Chemistry Commons^™

Structure Of 2,9-Dimethyl-1,10-Phenanthroline Hemihydrate, Doyle Britton, Larry C. Thompson, Richard C. Holz

Chemistry Faculty Research and Publications

C₁₄H₁₂N₂•½H₂O, M_r = 217•27, tetragonal I4₁/a, a = 14•258 (3), c = 22•286 (4) Å, V = 4531 (3) ų, Z = 16, D_x = 1•274 (1) g cm^-3, Mo Kα radiation λ = 0•71073 Å, µ = 0•74 cm^-1, F(000) = 1840, T = 297 K, R = 0•041 for 1196 unique observed reflections with I > 2σ(I). Pairs of dimethylphenanthroline molecules related by a twofold axis are bridged by water molecules lying on the twofold …

A Strategy For The Design Of Flame Retardants: Cross-Linking Processes, Charles A. Wilkie, Sunil J. Sirdesai, Thitivat Suebsaeng

Chemistry Faculty Research and Publications

Cross-linking is identified as an effective means for flame retardation of polymers and schemes for the cross-linking of poly(ethylene terephthalate) and poly(methyl methacrylate) are presented. For poly(ethylene terephthalate) the scheme involves polymerization of the initially produced vinyl ester. This is followed by chain-stripping, producing a polyene, and cyclization of this polyene. For poly(methyl methacrylate) the scheme entails the formation of anhydride linkages between adjacent polymer strands. Evidence is presented to show the efficacy of these processes and information is produced to aid in the identification of new flame retardants.

Anti-Cancer Action Of Metal Complexes: Electron Transfer And Oxidative Stress?, Peter Kovacic, William J. Popp, James R. Ames, Michael D. Ryan

Chemistry Faculty Research and Publications

Evidence is presented in support of an electron transfer mechanism for various metal complexes possessing anti-neoplastic properties. Cyclic voltammetry was performed on several metallocenes, bis(acetato)bis(imidazole)Cu(II), and coordination compounds (Cu or Fe) of the anti-tumor agents, bipyridine, phenanthroline, hydroxyurea, diethyldithiocarbamate, and α, α¹-bis(8-hydroxyquinolin-7-yl)-4-methoxytoluene. The favorable reduction potentials ranged from +0.5 to -0.5 V. Electrochemical behavior is correlated in some cases with structure and physiological activity. Relevant literature data are discussed.

Interactions Of Water-Soluble Metalloporphyrins With Nucleic Acids Studied By Resonance Raman Spectroscopy, Jinghua H. Schneider, Junichi Odo, Kazuo Nakamoto

Chemistry Faculty Research and Publications

The resonance Raman spectra of water-soluble porphyrins, M(TMpy-P4) (M = Cu(II), Ni(II) and Co(III)) and their mixtures with poly(dG-dC)₂, poly(dA-dT)₂ and calf thymus and salmon DNAs were measured using a divided rotating cell to determine the magnitudes of frequency shift and intensity variation resulting from M(TMpy-P4)-nucleic acid interactions. Bands II(Cβ-H bending, ˜ 1100 cm-1) and VIII(Cβ-Cβ stretch, ˜ 1570 cm-1) show a large and small upward shift, respectively, when Cu(TMpy-P4) and Ni(TMpy-P4) are intercalated at the G-C sites. In contrast, these bands show a small upward and downward shift, respectively, when Co(TMpy-P4) is groove-bound at the A-T …

Electron Transfer-Oxy Radical Mechanism For Anti-Cancer Agents: 9-Anilinoacridines, Peter Kovacic, James R. Ames, Michael D. Ryan

Chemistry Faculty Research and Publications

A possible mode of action involving electron transfer is advanced for the 9- anilinoacridines. The mechanism entails formation of toxic oxy radicals which destroy the neoplasm. Cyclic voltammetry was performed on iminium type ions derived by protonation of the acridines. Reductions were generally reversible with potentials of about - 0.60 V. Involvement of quinoidal metabolites is also a possibility. The relationship of electrochemical behavior to structure and physiological activity is addressed.

Structure Of L,L-Diphenylarsenanium Bromide Monohydrate, J. A. Campbell, R. Larsen, C. Campana, Sheldon E. Cremer, A. Gamliel

Chemistry Faculty Research and Publications

No abstract provided.

Structure Of L-Benzyl-2,2,3,3-Tetramethyl-L-Phenylphosphetanium Bromide, A Cyelobutane Derivative, J. A. Campbell, R. Larsen, C. Campana, Sheldon E. Cremer

Chemistry Faculty Research and Publications

No abstract provided.

Charge Transfer-Oxy Radical Mechanism For Anti-Cancer Agents, Peter Kovacic, James R. Ames, Paavo Lumme, Hannu Elo, O. Cox, Michael D. Ryan

Chemistry Faculty Research and Publications

The proposal is advanced that anti-cancer drugs generally function by charge transfer resulting in formation of toxic oxy radicals which destroy the neoplasm. Electrochemical studies were performed with some of the main types of agents: iminium ions (adenine iminium from alkylating species, iminium metabolite of 6-mercaptopurine, nitidine, other polynuclear iminiums) and metal complexes (Pt(II)diaquodiammine-guanosine, copper salicylaldoximes). Reduction potentials ranged from -0.4 to -1.2 V. Literature data for quinones are presented and radiation is discussed. Based on the theoretical framework, a rationale is offered for the carcinogen-anti-cancer paradox and the role of antioxidants.

Structure Of L,L-Diphenylphosphorinanium Bromide Monohydrate, J. A. Campbell, R. Larsen, R. Ekeland, Sheldon E. Cremer

Chemistry Faculty Research and Publications

No abstract provided.

Structure Of A Solvated Nickel(Ii) Complex Of (S)-2'-(N-Benzylprolyl)Aminoacetophenone And (R)-Valine Schiff Base, C25H29N3Nio3.1/2c4H8O. Conformational Calculation Of Diastereomeric Complexes Of (R)-Valine And (S)-Valine, Sergey V. Lindeman, T. V. Timofeeva, V. I. Maleyev, Yuri N. Belokon, M. G. Ryzhov, V. M. Belikov, Yuri T. Struchkov

Chemistry Faculty Research and Publications

No abstract provided.

The Structure Of 1-Tert-Butyl-2,2,3,4,4-Pentamethylphosphetane 1-Oxide, C12H25Op, J. A. Campbell, C. N. Caughlan, A. Fitzgerald, C. Campana, Sheldon E. Cremer

Chemistry Faculty Research and Publications

No abstract provided.

A Study Of Temperature Dependent Electrical Properties Of Ion-Implanted Gallium Arsenide, Shanmugam Sundaram

Master's Essays (1922 - )

Two samples, GaAs:Mg (p-type) and GaAs:Si (n-type), ion-implanted to the same does of 5x10¹² ions/cm². were investigated to study their temperature dependent electrical properties. The resistivities and Hall constant were determined directly by Van der Pauw Technique. Sheet carrier concentration and carries mobility were then calculated. The Silicon sample, in which the properties were relatively temperature independent, was found to be in the metallic conduction range. Hence the magnesium sample was chosen for further temperature dependency investigation.

The Electrochemical Oxidation Of Substituted Catechols, Michael D. Ryan, Alice Yueh, Wen-Yu Chen

Chemistry Faculty Research and Publications

The oxidation of substituted catechols was studied by cyclic voltammetry, chronoamperometry, rotating ring‐disk electrode, and coulometry. The results showed that the quinones that were formed from the oxidation of substituted catechols reacted with the basic forms of the starting material to yield the dimeric product. These products were generally unstable and rapidly polymerized or underwent some other irreversible reaction to form an electroinactive product. For 3,4‐dihydroxyacetophenone and propriophenone, the intermediate was stable long enough to be observed in cyclic voltammetry. The rate of the coupling reaction was found to correlate well with the Hammett ρ‐σ parameters and indicated that there …

The Solid State 13C-Nmr And 19F-Nmr Spectra Of Some Graphite Fluorides, Charles A. Wilkie, Gong-Yu Lin, Daniel T. Haworth

Chemistry Faculty Research and Publications

The solid state ¹³C nuclear magnetic resonance spectra of fluorinated graphites show two resonances, one of which is assigned to aromatic carbon and the other to aliphatic carbon. The resonances are very broad with the high-field resonance centered at about 35 ppm below tetramethylsilane (TMS) and a low-field resonance centered at about 160 ppm below tetramethylsilane. The high-field resonance is typical of an sp³-like carbon and the low-field resonance is assigned to sp²-like carbons. It is found that the aromatic resonance in graphite decreases with an increase in fluorination of the graphite fluorides examined in …

The Effect Of Slow Two‐Electron Transfers And Disproportionation On Cyclic Voltammograms, Michael D. Ryan

Chemistry Faculty Research and Publications

The EE mechanism (two‐electron transfer) for cyclic voltammetry was investigated in considerable detail along with the effect of disproportionation. The theory was developed for either the first or second electron transfer being slow while the other one was reversible. It was possible to develop generalized working curves for the height and shape of the wave regardless of the difference in E^o's and the values of α and K_s. This theory was then applied to the analysis of the reduction of benzil in the presence of alkaline earth ions in dimethylformamide.

The Solid State 13C-Nmr Spectra Of Some Carbides, Daniel T. Haworth, Charles A. Wilkie

Chemistry Faculty Research and Publications

The utility of NMR spectroscopy to the study of liquids or solids dissolved in liquids is well known. This technique has been used infrequently to studies in the solid state[I,2]. Work has been done on diamond, graphite and coa113-6]. The ¹³C-NMR of ebony and ivory have been studied by the magic angle technique[7]. The solid state ¹³C-NMR spectra of graphite and diamond can be interpreted in terms of tetrahedral (sp³) and trigonal planar (sp²) carbon atoms[8]. We now report our investigations using solid state ¹³C-NMR spectroscopy to study various types of carbides.

A Solid State 13C-Nmr Study Of Diamonds And Graphites, Charles A. Wilkie, Thomas C. Ehlert, Daniel T. Haworth

Chemistry Faculty Research and Publications

The ¹³C-NMR spectra of gem quality and industrial diamonds show two resonances with the more intense resonance at high field. Two resonances are also shown in ¹³C-NMR spectra of various graphites; however, the low field resonance is of greater intensity than the high field resonance in the graphites. The resonances are very broad and they are assigned to graphite type (sp²) carbon and diamond type (sp³) carbon.

The 13C-Nmr Solid State Spectroscopy Of Various Classes Of Coals, Charles A. Wilkie, Daniel T. Haworth

Chemistry Faculty Research and Publications

The ¹³C-NMR spectra of various classes of coal obtained in the solid state show two resonances, one of which is assigned to aromatic carbon and the other to aliphatic carbon. The resonances are very broad with the high field resonance centered at about 7 ppm below tetramethylsilane and a low field resonance centered at about 140 ppm below tetramethysilane. Based on our previous solid state ¹³C-NMR studies of graphite and diamond, the high field resonance is typical of a sp³ carbon whereas the low fields resonance is assigned to a sp² carbon whereas the low fields …

A 13C-Nmr Study Of Cis-Ti(Ac Ac)2Cl2, Daniel T. Haworth, Charles A. Wilkie

Chemistry Faculty Research and Publications

No abstract provided.

Effect Of Sodium Ions On The Electrochemical Reduction Of Diethyl Fumarate In Dimethylsulfoxide And Acetonitrile, Michael D. Ryan, Dennis H. Evans

Chemistry Faculty Research and Publications

No abstract provided.

A Study Of The Chelation Of Copper (Ii) With Various Indicators And Chelating Agents In A Non-Aqueous Solvent, Marian Rauch

Bachelors’ Theses

The chelation of Copper II in nonaqueous solvent systems has been under investigation, however, its application is generally limited to extraction methods. In recent years, considerable work has been done at Marquette to investigate spectrophotometric titrations of metals with various chelating agents in nonaque6us solvent systems to determine stability constants and as an important contribution to the field of direct analytical methods. The purpose of this work was to study the adsorption effects and the titration of various types of indicators when applied to the Copper II - Dibenzyldithiocarbamic Acid Zinc Salt Chelate and the Copper II-a -Benzoinoxime Chelate in …

A Study Of The Precipitation Of Lead Bromide Fluoride At Low Ph Values In The Presence Of Boron, David W. Freund

Bachelors’ Theses

The determination of fluorine has been an important analytical problem for some time. Volumetric, gravimetric and instrumental methods have been used with some degree of success. Each of these methods have been limited in some way and no completely satisfactory method for the determination of fluorine has been found. The most popular of these methods is the determination of fluorine as lead chloride fluoride. This method has the advantage of giving reasonably accurate results and the lead chloride fluoride precipitate gives an excellent conversion factor for fluorine due to its high molecular weight. The procedure requires no special or expensive …

Synthesis And Nuclear Magnetic Resonance Studies Of Some Boron And Nitrogen Substituted Borazines, Michael G. Henk

Master's Theses (1922-2009) Access restricted to Marquette Campus

From the time Stock and Pohland (44) first prepared borazine in 1926 until Schaeffer and Anderson (33) found a convenient method of preparing borazine in 1949, comparatively little work was done with this compound. Since 1949 work with borazine has progressed geometrically. Today there are a large number of borazines known (15, 36). However, fluorine substituted borazines were unknown until 1962 (29) and to this day very little work has been done with fluorine substituted borazines (2, 27, 30). Also, only a few unsymmetrical borazines have been prepared (38, 40, 41, 42). It would be desirable to have a convenient …

Determination Of The Ionization Potential Of Argon, Francis A. Brhely

Bachelors’ Theses

The introduction and discussion of a gas filled thyratron, with data and graphs determining the ionization potential of argon.

Determination Of Leadchlorofluoride With Sodium Formate Buffer, Bernadine K. Kasiewicz

Bachelors’ Theses

The method used for the leadchlorofluoride is a gravimetric method which is attempted to be improved by sutiable buffer to lower the pH to 2 - 2.5.

In this experiment, I am attempting to show that sodium formate may be a possible buffer for use with leadchlorofluoride.

Preparation And Infrared Spectrum Of Dimethyl Pinate In An Attempt To Determine The Configuration Of Pinic Acid, Margaret Schormuller

Bachelors’ Theses

The esters if pinic acid are in increasing demand for low temperature lubricants, and certain esters are also useful as plasticizers. In spite of the vast amount of work that has been done with pinic acid and its esters, its geometrical configuration has not yet been satisfactorily established. Stereoisomers may result from both geometrical and optical isomerism. If the cis configuration is assumed to be the dd-enantiomorph, a total of four enantiomorphs are possible.

A Study Of The Variables Affecting The Addition Of Nitrosyl Chloride To Alpha Methyl Styrene, Mary Jane Buchek

Bachelors’ Theses

While working with two compounds, one of which was an olefin, and the other which was Nitrosyl Chloride, Dr. N. Hoffman noticed that although a normal reaction appeared to be taking place, two relatively unusual products were obtained.

As the problem was suggested to me at this point, a literature search was started, first of all, to find out the specific mechanism governing the addition of Nitrosyl Chloride to olefins; secondly, to find out if anyone who had done any type of work at all with Nitrosyl Chloride had obtained the same unusual results as were obtained here; and finally, …

Gravimetric Determination Of Barium By Homogeneous Precipitation With Sulfamic Acid, Elizabeth Ann Kunst

Bachelors’ Theses

Work was undertaken to confirm the results reported by W.y. Wagner and J.A. Wuellner in Analytical Chemistry, 24, 1031 (1952) for the gravimetric determination of barium by homogeneous precipitation with sulfamic acid, to determine the effects produced by slight modifications in procedure, and to investigate the feasibility of separating mixtures of barium and calcium by this method.

On A Certain Subgroup Of The Group Of Isomorphisms, I, Of An Abelian Group Of Order Pn, And Type, Robert D. Pumford

Bachelors’ Theses

Any Abelian, G, of order pn, where p is prime and type (l,l,l,...) may be generated by a set of elements a1,a2,a3,...an each of order p. We shall now consider the group, I, o isomorphisms of G. If T is an isomorphism and a1, a2,...an are the independent generators of G, we have the following correspondence under T.

An Investigation Into The Effects Of Ultrasonic Sound Waves On The Electrolytic Oxidation Of The Ferrous Ion, David Joseph Leestma

Bachelors’ Theses

Upon becoming interested in the use of ozone as an oxidizing agent, the author found a reference in the current literature to the production of ozone by means of ultrasonic radiation. It was decided to investigate the effects of this ultrasonically produced ozone upon the ferrous ion. As far as the author has been able to determine, no work of this type has ever been published. This work, then, is of the nature of pioneering fundamental research.