Platinum(II)-based hydrogen-evolving catalysts linked to multipendant viologen acceptors: experimental and DFT indications for bimolecular pathways

Three new [PtCl(2)(bpy)] derivatives tethered to 2, 4, and 6 dicationic viologen moieties, [PtCl(2)(MV2)](4+) (1), [PtCl(2)(MV4)](8+) (2), and [PtCl(2)(MV6)](12+) (3), have been synthesized (MV2(4+)=5-ethoxycarbamoyl-5'-(N-R(1)-carbamoyl)-2,2'-bipyridine, MV4(8+)=5,5'-bis(N-R(1)-carbamoyl)-2,2'-bipyridine, and MV6(12+)=5,5'-bis(N-R(2)-carbamoyl)-2,2'-bipyridine, in which R(1)=Asp(NH-VG)-NH-VG, R(2)=Asp(NH-VG)-Asp(NH-VG)-NH-VG, and VG=-(CH(2))(2)-(+)NC(5)H(4)-C(5)H(4)N(+)-CH(3)). In spite of the higher charge storage capacity of 2 and 3 due to the higher number of acceptor groups (VG groups), compound 1 with the lowest number of VG tethers has turned out to exhibit an outstanding catalytic performance towards the hydrogen evolution from water. Quantitative analysis of UV/Vis-NIR absorption spectral changes during the photolysis for 2 and 3 reveal that approximately 2 electrons per molecule are stored over the acceptor groups during the photolysis, and the storage events saturate after 20 min. As for 1, the total number of electrons stored per molecule increases once during the initial 10 min and then abruptly decreases down to around 0.1 electrons per molecule at 20 min, during which the storage is maximized at 10-20 min with 0.6-0.7 electrons stored per molecule, thereby indicating that the rates of radical formation and consumption are balanced during the photochemical hydrogen evolution reaction. The electrical conductivity measurements reveal that ion-pair adducts (adducts with PF(6)(-) ions in solution) are formed by 2 and 3 but are not given by 1 under the catalysis conditions. These, together with the results of molecular mechanics calculations, reveal that stack of two [PtCl(2)(bpy)] units becomes unfavorable as the number of sterically bulky and highly charged VG units per molecule increases. We have therefore concluded that dimerization that leads to the formation of a Pt-Pt association is a key step in the effective catalytic enhancement with [PtCl(2)(bpy)]-type catalysts.     

6 Mcps photon-counting X-ray computed tomography system using a 25 mm/s-scan linear LSO–MPPC detector and its application to gadolinium imaging

6 Mcps photon counting was carried out using a detector consisting of a 1.0 mm-thick LSO [Lu₂(SiO₄)O] single-crystal scintillator and an MPPC (multipixel photon counter) module in an X-ray computed tomography (CT) system. The maximum count rate was 6 Mcps (mega counts per second) at a tube voltage of 100 kV and a tube current of 0.91 mA. Next, a photon-counting X-ray CT system consists of an X-ray generator, a turntable, a scan stage, a two-stage controller, the LSO–MPPC detector, a counter card (CC), and a personal computer (PC). Tomography is accomplished by repeated linear scans and rotations of an object, and projection curves of the object are obtained by the linear scan with a scan velocity of 25 mm/s. The pulses of the event signal from the module are counted by the CC in conjunction with the PC. The exposure time for obtaining a tomogram was 600 s at a scan step of 0.5 mm and a rotation step of 1.0°, and photon-counting CT was accomplished using gadolinium-based contrast media.     

Synthesis of maresin 1 and (7S)-isomer

Maresin 1 (with the 7R carbon) and (7S)-maresin 1 were synthesized stereoselectively. The conjugated triene system was constructed by Pd-catalyzed coupling of the trans cis-dienylborane (the C10–C22 part) with the trans vinyl iodide corresponding to the C1–C9 part. The stereogenic centers at C7 and C14 were created by Ru-catalyzed asymmetric reduction of ketone and asymmetric epoxidation/kinetic resolution of the racemic alcohol, respectively.     

Silica gel-promoted convenient synthesis of 2-bromo-3-hydroxybenzoate derivatives

A convenient silica gel-promoted synthesis of 2-bromo-3-hydroxybenzoate derivatives has been developed via the Diels–Alder reaction of furans with methyl 3-bromopropiolate, followed by a ring-opening aromatization. In addition, 2-bromo-3-methoxybenzoate, derived from 2-bromo-3-hydroxybenzoate with iodomethane, was found to be a good substrate for Pd-catalyzed cross-coupling reactions, despite its sterically hindered structure.     

Resolving double disulfide bond patterns in SNAP25B using liquid chromatography–ion trap mass spectrometry

Complex disulfide bond patterns in synaptosomal‐associated protein of 25 kD B (SNAP25B) are thought to regulate neurotransmitter release in response to oxidative stress. However, the steric feasibility of each possible disulfide pattern in SNAP25B has not been assessed. To assess the steric feasibility of hypothesized closely spaced complex disulfide patterning in SNAP25B and also the feasibility of identifying complex disulfide bond patterns with MS, we have developed a novel probabilistic analysis to unambiguously resolve complex double disulfide bond patterns by using an ion trap mass spectrometer. We analyzed fragmentation patterns of singly linked peptides to determine likely fragmentation events in an ion trap mass spectrometer and observed double and single backbone cleavage along with heterolytic cleavage of the disulfide bond. We modeled these same events in the doubly disulfide linked SNAP25B peptide and used a cumulative hypergeometric distribution with top–down scoring to both identify and differentiate these bonding patterns. Because of the presence of unique MS/MS peaks, two of the bonding patterns were directly identified. The third was assigned on the basis of full chromatographic separation and confirmed by modeling triple breakage fragments. In total, this work demonstrates the feasibility – and also limitations – of identification of complex intradisulfide patterns by using ion trap‐based collision‐induced dissociation‐based fragmentation methods. Copyright © 2013 John Wiley & Sons, Ltd.     

Syntheses of Metallaphosphorane Complexes and Berry Pseudorotation

Iron-, ruthenium-phosphoranes Cp'(CO) 2 M{P(OC 7 H 6 O) 2 }(Cp' = m 5 -C 5 H 5 , m 5 -C 5 Me 5 ; M = Ru, Fe), and cobalt-phosphoranes L(CO) 3 Co-{P(OC 7 H 6 O) 2 }(L = PPh 3 , PPh 2 Me) were prepared. From the variable-temperature 31 P NMR studies, the activation parameters for Berry pseudorotation were determined.     

SYNTHESES AND SOME PROPERTIES OF SULFOXIDES,SULFILIMINES, AMINOSULFONIUM SALTS AND SULFOXIMINES CONTAINING PYRIDINE NUCLEI

Abstract

Several 2-pyridyl sulfides (1) (e.g., methyl (1a), ethyl (1b), isopropyl (1c), benzyl (1d), 1-phenylethyl (1e), l-menthyl (If) 2-pyridyl sulfides; and bis(2-pyridylthio)methane (1g), and methyl 2-(N-oxy-pyridyl) sulfide (1h) were prepared by the usual method. Sulfoxides (2) were prepared by oxidation of the corresponding sulfides with m-chloroperbenzoic acid in good yields. A few sulfoxides were found to work as phase-transfer catalysts for some typical nucleophilic reactions in nonpolar solvents such as benzene, and in two-phase systems such as benzene-water. S-2-Pyridyl-N-(p-toluenesulfonyl) sulfilimines (3) were prepared upon treatment of sulfides with Chloramine-T. Hydrolysis of N-(p-toluenesulfonyl)-2-pyridyl-o-tolylsulfilimine (3i) with conc. sulfuric acid gave the corresponding free sulfilimine in a moderate yield. S-2-Pyridyl sulfoximines (4) were not obtained by the general method from the sulfoxides and hydrazoic acid. Alkyl-2-pyridyl sulfoximines, however, were obtained by oxidation of the free sulfilimines derived from the corresponding aminosulfonium salts (5) prepared by reaction of the sulfides with mesitylene-sulfonylhydroxylamine (MSH). These free sulfilimines and sulfoximines thus prepared were found to give adducts with a few copper salts.     

Study of poly(methylphenylsilylenemethylene) by elastic thermalization lifetime analysis

A new elastic thermalization lifetime analysis (ETLA) is applied to lifetime spectra of polymethylphenylsilenemethylene (PMPSM) measured as a function of time after quick and slow cooling from room to liquid nitrogen temperature. The results show that in this material the efficiency of positronium yield is extremely high (90%). It is found that at low temperature the efficiency is changed by the positron source irradiation. A structural relaxation is observed when the sample is cooled slowly, which is indicated by a gradual decrease in the mean size of the free-volume holes.     

Phase Diagram of the Neodymium Chloride-Sodium Chloride System

Differential thermal analysis was used to study the phase diagram of NdCl3-NaCl system. The peritectic reaction was found to occur at 540±7°C. The peritectic compound was confirmed to be Na3Nd5Cl18 by means of X-ray diffraction analysis. The homogeneity range Na3Nd5Cl18 could not be defined accurately, but appeared to be between 59 and 70 mol% of NdCl3 at temperatures between 300 and 540°C. This revised version was published online in July 2006 with corrections to the Cover Date.