Inorganic Chemistry Commons^™

Quantifying Factors That Influence Metal Ion Release In Photocaged Complexes Using Zincast Derivatives, Shawn Burdette

Shawn C. Burdette

Two generations of nitrobenzhydrol-based photocages for Zn2+ have been prepared and characterized. The first series includes the tridentate ZinCast-1 utilizes a bis-pyridin-2-ylmethyl-aniline ligand that forms a 5,5-chelate ring upon metal binding. The related photocages ZinCast-2 with a N-[2-(pyridine-2-yl)ethyl]-N-(pyridine-2-ylmethyl)aniline (5,6-chelate ring) and ZinCast-3 with a N,N-bis[2-(pyridine-2-yl)ethyl]aniline (6,6-chelate ring) were synthesized for comparative studies. The complexes formed by the ions Cu2+, Zn2+ and Cd2+ with three ZinCast and their photoproducts (ZinUnc) were interrogated by UV-Vis spectroscopy. The studies indicate that ZinCast-1 forms complexes of the highest stability and ZinCast-3 exhibits the most significant changes in metal affinity upon uncaging. These results suggest …

Syntheses, Hydrogen Bonding, And Metal Coordination Studies Of New Ferrocene Peptide Conjugates, Craig D. Colquhoun

Electronic Thesis and Dissertation Repository

The main goal of the research was the synthesis of new ferrocene peptideconjugates, to study the role of hydrogen bonding interactions, and the coordinationproperties of these systems. Ferrocene peptide conjugates have been extensivelystudied as models of protein secondary structures. Of particular interest weredisubstituted ferrocene derivatives such as ferrocene dicarboxylic acid, which have beenshown to be important in the design of peptide mimics. The inter-ring spacing betweentwo cyclopentadienyl rings in ferrocene has shown to be appropriate for forminghydrogen bonds between conjugated peptide chains, which are attached to the twocyclopentadienyl rings. Inter-ring spacing has proven to be of great importance for theformation …

Ogólnotechniczne Podstawy Biotechnologii Z Elementami Grafiki Inżynierskiej Ćw., Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Materiały Odstresowujące, Wojciech M. Budzianowski

Wojciech Budzianowski

No abstract provided.

Mox/Cnts Hetero-Structures For Gas Sensing Applications: Role Of Cnts Defects, G. Neri, S. G. Leonardi, N. Donato, C. Marichy, Jean-Philippe Tessonnier, M.-G. Willinger, Kyeong-Hwan Lee, N. Pinna

Jean-Philippe Tessonnier

The preparation, characterization and sensing properties of CNT composites with a thin metal oxide (MOx) surface layer is presented. Atomic layer deposition (ALD) was applied for the coating of the inner and outer CNTs walls with thin films of ZnO and SnO2 of precisely controlled thicknesses. Differently treated CNTs with different degree of surface functionalization were used as support for the oxide films. The sensing properties of the obtained composite materials towards NO2 were investigated and related to the morphological and microstructural characteristics of both the coating and support. SnO2-based composites on CNTs treated at 700 °C show enhanced performance …

Transmetallation Of A Lithium Porphyrin With Iron(Ii), Kidus Debesai

The Corinthian

Synthesis and characterization of the iron(III) derivative of the 2,3,7,8,12,13,17,18-octabromo-meso-tetrakis(N-methylpyridium-4-yl)porphyrin was accomplished via metal metathesis of the lithium porphyrin and iron(II) ion. Preliminary molecular orbital analysis of the iron(II) and iron(III) derivatives demonstrate that the iron(III) porphyrin exists at a lower energy state.

Progress Towards A Facile Synthesis Of A Gadolinium (Iii) Octabrominated Porphyrin, Tseng Xiong

The Corinthian

Towards preparing porphyrin complexes that combine contrast agent and photodynamic therapy capabilities at tumor sites, the Gd(III) porphyrin derivative of the octabrominated meso-tetrakis(N-methyl-4-pyridyl)porphyrin, GdTMPyPBr8 5+ was synthesized by refluxing Gd(III) ion with H3TMPyPBr8 5+ at pH 7. The metallocomplex was characterized by UV-visible spectroscopy and showed a Soret band shift from 503 nm to 463 nm at pH 7, suggesting that metal insertion of Gd(III) into the core of porphyrin ligand had occurred. However, synthesis of the Gd(III) complex required high temperatures and long reaction times. To circumvent these harsh conditions, the lithium porphyrin derivative was first prepared and subsequently …

Labeling And Monitoring The Distribution Of Anchoring Sites On Functionalized Cnts By Atomic Layer Deposition, Catherine Marichy, Jean-Philippe Tessonnier, Marta C. Ferro, Kyeong-Hwan Lee, Robert Schlogl, Nicola Pinna, Marc-Georg Willinger

Jean-Philippe Tessonnier

The chemical inertness of graphite and, in the case of tubes, of rolled up few layer graphene sheets, requires some degree of "defect engineering" for the fabrication of carbon based heterostructured materials. It is shown that atomic layer deposition provides a means to specifically label anchoring sites and can be used to characterize the surface functionality of differently treated carbon nanotubes. Direct observation of deposited titania by analytical transmission electron microscopy reveals the location and density of anchoring sites as well as structure related concentrations of functional groups on the surface of the tubes. Controlled functionalization of the tubes therefore …

Synthesis, Characterization And Computational Study Of [4]Octamethylferrocenophane, Benjamin Mark Wilson

Theses, Dissertations and Capstones

This thesis reports the synthesis of an organic molecule, 1,4-bis(2,3,4,5-tetramethylcyclopentadienyl)butane by two different methods, in about 75% and 85% crude yield. Deprotonation of this molecule followed by reaction with FeCl2 generated the tethered ferrocene, [4]octamethylferrocenophane. Although the yield was low in the first attempt (2%), this molecule has been characterized through NMR spectroscopy, X-ray crystallography, electronic spectroscopy, elemental analysis, and decomposition temperature. A computational study was performed to determine the energy gap between each minimum energy structure. It was found that the energy barrier was not high enough to prevent a rapid interconversion between the two structures of minimum energy …

Functionalized Ruthenatricarbadecaborane Via Selective Cage Iodination And Sonogashira Coupling Reactions, Ariane Perez-Gavilan, Larry Sneddon, Patrick J. Carroll

Articles

Selective iodination of the cyclopentadienylruthenium tricarbadecaboranyl complexes 1-(η5-C5H5)–2-Ph–closo-1,2,3,4-RuC3B7H9 (1) and 1-(η5-C5(CH3)5)–2-Ph–closo-1,2,3,4-RuC3B7H8 (2) to form their mono-iodo derivatives, 1-(η5-C5H5)–2-Ph–6-I–closo-1,2,3,4-RuC3B7H9 (3) and 1-(η5-C5(CH3)5)–2-Ph–6-I–closo-1,2,3,4-RuC3B7H8(4), was achieved in 90% yields by their reactions with ICl in CH2Cl2 solutions. Also isolated in trace amounts from the reaction with 2 was the di-iodo 1-(η5-C5(CH3)5)–2-Ph–6,11-I2–closo-1,2,3,4-RuC3B7H7, (5) complex. The sonication-promoted Sonogashira coupling reaction of 3 with terminal acetylenes catalyzed by Pd(dppf)Cl2/CuI yielded the functionalized ruthenatricarbadecaboranyl complexes 1-(η5-C5H5)–2-Ph–6-(Ph-C≡C)–closo-1,2,3,4-RuC3B7H8 (6), 1-(η5-C5H5)–2-Ph–6-[CH3CH2C(O)OCH2-C≡C]–closo-1,2,3,4-RuC3B7H8 (7), …

Synthesis And Characterization Of Group 5 Metal Complexes Containing Pyrazolate, Amidate, And Related Ligands As Potential Precursors For Thin Film Growth By Atomic Layer Deposition, Thuduwage Hiran Perera

Wayne State University Dissertations

Atomic Layer Deposition (ALD) is an advanced variant of Chemical Vapor Deposition (CVD) and is used to deposit smooth and conformal thin films for applications in the microelectronics industry. ALD requires metal precursors that are sufficiently volatile and thermally stable at elevated temperatures. Several group 5 ALD and CVD precursors were reported in the literature, which have been used to deposit TaN, NbN, Nb2O5, and Ta2O5 thin films. Synthesis of low and mid valent group 5 metal ALD precursors might give us access to deposit NbO2, Nb2O3, Ta2O3, and TaO2 thin films by low temperature ALD pathways upon applying mild …

Synthesis, Spectroscopic, And Electrochemical Properties Of 3d Metal And Ruthenium Complexes With Phenolate And Catecholate Ligands, Frank Donald Lesh

Wayne State University Dissertations

The integration of amphiphilic properties into transition metal coordination systems is a pertinent step toward the development of candidate metallosurfactant precursors for the formation of responsive monolayer films. This concept is intended to preserve the solution-observed redox, spectroscopic, and magnetic responses onto solid surfaces for potential application. Selected metal ions and various ligand designs are investigated to address the effect of coordination and protonation preferences on amphiphilic behavior, the aspects of new modular approaches for Langmuir film precursors of differentiated topologies to extend amphiphilicity and redox behavior, and the introduction of photosensitizing properties into electroactive metallosurfactant precursors. In an attempt …

Synthesis And Characterization Of Size Controlled Transitionmetal Phosphide Nanoparticles And Their Hydrodesulfurization Catalytic Activity, Galbokka Hewage Layan Savithra

Wayne State University Dissertations

Transition metal phosphides are promising catalysts for hydrodesulfurization (HDS). The size-dependent catalytic activity of these metal phosphides for hydrodesulfurization (HDS) remains unstudied because the traditional temperature programmed reduction (TPR) method used in catalyst preparation results in highly polydisperse particles.

The main goals of this dissertation research are (1) synthesize metal phosphide nanoparticles (Ni²P, Rh²P, and Pd⁵P²) with control of size and morphology using a solution based arrested precipitation method; (2) develop large scale synthesis of mesoporous silica encapsulated nanoparticles (Ni²P and Pd⁵P²) with controlled loading to …

Magnetic And Orbital Orders Coupled To Negative Thermal Expansion In Mott Insulators, Ca2ru1-Xmxo4 (M = 3d Transition Metal Ion), Tongfei Qi

Theses and Dissertations--Physics and Astronomy

Ca₂RuO₄ is a structurally-driven Mott insulator with a metal-insulator (MI) transition at T_MI = 357K, followed by a well-separated antiferromagnetic order at T_N = 110 K. Slightly substituting Ru with a 3d transition metal ion M effectively shifts T_MI and induces exotic magnetic behavior below T_N. Moreover, M doping for Ru produces negative thermal expansion in Ca₂Ru_1-xM_xO₄ (M = Cr, Mn, Fe or Cu); the lattice volume expands on cooling with a total volume expansion ratio reaching as high as 1%. The onset of the …

Metal Catalyzed Activation Of E-H Bonds, E = Si, Ge, Sn, Renzo Nelson Arias Ugarte

Open Access Theses & Dissertations

The present project covers the use of complexes of the type: (C5H5)M(CO)nLMe, (M = Fe, n = 1; L = CO, Ph3P; M = Mo, n = 2; L = CO, Ph3P); M(CO)6, (M = Cr, Mo, W) and M(CO)5NMe3 as catalysts for the activation of E-H bonds (E = Si, Ge and Sn). The work is divided in three sections; the first two involves dehydrogenation and the last one amide reduction.

Tunable Gold Nanostructures With Nanocapsules As Template Reaction Vessels, Balasubramanian Ramjee, Srujana Prayakarao, Sangbum Han, Wei Cao

Chemistry & Biochemistry Faculty Publications

Hollow, polymeric, thiol-ene resorcinarene nanocapsules can act as template reaction vessels for the synthesis of gold nanoshells or spherical aggregates of gold nanoparticles depending on the reaction conditions. The spherical nanoparticle aggregates were evaluated as catalysts in the biphasic reduction of 4-nitrophenol.

Synthesis And Flame Retardant Testing Of New Boronated And Phosphonated Aromatic Compounds, Vladimir Benin, Sravanthi Durganala, Alexander Morgan

Chemistry Faculty Publications

The present report describes the preparation and use of some dimethyl terephthalate derivatives in transition metal-catalyzed coupling reactions to produce new reactive flame retardants. Dimethyl iodoterephthalate and dimethyl 2,5-diiodoterephthalate were successfully employed in the preparation of phosphonic and boronic esters and acids. The latter were tested for heat release with a microcombustion calorimeter (ASTM D7309) to determine the potential for heat release reduction of these flame retardant molecules. The results showed that the addition of boronic or phosphonic acids greatly lowered the heat release, due to a condensed phase (char formation) mechanism. Adding ester groups to the boronic acids or …

Quantitative Analysis Of Some Important Metals And Metalloids In Tobacco Products By Inductively Coupled Plasma-Mass Spectrometry (Icp-Ms), Syed Ghulam Musharraf, Muhammad Shoaib, Amna Jabbar Siddiqui, Muhammad Najam-Ul-Haq, Aftab Ahmed

Pharmacy Faculty Articles and Research

Background: Large scale usage of tobacco causes a lot of health troubles in human. Various formulations of tobacco are extensively used by the people particularly in developing world. Besides several toxic tobacco constituents some metals and metalloids are also believed to pose health risks. This paper describes inductively coupled plasma-mass spectrometric (ICP-MS) quantification of some important metals and metalloids in various brands of smoked, sniffed, dipped and chewed tobacco products.

Results: A microwave-assisted digestion method was used for sample preparation. The method was validated by analyzing a certified reference material. Percentage relative standard deviation (% R.S.D.) between recovered …

Hydrogen Production From Biogas By Oxy-Reforming: Reaction System Analysis, Aleksandra Terlecka, Wojciech M. Budzianowski

Wojciech Budzianowski

Oxy-reforming is emerging as an interesting alternative to conventional methods of hydrogen generation. The current article characterises this process through analysis of individual reactions: SMR (steam methane reforming), WGS (water gas shift) and CPO (catalytic partial oxidation). Analyses relate to optimisation of thermal conditions thus enabling cost-effectivenes of the process.

Chemistry Of Dinucleating Macrocyclic Ligand And Their Complexes, Mohammad Mansoob Khan Dr

Dr. Mohammad Mansoob Khan

No abstract provided.