The Nafion-112 PEM and low platinum loading E-TEK electrode yielded very high power density, of the order of 0.95 W/cm². The energy-conversion efficiency, the degree of platinum utilization and stability for PEMFC using Nafion 112 and E-TEK electrode were also investigated.

Electrochemical Studies Of Metal Complexes In Solution, Ye-Xiang Tong, Bei-Sheng Kang, Qi-Qin Yang

Journal of Electrochemistry

The prospectus of electrochemical studies of metal complexes in solution have been introduced as a background of our research work. The electrochemical behaviors of the metal complexes and clusters have been investigated by many kinds of electrochemical methods. The content includes the standard electrode potential and the related equilibrium constant, electrochemical kinetics and the related behavior of structure, electrocatalysis and electrosynthesis of metal complexes. The electrode reaction mechanisms of the complexes have been approached. The methods for measuring some thermodynamic and kinetic parameters of the complexes are also given. Electrochemical studies would provid many kinds of important information for studying …

Photoelectrochemical Studies On The Tio2 Nanostructured Porous Film Sensitized By Cyanine Dye, Li Zhang, Mai-Zhi Yang, Xue-Bin Qiao, Yan-Zhong Hao, En-Qing Gao, Sheng-Min Cai

Journal of Electrochemistry

The photoelectrochemical behaviors of the TiO₂ nanostructured porous film sensitized by cyanine dye were investigated in this paper. The results showed that the excitaed state level matched the conduction band edge of TiO₂ nanoparticle. Therefore the sensitization of the dye can increase the photocurrent intensity of the TiO₂ nanostructured electrode obviously and results in a red-shift of optical absorption from the ultra-violet region to the visible. As a result, the light-to-electricity conversion efficiency was improved evidently, the maximum value of IPCE has reached 12.1%.

Electro-Oxidation Of Phenol On Sno2/Ti Electrodes Prepared By Thermal Oxidation, Qing-Song Zhang, Hui-Huang Wu

Journal of Electrochemistry

A SnO₂/Ti electrode prepared by thermal oxidation was used as the anode for galvanostatic electrolysis in acidic solution containing phenol, the time-dependances of phenol concentration, chemical oxygen demand in solution(COD) and instantaneous current efficiency were determined during electrolysis. The results show that with the SnO₂/Ti anode instead of Pt, the COD significantly decreases at the same charge passage, and average current efficiency of oxidation increases by three times. The mechanism for phenol oxidation at two electrodes was discussed.

Investigation Of Sodium Hypophosphite Anodic Oxidizing Behavior In The Process Of Acid Electroless Nickel Deposition, Mei-Yuan Wang, Ya-Fei Kuang, Yan Xu

Journal of Electrochemistry

The anodic oxidizing behavior of sodium hypophosphite in the process of electroless nickle deposition (pH=5.5) was investigated with the linear potential sweep method and alternating current impedance. The results indicated that, the oxidation of NaH₂PO₂ was a complicated electrochemical process and affected by the concentration of NaH₂PO₂, the temperature of the bath, the sweep rate and the existence of nickel ion. The NaH₂PO₂ electrooxidation reaction was very likely preceded by heterogeneous interface transformation process, which might be the control step of the whole anodic process.

The Preparation Of Flexible Polymeric Anode And The Measurement Of Its Protective Ability For Cathodic Protection, Ai-Ling Du, He-Ming Zhang, Ming-Zong Zhang, Shi-De Ma

Journal of Electrochemistry

The flexible electrode, whose shape can be changed freely, was made of ethenyl copolymer and conductive component and proper amount of additive for cathodic protection. The resistance of electrode was measured.In low concentration of H₂SO₄, the flexible electrode can be used as auxiliary anode to protect the carbon steel. The protection ability of the flexible auxiliary anode was measured too.