Synthesis, spectral properties of aluminum polymeric phthalocyanine carboxyl with low aggregation in aqueous solution

A water soluble poly-[tetrakis-（2,3-dicarboxylate phenoxy） methyl methan] aluminum phthalocyanine （AIPPc.（COOH）x） has been synthesized from the cyclization of tetranuclear phthalonitrile and succes- sive hydrolysis of cyano in alkaline solution, The absorption spectra showed low aggregation of this compound in pH 9.18 buffer than that of existing water soluble phthalocyanine compounds. With the addition of Triton X 100, an enhancement of fluorescence emission with quantum yield from 0.4 to 0.83 was observed; contrarily, it was thoroughly quenched by the addition of CATB in suit, A longer life time of singlet state was also detected in presence of Triton X 100. The result indicates that AIPPc.（COOH）x is desired to investigate in fluorescent probe or in fluorescence imaging diagnose.     

铁酸锌焙烧后的还原行为及氨浸特性

A novel method for recovering zinc from zinc ferrite by reduction roasting–ammonia leaching was studied in this paper. The reduction thermodynamic of zinc ferrite by CO was analyzed. The effects of roasting parameters on the phase transformation and conversion rate of zinc ferrite, and the leaching behavior of zinc from the reductive roasted samples by ammonia leaching, were experimentally investigated. The mineralogical phase compositions and chemical compositions of the samples were characterized by X-ray diffraction and chemical titration methods, respectively. The results showed that most of the zinc ferrite was transformed to zinc oxide and magnetite after weak reduction roasting. 86.43% of the zinc ferrite was transformed to zinc oxide under the optimum conditions: CO partial pressure of 25%, roasting temperature of 750°C, and roasting duration of 45 min. Finally, under the optimal leaching conditions, 78.12% of zinc was leached into the solution from the roasted zinc ferrite while all iron-bearing materials were kept in the leaching residue. The leaching conditions are listed as follows: leaching duration of 90 min, ammonia solution with 6 mol/L concentration, leaching temperature of 50°C, solid-to-liquid ratio of 40 g/L, and stirring speed of 200 r/min.     

Characteristics of the reduction behavior of zinc ferrite and ammonia leaching after roasting

A novel method for recovering zinc from zinc ferrite by reduction roasting–ammonia leaching was studied in this paper. The reduction thermodynamic of zinc ferrite by CO was analyzed. The effects of roasting parameters on the phase transformation and conversion rate of zinc ferrite, and the leaching behavior of zinc from the reductive roasted samples by ammonia leaching, were experimentally investigated. The mineralogical phase compositions and chemical compositions of the samples were characterized by X-ray diffraction and chemical titration methods, respectively. The results showed that most of the zinc ferrite was transformed to zinc oxide and magnetite after weak reduction roasting. 86.43% of the zinc ferrite was transformed to zinc oxide under the optimum conditions: CO partial pressure of 25%, roasting temperature of 750°C, and roasting duration of 45 min. Finally, under the optimal leaching conditions, 78.12% of zinc was leached into the solution from the roasted zinc ferrite while all iron-bearing materials were kept in the leaching residue. The leaching conditions are listed as follows: leaching duration of 90 min,ammonia solution with 6 mol/L concentration, leaching temperature of 50°C, solid-to-liquid ratio of 40 g/L, and stirring speed of 200 r/min.     

Microplate chemiluminescence enzyme immunoassay for the quantitative evaluation of carbohydrate antigen 72-4 in human serum

A highly sensitive and specific microplate chemiluminescence enzyme immunoassay （CLEIA） was developed for the quantitative evaluation of carbohydrate antigen 72-4 （CA72-4） in human serum, using luminol-H2O2 catalyzed by horseradish peroxidase （HRP） as the chemiluminescence system. The simple and quick determination was accomplished through a sandwich reaction mode. Several physicochemical parameters of the immunoreaction, including incubation conditions, antibody coating conditions, dilution ratio of anti-CA72-4-HRP conjugate, and chemiluminescence reaction time, were studied and optimized. The proposed method exhibited a linear range of 0-200 U/mL with correlation coefficient and detection limit of 0.9995 and 0.18 U/mL, respectively. The inter-assay and intra-assay coefficients of variation （CV） were both less than 10%. The average recovery of two clinical sera with low and high concentration CA72-4 was 99.3% and 98.7%, respectively. Normal tumor markers, including AFP, CEA, CA24-2, CA19-9 and CA15-3, did not cross-react with each other. The method＇s stability was evaluated by assessing its analytical performance after storing the immunoreagents at 4℃ and 37℃ for 7 days. Little difference was found, indicating satisfactory stability of the method. The present method has been successfully applied to the detection of CA72-4 human serum, and showed a good correlation with the commercially available ELISA kit （r^2=0.9383）. This method showed great potential in the fabrication of diagnostic kit for CA72-4, and could be well used in diagnosis of cancer in clinical practice.     

Specific anti-tumor effect induced by attenuated <Emphasis Type="Italic">Salmonella typhimurium</Emphasis> vaccine expressing extracellular region of vascular endothelial growth factor receptor 2

The purposes of this research were to study the stable expression of exogenous gene encoding therapeutic protein in attenuated Salmonella typhimurium, observe the metabolism of oral gene vaccine carried by attenuated Salmonella typhimurium in BALB/c mouse, and investigate the feasibility of prevention and treatment of tumors by the recombinant bacteria. Recombinant plasmid pcDNA3.1＋ VEGFR2（n1-7） was transformed into competent attenuated Salmonella typhimuriurn SL3261 to develop oral DNA vaccine SL3261-pcDNA3.1＋VEGFR2（n1-7）. To observe whether the exogenous gene can be expressed in the recombinant bacteria, PCR was performed to amplify the CMV promoter of the eukaryotic expression vector as the proof of stable expression of exogenous protein; transmission elec- tron microscopy （TEM） was applied to observe the morphology of the recombinant bacteria to confirm that the exogenous gene has no impact on the growth of the bacteria, and then BALB/c mice were immunized with the gene vaccine. After inoculation of the gene vaccine, the recombinant bacteria SL3261 could be detected in the tissues such as small intestine, colon, liver and spleen. And then, mice in each group were challenged with tumor cells. The results of animal experiment showed that tumor growth of the mice in experimental group was inhibited and survival time of immunized mice was prolonged compared with control groups. A higher lymphocyte infiltration in tumors from animals treated with DNA vaccine was observed. Immunohistochemical analysis of tumor samples revealed an enhanced accumulation of CD8^＋ cytotoxic T lymphocytes, as well as an increase in CD4^＋ cells in the tumore of animals treated with the oral gene vaccine compared to tumors from control group mice. UI- trestructure of the tumor tissue showed that tumor cells in the samples of the immunized mice were well-differentiated. Our research confirmed that the exogenous gene can be stably expressed in the attenuated Salmonella typhimurium and has no impact on the growth of the r     

Synthesis and Application of a Polymeric Crosslinking Agent for Improving Fixation of Vinylsulfone-type Dyes on Cotton by a Pad-drycure Process

A new class of novel polymeric crosslinging agent （NPCA）, which contained silane coupling group and the epoxy groups, was designed and synthesized in our laboratory. NPCA was a non-formaldehyde multifunctional crosslinking polymer. The cotton fabrics dyed with 8.0% （owf） Vinylsulpone-type dyes were treated with 3.0%- 4.0% NPCA, 0.5 mol/L potassium thiocyanate as a catalyst, then padded through two dips and two nips to reach a wet pickup of 80%- 85%, then dried at 80℃ for 2 minutes and cured in oven at 140- 150℃ for 3 minutes. Crocking fastness and fixation （%） were improved with up to 1.0 -1. 5 units, 35%- 50%, respectively. And there was little difference between the color yield of dyed fabrics before and after the treatment at certain conditions. The possible crosslinking mechanism of NPCA was also investigated. It was concluded that NPCA can improve colorfastness of cotton fabric by means of the three-dimensional network, covalent bonding and other molecular forces.     

(NH4)2SO4焙烧?浸出法从氧化锌矿石中提取锌

An improved method of (NH₄)₂SO₄ roasting followed by water leaching to utilize zinc oxidized ores was studied. The operating parameters were obtained by investigating the effects of the molar ratio of (NH₄)₂SO₄ to zinc, roasting temperature, and holding time on zinc extraction. The roasting process followed the chemical reaction control mechanism with the apparent activation energy value of 41.74 kJ·mol?1. The transformation of mineral phases in roasting was identified by X-ray diffraction analysis combined with thermogravimetry–differential thermal analysis curves. The water leaching conditions, including the leaching temperature, leaching time, stirring velocity, and liquid-to-solid ratio, were discussed, and the leaching kinetics was studied. The reaction rate was obtained under outer diffusion without product layer control; the values of the apparent activation energy for two stages were 4.12 and 8.19 kJ·mol?1. The maximum zinc extraction ratio reached 96% while the efficiency of iron extraction was approximately 32% under appropriate conditions. This work offers an effective method for the comprehensive use of zinc oxidized ores.     

Effect of copper excess on peripheral blood T-lymphocytes in the chicken

Experimental study was conducted to examine the effect of copper excess on the peripheral blood T-lymphocyte by the methods of flow cytometry （FCM） and experimental pathology. 420 one-day-old Avian chickens were randomly divided into seven groups, and fed on diets as follows： 1. controls （Cu 11mg/kg） and 2. copper excess （ Cu 100mg/kg, copper excess group Ⅰ; Cu 200mg/kg, copper excess group Ⅱ; Cu 30（hng/kg, copper excess group Ⅲ; Cu 400mg/kg, copper excess group Ⅳ; Cu 500mg/kg, copper excess group Ⅴ; Cu 600mg/kg, copper excess group VI） for six weeks. The results were as follows- 1 ） In thymus, lymphocytes in the medulla were decreased in number in copper excess groups Ⅲ,Ⅳ,Ⅴ, and Ⅵ, and the increased and enlarged thymic corpuscles and the proliferated reticular cells were also observed in both copper excess group V and copper excess group VI in comparison with those of control group. 2） The percentage of CD4＋ T cells was markedly decreased from 2 to 6 weeks of age in copper excess groups Ⅳ, Ⅴ and Ⅵ （P 〈0.05 or P 〈0.01）. 3） The percentage of CD8＋ T cell was not varied in six copper excess groups during the experiment when compared with that of control group （ P 〉 0.05 ）. 4） The CD4 ＋ / CD8＋ ratio was lower from 2 to 6 weeks of age in copper excess groups Ⅳ, Ⅴ and VI than in control group （ P 〈0.05 or P 〈0.01）. 5） It was concluded that dietary copper in excess of 300mg / kg suppressed the development of T-lymphocytes and reduced the percentage of CD4＋ T cells and the CD4＋/CD8＋ ratio, and resulted in pathological injury of the thymus. Cellular immune function was finally impaired.     

Low Temperature Dyeing and Shrinkage-Resistance Finishing of Wool by Composition of Salt-Ammonia and Enzyme Treatment

Wool top and knitted fabric were treated with ammonia in the presence of sodium chloride （salt-ammonia process）. The effectiveness of salt-ammonia process traditionally used as pretreatment for low temperature dyeing has been investigated for conferring shrink-resistance of wool. The pretreatmont of salt-ammonia process followed by enzymatic treatment has been proved that contribute to not only the enhancement of dyeing behavionr but also shrinkage-resistance in the present studies. A novel composition of salt-ammonia pretreatment, oxidized and reduced treatment as well as protease modification was recommended to achieve low temperature dyeing and shrinkage-resistance of wool. At the same time, the process conditions were optimized by orthogonal array and assessed by dye uptake rate, weight loss and area shrinkage. Laboratory experiments showed that the knitted fabric treated according to optimized conditions of the combined process, achieved not only improvement of dye abilities but also the strict requirement of machine-washable, representing a possible alternative to chlorination.     

Gold nanoparticles based digital color analysis for quinidine detection

In this contribution,we developed a novel digital color analysis of gold nanoparticles(AuNPs) for pharmaceutical detection by choosing quinidine as an example.It was found that the color of AuNPs colloid solution changed from red to blue in the presence of different concentrations of quinidine,and the color information of each solution could be digitalized with tricolor(RGB) system.Under the optimum conditions,the R value of the solution was found to be linear with the natural logarithm of concentration of quinidine in the range of 112 384 nmol/L.This method has the advantages of rapid,economical and simple,and can serve as a potential alternative to traditional spectrophotometry for practical use.     

β-四(羧基苯氧基)锌酞菁配合物的合成与光谱性质研究

以4-（4-羧基苯氧基）-1，2-苯二甲腈为前体化合物合成了具有水溶性的β-四（羧基苯氧基）锌酞菁（p-HPcZn）．p-HPcZn具有较好的水溶性，可溶于多种极性溶剂中．光谱实验结果表明，醇类溶剂的碳链增长对p-HPcZn的λmax几乎没有影响，而在非醇类溶剂中λmax随溶剂的配位能力的增加而有所红移.     

新型不对称酞菁的制备与表征

以4-(对叔丁基苯氧基)邻苯二腈、1,3-二亚胺基异吲哚啉和二水乙酸合铜为原料合成了2(3)-(对叔丁基苯氧基)酞菁铜,并通过元素分析、红外、紫外-可见光谱和质谱的表征证实产物即为目标化合物.     

糖基-羧基酞菁锌偶联衍生物的合成及相关性质

以碳酸钾为催化剂分别将1（4）,8（11）,15（18）,22（25）－四（4－羧基苯氧基）酞菁锌（1）和卜（4-羧基苯氧基）酞菁锌（2）与溴代乙酰糖基（乳糖、麦芽糖和葡萄糖）偶联,得到5种糖基酞菁偶联衍生物,IR,MS和UV—Vis光谱证实羧基酞菁与糖基成功偶联．糖基过量时,由1主要获得糖基二取代产物．溶解性和稳定性研究表明：5种偶联衍生物易溶或可溶于DMF、丙酮、THF、氯仿和甲醇中,不溶于水,它们在DMF中避光均能稳定存在．在DMF、丙酮、THF、甲醇和氯仿中它们显示相似的酞菁单体的电子吸收光谱,在体积分数O．1％DMF的水中出现聚集,这些体系中的Q带特征吸收峰位于670～690nm;在DMF和含O．1％DMF的水中的荧光量子产率分别为0．358－0．721与0．121～O．198,为原酞菁（1和2）的2～3倍和3～5倍．     

CuPc/H2PtCl6有机半导体毒气传感器的制备与性能

针对有毒有害气体的监测问题,采用有机合成工艺制备了CuPc有机半导体材料,并对其进行杂化处理和电极设计,形成了具有较佳性能的毒气传感器．以对甲基苯酚、4-硝基邻苯二晴为原材料,以N,N-二甲基甲酰胺为溶剂,在N\-2保护和碳酸钾的催化作用下合成酞菁分子碎片,再以共溶技术合成了4取代对甲苯氧基CuPc．然后,按照一定比例将CuPc和H\-2 PtCl\-6共溶在甲醇溶液中,杂化合成了有机半导体CuPc/H\-2PtCl\-6气敏材料．并采用多孔电极结构结合真空饺技术形成气敏薄膜型传感器．质谱和红外吸收光谱分析验证了合成工艺路线的正确性．电子扫描观察了多孔电极和气敏膜的微观形貌．气敏性能测试表明,CuPe/H\-2PtCl\-6对Cl\-2和H\-2S等有毒气体有较好的敏感性和选择性．     

苯磺酸锌对PVC的热稳定性能

以苯磺酸衍生物和氧化锌为原料,制备甲基苯磺酸锌、对氨基苯磺酸锌、十二烷基苯磺酸锌,并对产品进行了元素分析;以硬脂酸锌为对照物,测试了三种苯磺酸锌对聚氯乙烯塑料（PVC）的热稳定性能;通过热老化箱实验法、刚果红试纸法对苯磺酸锌类化合物及其互配系统进行了综合评价.结果表明,甲基苯磺酸锌、对氨基苯磺酸锌对PVC有较好的长期热稳定性能,且与硬脂酸钙具有一定的协同作用.     

N-(2-甲氧基-5-甲酰基苄基)亚胺基二乙酸的合成及表征

以4－甲氧基苯甲醛为原料，在无水氯化锌催化下，用浓盐酸和40％甲醛溶液进行氯甲基化反应制得取代氯苄，再以新制的无水碳酸钾为质子吸收剂、干燥的乙腈为溶剂，与亚氨基二乙酸二乙酯进行N－烷基化反就，然后用Ba(OH)2－水悬浮液进行了水解得到N－（2－甲氧基－5－甲酰基苄基）亚胺基二乙酸的钡盐沉淀，最后用烯硫酸处理得到N－（2－甲氧基－5－甲酰基苄基）亚胺基二乙酸，该方法产率高，工艺简单，通过^1H NMR、IR和元素分析对所得化合物的结构进行了表征。     

OTS修饰的酞菁锌薄膜晶体管

制备并提纯了酞菁锌(ZnPc)有机场效应晶体管,该薄膜器件以具有大π键的ZnPc作为载流子传输有源层,以自制的热生长SiO2膜层作为晶体管的栅绝缘层,经长链两亲分子十八烷基三氯硅烷(OTS)修饰以后,具有复合双绝缘层的结构.测试结果显示:以此为基础制备的器件具有良好的I-V输出特性,OTS/SiO2复合双绝缘层的器件结构能有效改进有机薄膜晶体管的性能.     

2,3,9,10,16,17,23,24-八甲氧基酞菁的合成及表征

以邻苯二甲醚为初始原料,合成六种2,3,9,10,16,17,23,24-八甲氧基金属酞菁配合物,并对产物进行了红外(IR)、紫外可见(UV/ Vis)光谱表征以及可溶性分析.对比发现各种酞菁IR光谱几乎相同,但是UV/ Vis光谱中甲氧基锌酞菁红移最大,而甲氧基钴酞菁溶解性最好.     

无水溴化锌催化合成反-4-苯乙烯基吡啶

以甲苯为溶剂,无水溴化锌为催化剂,苯甲醛与4-甲基吡啶进行缩合反应生成了反-4-苯乙烯基吡啶.最佳反应条件是,苯甲醛与4-甲基吡啶物质的量的比为1.0∶1.5,无水溴化锌与苯甲醛物质的量比为2.0∶3.0,反应温度为85℃,产物收率为68.32%.研究还发现,在相同条件下,以无水氯化锌为催化剂,可以得到一种晶体(4-甲基吡啶)氯化锌,X-单晶衍射分析表明,该晶体属单斜晶系,空间群为P2(1)/c,晶胞参数为a=1.434 1(4)nm,b=0.789 3(4)nm,c=1.350 4(9)nm,β=100.656 0(10)°,晶胞内分子数为4.作为配体4-甲基吡啶不与苯甲醛发生缩合反应.