Cyclometalated Iridium(III) and Rhodium(III) Complexes Containing Naphthyridine Ligands: Synthesis,Characterization and Biological Studies

The synthesis, crystal structure, and biological activity of new bis‐cyclometalated compounds [M(ptpy)₂(4‐chloro‐2‐methyl‐1,8‐naphthyridine)]PF₆ [M = Rh ( 1 ); M = Ir ( 2 ); ptpy = 2‐(p‐tolyl)pyridinato] and [M(ptpy)₂(2‐methyl‐1,8‐naphthyridine)]PF₆ [M = Rh ( 3 ); M = Ir ( 4 )] are described. The new compounds were prepared by the reaction of [{M(μ‐Cl)(ptpy)₂}₂] (M = Rh, Ir) with the corresponding naphthyridine ligands. The molecular structures of compounds 1 , 3 , and 4 were confirmed by single‐crystal X‐ray diffraction studies.     

Metal-acetylide addition to tetracyanoethylene

Two push-pull chromophores that have shown utility in the field of molecular electronics and non-linear optics are DDMEBT (1, 2-(4-dimethylamino)phenyl)-3-((4-(dimethylamino)phenyl)ethynyl)buta-1,3-diene-1,1,4,4-tetracarbonitrile) and TDMEE (2, 4-(4-dimethylamino)phenyl)but-1-en-3-yne-1,1,2-tricarbonitrile). Unfortunately, the methods reported for their synthesis give variable yields, use toxic solvents, and only provide small amounts of material. We report improved synthetic protocols, providing access to larger quantities of material. By investigating multiple metal-acetylides of 4-ethynyl-N,N-dimethylaniline and their subsequent addition to TCNE, we obtained various products depending on the identity of the metal ion. This led to the simple synthesis of push-pull chromophoric compounds.     

Phosphoprotein Analysis by MALDI-TOF Mass Spectrometry using On-Probe Tandem Proteolysis and Dephosphorylation

In this investigation, methods based on on-probe enzymatic cleavage matrix-assisted laser desorption/ionization time-of-flight mass spectrometric (MALDI-TOF-MS) analyses have been developed, allowing the rapid assignment of phosphorylation sites within phosphoproteins. The procedures involved robotic sample deposition of a phosphoprotein, such as intact bovine β-casein, on stainless steel or gold MALDI plates, on-probe proteolysis with trypsin for 10–180?s at 37°C, on-probe dephosphorylation for 1–10?min at 37°C with alkaline phosphatase, followed by differential mass spectrometry with peptide mass mapping. The dephosphorylation conditions were initially optimized using in-solution tryptic digestion of the phosphoprotein performed in the presence of MS-compatible anionic surfactant sodium 3-[(2-methyl-2-undecyl-1,3-dioxolan-4-yl)methoxy]-1-propanesulfonate. Two methods of trypsin deactivation were investigated, cooling and quenching by acidification, which resulted in the surfactant either staying intact or becoming cleaved, respectively. Since the surfactant had no detrimental effects on dephosphorylation of phosphopeptides, the acidification and neutralization steps were not included in the final analytical method. A protocol, comprising on-probe tandem, surfactant-aided proteolysis for 3?min followed by on-probe dephosphorylation for 10?min was thus established, allowing the rapid identification of location and sequence of phosphopeptides within a phosphoprotein by these procedures.     

Synthesis of two new thioesters bearing ferrocene: Vibrational characterization and ab initio calculations. X-ray crystal structure of S-(2-methoxyphenyl)ferrocenecarbothioate

Structural and conformational properties of S-benzyl ferrocenecarbothioate (I) and S-(2-methoxyphenyl) ferrocenecarbothioate (II) are analyzed using data obtained from X-ray diffraction, vibrational data and theoretical calculations. According to chemical quantum calculations, the synperiplanar and antiperiplanar forms are found as the first and second more stable conformations, respectively, for the title compounds. The geometric parameters and normal modes of vibration were calculated using a density functional theory method (B3LYP) and the 6-31+G∗∗ basis set for all atoms except for iron. For this atom the calculations were carried out with the Lanl2dz basis set. The calculated parameters are in good agreement with the corresponding X-ray diffraction values. The combined experimental and theoretical approach allows a consistent assignment for most of the fundamental modes.     

Biofuel Combustion Chemistry: From Ethanol to Biodiesel

Biofuels, such as bio‐ethanol, bio‐butanol, and biodiesel, are of increasing interest as alternatives to petroleum‐based transportation fuels because they offer the long‐term promise of fuel‐source regenerability and reduced climatic impact. Current discussions emphasize the processes to make such alternative fuels and fuel additives, the compatibility of these substances with current fuel‐delivery infrastructure and engine performance, and the competition between biofuel and food production. However, the combustion chemistry of the compounds that constitute typical biofuels, including alcohols, ethers, and esters, has not received similar public attention. Herein we highlight some characteristic aspects of the chemical pathways in the combustion of prototypical representatives of potential biofuels. The discussion focuses on the decomposition and oxidation mechanisms and the formation of undesired, harmful, or toxic emissions, with an emphasis on transportation fuels. New insights into the vastly diverse and complex chemical reaction networks of biofuel combustion are enabled by recent experimental investigations and complementary combustion modeling. Understanding key elements of this chemistry is an important step towards the intelligent selection of next‐generation alternative fuels.     

Uranium speciation in biofilms studied by laser fluorescence techniques

Biofilms may immobilize toxic heavy metals in the environment and thereby influence their migration behaviour. The mechanisms of these processes are currently not understood, because the complexity of such biofilms creates many discrete geochemical microenvironments which may differ from the surrounding bulk solution in their bacterial diversity, their prevailing geochemical properties, e.g. pH and dissolved oxygen concentration, the presence of organic molecules, e.g. metabolites, and many more, all of which may affect metal speciation. To obtain such information, which is necessary for performance assessment studies or the development of new cost-effective strategies for cleaning waste waters, it is very important to develop new non-invasive methods applicable to study the interactions of metals within biofilm systems. Laser fluorescence techniques have some superior features, above all very high sensitivity for fluorescent heavy metals. An approach combining confocal laser scanning microscopy and laser-induced fluorescence spectroscopy for study of the interactions of biofilms with uranium is presented. It was found that coupling these techniques furnishes a promising tool for in-situ non-invasive study of fluorescent heavy metals within biofilm systems. Information on uranium speciation and uranium redox states can be obtained.     

Preparation, IR spectroscopy, and time-of-flight mass spectrometry of halogenated and methylated Si(111)

The preparation of chlorine-, bromine-, and iodine-terminated silicon surfaces (Si(111):Cl, Br, and I) using atomically flat Si(111)-(1×1):H is described. The halogenated surfaces were obtained by photochemically induced radical substitution reactions with the corresponding dihalogen in a Schlenk tube by conventional inert gas chemistry. The nucleophilic substitution of the Si-Cl functionality with the Grignard reagent (CH₃MgCl) resulted in the unreconstructed methylated Si(111)-(1×1):CH₃ surface. The halogenated and methylated silicon surfaces were characterized by Fourier transform infrared (FTIR) spectroscopy and laser-induced desorption of monolayers (LIDOM). Calibration of the desorption temperature via analysis of time-of-flight (TOF) distributions as a function of laser fluence allowed the determination of the originally emitted neutral fragments by TOF mass spectrometry using electron-impact ionization. The halogens were desorbed atomically and as SiX _n (X = Cl, Br) clusters. The methyl groups mainly desorbed as methyl and ethyl fragments and a small amount of ⁺SiCH₃.     

Dielectric properties of thin-film ZrO<Subscript>2</Subscript> up to 50 GHz for RF MEMS switches

The dielectric properties of zirconium dioxide (ZrO₂) ceramic thin films were characterized up to 50 GHz using coplanar waveguides (CPWs) and metal–insulator–metal (MIM) capacitors with top circular electrodes. The ZrO₂ films were deposited using a chemical solution onto high-resistivity Si wafers and metal layers. The real part of the dielectric constant of approximately 22 and 26 was extracted at 50 GHz for CPW and MIM structures, respectively, and the loss tangent was approximately 0.09 at 50 GHz. C–V and I–V measurements were carried out to determine low-frequency and DC dielectric properties. The measurement results indicate that ZrO₂ is a promising material to be used as a dielectric layer for radio-frequency (RF) microelectromechanical systems (MEMS) capacitive switches.