Mixed effect of the supporting electrolyte and the zinc anode in the electrochemical homocoupling of 2-bromopyridines catalyzed by nickel complexes in an undivided cell

[reactions: see text] Nickel-catalyzed electroreductive homocoupling of 2-bromomethylpyridines and 2-bromopyridine has been investigated in an undivided cell in the presence of a zinc sacrificial anode. A series of reactions were performed with various types and concentrations of supporting electrolyte. It was observed that a key step in this process is the formation of an arylzinc through a nickel-zinc transmetalation. This intermediate can be transformed back to the reactive arylnickel species to afford the homocoupling as the final product. The back process from the arylzinc intermediate is, however, suppressed in the presence of high concentration (0.2 M) of tetraalkylammonium salts. On the contrary, with NaI, the formation of the dimer is not prevented, whatever the NaI concentration.     

Synthesis of nanoscale NbSe2 materials from molecular precursors

This communication describes a new synthetic approach to one- (1D) and two-dimensional (2D) NbSe2 nanoscale materials using soft chemical methods. Our one-pot synthesis provides a direct route to control the morphology of nanostructures that can exhibit complex electronic properties, and can produce layered, nanocrystalline materials in high yield.     

The role of chelating diamine ligands in the goldberg reaction: a kinetic study on the copper-catalyzed amidation of aryl iodides

The mechanistic details of the Cu-catalyzed amidation of aryl iodides are presented. The kinetic data suggest that the diamine ligand prevents multiple ligation of the amide. The formation of an amidocuprate species external to the catalytic cycle helped to rationalize the dependence on diamine concentration and the inverse dependence on amide concentration at low diamine concentrations. The intermediacy of a Cu(I) amidate was established through both its chemical and kinetic competency.     

An extremely stable and orthogonal DNA base pair with a simplified three-carbon backbone

A nucleotide C3HQ with a minimal three-carbon backbone displays unprecedented pairing strength and orthogonality in a homopair C3HQ:C3HQ in the presence of one equivalent of Cu2+. The pairing stability in DNA even exceeds the related base pair having the regular 2'-deoxyribose backbone. This discovery of a synergy between an artificial backbone and base-pairing scheme opens new avenues for the economical design of modified oligonucleotides with tailored properties.     

Air-breathing laminar flow-based microfluidic fuel cell

This communication reports the design and characterization of an air-breathing laminar flow-based microfluidic fuel cell (LFFC). The performance of previous LFFC designs was cathode-limited due to the poor solubility and slow transport of oxygen in aqueous media. Introduction of an air-breathing gas diffusion electrode as the cathode addresses these mass transfer issues. With this design change, the cathode is exposed to a higher oxygen concentration, and more importantly, the rate of oxygen replenishment in the depletion boundary layer on the cathode is greatly enhanced as a result of the 4 orders of magnitude higher diffusion coefficient of oxygen in air as opposed to that in aqueous media. The power densities of the present air-breathing LFFCs are 5 times higher (26 mW/cm2) than those for LFFCs operated using formic acid solutions as the fuel stream and an oxygen-saturated aqueous stream at the cathode ( approximately 5 mW/cm2). With the performance-limiting issues at the cathode mitigated, these air-breathing LFFCs can now be further developed to fully exploit their advantages of direct control over fuel crossover and the ability to individually tailor the chemical composition of the cathode and anode media to enhance electrode performance and fuel utilization, thus increasing the potential of laminar flow-based fuel cells.     

A mechanism for transition-metal nanoparticle self-assembly

The four-step mechanism by which transition-metal nanoclusters or bulk-metal films self-assemble from metal salts under reductive conditions has been discovered. The presence of two autocatalytic steps in the same reaction scheme--double autocatalysis--is the key to the sharp "turn-on" feature after an induction period observed in the signature kinetic curves. Predictions of the new mechanism that are tested experimentally include the following: that low concentrations and high temperatures will favor nanoclusters over bulk-metal film formation; that bulk-metal is formed in some, if not many, literature syntheses reporting only Pt(0) nanoclusters; and that added ligands are one key to turning on the new mechanism. Particle-size-dependent metal-ligand bond dissociation energies are another implication from this mechanistic work.     

Cluster size selectivity in the product distribution of ethene dehydrogenation on niobium clusters

Ethene reactions with niobium atoms and clusters containing up to 25 constituent atoms have been studied in a fast-flow metal cluster reactor. The clusters react with ethene at about the gas-kinetic collision rate, indicating a barrierless association process as the cluster removal step. Exceptions are Nb8 and Nb10, for which a significantly diminished rate is observed, reflecting some cluster size selectivity. Analysis of the experimental primary product masses indicates dehydrogenation of ethene for all clusters save Nb10, yielding either Nb(n)C2H2 or Nb(n)C2. Over the range Nb-Nb6, the extent of dehydrogenation increases with cluster size, then decreases for larger clusters. For many clusters, secondary and tertiary product masses are also observed, showing varying degrees of dehydrogenation corresponding to net addition of C2H4, C2H2, or C2. With Nb atoms and several small clusters, formal addition of at least six ethene molecules is observed, suggesting a polymerization process may be active. Kinetic analysis of the Nb atom and several Nb(n) cluster reactions with ethene shows that the process is consistent with sequential addition of ethene units at rates corresponding approximately to the gas-kinetic collision frequency for several consecutive reacting ethene molecules. Some variation in the rate of ethene pick up is found, which likely reflects small energy barriers or steric constraints associated with individual mechanistic steps. Density functional calculations of structures of Nb clusters up to Nb(6), and the reaction products Nb(n)C2H2 and Nb(n)C2 (n = 1...6) are presented. Investigation of the thermochemistry for the dehydrogenation of ethene to form molecular hydrogen, for the Nb atom and clusters up to Nb6, demonstrates that the exergonicity of the formation of Nb(n)C2 species increases with cluster size over this range, which supports the proposal that the extent of dehydrogenation is determined primarily by thermodynamic constraints. Analysis of the structural variations present in the cluster species studied shows an increase in C-H bond lengths with cluster size that closely correlates with the increased thermodynamic drive to full dehydrogenation. This correlation strongly suggests that all steps in the reaction are barrierless, and that weakening of the C-H bonds is directly reflected in the thermodynamics of the overall dehydrogenation process. It is also demonstrated that reaction exergonicity in the initial partial dehydrogenation step must be carried through as excess internal energy into the second dehydrogenation step.     

Equisetin biosynthesis in Fusarium heterosporum

An iterative polyketide synthase-peptide synthetase hybrid assembles the HIV-1 integrase inhibitory tetramic acid, equisetin, in the filamentous fungus Fusarium heterosporum.     

Synthesis of cationic porphyrin modified amino acids

Derivatives of amino acids bearing a porphyrin moiety on a side chain were synthesized by coupling a porphyrin to a glutamic acid side chain; the utility of these compounds was demonstrated by their use in solid-phase synthesis of a peptide bearing a cationic porphyrin and by studying its DNA-binding properties.     

Maturation grade of coals as revealed by Raman spectroscopy: progress and problems

The present study questions the sensitivity and the accuracy of Raman spectroscopy as a tool for determining the maturity of natural organic matter (NOM). It focuses on the definition of optimized experimental parameters in order to maximize the quality of the Raman signal and control the accuracy and reproducibility of measurements. A series of 11 coals has been investigated, sampling a wide maturity range (2-7% vitrinite reflectance VR). The role of experimental parameters is first investigated. An excitation wavelength of 514.5 nm gives better results than 457.9 and 632.8 nm, minimizing the fluorescence background observed in the spectra of low-rank coals. Both Raman and fluorescence spectra were investigated with time-resolved experiments in air and argon. These data show that fluorescence and Raman spectra are sensitive to acquisition time and laser power parameters, and reveal a physicochemical instability of the samples under laser irradiation, mostly due to photo-oxidation processes. These data clearly show that the experiments, especially in air, should be performed with strictly constant acquisition parameters. In addition, the results of a whole series of coal measurements performed in air under constant experimental conditions show that Raman spectroscopy is definitely sensitive to the maturity of coal samples with VR> approximately 1%. The most sensitive spectral maturity tracers are the width of the D-band (FWHM-D), the ratio of the peak intensities of the D- and G-bands (I(D)/I(G)), the normalized ratio of the band integrated intensities A(D)/[A(D)+A(G)] for the maturity range VR=3-7% and the width of the G-band (FWHM-G) for VR=1-5%. However, the accuracy and reproducibility are definitely weaker in such measurements compared to the standard VR. Future work must solve the problem of sample stability under laser irradiation, and greatly increase the number of samples to improve the statistical significance of the results.