A metal-organic framework with highly polar pore surfaces: selective CO2 adsorption and guest-dependent on/off emission properties

A 3D porous Zn(II) metal-organic framework {[Zn(2)(H(2)dht)(dht)(0.5)(azpy)(0.5)(H(2)O)]·4H(2)O} (1; H(2)dht=dihydroxyterphthalate, azpy=4,4'-azobipyridine) has been synthesised by employing 2,5-dihydroxyterephthalic acid (H(4)dht), a multidentate ligand and 4,4'-azobipyridine by solvent-diffusion techniques at room temperature. The as-synthesised framework furnishes two different types of channels: one calyx-shaped along the [001] direction and another rectangle-shaped along the [101] direction occupied by guest water molecules. The dehydrated framework, {[Zn(2)(H(2)dht)(dht)(0.5)(azpy)(0.5)]} (1') provides 52.7% void volume to the total unit-cell volume. The pore surfaces of 1' are decorated with unsaturated Zn(II) sites and pendant hydroxyl groups of H(2)dht linker, thereby resulting in a highly polar pore surface. The dehydrated framework 1' shows highly selective adsorption of CO(2) over other gases, such as N(2), H(2), O(2) and Ar, at 195 K. Photoluminescence studies revealed that compound 1 exhibits green emission (λ(max)≈530 nm) on the basis of the excited-state intramolecular proton-transfer (ESIPT) process of the H(2)dht linker; no emission was observed in dehydrated solid 1'. Such guest-induced on/off emission has been correlated to the structural transformation and concomitant breaking and reforming of the OH···OCO hydrogen-bonding interaction in the H(2)dht linker in 1'/1.     

Combined cation-π and anion-π interactions for zwitterion recognition

Brothers and enemies: Anion-π and cation-π interactions act in a synergistic way when gathered in the molecular cavity of a hemicryptophane host, affording an efficient contribution (-170?kJ?mol(-1)) in zwitterion recognition. NMR titration experiments and calculations reveal the positioning of the guest in the cavity of the heteroditopic receptor. This study emphasizes the importance of anion-π bonds in host-guest chemistry.     

病态分析体系有偏估计的研究

运用广义岭估计和Ｌｉｕｋｅｊｉａｎ提出的有偏估计，对病态分析体系进行了数值模拟和实际光度测定，结果表明，广义岭估计显优于最小二乘估计，Ｌｉｕｋｅｊｉａｎ法有功效，可和为解析病态分析体系的化学计量学方法。     

Electronic tongue for quality assessment of ethanol, vodka and eau-de-vie

Rapid quality assessment of alcoholic beverages, including brand identification and detection of products of unacceptable quality or counterfeits is an important practical task. In the present work the multisensor electronic tongue system (ET), based on array of potentiometric chemical sensors was applied to recognition and classification of spirits such as vodka and ethanol used for vodka production and also for eau-de-vie in cognac production. The ET system was capable of detecting presence of contaminant substances in vodka in concentrations exceeding allowed levels as well as of distinguishing vodka complying and not complying with state quality standards. Ten brands of vodka produced at the same distillery using water and ethanol of different purity and various taste additives were discriminated using the instrument. The ET could distinguish synthetic and alimentary grain ethanol as well as alimentary ethanol of different grades (i.e. different degree of purification). A feasibility study was run on several eau-de-vie samples, which included fresh and aged eau-de-vie as well as samples produced using different distillation technology and samples kept in contact with different kinds of oak. The electronic tongue showed a promise as an analytical instrument for rapid quality assessment of spirits.     

Preparation and characterisation of thermoresponsive poly[(N-isopropylacrylamide-co-acrylamide-co-(hydroxyethyl acrylate)] microspheres as a matrix for the pulsed release of drugs

Despite the large number of publications and patents concerning pH/thermoresponsive polymers, few data are available concerning the preparation of thermoresponsive cross-linked microspheres from preformed polymers. Therefore, N-isopropylacrylamide-co-acrylamide-co-(2-hydroxyethyl acrylate) copolymers were obtained as a new thermoresponsive material with a lower critical solution temperature (LCST) around 36 degrees C, in phosphate buffer at pH 7.4, and with a cross-linkable OH group in their structure. The LCST value was determined both by UV spectroscopy and microcalorimetric analysis. These copolymers were solubilised in acidified aqueous solution below their LCST, dispersed in mineral oil, and transformed into stable microspheres by cross-linking with glutaraldehyde. The thermoresponsive microspheres were characterised by optical and scanning electron microscopy, degree of swelling, and water retention. The pore dimensions of the microspheres and the retention volumes of some drugs and typical compounds were evaluated at different temperatures by liquid chromatography. Indomethacin, as a model drug, was included in the microspheres by the solvent evaporation method. Finally, the influence of temperature and of temperature cycling on drug release was investigated.     

Unfused Nonfullerene Acceptors Based on Simple Dipolar Merocyanines

Merocyanine (MC) dyes exhibit facile synthesis and attractive optical properties, making them widely studied as the donor materials in organic solar cells (OSCs). In this study, for the first time, simple indole-based MCs are successfully designed as unfused nonfullerene acceptors (NFAs) for OSCs by forming dimers with A−D-π-D−A structure, which possess enhanced photostability compared to the well-known ITIC acceptor and high electron mobility in blend films. When blended with P3HT donor, one of the dimers, i. e. Z2, shows a good cell efficiency of 3.53 %, which outperforms the performance of most of P3HT/NFA blends, particularly for unfused systems, and thus indicates good potential of simple MCs as NFAs.     

Local Distortions in a Prototypical Zeolite Framework Containing Double Four-Ring Cages: The Role of Framework Composition and Organic Guests**

Cube-like double four-ring (d4r) cages are among the most frequent building units of zeolites and zeotypes. In materials synthesised in fluoride-containing media, the fluoride anions are preferentially incorporated in these cages. In order to study the impact of framework composition and organic structure-directing agents (OSDAs) on the possible occurrence of local distortions of fluoride-containing d4r cages, density functional theory (DFT) calculations and DFT-based molecular dynamics simulations were performed for AST-type zeotypes, considering four different compositions (SiO₂, GeO₂, AlPO₄, GaPO₄) and two different OSDA cations (tetramethylammonium [TMA] and quinuclidinium [QNU]). All systems except SiO₂-AST show significant deformations, with a pyritohedron-like distortion of the d4r cages occurring in GeO₂- and GaPO₄-AST, and a displacement of the fluoride anions towards one of the corners of the cage in AlPO₄- and GaPO₄-AST. While the distortions occur at random in TMA-containing zeotypes, they exhibit a preferential orientation in systems that incorporate QNU cations. In addition to providing detailed understanding of the local structure of a complex host-guest system on the picosecond timescale, this work indicates the possibility to stabilise ordered distortions through a judicious choice of the OSDA, which might enable a tuning of the material's properties.