Synthesis of novel side‐chain triphenylamine polymers with azobenzene moieties via RAFT polymerization and investigation on their photoelectric properties

Two novel and well‐defined polymers, poly[6‐(5‐(diphenylamino)‐2‐((4‐methoxyphenyl)diazenyl)phenoxy)hexyl methacrylate] (PDMMA) and poly[6‐(4‐((3‐ethynylphenyl)diazenyl) phenoxy)hexyl methacrylate] (PDPMMA), which bear triphenylamine (TPA) incorporated to azobenzene either directly (PDMMA) or with an interval (PDPMMA) as pendant groups were successfully prepared via reversible addition‐fragmentation chain transfer polymerization technique. The electrochemical behaviors of PDPMMA and PDMMA were investigated by cyclic voltammograms (CV) measurement. The hole mobilities of the polymer films were determined by fitting the J‐V (current‐voltage) curve into the space‐charge‐limited current method. The influence of photoisomerization of the azobenzene moiety on the behaviors of fluorescence emission, CV and hole mobilities of these two polymers were studied. The fluorescent emission intensities of these two polymers in CH₂Cl₂ were increased by about 100 times after UV irradiation. The oxidation peak currents (I_OX) of the PDMMA and PDPMMA in CH₂Cl₂ were increased after UV irradiation. The photoisomerization of the azobenzene moiety in PDMMA had significant effect on the electrochemical behavior, compared with that in PDPMMA. The changes of the hole mobility before and after UV irradiation were very small for both polymers. The HOMO energies (E_HOMO, HOMO: the highest occupied molecular orbital) of side chain moieties of TPA incorporated with cis‐isomer and trans‐isomer of azobenzene in PDMMA and PDPMMA were obtained by theoretical calculation, which are basically consistent with the experimental results. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Novel ether-functional spiro-tetronic acid derivatives: molecule design, convenient synthesis and biological evaluation

A novel series of ether functionalization of spiro-tetronic acid derivatives have been designed and conveniently synthesized via three steps, including esterification, one-pot heterocyclization, and etherification reactions. The target molecules have been identified on the basis of analytical spectra data. All newly synthesized compounds have been screened for their potential insecticidal activity against Heliothis armigera and Plutella xylostella compared with spirodiclofen by standard method.     

Application of alkoxide in catalytic transfer hydrogenation of unsaturated nitrogen compounds

Alcoholate was utilized in catalytic transfer hydrogenation of unsaturated nitrogen compounds. In the reduction of nitro compounds, oximes and imines, alkoxide was used as the promoter, with alcohol as the hydrogen source, while in the reduction of nitriles, alkoxide was used as the hydrogen source.     

Co-precipitation synthesis of precursor with lactic acid acting as chelating agent and the electrochemical properties of LiNi0.5Co0.2Mn0.3O2 cathode materials for lithium-ion battery

Journal of Solid State Electrochemistry - Hydroxide precursor Ni0.5Co0.2Mn0.3(OH)2 was successfully prepared by co-precipitation using lactic acid as the environment-friendly chelating agent. And...     

Palladium-catalyzed cycloaromatization polymerization of enediynes

Bergman cyclization has shown great promise in constructing conjugated polymers.However,the application of this reaction in polymer science is still limited due to the harsh reaction condition and ill-defined structure of the achieved polymers.To this end,the cycloaromatization polymerization of enediynes catalyzed by a series of transition metal catalysts is investigated in this work,by taking advantage of the coordination chemistry of the enediyne with the transition metal complexes.According to the nuclear magnetic resonance (NMR),Fourier transform infrared (FTIR),ultraviolet-visble (UV-Vis) spectroscopies and matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) analysis,the cycloaromatization polymerization of enediynes proceeds under milder conditions and in a more controlled manner in the presence of palladium(Ⅱ) complexes,giving structurally regulated conjugated polymers in high yields.     

Synthesis, structure and solution properties of the novel polyampholytes based on cellulose

A novel cellulose-based polyampholyte derivative, carboxylethyl quaternized cellulose (CEQC), was homogeneously synthesized by introducing positively charged quaternary ammonium groups and negatively charged carboxyl groups to the backbone of cellulose. The structure and dilute solution properties of CEQCs were characterized with elemental analysis, FTIR, NMR, viscometer, light scattering and zeta-potential measurement. The nitrogen content and total degree of substituent of acylamino and carboxyl groups increased with an increase of the molar ratio of acrylamide to the anhydroglucose unit of quaternized cellulose (QC). The salt-resistance of CEQC was improved remarkably by introducing opposite charged carboxyl to the QC chains. The intrinsic viscosity of the prepared polyampholytes was found to be very sensitive to the pH of the solutions. CEQC-1, the sample with relative low content of carboxyl groups, behaved as a classical cationic polyelectrolyte. However, CEQC-2 and CEQC-3, the samples with higher content of carboxyl groups, displayed typical polyampholyte behavior, and the isoelectric points (IEP) were determined to be 5.0 and 3.8 respectively. This work provided a facile method for the synthesis of novel cellulose-based polyampholytes with different IEP.     

Urinary metabonomic study using a CUMS rat model of depression

Chronic unpredictable mild stress (CUMS) is a well‐validated model of depression. In this study, a urinary metabonomics method based on the NMR spectrometry was used to study the metabolic perturbation in CUMS‐induced rat depression model. With pattern recognition analysis, a clear separation of CUMS rats and healthy controls was achieved, and nine endogenous metabolites contributing to the separation were identified. CUMS‐treated rats were characterized by the increase of glycine, pyruvate, glutamine, and asparagines, as well as the decrease of 2‐oxoglutarate, dimethylglycine, citrate, succinate, and acetate. The urinary biochemical changes related to the metabolic disturbance in CUMS induced depression, and the possible correlations with live qi stagnation in traditional Chinese medicine are discussed. The work shows that CUMS is a reliable model for studying depression, and the noninvasive urinary metabolomic method is a valuable tool to investigate the biochemical pertubations in depression as an early diagnostic means. Copyright © 2012 John Wiley & Sons, Ltd.     

The effect of phosphate buffer solutions on uniconazole complexation with hydroxypropyl-β-cyclodextrin and methyl-β-cyclodextrin

The inclusion complexes of uniconazole [(E)-1-(4-chlorophenyl)-4,4-dimethyl-2-(1,2,4-triazol-lyl)-1-penten-3-ol, UCZ] with two cyclodextrin derivatives, hydroxypropyl-β-cyclodextrin (HP-β-CD) and methylated-β-cyclodextrin (Me-β-CD), were prepared and characterized by ¹H NMR and FT-IR. The phase solubility of UCZ and HP-β-CD, UCZ and Me-β-CD, which displays the ability of CDs complexation and solubilization, was studied in aqueous solutions and phosphate buffer solutions (PBS) with different property pH values (6.2, 7.2, 8.0). The solubility results indicated that the pH of PBS showed more enhancement on the interaction of HP-β-CD and UCZ than Me-β-CD with the increasing pH value, and the optimal pH value for complexation of UCZ and HP-β-CD, UCZ and Me-β-CD was at 8.0 and at 7.2, respectively. These were also determined by UCZ release behavior and dissolution studies of the complexes in solid state.