Photoelectrocatalytic decomposition of gaseous isopropanol in a polymer electrolyte photoreactor

A photoelectrochemical reactor constructed as a proton exchange membrane fuel cell was utilized to electrochemically enhance the photocatalytic decomposition of gas-phase isopropanol. Nafion membrane was employed to serve as solid electrolyte to establish an electrochemical circuit for the gaseous photocatalytic reaction. The electrical current density of photoanode was found to correspond to the variation of the applied bias and relative humidity of the inlet gas. Photocatalytic decomposition rate was remarkably increased by 20 % by applying a bias potential of 5 V. The effect of relative humidity exhibited multiple effects for membrane conductivity of Nafion and efficiency of photocatalytic decomposition reaction.     

Self‐Assembly of Anionic Porphyrins and Alkaline or Alkaline Earth Metal Ions Mediated by Cucurbit[7,8]uril

Nanoscaled coordination polymers based on biologically prevalent ions have potential applications in drug delivery and biomedical imaging. Herein, coordination polymer nanoparticles of anionic porphyrins, including meso‐tetra(4‐carboxyphenyl)‐porphyrin (H₂TCPP^4?) and meso‐tetra(4‐sulfonatophenyl)‐porphyrin (H₂TPPS^4?), and alkaline or alkaline earth metal cations, such as K⁺ and Ca²⁺, were constructed in aqueous solution in the presence of cucurbit[7]uril (CB7) or cucurbit[8]uril (CB8). UV/Vis absorption and fluorescence spectroscopy, dynamic light scattering (DLS), scanning electron spectroscopy (SEM), and atomic force microscopy (AFM) were applied to explore the assembly and particle formation of porphyrin anions and metal cations mediated by CBn. The particle size depends on the kinds of CBn and metal cations and their concentrations. The uptake of H₂TPPS^4? particles by tumor cells (A549 cells) was found to be more efficient than H₂TPPS^4? at 37 °C, showing the application potential of such assembled particles in biology and medicine.     

One inorganic-organic hybrid derived from reduced molybdophosphate and trinuclear cadmium(Ⅱ) fragment

One new polyoxometalate (POM)-based inorganic-organic hybrid [Cd3Ⅱ(HPO4)(Hbpp)(H2O)2]{CdⅡ[P4- Mo6O28H3.5(OH)3]2} (H4tpb)·7H2O (1) (bpp = 1,3-bis-(4-pyridyl)propane, tpb = 1,2,4,5-tetra(4-pyridyl)-benzene) constructed from reduced molybdophosphate [P4Mo6O28H3.5(OH)3]5.5- (P4Mo6), trinuclear CdⅡ-phosphate-Hbpp fragment and protonated tpb has been hydrothermally synthesized and structurally characterized by IR, elemental analyses and single crystal X-ray diffraction. The complex 1 crystallizes in the monoclinic system with the space group P21/c and cell parameters of a = 15.672(12)Å, b = 23.839(19)Å, c = 27.654(2)Å, β = 115.850(10)8, V = 9297.9(12) Å3, Z = 4, R1 = 0.0534 and wR2 = 0.1135. In complex 1, the P4Mo6 units are bridged by CdⅡ ions to form the classic sandwich-type [Cd(P4Mo6)2] dimers, which are further connected into a two dimensional network via the trinuclear CdⅡ subunits. The tpb is synthesized in situ from the bpp ligands and connects the adjacent 2D layers into a 3D supramolecular framework through hydrogen bonding interactions. The electrochemical and fluorescent properties of complex 1 have been investigated.     

Patterning Surfaces for Controlled Platelet Adhesion and Detection of Dysfunctional Platelets

Platelets play a fundamental role in thrombus formation and in the pathogenesis of arterial thrombosis. Patterning surfaces for controlled platelet adhesion paves the way for adhesion and activation mechanisms in platelets and detection of platelet functional defects. Here, a new and simple method based on controlled polymerization of 2‐methacryloyloxyethyl phosphorylcholine (MPC) on the surface of styrene‐block‐(ethylene‐co‐butylene)‐block‐styrene (SEBS) is shown. The competition between polymerization and degradation enables platelet adhesion on SEBS to be switched on and off. The adhesive sites of the platelets can be down to single cell level, and the dysfunctional platelets can be quantitatively detected.

     

Application of solid‐phase microextraction to the determination of polycyclic aromatic sulfur heterocycles in Bohai Sea crude oils

A simple and rapid solid‐phase microextraction approach for the isolation of polycyclic aromatic sulfur heterocycles from the aromatic fraction of crude oil is described. 8‐Hydroxyquinoline silica gel impregnated with palladium chloride was used as a sorbent material for extraction. Operational parameters of the extraction solvents have been evaluated and optimized. Benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene and their C₁–C₄ alkyl derivatives were identified and quantified by GC–MS. Under optimum conditions, the limits of detection for benzothiophene, dibenzothiophene, and benzo[b]naphtho[1,2‐d]thiophene were 0.277, 0.193, and 0.597 μg/g oil, respectively. The recoveries for the polycyclic aromatic sulfur heterocycles ranged from 81.5 to 92.1%, and the linear dynamic range was from 10 to 1000 ng/mL. The developed methodology was tested in the characterization of crude oil samples collected at the DY, SZ, ZH, and HC petroleum oil fields of the Bohai Sea. The results proved that SPE coupled with GC–MS is a promising tool for the quantitative analysis of polycyclic aromatic sulfur heterocycles in crude oils, especially for oil samples with low concentrations of polycyclic aromatic sulfur heterocycles.     

Theoretical studies on selectivities in the Staudinger reaction of vicinal diimines and ketenes

The selectivities,including peri-,regio-,and diastereoselectivities,in the Staudinger reaction involving vicinal diimines and ketenes were investigated theoretically via the density functional theory(DFT) calculation.The results indicate that vicinal diimines prefer stepwise [2+2] cycloaddition rather than [2+4] cycloaddition to generate cis-4-imino-β-lactams.The diimines attack the less sterically hindered exo-side of ketenes to generate zwitterionic intermediates,which directly undergo a conrotatory ring closure to produce cis-4-imino-β-lactams whatever diimines with less or more bulky N-substituents.For unsymmetric vicinal ketoaldehyde-derived diimines,their ketimines attack the exo-side of ketenes and undergo a conrotatory ring closure to produce cis-4-aldimino-β-lactams due to less steric effect.The current theoretical studies provide very important information for in-depth understanding of the selective formation of mono-cis-β-lactams from vicinal diimines and ketenes.     

2,2′‐Anhydro‐1‐(3′,5′‐di‐O‐acetyl‐β‐D‐arabinofuranosyl)uracil,a cyclouridine nucleoside with a C4′‐endo furanosyl conformation

2,2′‐Anhydro‐1‐(3′,5′‐di‐O‐acetyl‐β‐D‐arabinofuranosyl)uracil, C₁₃H₁₄N₂O₇, was obtained by refluxing 2′,3′‐O‐(methoxymethylene)uridine in acetic anhydride. The structure exhibits a nearly perfect C4′‐endo (⁴E) conformation. The best four‐atom plane of the five‐membered furanose ring is O—C—C—C, involving the C atoms of the fused five‐membered oxazolidine ring, and the torsion angle is only −0.4 (2)°. The oxazolidine ring is essentially coplanar with the six‐membered uracil ring [r.m.s. deviation = 0.012 (5) Å and dihedral angle = −3.2 (3)°]. The conformation at the exocyclic C—C bond is gauche–trans which is stabilized by various C—H...π and C—O...π interactions.     

First Total Syntheses of 4′-0-Geranylisoliquiritigenin And 4′-O-Geranylnarigenin

The title compounds, 4'-0-geranylisoliquiritigenin and 4'-0-geranylnaringenin isolated from Millettia ferruginea and Borania coerulescens respectively, were first synthesized starting from geranyl bromide, 4-hydroxybenzaldehyde and O-hydroxy acetophenones by the condensation reaction and demethoxymethylation as key steps.