Programmable Polymer‐Based Supramolecular Temperature Sensor with a Memory Function

A new class of polymeric thermometers with a memory function is reported that is based on the supramolecular host–guest interactions of poly(N‐isopropylacrylamide) (PNIPAM) with side‐chain naphthalene guest moieties and the tetracationic macrocycle cyclobis(paraquat‐p‐phenylene) (CBPQT⁴⁺) as the host. This supramolecular thermometer exhibits a memory function for the thermal history of the solution, which arises from the large hysteresis of the thermoresponsive LCST phase transition (LCST=lower critical solution temperature). This hysteresis is based on the formation of a metastable soluble state that consists of the PNIPAM–CBPQT⁴⁺ host–guest complex. When heated above the transition temperature, the polymer collapses, and the host–guest interactions are disrupted, making the polymer more hydrophobic and less soluble in water. Aside from providing fundamental insights into the kinetic control of supramolecular assemblies, the developed thermometer with a memory function might find use in applications spanning the physical and biological sciences.     

5-Bromo- and 3,5-dibromo-2-hydroxy-N-phenylbenzamides — inhibitors of photosynthesis

5-Bromo-(Br-PBA) and 3,5-dibromo-2-hydroxy-N-phenylbenzamides (Br₂-PBA) inhibited photosynthetic electron transport (PET) and their inhibitory efficiency depended on the compound lipophilicity as well as on the electronic properties of the R substituent in the N-phenyl moiety. Br-PBA showed higher PET inhibiting activity than Br₂-PBA with the same R substituent. The most effective inhibitors in the tested series were the derivatives with R = 3-F (Br-PBA; IC₅₀ = 4.3 μmol dm^?3) and R = 3-Cl (Br₂-PBA; IC₅₀ = 8.6 μmol dm^?3). Bilinear dependence of the PET inhibiting activity on the lipophilicity of the compounds as well as on the Hammett constant, σ, of the R substituent was observed for both investigated series. Using EPR spectroscopy it was found that the site of action of the tested compounds in the photosynthetic apparatus is situated on the donor side of PS 2, in D^· or in the Z^·/D^· intermediates. Interaction of the studied compounds with chlorophyll a and aromatic amino acids present in the pigment-protein complexes mainly in photosystem 2 was documented by fluorescence spectroscopy.     

Effect of temperature on the equilibrium and kinetics of galactose,glucose, and lactose adsorption on a cation exchanger

Galacto-oligosaccharides are typically produced by an enzymatic reaction when the post-reaction mixture contains considerable amounts of lactose and glucose and a smaller amount of galactose. In order to develop a process of chromatographic removal of saccharide impurities, adsorption equilibria and kinetics of these di- and monosaccharides were investigated for Diaion UBK 530, an industrialgrade strong cation-exchanger in the Na⁺ form. Frontal chromatographic experiments were carried out in the temperature range of 30–70°C and a broad interval of saccharide concentrations up to 350 g L^?1. Breakthrough curves were described using the equilibrium-dispersive model with the linear adsorption isotherm. Both the distribution and the axial dispersion coefficient values depended on the saccharide molecule type and size. No significant effect of temperature or concentration on the distribution coefficient was observed. The apparent dispersion coefficients of all saccharides exhibited some decrease with the temperature, which was caused by the decrease of the intraparticle mass transfer resistance. An analysis showed that both the intraparticle mass transfer and the axial dispersion had a significant influence on the front dispersion.     

Enantioselective olefin epoxidation using homologous amine and iminium catalysts—a direct comparison

Homologous biphenyl and (diastereomeric) binaphthyl tertiary azepines and quaternary iminium salts were prepared from (+)-(S,S)-l-acetonamine. Both the amines and iminium ions behave as effective catalysts for the enantioselective epoxidation of unfunctionalized olefins (ee up to 83%).     

Electron ionization induced fragmentation of macrocyclic amines C n H2n−1NH2: Evidence for the rearrangement of aminocarbene radical cations and a comparison with long-chain esters

A general mechanism is proposed for the fragmentation of macrocyclic amines under electron ionization (EI). The mechanism involves their rearrangement into long-chain enamines followed by the transfer of the aminocarbene radical cation [CHNH₂]^+? through large-ring transition states. A similar mechanism could be applied also to the El-induced fragmentation of long-chain esters with the transfer of the methoxyhydroxycarbene [C(OH)(OCH3)]^+? radical cation.     

External influence on magnetic properties of Fe-based nanocrystalline alloys

Amorphous and nanocrystalline ribbons of NANOPERM, FINEMET and HITPERM were studied by Mössbauer spectroscopy (MS) after the influence of external factors: different annealing atmospheres, tensile stress and several kinds of corrosion. MS is a suitable tool for such studies because the spectral parameters are very sensitive to changes in the vicinity of the probe — ⁵⁷Fe nuclei. The most sensitive parameters were hyperfine magnetic field in crystalline component, average hyperfine field in amorphous component and direction of net magnetic moments. Influence of external factors modified also the structure of the alloys, i.e. new or modified phases were identified by MS phase analysis.     

Kinetics of oxidation in various forms of carbon

In this work the kinetics of the high-temperature oxidation of the powder amorphous carbon and bulk single-wall carbon nanotubes is studied. The thermal degradation of the sample is measured by differential scanning calorimetry using the continuous heating regime up to 1273 K. Also, the oxidation resistance of the samples is evaluated by the mass loss in a thermogravimetric analyzer. Both flowing and static oxygen and dry-air atmospheres are used. The specific role of the external diffusivity of the reagent gas is analyzed. The kinetics of the chemical reaction is specified using the Kissinger, Coats and Redfern methods.     

Thermal,spectral and biological properties of Zn(II) complex compounds with phenazone

The thermal decomposition of the complexes Zn(form)₂⋅2phen (I), Zn(ac)₂⋅2phen (II), Zn(prop)₂⋅2phen (III), Zn(but)₂⋅2phen (IV), where phen=phenazone, form=formiate, ac=acetate, prop=propionate, but=butyrate has been studied in air by TG/DTG and DTA methods. The possible mechanism of the thermal decomposition was proposed. The final product of thermal decomposition was ZnO. IR data show unidentate coordination of carboxylate group to Zn(II) ion. The complexes were tested against various strains of microorganisms and their efficiency decrease in the sequence yeasts >bacteria>filamentous fungi.     

赣南三地绿茶中微量元素含量的测定

选用了赣南宁都小布岩茶、上犹梅林毛尖茶及定南六台山茶，用火焰原子吸收分光光度法对这三类绿茶中的微量元素Ca、Zn、Mg、Mn、Fe、Cu、Pb的含量进行了测定。方法简单，精密度和灵敏度高，回收率为101％-92％，结果可靠。     

Photoisomerizable bipyridine ligands and macroligands: absorption, photoisomerization properties and theoretical study.

Two 2,2'-bipyridines, substituted at the 4,4'-positions by p-dialkylaminophenylazostyryl moieties p-R2N-C6H4-N=N-C6H4-CH=CH-[6 a, R2N=nBu2N; 6 b, R2N=(nBu)(C4H8OTHP)N; 6 c, R2N=(nBu)(C4H8OH)N], were successfully synthesized by using Wadworth-Emmons reactions. The X-ray structure of 6 a has been determined. Esterification of 6 c with 2-bromoisobutyroylbromide afforded 6 d. This ligand was used as an initiator for the living radical polymerization of methylmethacrylate (MMA) and gave rise to macroligand 6 e. Thin films of good optical quality were obtained by the spin-coating technique. Photoisomerization experiments were carried out on 6 a in solution and on 6 e in both solution and film, and the kinetics of photochemical (E/Z) and thermal (Z/E) isomerization were investigated. They were found to show Z-E back isomerization typical of aminoazobenzene-type rather than of push-pull-type molecules. Density functional theoretical (TD-DFT) calculations were performed on model compound 6 a' (R2N=Me2N) to understand the structural and electronic transitions of the corresponding E-E, E-Z and Z-Z isomers. It was found that the E-E isomer is almost planar as observed experimentally by X-ray diffraction, whereas the Z-Z isomer, which is 35.4 kcal mol(-1) less stable than the E-E isomer, is nonplanar. The theoretical studies also reveal that several transitions of pi-pi*, n-pi* and charge-transfer (CT) types, are involved in the long-wavelength transition of 6 a (E-E). The same observations can be made for the (Z-Z) isomer, and the TD-DFT simulated spectrum fits quite nicely to the experimental, reproducing and explaining the apparition of a blue-shifted charge-transfer band at 390 nm.