A series of tetrahomodioxacalix[4]biscrown-n. Syntheses, crystal structures, and metal binding abilities

A series of novel tetrahomodioxacalix[4]biscrowns with crown-2, crown-3, crown-4, crown-5, and crown-6 units were synthesized. Conformations of each product are dependent on the base used and their conformation stabilities. All conformations were proven by NMR spectra and/or X-ray crystal structures. The 1,3-alternate homodioxacalix[4]biscrown-4 (4b) shows the best selectivity for K+, whereas the 1,3-alternate homodioxacalix[4]crown-5 (5) does for Cs+. Those selectivities are attributable to electrostatic interaction between the metal ion and the crown ring, as well as a pi-metal complexation. However, the C-1,2-alternate conformation does not take the metal ions regardless of the crown species as a result of steric hindrance from the methylene bridge of an ArCH2Ar unit.     

Novel Sesquiterpenes from the Fungus Lactarius piperatus

Four novel sesquiterpenes, namely 7α,8β,13‐trihydroxy‐5,13‐marasmanolide ( 2 ), isoplorantinone ( 5 ), 4,8,14‐trihydroxyilludala‐2,6,8‐triene ( 6 ), and 8‐hydroxy‐8,9‐secolactara‐1,6‐dien‐5,13‐olide ( 10 ), together with six known ones, 7α,8β‐dihydroxy‐5,13‐marasmanolide ( 1) , 7α,8α‐dihydroxy‐5,13‐marasmanolide ( 3 ), isolactarorufin ( 4 ), blennin A ( 7 ), blennin D ( 8 ), and lactarorufin ( 9 ), were isolated from the ethanolic extract of Lactarius piperatus. The structures of these sesquiterpenes, representing diversified structural types, were determined mainly by spectroscopic methods, especially 2D‐NMR techniques. The structure of 6 was further confirmed by a single‐crystal X‐ray‐diffraction determination.     

Control of Enzymatic Degradation of Microbial Polyesters by Plasma Modification

The rate of enzymatic degradation of surface‐modified microbial polyesters, poly[(R)‐3‐hydroxybutyrate] and poly[(R)‐3‐hydroxybutyrate‐co‐3‐hydroxyvalerate], was studied. The plasma treatments were carried out in a CF₃H or O₂ environment. It was found that the CF₃H plasma‐treated polyesters exhibited significant retardation of enzymatic erosion because of the surface fluorocarbon groups induced by CF₃H plasma. These surface fluorocarbon groups act as retardants on enzymatic degradation due to increased hydrophobicity and of the inactivity of enzymes. However, the increased surface hydrophilicity of polyesters induced by O₂ plasma results in no significant acceleration of the enzymatic erosion, which may be due to the thin modified layer.

Weight loss profiles of P(3HB) film exposed to CF₃H plasma as a function of plasma exposure time.     

Complexation mechanism of olefin with silver ions dissolved in a polymer matrix and its effect on facilitated olefin transport

Remarkable separation performance of olefin/paraffin mixtures was previously reported by facilitated olefin transport through silver-based polymer electrolyte membranes. The mechanism of facilitated olefin transport in solid membranes of AgCF3SO3 dissolved in poly(N-vinyl pyrrolidone) (PVP) is investigated. In silver polymer electrolyte membranes, only free anions are present up to the 2:1 mole ratio of [C=O]:[Ag], and ion pairs start to form at a ratio of 1:1, followed by higher-order ionic aggregates above a ratio of 1:2. At silver concentrations above 3:1, the propylene permeance increases almost linearly with the total silver concentration, unexpectedly, regardless of the silver ionic constituents. It was also found that all the silver constituents, including ion pairs and higher order ionic aggregates, were completely redissolved into free anions under the propylene environment; this suggests that propylene can be a good ligand for the silver cation. From these experimental findings, a new mechanism for the complexation reaction between propylenes and silver salts in silver-polymer electrolytes was proposed. The new mechanism is consistent with the linearity between the propylene permeance and the total silver concentration regardless of the kind of the silver constituents. Therefore, the facilitated propylene transport through silver-polymer electrolytes may be associated mainly with the silver cation weakly coordinated with both carbonyl oxygen atoms and propylene.     

用硼酸作催化剂一锅法合成双（二氢化嘧啶酮-4-基）苯

A simple effective synthesis of bis(dihydropyrimidinone-4-yl)benzene derivatives, using boric acid as catalyst,from isophthalic aldehyde or terephthalic aldehyde, 1,3-dicarbonyl compounds and urea or thiourea in glacial acetic acid was described. As the expansion of the classical Biginelli reaction, this method has the advantage of excellent yields 83%-94% and short reaction time 0.5-1.5 h.     

On-channel base stacking in microchip capillary gel electrophoresis for high-sensitivity DNA fragment analysis

We evaluated a novel strategy for high-sensitivity DNA fragment analysis in a conventional glass double-T microfluidic chip. The microchip allows for a DNA on-channel concentration based on base stacking (BS) with a microchip capillary gel electrophoretic (MCGE) separation step in a poly(vinylpyrrolidone) (PVP) sieving matrix. Depending if low conductivity caused a neutralization reaction between the hydroxide ions and the run buffer component Tris+, the stacking of DNA fragments were processed in the microchip. Compared to a conventional MCGE separation with a normal electrokinetic injection, the peak heights of 50-2650-base pair (bp) DNA fragments on the MCGE-BS separation were increased 3.9-8.0-fold. When we applied the MCGE-BS method to the analysis of a clinical sample of bovine theileria after PCR reaction, the peak height intensity of the amplified 816-bp DNA fragment from the 18S rRNA of T. buffeli was enhanced 7.0-fold compared to that of the normal injection method.     

Exploration of the nature of active Ti species in metallic Ti-doped NaAlH4

Clarification of the nature of active Ti species has been a key challenge in developing Ti-doped NaAlH(4) as a potential hydrogen storage medium. Previously, it has been greatly hindered by the invisibility of Ti-containing species in conventional analysis techniques. In the present study, for the first time, the catalytically active Ti-containing species have been definitely identified by X-ray diffraction in the hydrides doped with metallic Ti. It was found that mechanical milling of a NaH/Al mixture or NaAlH(4) with metallic Ti powder resulted in the formation of nanocrystalline Ti hydrides. The variation of the preparation conditions during the doping process leads to a slight composition variation of the Ti hydrides. The catalytic enhancement arising upon doping the hydride with commercial TiH(2) was quite similar to that achieved in the hydrides doped with metallic Ti. Moreover, the cycling stability that was previously established in metallic Ti-doped hydrides was also observed in the hydrides doped with TiH(2). These results clearly demonstrate that the in situ formed Ti hydrides act as active species to catalyze the reversible dehydrogenation of NaAlH(4). The mechanism by which Ti hydrides catalyze the reversible de-/hydrogenation reactions of NaAlH(4) was discussed.     

Synthesis,Spectroscopic Studies,and Crystal Structures of Phenylorganotin Derivatives with [Bis(2,6‐dimethylphenyl)amino]benzoic Acid: Novel Antituberculosis Agents

The novel triphenyl adduct of 2‐[(2,6‐dimethylphenyl)amino]benzoic acid (HDMPA; 1 ), i.e., [SnPh₃(DMPA)] ( 2 ), the dimeric tetraorganostannoxane [Ph₂(DMPA)SnOSn(DMPA)Ph₂]₂ ( 3 ), and the monomeric adduct [SnPh₂(DMPA)₂] ( 4 ), where DMPA is monodeprotonated HDMPA, have been prepared and structurally characterized by means of IR, ¹H‐NMR, and ¹³C‐NMR spectroscopy. The structures of 1 and 2 have been determined by X‐ray crystallography. Single‐crystal X‐ray‐diffraction analysis of 1 revealed that there are two molecules in the asymmetric unit, HD1 and HD2 , differing in conformation, both forming centrosymmetric dimers linked by H‐bonds between the carboxylic O‐atoms. X‐Ray analysis of 2 revealed a pentacoordinate structure containing Ph₃Sn coordinated to the carboxylato group. Significant C? H/π interactions and intramolecular H‐bonds stabilize the structures of 1 and 2 , which self‐assembled via C? H/π and π/π‐stacking interactions. The Ph₃Sn adduct 2 was found to be a promising antimycobacterial lead compound, displaying activity against Mycobacterium tuberculosis H37Rv. The cytotoxiciy in the Vero cell line is also reported.     

Novel Hydrogen‐bond Three Dimensional Networks Generated from the Reaction of Metal Nitrate Hydrate (M = Co,Ni) with Ammonium Thiocynate and Bidentate Ligand Piperazine

The reaction of Co(NO₃)₂·6H₂O with two equivalents of PPz (PPz = piperazine hexahydrate) and two equivalents of NH₄SCN in CH₃OH afforded the complex [Co(NCS)₂(PPz)₂(CH₃OH)₂]. The reaction of Ni(NO₃)₂·6H₂O with two equivalents of PPz and four equivalents of NH₄SCN in CH₃OH afforded the complex [Ni(NCS)₄(PPz)₂]. Their IR spectra have been recorded and the structures have been determined. Crystal data for 1 : space group P&1bar;, a = 6.7208(6) Å, b = 8.4310(8) Å, c = 8.5923(8) Å, a = 77.881(2)°, β = 76.342(2)°, γ = 83.936(2)°, V = 461.75(1) ų, Z = 1 with final residuals R1 = 0.0650 and wR2 = 0.1725. Crystal data for 2 : space group P2(1)/n, a = 7.4209(6) Å, b = 11.0231(9) Å, c = 12.317(1) Å, β = 96.642(9)°, V = 1000.9(2) ų, Z = 2 with final residuals R1 = 0.0378 and wR2 = 0.0809. Important NCS—H‐N and O‐H—N(PPz) hydrogen‐bonding interactions in compound 1 and NCS···H‐N hydrogen‐bonding interactions and NCS—SCN interactions in compound 2 play a significant role in aligning the polymer strands in crystalline solids.     

Self－assembly of Novel Hetero[3]rotaxane, [2]Rotaxanes and [2]Catenane

One linear template 13 and one cyclophane template 15, both incorporating two electron rich 1,4‐dialkoxybenzene units and one diamide unit, have been synthesized. By utilizing donor‐acceptor interaction and/or intermolecular hydrogen bonding assembling principles, one novel hetero[3]rotazane 22·4Cl, possessing one neutral and one tetracationic ring components, has been synthesized from 13, through neutral [2]rotaxane 21 as intermediate. With 15 as template, tetracationic [2]catenane 23·4PF₆ was assembled by using donor‐acceptor interaction, but no neutral [2]rotaxane could be obtained under the typical conditions of hydrogen bonding assembling principle. The interlocked supramolecular compounds have been characterized and their spectral properties are investigated.