添加剂对氯化钠结晶的影响

考察了不同添加剂种类、用量及蒸发结晶温度对氯化钠晶体形状、堆密度的影响。实验结果表明,添加剂葡萄糖和山梨醇对氯化钠晶体形状影响较明显。当蒸发温度60℃、葡萄糖用量0.15%~0.20%(占氯化钠的质量分数)时,有较多的星型晶体,且产品堆密度比不加添加剂时低;当蒸发温度75℃、山梨醇用量(占氯化钠的质量分数)0.05%~0.15%时,氯化钠晶体的形状变化较大,堆密度明显降低,且效果优于添加剂葡萄糖。     

Synthesis of magnetite/polyamino-ester dendrimer based on PCL/PEG amphiphilic copolymers via convergent approach for targeted diagnosis and therapy

The aim in this study is to synthesize amphiphilic linear-dendritic-linear block copolymers consisting of a poly ?-caprolactone linear block, poly(amino-ester) dendritic block and m-PEG linear block. G1, G2 and G3 dendrons were produced by sequential acrylation and Micheal addition reactions, using required amounts of acryloyl chloride and diethanolamine respectively to achieve quantitative growth. Amphiphilic dendrons were synthesized from the reaction of hydroxyl group of G1, G2 and G3 with mPEG-adipoyl chloride and their structures were characterized by FT-IR and ¹H NMR spectroscopy. The amphiphilic dendrons can self-assemble and form micelles in water. Their critical micelle concentration (CMC), particle size and zeta potential were determined by fluorescence spectroscopy and dynamic light scattering, respectively. Convergent dendrimers were prepared by self-assembly of the dendrons around oleic acid-stabilized Fe₃O₄ nanoparticles via the ligand exchange method and their morphologies were characterized by transmission electron microscopy (TEM). The in-vitro release behavior of quercetin from dendrimers and hydrolytic degradation of them were investigated at two pHs (7.4 and 5.8).     

A new two‐phase route to cadmium sulfide quantum dots using amphiphilic hyperbranched polymers as unimolecular nanoreactors

A new two‐phase route was developed to prepare monodisperse cadmium sulfide (CdS) quantum dots (QDs) with a narrow size distribution. In a two‐phase system, chloroform and water were used as separate solvents for palmitoyl chloride functionalized hyperbranched polyamidoamine (HPAMAM‐PC) and cadmium acetate/sodium sulfide, respectively. The amphiphilic HPAMAM‐PC, with a hydrophilic dendritic core and hydrophobic arms, formed stable unimolecular micelles in chloroform and was used to encapsulate aqueous Cd²⁺ ions. After the reaction with S²⁻ ions from the aqueous phase, monodisperse and uniform‐sized CdS QDs stabilized by HPAMAM‐PC unimolecular micelles were obtained. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci 120:991–997, 2011     

Evaluation of organic additives as levelling agents for zinc electrowinning from chloride electrolytes

The effects of various organic additives: Pearl glue, Separan NP10, Percol 140 and tetraalkylammonium chlorides, on zinc deposit morphology and orientation and on the current efficiency and energy requirement for zinc electrowinning from chloride electrolyte have been determined and compared. Tetrabutylammonium chloride (TBAC1) was more effective than Pearl glue, Separan NP10 or Percol 140 in smoothing the deposit, refining the grain size and eliminating dendritic growth. TBACl was also the most effective of the tetraalkylammonium chlorides studied. Tetraethylammonium chloride (TEACl) had little effect on the deposit grain size even at concentrations as high as 60 mg dm^–3. Tetrapropylammonium chloride (TPrAG) was more effective than TEACl but less effective than TBACl. Small additions (10 mg dm^–3) of tetrapentylammonium chloride (TPACl) produced a very fine-grained deposit, but the deposit edges were rougher than in the presence of TBACl.     

Synthesis and Characterization of First Generation Dendritic Azidoesters

A new class of first generation azido‐terminated dendritic esters have been synthesized by four step processes. The final products and the intermediates are characterized by IR, ¹H NMR, and elemental analysis. Thermal studies revealed that these dendritic esters were thermally stable up to ∼190 °C and the glass transition temperature was found to be −54 and −32 °C, respectively.     

Synthesis of Dendritic Nano‐Sized Nickel for use as Anode Material in an Alkaline Membrane Fuel Cell

Dendritic nano‐sized nickel nanoparticles were synthesised using a hydrazine reduction method in ethylene glycol from a nickel chloride precursor. The resulting particles were characterised by X‐ray diffraction (XRD), scanning electron microscopy (SEM) and Transmission Electron Microscopy (TEM). Dendritic nickel has a network structure which is ideal to be used as electrode for electrochemical devices such as fuel cells. The prepared dendritic nickel nanoparticles were used as anodes for an alkaline membrane fuel cell using poly(vinyl)alcohol (PVA)/tetraethyl ammonium chloride (TEAC) alkaline blend electrolyte membrane with a PVA/TEAC ratio of 1:5. A current density of 11.5 mA cm^–2 has been achieved when methanol was used as the fuel.     

A Highly Active and Recyclable Catalyst: Phosphine Dendrimer‐Stabilized Nickel Nanoparticles for the Suzuki Coupling Reaction

We report here the first dendritic phosphine‐stabilized nickel nanoparticles, which can be prepared from nickel(II) chloride, a third generation phosphine dendrimer and the surfactant tetraoctylammonium bromide (TOABr) by two‐phase reduction using sodium borohydride. The resulting nickel nanoparticles are found to be a highly active and recyclable catalyst for Suzuki coupling reactions, especially those extended to aryl chloride substrates, affording the biaryls in moderate to good yields.     

转基因树突状细胞激活细胞毒性T细胞特异性杀伤淋巴瘤的体外实验

目的 探讨转基因树突状细胞激活细胞毒性T细胞产生抗淋巴瘤的特异性细胞免疫反应。方法 采用人骨髓来源的髓系前体细胞,在人细胞因子IL-4、GM-CSF和INF-α诱导下,在体外生成大量树突状细胞。将制备好的含有IgVH1核酸质粒,用脂质体法转染树突状细胞。转染成功的树突状细胞与外周血T淋巴细胞共培养,激活特异性CTL细胞,与阳性表达IgVH1的人淋巴瘤Namalwa细胞反应,用3H-TdR掺入法观察CLLs对瘤细胞的特异性杀伤效应。结果 树突状细胞能够用脂质体方法转染IgVH1核酸质粒,并且有效递呈给外周血T细胞,对表达IgVH1的人淋巴瘤Namalwa细胞产生特异性免疫杀伤活性,与对照组相比差异有显著意义（P<0.01）。结论 体外诱导扩增的 DC能够转染 IgVH1核酸质粒,体外激活T淋巴细胞,产生特异性细胞毒效应。     

EFFECT OF DISSOLVED INORGANIC SALTS ON THE VAPOR-LIQUID EQUILIBRIA AND ENTHALPY OF MIXING OF THE METHANOL-ETHYL ACETATE SYSTEM

The effect of three inorganic chloride salts, namely, sodium chloride, calcium chloride and zinc chloride on the vapor-liquid equilibria (VLE) and heat of mixing (h.o.m) of the methanol-ethyl acetate system has been investigated under the atmospheric conditions of 760 ± 3 mm Hg pressure. In the experimentation for VLE a Smith and Bonner type equilibrium still was used while in h.o.m. determination a calorimeter connected to a microprocessor-based control unit (MIPROC) which displays digitally the heat of mixing values in calories was employed. All the three salts dissolved to various concentration levels in the solvent mixture brought about a decrease in the azeotropic composition (expressed in terms of mole fraction of methanol) from 0.75 to values like 0.50, 0.37 and 0.18 depending upon the salt added and its concentration level. The salts sodium chloride and calcium chloride which are more soluble in methanol have been found to salt-in that component but with a peculiarity in that, in methanol-rich region the salting-in effect was substantial while in the methanol-lean region it is only marginal. The addition of salt zinc chloride which is more soluble in ethyl acetate results in an anomalous behaviour.

As for the salt effect on h.o.m., the addition of calcium chloride brought about a significant enhancement in the h.o.m values while the salts sodium chloride and zinc chloride (which could be added only to about 5% by weight concentration due to the experimental difficulties) entailed a decrease and lateral shift respectively in the h.o.m. values.

The VLE and h.o.m data which were found to be thermodynamically consistent have been correlated respectively by NRTL, Wilson and by a model similar to the Scatchard series type equation.     

两性聚酰胺-胺树状聚合物的合成及絮凝性能

用Michael加成反应对G4.0聚酰胺-胺(PAMAM)树状聚合物分子进行了表面修饰改性。分别以丙烯酰氧基乙基三甲基氯化铵(DAC)、丙烯酸钠(SAA)、2-丙烯酰胺-2-甲基丙磺酸(AMPS)为端基改性剂,在N2气氛下50℃甲醇溶液中,反应投料比n(PAMAM)∶n(DAC)∶n(SAA或AMPS)=1∶16∶16时,反应96 h,合成出了两性聚酰胺-胺树状聚合物。絮凝性能实验结果表明,合成产物具有一定的絮凝性能,且与聚丙烯酰胺复配效果更好,最佳絮凝效果条件为:m(G4.0/DAC/AMPS)∶m(PAM)=1∶4;投药量16 mg/L;絮凝沉降时间20 min;pH=8~9。     

Chlorinated Phenoxaphosphine and 9-Methylenexanthene

2,3,7,8-Tetrachlorophenoxaphosphine (Ic), 2,3,6,7,11-pentachloro-9-methylenexanthene (Id) and 2,3,6,7-tetrachloro-9-bromomethylenexanthene (If) have been prepared by the aluminium chloride catalysed condensation of 3,4-dichlorophenyl ether (II) with phosphorus trichloride, chloroacetyl chloride and bromoacetyl chloride, respectively.     

二烷基酰亚胺萃取剂的合成与表征

以丙酰氯、正戊酰氯、正庚酰氯为酰化试剂,在温度≤10℃下分别与氨水反应生成丙酰胺、正戊酰胺和正庚酰胺. 以吡啶作缚酸剂,将生成的酰胺与含相同碳链长的酰氯在温度≤0℃下反应,得到3种具有对称结构的含直链烷基的二烷基酰亚胺(二丙酰亚胺、二正戊酰亚胺和二正庚酰亚胺),对终产物进行了表征. 结果表明,以乙醇为良溶剂、水为不良溶剂,经多次重结晶后其最终产率分别为30%, 35%, 33%,终产物的熔点分别为153.7~154.0, 91.5~91.7, 89.0~89.5℃,二烷基酰亚胺纯度大于99%.     

二(三氯甲基)碳酸酯法合成酰氯化合物

采用二(三氯甲基)碳酸酯与相应的羧酸反应,合成了8个具有代表性的酰氯化合物：顺,反-2,2-二甲基-3-(2,2-二氯乙烯基)环丙烷羧酰氯、顺-2,2-二甲基-3-(2-氯-3,3,3-三氟丙-1-烯基)环丙烷羧酰氯、氯乙酰氯、三氯乙酰氯、苯甲酰氯、邻氯苯甲酰氯、邻甲基苯甲酰氯、反-3-苯基-2-丙烯酰氯,收率为82．1％-91．7％,纯度为96．4％-98．9％,     

甲烷氯化物催化偶联合成氯乙烯单体新技术

简要介绍了几种主要的氯乙烯单体生产工艺,证明了甲烷氯化物催化偶联合成氯乙烯单体新技术的热力学可行性,并在实验室分别以一氯甲烷和二氯甲烷为原料成功合成出氯乙烯单体,最后指出了这一新技术的优势.     

气相色谱法分析尾气中的氯乙烯和乙炔

采用附有FID检测器和AT.氧化铝毛细管柱的色谱仪对尾气中的氯乙烯和乙炔进行外标法定量测定。该方法简便、快速、准确,测定的氯乙烯相对标准偏差、回收率分别为4.0%、99.5%,乙炔相对标准偏差、回收率分别为4.6%、99.8%。     

多乙烯多胺桥联受阻酚类抗氧剂的合成及其清除DPPH·性能

以二乙烯三胺和三乙烯四胺为桥联基,β-(3,5-二叔丁基-4-羟基苯基)丙酰氯为抗氧化功能基团,通过酰胺化缩合反应合成了两类具有不同对位桥联基团的受阻酚类抗氧剂。采用傅里叶红外光谱和核磁共振氢谱证实了合成的多乙烯多胺桥联受阻酚类抗氧剂的化学结构。DPPH法研究了多乙烯多胺桥联受阻酚类抗氧剂清除自由基的性能,并探索了酚羟基个数和对位桥联基结构对受阻酚类抗氧剂清除自由基性能的影响。结果表明,多乙烯多胺桥联受阻酚类抗氧剂具有良好的清除DPPH·能力,且随着抗氧剂分子中酚羟基个数的增加,清除DPPH·的活性增加,分子中含有4个酚羟基的三乙烯四胺受阻酚类抗氧剂的抗氧化效率（AE）达到2.65×10^-2 L/(mol·s)。对位桥联基结构对受阻酚类抗氧剂清除DPPH·能力有较大影响,季戊四醇为桥联基的受阻酚类抗氧剂1010清除DPPH·能力最强,其抗氧化效率（AE）为3.08×10^-2L/(mol·s);乙二胺为核的1.0代树枝状受阻酚类抗氧剂清除DPPH·能力最弱,其抗氧化效率（AE）为2.60×10^-2 L/(mol·s)。     

非水解溶胶-凝胶法合成镁铝尖晶石纳米粉体及其烧结性能

以无水氯化铝、无水氯化镁为前驱体和无水乙醇为氧供体,采用非水解溶胶-凝胶法合成镁铝尖晶石纳米粉体,利用XRD、SEM和激光粒度等表征了粉体晶相、颗粒粒径与形貌及烧结性能。结果表明,在900℃可合成单一镁铝尖晶石纳米粉体,一次粒子平均粒径为50nm左右,存在可通过球磨消除的软团聚,在1600℃烧结3h可以得到气孔少、颗粒结合紧密、相对致密的镁铝尖晶石烧结体。     

非水解溶胶-凝胶法合成镁铝尖晶石纳米粉体及其烧结性能

以无水氯化铝、无水氯化镁为前驱体和无水乙醇为氧供体，采用非水解溶胶-凝胶法合成镁铝尖晶石纳米粉体，利用XRD、SEM和激光粒度等表征了粉体晶相、颗粒粒径与形貌及烧结性能。结果表明，在900℃可合成单一镁铝尖晶石纳米粉体，一次粒子平均粒径为50nm左右，存在可通过球磨消除的软团聚，在1600℃烧结3h可以得到气孔少、颗粒结合紧密、相对致密的镁铝尖晶石烧结体。     

Linear‐dendritic copolymers as nanocatalysts

Functionalized poly(ethylene glycol) (PEG) containing four chloride end functional groups (PEG‐Cl₄) was synthesized through reaction between cyanuric chloride and PEG‐(OH)₂. Chloride end functional groups of PEG‐Cl₄ were able to initiate the ring opening polymerization of 2‐ethyl‐2‐oxazoline and star copolymers containing a PEG core, and poly(2‐ethyl‐2‐oxazoline) (POX) arms were obtained. Polymerization was quenched using diethanolamine, and star copolymers containing hydroxyl end functional groups (PEG‐POX‐OH) were obtained. ε‐Caprolactone was then polymerized using the hydroxyl end functional groups of star copolymers and amphiphilic linear‐dendritic copolymers containing PEG and POX, and poly(caprolactone) (PCL) blocks were synthesized. Linear‐dendritic copolymers were able to load the organic and inorganic guest molecules. Application of host‐guest systems such as nanocatalyst for Heck chemical reaction was also investigated. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

Two Spectrophotometric Methods for the Assay of Benzalkonium Chloride in Bandage Samples

Two rapid, direct, extraction‐free spectrophotometric procedures were developed for the determination of benzalkonium chloride. The procedures were based on the formation of mixed dye‐surfactant aggregates between eosine Y and benzalkonium chloride (Method A), or between eosine B and benzalkonium chloride (Method B) in Clark‐Lubs medium by measuring the increase in absorbance at 556 and 550 nm, respectively. Beer's law was obeyed in the concentration range of 0.5–12 and 0.5–12 μg mL^?1 for benzalkonium chloride with good precision and accuracy, whose limits of detection were 0.1 μg mL^?1 at 556 nm for Method A and 0.2 μg mL^?1 at 550 nm for Method B, respectively. The proposed procedures were successfully applied to the assay of benzalkonium chloride in bandages. The analytical results of the real samples were in good agreement with those by HPLC.