聚苯乙烯磺酸掺杂聚苯胺的合成

以苯胺（An）为单体，过硫酸铵（APS）为氧化剂，在聚苯乙烯磺酸（PSSA）的水溶液中，合成了可完全溶于水的PSSA掺杂PAn。研究了An浓度，PSSA浓度，APS浓度，APS的滴加时间，反应时间及温度对An聚合反应及其产物的水溶性，导电性及特性粘度[η]的影响。结果表明：在比较宽的实验条件下，都可以合成出具有良好导电性的可溶于水的PSSA掺杂PAn；其中当An：PSSA:APS的摩尔比为1．7：2．5：1，APS溶液的滴加时间为3h，反应时间为1h，反应温度为14℃时，得到的掺杂PAn导电率最高达0．156S／cm。     

Monitoring the removal of carbonate from alkali metal hydroxide solutions using gas diffusion flow injection

Monitoring the removal of carbonate from alkali metal hydroxide (MOH, M = K, Na) solutions with calcium oxide (CaO) was studied using a newly developed method for the determination of trace amounts of total carbonate (TC) in alkaline solutions based on a flow injection (FI) technique coupled with a gas diffusion system. The optimized conditions of the FI system were as follows: the flow rate of each carrier, reaction solution (H2SO4) and receptor solution (Cresol Red, pH 8.9) was 0.25 ml min(-1), the sample size was 0.1 ml and the concentration of H2SO4 in the reaction solution was 0.09 M. The limit of detection of TC by the proposed method was 4 x 10(-7) M. The removal efficiency of carbonate was affected by the amount of CaO added, the shaking time of the solutions and the concentration of MOH. For 1 M NaOH and KOH solution, the removal efficiency of carbonate was about 99% and the concentration of residual carbonate was 4 x 10(-5) and 1.2 X 10(-4) M, respectively, when the amount of CaO added was 2 g l(-1) and the shaking time was 16 h.     

Effect of pendent group structures on the chemical selectivity and performance of sulfonated copolymers as novel pseudophases in electrokinetic chromatography

Amphiphilic copolymers of 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) with dihydrocholesteryl acrylate (pDHCHAt) or tert-octyl acrylamide (ptOAm) as comonomers were synthesized, characterized and used as new polymeric pseudostationary phases in electrokinetic chromatography. High-efficiency separations with theoretical plates around 500,000 to 870,000/m were achieved. Linear solvation energy relationships analysis of 20 solutes was performed to investigate the retention mechanism. Polycyclic aromatic hydrocarbons (PAHs) were separated under 30% v/v acetonitrile. The separation of nine aromatic model solutes by pDHCHAt showed significantly different selectivity from that of sodium dodecyl sulfate. Although only minor difference in selectivity was found for small aromatic compounds on pDHCHAt and poly(AMPS-lauryl acrylate), significantly different retention mechanism was found for PAHs and n-dodecanophenone comparing both copolymers. Significant chemical selectivity difference was found for selected small aromatic compounds on ptOAm and poly(AMPS-stearyl acrylamide).     

Comparative spectroscopic and electrochemical properties of bis(octakis(dodecylthio)naphthalocyaninato)europium(III) and bis(tetra-tert-butylnaphthalocyaninato)europium(III) complexes

Bis(substituted-2,3-naphthalocyaninato)europium(III) complexes: bis(octakis(dodecylthio)-2,3-naphthalocyaninato)europium(III) (Eu[2,3-Nc(SC12H25)8]2, 1) and bis(tetra-tert-butyl-2,3- naphthalocyaninato)europium(III) (Eu[2,3-Nc(t-Bu)4]2, 2) have been synthesized by cyclic tetramerization of naphthalonitriles with Eu(acac)3.H2O in the presence of 1,8-diazabicyclo[5.4.0]undec-7-ene (DBU) in refluxing n-octanol. These compounds were characterized by UV-visible, magnetic circular dichroism (MCD), near-IR, IR, EPR, and mass spectroscopies. The absorption and MCD spectra of 1 showed splitting of the Q band, with peaks at 700 and 784 nm, red shifted from the Q band of 2 at 763 nm. The absorption and MCD spectral band deconvolution calculations of complex 1 gave two A terms in the Q-band region. The A terms are assigned to 2A2-->2E1 transitions. Cyclic voltammograms of 1 and 2 showed reversible oxidation couples at E1/2 = -0.28 V (for 2) and -0.25 V (for 1) vs ferrocenium/ferrocene (Fc+/Fc). The second oxidation exhibited a complicated behavior for both complexes. The reduction couples for 2 were observed at E1/2 = -0.61, -1.64, -1.97, and -2.42 V, and for 1 they were observed at E1/2 = -0.62, -1.60, -1.86, and -2.27 V vs Fc+/Fc. Spectral changes observed on chemical oxidation and reduction of the complexes are presented, and the behaviors of 1 and 2 are compared.     

Tracking the optical mass centroid of single electroactive nanoparticles reveals the electrochemically inactive zone

The inevitable microstructural defects, including cracks, grain boundaries and cavities, make a portion of the material inaccessible to electrons and ions, becoming the incentives for electrochemically inactive zones in single entity. Herein, we introduced dark field microscopy to study the variation of scattering spectrum and optical mass centroid (OMC) of single Prussian blue nanoparticles during electrochemical reaction. The “dark zone” embedded in a single electroactive nanoparticle resulted in the incomplete reaction, and consequently led to the misalignment of OMC for different electrochemical intermediate states. We further revealed the dark zones such as lattice defects in the same entity, which were externally manifested as the fixed pathway for OMC for the migration of potassium ions. This method opens up enormous potentiality to optically access the heterogeneous intraparticle dark zones, with implications for evaluating the crystallinity and electrochemical recyclability of single electroactive nano-objects.

The schematic of single cubic-shaped Prussian blue (PB) mesocrystals formed by the oriented aggregation of small nanocrystals. The dark-field images of single PB nanoparticle at PB and Prussian white (PW) states, respectively.     

Design of a calcium-binding protein with desired structure in a cell adhesion molecule

Ca2+, "a signal of life and death", controls numerous cellular processes through interactions with proteins. An effective approach to understanding the role of Ca2+ is the design of a Ca2+-binding protein with predicted structural and functional properties. To design de novo Ca2+-binding sites in proteins is challenging due to the high coordination numbers and the incorporation of charged ligand residues, in addition to Ca2+-induced conformational change. Here, we demonstrate the successful design of a Ca2+-binding site in the non-Ca2+-binding cell adhesion protein CD2. This designed protein, Ca.CD2, exhibits selectivity for Ca2+ versus other di- and monovalent cations. In addition, La3+ (Kd 5.0 microM) and Tb3+ (Kd 6.6 microM) bind to the designed protein somewhat more tightly than does Ca2+ (Kd 1.4 mM). More interestingly, Ca.CD2 retains the native ability to associate with the natural target molecule. The solution structure reveals that Ca.CD2 binds Ca2+ at the intended site with the designed arrangement, which validates our general strategy for designing de novo Ca2+-binding proteins. The structural information also provides a close view of structural determinants that are necessary for a functional protein to accommodate the metal-binding site. This first success in designing Ca2+-binding proteins with desired structural and functional properties opens a new avenue in unveiling key determinants to Ca2+ binding, the mechanism of Ca2+ signaling, and Ca2+-dependent cell adhesion, while avoiding the complexities of the global conformational changes and cooperativity in natural Ca2+-binding proteins. It also represents a major achievement toward designing functional proteins controlled by Ca2+ binding.     

Mössbauer and electric conductivity studies of bidentate base adducts of acetylacetonatoiron(II)

Summary Bidentate bridging base polymer complexes of acetylacetonatoiron(II) [Fe(acac)₂L]_n, where L=pyrazine(pyz), 4,4-bipyridine(bpy),trans-1,2-bis(4-pyridyl)ethylene(bpe), 1,2-bis(4-pyridyl)ethane(bpa) and 4,4-trimethylene bipyridine(tmbpy), have been prepared, characterized and oxidized by iodine to give a range of iron(III) and iron(II) complexes [Fe(acac)₂L · I_x]_n] in which the Fe^III/Fe^II ratios were established by Mössbauer spectroscopy. The electric conductivities of compressed pellets of the polysalts were obtained. The conductivities and Mössbauer parameters (I.S. and Q.S.) both change with respect to the kind of bidentate bridging bases.The conjugation of bridged ligand markedly affects the conductivity of the complexes.     

添加剂对SiO电性能的影响及其机理分析

SiO_x/CoO and SiO/Li₂CO₃ composite materials were prepared by mechanical ball-milling. The structures of the obtained materials were characterized by X-ray diffraction (XRD). And scanning electron microscopes (SEM) of three samples after 20 cycles were also given. In addition， the electrochemical performances of three materials with galvanostatic charge-discharge cycling were investigated. The results show that the composite samples have larger initial reversible capacities and better cycle performance than pure SiO. Also，a schematic diagram showing the buffer effects of Li₂CO₃ addition and the mechanism of improving electrochemical performance by adding Li₂CO₃ are suggested.     

Ag/ZrO2催化剂上的1,2-丙二醇选择性气相氧化反应

采用浸渍法制备了一系列Ag/ZrO₂催化剂, 考察了Ag/ZrO₂催化剂对1,2-丙二醇选择性氧化合成丙酮醛反应的催化性能. 实验结果表明: 在原料气配比为V(N₂)∶V(O₂)＝300∶19, n(O₂)/n(alcohol)＝1.2, 反应物液时空速为3.2 g/(g•h), 反应温度为673 K时, 1,2-丙二醇选择性氧化合成丙酮醛反应的转化率为95.7%, 选择性为55.3%, 高于传统电解银催化剂. UV-Vis DRS和XPS的研究结果表明: 在Ag/ZrO₂催化剂上存在大量的Ag^＋和Ag_n^δ＋有利于促进催化活性的提高.