Selective photochemistry at stereogenic metal and ligand centers of cis-[Ru(diphosphine)2(H)2]: preparative, NMR, solid state, and laser flash studies

Three ruthenium complexes Λ-[cis-Ru((R,R)-Me-BPE)(2)(H)(2)] Λ-R,R-Ru1H(2), Δ-[cis-Ru((S,S)-Me-DuPHOS)(2)(H)(2)] Δ-S,S-Ru2H(2), and Λ-[cis-Ru((R,R)-Me-DuPHOS)(2)(H)(2)] Λ-R,R-Ru2H(2) (1 = (Me-BPE)(2), 2 = (Me-DuPHOS)(2)) were characterized by multinuclear NMR and CD spectroscopy in solution and by X-ray crystallography. The chiral ligands allow the full control of stereochemistry and enable mechanistic studies not otherwise available. Oxidative addition of E-H bonds (E = H, B, Si, C) was studied by steady state and laser flash photolysis in the presence of substrates. Steady state photolysis shows formation of single products with one stereoisomer. Solid state structures and circular dichroism spectra reveal a change in configuration at ruthenium for some Δ-S,S-Ru2H(2)/Λ-R,R-Ru2H(2) photoproducts from Λ to Δ (or vice versa) while the configuration for Λ-R,R-Ru1H(2) products remains unchanged as Λ. The X-ray structure of silyl hydride photoproducts suggests a residual H(1)···Si(1) interaction for Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(Et(2)SiH)(H)] and Δ-[cis-Ru((R,R)-Me-DuPHOS)(2)(PhSiH(2))(H)] but not for their Ru(R,R-BPE)(2) analogues. Molecular structures were also determined for Λ-[cis-Ru((R,R)-Me-BPE)(2)(Bpin)(H)], Λ-[Ru((S,S)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], Δ-[Ru((R,R)-Me-DuPHOS)(2)(η(2)-C(2)H(4))], and trans-[Ru((R,R)-Me-DuPHOS)(2)(C(6)F(5))(H)]. In situ laser photolysis in the presence of p-H(2) generates hyperpolarized NMR spectra because of magnetically inequivalent hydrides; these experiments and low temperature photolysis with D(2) reveal that the loss of hydride ligands is concerted. The reaction intermediates [Ru(DuPHOS)(2)] and [Ru(BPE)(2)] were detected by laser flash photolysis and have spectra consistent with approximate square-planar Ru(0) structures. The rates of their reactions with H(2), D(2), HBpin, and PhSiH(3) were measured by transient kinetics. Rate constants are significantly faster for [Ru(BPE)(2)] than for [Ru(DuPHOS)(2)] and follow the substrate order H(2) > D(2) > PhSiH(3) > HBpin.     

A Combined Kinetic and Thermodynamic Approach for the Interpretation of Continuous‐Flow Heterogeneous Catalytic Processes

The heterogeneous proline‐catalyzed aldol reaction was investigated under continuous‐flow conditions by means of a packed‐bed microreactor. Reaction‐progress kinetic analysis (RPKA) was used in combination with nonlinear chromatography for the interpretation, under synthetically relevant conditions, of important mechanistic aspects of the heterogeneous catalytic process at a molecular level. The information gathered by RPKA and nonlinear chromatography proved to be highly complementary and allowed for the assessment of optimal operating variables. In particular, the determination of the rate‐determining step was pivotal for optimizing the feed composition. On the other hand, the competitive product inhibition was responsible for the unexpected decrease in the reaction yield following an apparently obvious variation in the feed composition. The study was facilitated by a suitable 2D instrumental arrangement for simultaneous flow reaction and online flow‐injection analysis.     

A Comparative Study of Biocathodes Based on Multiwall Carbon Nanotube Buckypapers Modified with Three Different Multicopper Oxidases

14 Single‐ and multi‐walled carbon nanotubes from different sources were characterized in detail, and the characteristics obtained were carefully analyzed. The carbon material with the highest capacitance, and also other superior properties (“Taunit‐M” from “NanoTechCenter”, Russia), was chosen for further modification and fabrication of buckypaper based electrodes. These electrodes were biomodified with plant and fungal laccases, as well as fungal bilirubin oxidase. The designed biocathodes were investigated in simple buffers and also in a complex physiological fluid (human serum). Biocathodes based on immobilized fungal laccase were bioelectrocatalytically inactive in chloride containing media at neutral pH. In spite of the quite high current densities realized using biodevices based on plant laccase and fungal bilirubin oxidase, the limited thermal stability of the enzymes renders the biocathodes inadequate for practical applications in implanted situations.     

Cobalt(II) and cadmium(II) square grids supported with 4,4′‐bipyrazole and accommodating 3‐carboxyadamantane‐1‐carboxylate

In poly[[bis(μ‐4,4′‐bi‐1H‐pyrazole‐κ²N²:N^2′)bis(3‐carboxyadamantane‐1‐carboxylato‐κO¹)cobalt(II)] dihydrate], {[Co(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (I), the Co²⁺ cation lies on an inversion centre and the 4,4′‐bipyrazole (4,4′‐bpz) ligands are also situated across centres of inversion. In its non‐isomorphous cadmium analogue, {[Cd(C₁₂H₁₅O₄)₂(C₆H₆N₄)₂]·2H₂O}_n, (II), the Cd²⁺ cation lies on a twofold axis. In both compounds, the metal cations adopt an octahedral coordination, with four pyrazole N atoms in the equatorial plane [Co—N = 2.156 (2) and 2.162 (2) Å; Cd—N = 2.298 (2) and 2.321 (2) Å] and two axial carboxylate O atoms [Co—O = 2.1547 (18) Å and Cd—O = 2.347 (2) Å]. In both structures, interligand hydrogen bonding [N...O = 2.682 (3)–2.819 (3) Å] is essential for stabilization of the MN₄O₂ environment with its unusually high (for bulky adamantanecarboxylates) number of coordinated N‐donor co‐ligands. The compounds adopt two‐dimensional coordination connectivities and exist as square‐grid [M(4,4′‐bpz)₂]_n networks accommodating monodentate carboxylate ligands. The interlayer linkage is provided by hydrogen bonds from the carboxylic acid groups via the solvent water molecules [O...O = 2.565 (3) and 2.616 (3) Å] to the carboxylate groups in the next layer [O...O = 2.717 (3)–2.841 (3) Å], thereby extending the structures in the third dimension.     

Anomeric effect in N-azidomethylpyrrolidine: gas-phase electron diffraction and theoretical study

Gas-phase electron-diffraction data and high-level quantum chemical calculations have been used to study the conformational behaviour of N-azidomethylpyrrolidine. The two most stable conformers with a relative abundance of about 80% at 298 K possess gauche orientation of the azidomethyl group around the C-N(pyr) bond (C-N(azido)gauche with respect to the endocyclic N(pyr)-C bond). This orientation is a strong manifestation of an anomeric effect. The influence of the anomeric effect is also reflected in shortening of the C-N(pyr) bond and lengthening of the C-N(azido) bond as compared to such bonds in other compounds.     

Chemical tailoring of fullerene acceptors: synthesis, structures and electrochemical properties of perfluoroisopropylfullerenes

High-temperature syntheses of the new C(60)(i-C(3)F(7))(2,4,6) and C(70)(i-C(3)F(7))(2,4) isomers and their characterization by spectroscopic methods, X-ray crystallography, cyclic voltammetry and density functional theory provide compelling evidence that they are superior electron acceptors than trifluoromethylfullerenes.     

Determination of per- and polyfluorinated substances in airborne particulate matter by microwave-assisted extraction and liquid chromatography-tandem mass spectrometry

A sensitive and confirmatory analytical method has been developed for the determination of 12 ionic per- and polyfluorinated alkyl substances (PFAS) in fine airborne particulate matter (PM2.5) at trace levels. The proposed method includes extraction of PM2.5-bound PFAS by microwave-assisted extraction (MAE) followed by centrifugation and injection into the liquid chromatograph coupled to a triple quadrupole tandem mass spectrometry system (LC-MS/MS). The main parameters affecting the performance of MAE were optimised using statistical design of experiments (DoE). Recoveries ranged from 83 to 120% and the method quantification limit (MQL) was 1.4 pg m(-3), when air volumes of 720 m(3) were sampled. This method was successfully applied to 41 samples collected from five stations of the monitoring network of the Valencian Regional Government (Spain) during April-July 2010. Eight out of 12 PFCs investigated were quantified in at least one sample (PFBA, PFPeA, PFHxS, 6:2 FTS, PFOA, PFNA, PFOS and PFDA). The measured concentrations ranged from 1.4 to 34.3 pg m(-3).     

Investigation of confined ionic liquid in nanostructured materials by a combination of SANS, contrast-matching SANS, and nitrogen adsorption

Small-angle neutron scattering (SANS), contrast-matching SANS, and nitrogen adsorption have been utilized to investigate the confined ionic liquid (IL) [bmim][PF(6)] phase in ordered mesoporous silica MCM-41 and SBA-15. The results suggest that the pores of SBA-15 are completely filled with IL whereas a small fraction of the pore volume, the pore "core", of MCM-41 is empty. The contrast-matching SANS measurements confirm the enhanced solubility of water in IL. In addition, they provide strong evidence that water does not enter the empty pore core of MCM-41, possibly because of the preferred orientation of the IL molecules in the adsorbed layer.     

Characterisation of exosomes derived from human cells by nanoparticle tracking analysis and scanning electron microscopy

Exosomes from three different cell types (HEK 293T, ECFC, MSC) were characterised by scanning electron microscopy (SEM), dynamic light scattering (DLS) and nanoparticle tracking analysis (NTA). The diameter was around 110 nm for the three cell types. The stability of exosomes was examined during storage at -20°C, 4°C, and 37°C. The size of the exosomes decreased at 4°C and 37°C, indicating a structural change or degradation. Multiple freezing to -20°C and thawing did not affect the exosome size. Multiple ultracentrifugation also did not change the exosome size.