Multiferroic materials based on organic transition-metal molecular nanowires

We report on the density functional theory aided design of a variety of organic ferroelectric and multiferroic materials by functionalizing crystallized transition-metal molecular sandwich nanowires with chemical groups such as -F, -Cl, -CN, -NO(2), ═O, and -OH. Such functionalized polar wires exhibit molecular reorientation in response to an electric field. Ferroelectric polarizations as large as 23.0 μC/cm(2) are predicted in crystals based on fully hydroxylized sandwich nanowires. Furthermore, we find that organic nanowires formed by sandwiching transition-metal atoms in croconic and rhodizonic acids, dihydroxybenzoquinone, dichloro-dihydroxy-p-benzoquinone, or benzene decorated by -COOH groups exhibit ordered magnetic moments, leading to a multiferroic organometallic crystal. When crystallized through hydrogen bonds, the microscopic molecular reorientation translates into a switchable polarization through proton transfer. A giant interface magnetoelectric response that is orders of magnitude greater than previously reported for conventional oxide heterostructure interfaces is predicted.     

In situ synthesis of nickel tiara-like clusters with two different thiolate bridges

Four nickel clusters, cyclo-[{Ni(μ-S(i)Pr)(μ-SMe)}(6)] (1), cyclo-[{Ni(μ-StBu)(μ-SMe)}(6)] (2), cyclo-[{Ni(μ-S(i)Pr)(μ-SEt)}(6)] (3) and cyclo-[{Ni(μ-StBu)(μ-SEt)}(10)] (4), based on thiolate ligands have been successfully synthesized and characterized by elemental analysis, FT-IR spectra, UV-vis-NIR spectra, powder X-ray diffraction and single-crystal X-ray diffraction. Intriguingly, the SMe and SEt ligands are generated from solvothermal in situ ligand synthesis through the cleavage of the S-S bond respectively. The four nickel thiolate clusters exhibit tiara-like frameworks consisting of two different types of thiolate ligands.     

A practical electromediated ipso-hydroxylation of aryl and alkyl boronic acids under an air atmosphere

An efficient electromediated aerobic ipso-hydroxylation reaction of aryl and alkyl boronic acids has been developed. Furthermore, mechanistic insight into the role of superoxide anions in this reaction has also been provided based on electrochemical studies and experimental results.     

Self-templated synthesis of single-crystal and single-domain ferroelectric nanoplates

Free-standing single-crystal PbTiO(3) nanoplates were synthesized by a facile hydrothermal method. A "self-templated" crystal growth is presumed to lead to the formation of the PbTiO(3) nanoplates, which have ferroelectric single-domain structures, whose polarization areas can be manipulated by writing and reading. The nanoplates are also effective catalysts for the oxidation of carbon monoxide.     

Sensitive detection of H(2)O(2) and H(2)O(2)-related reactant with Ru(bipy)(2)(7,8-dimethyl-dipyridophenazine)(2+) and oligodeoxyribonucleotide

A sensor for H(2)O(2) and H(2)O(2)-related reactant was constructed with oligonucleotides and Ru(bipy)(2)dppx(2+) (bipy = 2,2'-bipyridine, dppx = 7,8-dimethyl-dipyridophenazine), which was performed by converting the H(2)O(2)-induced DNA cleavage into the change of luminescence. The 'DNA light switch' Ru(bipy)(2)dppx(2+) could emit strong luminescence in the presence of dsDNA. DNA cleavage occurred upon addition of H(2)O(2) due to the Fenton reaction, which resulted in the decrease of the luminescence of Ru(bipy)(2)dppx(2+). Therefore, the luminescence intensity depended on the concentration of H(2)O(2) and H(2)O(2)-related reactants, and the detection limits for H(2)O(2), uric acid and cholesterol were 0.20 μM, 0.46 μM and 1.25 μM, respectively. The recovery varied between 94.0% and 105.0% when the assay was applied to the determination of uric acid and cholesterol in biological samples, which demonstrated the good practicability of the assay.     

Synthesis of Bicyclic Imidazoles via [2 + 3] Cycloaddition between Nitriles and Regioselectively Generated α-Imino Gold Carbene Intermediates

The cyclic α-imino gold carbene intermediate B is most likely generated in situ via regioselective nitrene transfer from an azido group to a tethered terminal alkyne in the presence of a gold catalyst and at ambient temperature. This highly electrophilic intermediate can react with a weakly nucleophilic nitrile, which is used as the reaction solvent, to deliver a bicyclic imidazole rapidly in an overall bimolecular [2 + 2 + 1] cycloaddition and in mostly serviceable yield. The competing intramolecular Huisgen reaction, although likely also catalyzed by gold, is minimized by using AuCl(3) as the catalyst.     

Pillar[5]arene-based polymeric architectures constructed by orthogonal supramolecular interactions

Ureidopyrimidinone functionalized pillar[5]arene (UPyP5) was synthesized and employed to complex with a bisparaquat derivative (G) to form supramolecular polymers at relatively high concentration. The orthogonal binding interactions including quadruple hydrogen bonding and host-guest interaction should play vital roles in the construction of this linear assembly.     

Liquid-liquid/solid three-phase high-speed counter-current chromatography, a new technique for separation of polyphenols from Geranium wilfordii Maxim

High-speed counter-current chromatography using a new liquid-liquid/solid three-phase system was used for the separation of the polyphenols corilagin and geraniin from a crude extract of Geranium wilfordii Maxim in one step. The optimized three-phase system was composed of n-hexane/ethyl acetate/methanol/acetic acid/water and to which was added 10-μm average diameter microspheres of cross-linked 12% agarose at the ratio of 0.2:10:2:1:5 and 0.1 g/mL, respectively. The purities of geraniin and corilagin were 82 and 90%, which were determined by HPLC at 280 nm. A 14.5 and 7 mg of geraniin and corilagin were purified from 160 mg crude extract with the yields of 70 and 78%, respectively.     

Can curcumin food and <Emphasis Type="Italic">Bacillus subtilis</Emphasis> drug be taken simultaneously?

Curcumin (CUR), a frequently-used food additive and flavorings, has been reported to be safe at a wide dose range. Bacillus subtilis (B. subtilis) is commonly found in soil and decomposing organic matter, and it was reported beneficial for humans when ingested. Up to now, there have been no contraindication of B. subtilis except for the avoidance of the drug combination with antibiotics, and the interaction of food and B. subtilis drug is blank. In this study, the interaction of CUR and B. subtilis was investigated. Microcalorimetry was applied to evaluate the effect of CUR on B. subtilis growth. By analyzing the main parameters extracted from the heat-flow power–time curves, it was concluded that CUR could inhibit the growth of B. subtilis, and the 50% inhibiting concentration (IC₅₀) valued 109.9 μg mL⁻¹. The results revealed that it is unreasonable to take CUR and B. subtilis at the same time, and it also provided a new way for the investigation of the interaction between food and drug. Meanwhile, this study indicated that the safety of CUR should be re-evaluated.     

Visible to ultraviolet up-conversion in a novel rare earth-free up-converting phosphor

A novel up-converting phosphor,Na_xAl_yF_x+3y/CaF2（0.3 < x < 0.5,0 < y < 0.1） composite,is prepared by a hydrothermal process at 180°C and an annealing treatment at 500℃.X-ray diffraction（XRD） pattern indicates that Na_xAl_yF_x+3y/CaF₂ is a composite consisting of NaF,Na₃ AlF₆,and CaF₂.The up-conversion luminescence properties of this phosphor are investigated by fluorescence spectrometer.Results show that Na_xAl_yF_x+3y/CaF₂ exhibits visible-to-ultraviolet up-conversion luminescence properties.The emission peaks at 316 and 336 nm are observed when excited by 610 nm,the luminescence lifetime of the emissions is great than 18 ms,and the internal fluorescence quantum yield is 4.2%.Additionally,the luminescent mechanism of this phosphor is also mentioned.