Enhanced hardness in B-doped ZnO thin films on fused quartz substrates by pulsed-laser deposition

B-doped ZnO thin films have been fabricated on fused quartz substrates using boron-ZnO mosaic target by pulsed-laser deposition technique, and the mechanical properties have been studied by nanoindentation continuous stiffness measurement technique and transmission electron microscope (TEM). Nanoindentation measurement revealed that the hardness of B-doped ZnO films, 9.32 ± 0.90 to 12.10 ± 1.00 GPa, is much greater than that of undoped ZnO films and very close to that of traditional semiconductor Si. The mean transmittance (%) is larger than 81% in the visible range (380-780 nm) for all the films, and the Hall effect measurement showed that the carrier density is around 2 × 10²⁰ cm⁻³ and the resistivity lower than 3 × 10⁻³ Ω cm. TEM characteristics show undoped thin films have more amorphous area between grains while the B-doped ZnO films have thin grain boundaries. We suggest that the grain boundaries act as the strain compensation sites and the decrease in thickness of grain boundaries enhances the hardness of the B-doped ZnO films.     

Synthesis of monodisperse poly(chloromethylstyrene-co-divinylbenzene) beads and their application in separation of biopolymers

The monodisperse, porous poly(chloromethylstyrene-co-divinylbenzene) beads of 7.9 microm were prepared by a single-step swelling and polymerization method. The seed particles prepared by dispersion polymerization exhibited good absorption of the monomer phase. Based on this media, a weak cation-exchange (WCX) stationary phase for HPLC was synthesized by a new chemically modified method. The prepared resin has advantages of biopolymer separation, high column efficiency, low column backpressure, high protein mass recovery, and good resolution for proteins. The dynamic protein-loading capacity of the synthesized WCX packings was 18.2 mg/g. Five proteins were separated in 3.0 min using the synthesized WCX stationary phase. The experimental results show that the obtained WCX resin has very weak hydrophobicity. The WCX resin was also used for the rapid separation and purification of lysozyme from egg white in 5.0 min with only one step. The purity and specific bioactivity of the purified lysozyme were found to be more than 93% and 70 245 U/mg, respectively.     

Preparation of weak cation exchange packings based on monodisperse poly(glycidyl methacrylate-<Emphasis Type="Italic">co</Emphasis>-ethylene dimethacrylate) beads and their chromatographic properties

The monodisperse, macroporous poly(glycidyl methacrylate- co-ethylene dimethacrylate) beads were synthesized by a single-step swelling and polymerization method. Based on this media, a weak cation exchange (WCX) stationary phase for HPLC was synthesized by a new chemically modified method. The prepared resin has advantages for biopolymer separation, high column efficiency, low column backpressure, high protein mass recovery, and good resolution for proteins. The measured bioactivity recovery for lysozyme was 98+/-5%. The dynamic protein loading capacity of the WCX packings was 17.3 mg g(-1). The experimental results show that the synthesized WCX resin has very weak hydrophobicity.     

Molecular‐level structures at poly(4‐vinyl pyridine)/acid interfaces probed by nonlinear vibrational spectroscopy

The molecular structures of the interfaces between a solid poly(4‐vinyl pyridine) (P4VP) surface and poly(acrylic acid) (PAA) as well as hydrochloric acid (HCl) solutions were probed using sum frequency generation (SFG) vibrational spectroscopy in situ in real time. Spectroscopic results clearly reveal that the PAA molecules are adsorbed onto the P4VP surface via hydrogen bonding at the P4VP/PAA solution interface while the P4VP surface is protonated at the P4VP/HCl solution interface. Consequently, the water molecules near the interfaces are strongly perturbed by these two interactions, exhibiting different orderings at the two interfaces. This work clearly demonstrates the power of studying the interfacial molecular‐level structures via nonlinear vibrational spectroscopy when molecular adsorption happens at the solid–liquid interface and paves a way for our future study on tracing the adsorption dynamics of polymer chains onto solid surfaces. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2016 , 54, 848–852     

Novel Synthesis of Aza-phthalimidine Hydroxylactams

A novel and convenient synthetic route for preparing aza-phthalimidine hydroxylactams (5a–j) by N-bromosuccinimide (NBS) was developed. This method involved the substitution reactions of substrates (3a–j) with NBS via unstable intermediate bromides (4a–j) rapidly hydrolyzed into hydroxyl products in the course of the workup process.     

乙炔氢氯化反应中的负载金-离子液体催化剂:离子态金物种的稳定机制

聚氯乙烯(PVC)作为世界通用工程塑料之一,具有优异的物理、化学和机械性能,在工业、农业、建筑、包装、电力等行业中应用广泛.氯乙烯是生产聚氯乙烯的重要单体.氯乙烯的生产主要有电石法和乙烯法两种工艺路线,由于我国“贫油、富煤、少气”的资源现状,电石法产能占全部产能的83%以上.电石法生产氯乙烯的原理是在氯化汞催化剂存在下,将电石水解精制后的乙炔气与氯化氢加成直接合成氯乙烯.随着节能减排及环保要求的逐渐提高和国际涉汞公约的实施,开发新一代绿色无汞催化剂具有重要的战略意义.近年来,金基催化剂是无汞催化剂基础研究和技术开发中最重要的方向.在之前的工作中,我们课题组首先报道了负载离子液体-金催化剂体系(Au-SILP)在电石法生产氯乙烯工艺中的应用,并发现离子液体的存在可以显著提高金活性物种在载体表面的分散度和稳定其化学价态.在后续研究中,我们在负载离子液体-金催化体系中引入金属铜离子(Cu^2+),利用反应过程中Au-Cu之间的氧化还原循环,设计并制备了金属铜基配位离子液体,构建了负载离子液体-金-铜催化剂体系.铜离子的引入形成了一个催化剂自身维持氧化态的微环境,实现了被还原金物种的原位氧化再生.本文在上述研究基础上,利用配位离子液体[Bmim][N(CN)2]中[N(CN)2^–]阴离子和阳离子金之间的强配位作用,构建出比Au-Cl键更稳定的Au–N键,并通过X射线光电子能谱(XPS)、球差校正-扫描透射电镜(AC-STEM)和扩展X射线吸收精细结构(EXAFS)表征证明了Au以单原子状态存在于载体表面.制备的Au-N(CN)2/AC催化剂在乙炔氢氯化反应中表现出比Au-Cl/AC和Au/AC催化剂更高的稳定性和催化活性以及更短的诱导期.进一步表征分析发现,[N(CN)2^–]配体促进了阳离子金和配体之间的电子转移,提高了阳离子金的电子云密度,削弱了乙炔在阳离子金上的吸附强度,抑制了其还原,提高了催化剂的稳定性.更重要的是,与阳离子金配位的[N(CN)2^–]配体使得反应过程中的氯化氢在氮位点发生化学解离,促进了氯化氢活化,同时降低了反应能垒.对负载配位离子液体-金催化体系反应诱导期的分析结果表明,反应诱导期与反应物(乙炔、氯化氢)分子在离子液体层中的溶解度无关,而主要取决于催化剂中Au(Ⅲ)物种的含量和反应物分子在离子液体中的扩散速率.上述研究结果进一步深化了离子液体和活性金物种之间电子的作用机理,建立了负载离子液体-金催化剂体系对反应物的活化机制和反应机理,为进一步开发具有工业应用价值的乙炔氢氯化反应无汞催化剂提供了科学基础和参考.     

Imidazole derivatives as the organic precursor of ZnO nano particle

N₁-Hydroxy-2,4,5-trisubstituted imidazoles were synthesized starting from 1,2-diketones. The crystal structure of 4,5-dimethyl-2-(3-nitrophenyl)-1H-imidazol-1-ol has been determined. An unusual intermolecular hydrogen bonding through the association of water molecule has been reported. These imidazole derivatives can be thought of as the organic precursor for the synthesis of zinc oxide nano particles.     

Synthesis of polyacrylaminoimidazole chelating fiber and properties of concentration and separation of trace Au, Hg and Pd from samples

A novel polyacrylaminoimidazole chelating fiber is synthesized simply and rapidly from nitrilon (an acrylonitrile-based synthetic fiber) and used for the preconcentration and separation of trace Au(III), Hg(II) and Pd(IV) ions from solution samples. The analyzed ions can be quantitatively concentrated by the fiber up to a flow rate of 15.0 mlmin(-1) at pH 3 and can also be desorbed with 15 ml of 4 M HCl+3% thiourea from the fiber column, with recoveries of 96.5-100%. The chelating fiber is reused ten times; the recoveries of these ions are still over 92%, and 100-1000 times of excess of Fe(III), Al(III), Ca(II), Mg(II), Ni(II), Mn(II), Cu(II), Zn(II) and Cd(II) causes no interference in the determination of these ions by inductively coupled plasma atomic emission spectrometry. The capacities of the fiber for the analytes are in the range of 1.56-2.92 mmolg(-1). The results show that the relative standard deviations for the determination of 50.0 ngml(-1) each of Au(III), Hg(IV) and Pd(IV) are in the range of 0.7-2.1%. The recoveries of a standard added in real solution samples are between 97 and 99%, and the concentration of each ion in powder sample detected by the method is in good agreement with the certified value.