Chemistry Commons^™

Archean Phosphorus Liberation Induced By Iron Redox Geochemistry, Barry Herschy, Sae Jung Chang, Ruth Blake, Aivo Lepland, Heather Abbott-Lyon, Jacqueline Sampson, Zachary Atlas, Terence P. Kee, Matthew A. Pasek

Faculty Publications

The element phosphorus (P) is central to ecosystem growth and is proposed to be a limiting nutrient for life. The Archean ocean may have been strongly phosphorus-limited due to the selective binding of phosphate to iron oxyhydroxide. Here we report a new route to solubilizing phosphorus in the ancient oceans: reduction of phosphate to phosphite by iron(II) at low (<200 >°C) diagenetic temperatures. Reduction of phosphate to phosphite was likely widespread in the Archean, as the reaction occurs rapidly and is demonstrated from thermochemical modeling, experimental analogs, and detection of phosphite in early Archean rocks. We further demonstrate that the ...

Characterization And Quantification Of Covalent Modification Of Proteins Using Mass Spectrometry, Pratikkumar N. Rathod

All Dissertations, Theses, and Capstone Projects

Identification and characterization of various post-translational modifications of protein is a key to understanding many unknown cellular processes. In the last few decades, mass spectrometry has evolved as an essential and effective analytical tool for qualitative and quantitative analysis of proteins. In this research, we have developed a novel MALDI-MS² based quantification method for Desmosine and Isodesmosine, which served as cross-linking amino acids of elastin, in order to measure the elastin degradation in the body. This is the first quantification method that not only illustrates the potential of MALDI-Ion Trap MS², but also improvement over the current LC-MS ...

Nmr Characterizations Of Candidate Battery Electrolytes, Stephen A. Munoz

All Dissertations, Theses, and Capstone Projects

Enormous strides have been made in next-generation power sources to build a more sustainable society. Energy storage has become a limiting factor in our progress, and there are huge environmental and financial incentives to find the next step forward in battery technology. This work discusses NMR methods for characterizing materials for use in battery application, with a special focus on relaxometry and diffusometry. Examples are provided of various recent investigations involving novel candidate electrolyte materials with different collaborators. Works discussed in this thesis include: the characterization of a new disruptive solid polymer electrolyte technology, investigations of the dynamics of super ...

Determination Of Polar Solvents By Static Headspace Extraction – Gas Chromatography (She-Gc), Michael Sithersingh

Seton Hall University Dissertations and Theses (ETDs)

ABSTRACT

The term “headspace” is defined as the vapor that forms above or around a liquid or solid sample in a closed container. Usually, the vapor is above the liquid or solid at the top of the container, hence the term headspace. Headspace sampling is a method for separating volatile materials that may be extracted from a more solid sample matrix and then analyzed using gas chromatography. Headspace extraction refers to the collection and analysis of the vapor phase in the container. The Static Headspace Extraction – Gas Chromatography (SHE-GC) technique has been used since the early days of Gas Chromatography ...

Theoretical Study Of Structure And Reactions Of Metalated Oximes And Oxime Ethers, Rainer Glaser, Andrew J. Streitwieser

Rainer Glaser

The potential energy surfaces of acetaldoxime carbanion and its ion pairs formed with lithium and sodium cations ions have been explored with ab initio methods to model and study the regiochemistry of metalated oxime ethers. Planar structures of the carbanions produced by deprotonating acetaldoxime are minima on the potential energy surface. The syn-isomer is 2.6 Kcal/mole more stable than the anti. This difference is not a manifestation of cyclic conjugation but more likely is a result of electrostatic effects. Two chiral and almost isoenergetic minima have been located for the ion pairs formed by either of the isomeric ...

Symmetrically H-Bridged Dimer Of 2-Carboxylatobenzenediazonium. The 1:1 Complex Between 2-Carboxybenzenediazonium Chloride And Benzenediazonium-2-Carboxylate, Christopher J. Horan, Paul E. Haney, Charles Leslie Barnes, Rainer Glaser

Rainer Glaser

The two zwitterions in the H-bridged dimer of 2-carboxylatobenzenediazonim (1) are linked by a crystallographically symmetric O⋯Hctdot;O hydrogen bond with an O⋯O distance of 2.436 (3) Å. Comparison of the (1) with the other benzenediazonium salts shows that the phenyl ring distortions in (1) are determined primarily by the diazonium substituent with only modest additional effects by the carboxylato group. Intramolecular neighboring goup interactions between the N₂ group and the orthoCOO(H) group are indicated and are discussed. The terminal N atom of the diazonium group is bent away from the neighboring carboxylato group ...

Polycyclic Aromatic Hydrocarbons With Aliphatic Sidegroups: Intensity Scaling For The C-H Stretching Modes And Astrophysical Implications, Xuejuan Yang, Aigen Li, Rainer Glaser, Jianxin Zhong

Rainer Glaser

The so-called unidentified infrared emission (UIE) features at 3.3, 6.2, 7.7, 8.6, and 11.3 μm ubiquitously seen in a wide variety of astrophysical regions are generally attributed to polycyclic aromatic hydrocarbon (PAH) molecules. Astronomical PAHs may have an aliphatic component, as revealed by the detection in many UIE sources of the aliphatic C-H stretching feature at 3.4 mm. The ratio of the observed intensity of the 3.4 mm feature to that of the 3.3 μm aromatic C-H feature allows one to estimate the aliphatic fraction of the UIE carriers. This requires knowledge ...

Planarity Of Para Hexaphenyl, Suchismita Guha, Wilhelm Graupner, Roland Resel, Meera Chandrasekhar, H. R. Chandrasekhar, Rainer Glaser, Günther Leising

Rainer Glaser

We present experimental and theoretical findings on the geometry of polycrystalline para hexaphenyl via Raman scattering. The planarity of the molecule is affected by hydrostatic pressure and temperature. Our studies indicate that the potential energy curve which governs the torsional motion between neighboring phenyl rings is "W" shaped. We determine the activation energy to promote the molecule from a nonplanar to a planar state to be 0.04 eV, in good agreement with our quantum chemical calculations. From the relative intensities of the 1280cm^-1 to the 1220cm^-1 Raman modes we show that high pressure planarizes the molecules, modifying ...

Ammonia Elimination From Protonated Nucleobases And Related Synthetic Substrates, Ming Qian, Shuo Yang, Hong Wu, Papiya S. Majumdar, Nathan D. Leigh, Rainer Glaser

Rainer Glaser

The results are reported of mass-spectrometric studies of the nucleobases adenine 1h (1, R = H), guanine 2h, and cytosine 3h. The protonated nucleobases are generated by electrospray ionization of adenosine 1r (1, R = ribose), guanosine 2r, and deoxycytidine 3d (3, R = deoxyribose) and their fragmentations were studied with tandem mass spectrometry. In contrast to previous EI-MS studies of the nucleobases, NH₃ elimination does present a major path for the fragmentations of the ions [1h + H]⁺, [2h + H]⁺, and [3h + H]⁺. The ion [2h + H - NH₃]⁺ also was generated from the acyclic precursor 5-cyanoamino-4-oxomethylene-dihydroimidazole 13h and from the ...

4-Methoxybenzaldehyde Pentafluorophenyl-Methylidenehydrazone, Michael A. Lewis, Charles Leslie Barnes, Bruce A. Hathaway, Rainer Glaser

Rainer Glaser

The crystal structure of the mixed azine C₁₅H₉F₅N₂O is described. The molecule has a high degree of planarity. The two phenyl rings deviate from perfect planarity by less than 2° and the dihedral angles between the ipso-C atoms and the azine bridge also show a minute deviation from planarity of less than 2°. The only dihedral angle that indicates any significant twisting is the dihedral angle about the azine bridge [C1-N1-N2-C8 174.8 (6)°], and even this one is relatively small. Face-to-face arene-arene contacts are the dominant intermolecular interactions. There are ...

(±)-1-Methyl-1,3,6-Triphenyl-7-(2-Phenylpropenyl)-1, 2-Dihydronaphthalene, Yongqiang Sui, Charles Leslie Barnes, Rainer Glaser

Rainer Glaser

The crystal structure of the title compound, C₃₈H₃₂, presents a novel framework that combines the functionalities of a 1,6-diarene-substituted 1,2-dihydronaphthalene (DHN) with a 1,4-distyrylbenzene (DSB) to form a crossed bis-diarene. The lamellar crystal structure is held together by arene-arene interactions. While the orientations of the phenyl rings of the DSB units alternate within both the R and the S substructures, the homochiral substructures feature opposing polarity along the long axes of the DHN-based diarenes.

4-Chloroacetophenone [1-(4-Methoxyphenyl)Ethylidene]Hydrazone, Michael A. Lewis, Charles Leslie Barnes, Rainer Glaser

Rainer Glaser

The crystal structure of the title mixed azine, C₁₇H₁₇CIN₂O, contains four independent molecules, A-D, and molecule B is disordered. All four molecules have an N-N gauche conformation, with C-N-N-C torsion angles of 136.5 (4), 137.0 (4), -134.7 (4) and -134.7 (4)°, respectively. The phenyl rings are also somewhat twisted with respect to the plane defined by C_ipso and the imine bond. On average, the combined effect of these twists results in an angle of 64.7° between the best planes of the two phenyl rings. Arene-arene double T-contacts are ...

2-Carboxybenzenediazonium Chloride Monohydrate, Christopher J. Horan, Charles Leslie Barnes, Rainer Glaser

Rainer Glaser

C₇H₅N₂O₂ ⁺.Cl^-H₂O, M_r = 202.60, monoclinic, C2c, a = 25.62(3), b = 4.964(2), c = 14.900 (14)Å, β = 107.15 (4)°, V = 1811 (3)ų, Z = 8, D_x = 1.486 g cm^-3, λ(Mo Kα) = 0.71073 Å, µ = 3.9 cm^-1, F(000) = 832, T = 298 K, R = 0.035 for 1275 observed reflections. The terminal N atom of the diazonium group is bent away from the carboxyl group. The N₂ and the carboxyl group are on opposite sides ...

Infra-Red Microwave Spectra, Overtones, Degeneracy And Thermal Populations All In One Diagram, Carl W. David

Chemistry Education Materials

An old drawing, which had an error in it, is re-presented (corrected) for understanding the relationships in diatomic vibrational-rotational interactions at the introductory level.

Electronic Effect Of Platinum Alloy Catalysts On Olefin Hydrogenation Kinetics, Colin Reedy, Jeff Miller, Stephen Purdy

The Summer Undergraduate Research Fellowship (SURF) Symposium

Dehydrogenation of alkanes is the first step in transforming light hydrocarbons into liquid fuels and chemicals. This process has traditionally used platinum alloys as catalysts. Alloys are used industrially because they have a greater selectivity than monometallic platinum. Alloying platinum with an inactive promoter modifies the crystalline structure of the surface (geometric effect), and the 5d electrons in platinum responsible for chemistry (electronic effect); both have been suggested to be primarily responsible for dehydrogenation selectivity in platinum alloys. Alloy catalysts have been synthesized using early 3d transition metal promoters with the same Pt₃M crystal structure. X-Ray Absorption Spectroscopy ...

Examining The Effects Of Amino And Thiolate Ligands On The Reactivity And Selectivity Of Palladium On Carbon In Hydrogenation Reactions, Eric Liu, Christina Li

The Summer Undergraduate Research Fellowship (SURF) Symposium

Heterogeneous catalysts are used widely by chemical and energy industries because they show high reactivity but often suffer from lack of selectivity. On the other hand, ligands are commonly used in homogeneous catalysts to control the reactivity and selectivity; however, the effects of the ligands on the steric and electronic properties of heterogeneous catalysts are less understood. We examine the effects of four different ligands: 1-adamantanethiol, 1-adamantylamine, 1-dodecanethiol, and 1-dodecylamine, for the commercial hydrogenation catalyst palladium on carbon. Hydrogenation reactions are used as a screening tool to see the behavior that the different catalysts exhibit in the presence of unsaturated ...

Thienoisatin Oligomers As N-Type Molecular Semiconductors, Natalie M. Kadlubowski, Xuyi Luo, Jianguo Mei

The Summer Undergraduate Research Fellowship (SURF) Symposium

Organic field effect transistors (OFETs) offer many advantages compared to traditional inorganic transistors, such as flexibility and solution processability. In this study we design and synthesize two thienoisatin-based organic semiconducting small molecules, then investigate their electronic properties in n-type OFETs. To introduce n-type charge transport, electron-withdrawing dicarbonitrile moieties were installed on thienoisoindigo and bis-thienoisatin molecules, which led to a quinoidal conjugation on thienoisoindigo, while maintaining an aromatic conjugation on the bis-thienoisatin. Following the syntheses, the molecules were characterized to determine highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) levels via cyclic voltammetry, as well as any potential ...

Synthesis, Characterization, And Crystal Structure Of The (Η5-C5ph5)Cr(Co)3 Radical, Ray J. Hoobler, Marc A. Hutton, Mills M. Dillard, Michael Castellani, Arnold L. Rheingold, Anne L. Rieger, Philip H. Rieger, Thomas C. Richards, William E. Geiger

Michael P. Castellani

The reaction between Cr(CO)₆ and Na(C₅Ph₅ ) in refluxing diglyme yields [Na(diglyme)_3/2][(C₅Ph₅)Cr(CO)₃], 1. Metathesis of 1 with [Ph₃P=N=PPh₃ ]Cl in CH₂Cl₂ yields [Ph₃P=N=PPh₃][(C₅Ph₅)Cr(CO)₃], 2. Oxidation of 1 by AgBF4 in cold THF under an argon atmosphere produces (C₅Ph₅)Cr(CO)₃, 3. Complexes 2 and 3 form a redox pair connected by a quasireversible one-electron process, E⁰ = -0.69 V vs ...

Synthesis And X-Ray Crystal Structure Of [(C5ph5)Crcl(Μ-Cl)2tl]2: An Example Of The Rare M-X-Tli Linkage (X = Halide), K. Brian Davis, T. David Harris, Michael Castellani, James A. Golen, Arnold L. Rheingold

Michael P. Castellani

Reaction of solid TlCl with [(C5Ph5)CrCl(m-Cl)]2 in CH2Cl2 solvent yields the monomeric complex (C5Ph5)CrCl(m-Cl)2Tl in 80% isolated yield. The C5H5 and C5Me5 analogues do not react with TlCl suggesting a steric basis for the reaction of the C5Ph5 material. An X-ray crystal structure of [(C5Ph5)CrCl(m-Cl)2Tl]2•2CH2Cl2 was obtained.

Substitution Reactions Of (C5ph5)Cr(Co)3: Structural, Electrochemical, And Spectroscopic Characterization Of (C5ph5)Cr(Co)2l, L = Pme3, Pme2ph, P(Ome)3, D. John Hammack, Mills M. Dillard, Michael Castellani, Arnold L. Rheingold, Anne L. Rieger, Philip H. Rieger

Michael P. Castellani

The radical complex (C₅Ph₅)Cr(CO)₃ reacts with small, neutral, monodentate Lewis bases (PMe₃, PMe₂Ph, P(OMe)₃) in THF at −78 °C (PMe₂Ph reacts at ambient temperature) to yield the monomeric substitution products (C₅Ph₅)Cr(CO)₂L·THF as thermally stable solids. Electrochemical and spectroscopic data are provided. An X-ray crystal structure of the hemisolvate (C₅Ph₅)Cr(CO)₂PMe₃·0.5THF was obtained. Frozen-solution ESR spectra of (C₅Ph₅)Cr(CO)₂L in toluene are comparable to those ...