氨法脱硫中亚硫酸铵的氧化工艺参数

通过改变亚硫酸铵初始浓度、硫酸铵初始浓度、反应温度、混合液pH值、空气流量、催化剂浓度, 研究氨法脱硫中亚硫酸铵氧化率的变化. 结果表明: (NH₄)₂SO₃的浓度与 (NH₄)₂SO₃的氧化率成反比关系; 初始 (NH₄)₂SO₄浓度越大, (NH₄)₂SO₃氧化率越低; 当反应温度为40~60 ℃时, 随着温度的升高,  (NH₄)₂SO₃的氧化率不断增大;  (NH₄)₂SO₃氧化率受混合溶液pH值的影响, 较合适的pH值为5.5; 当空气流量为100~400 L/h时, 随着空气流量的增大,  (NH₄)₂SO₃的氧化率增大; 随着催化剂CoSO₄浓度升高,  (NH₄)₂SO₃氧化率增大.结合氨法脱硫工程实例考虑, 当反应温度控制在50 ℃ 左右, (NH₄)₂SO₃采用低浓度氧化, 混合液pH值为5.5, 空气流量为300 L/h, 催化剂浓度较高时, (NH₄)₂SO₃的氧化率较高.     

Efficient and selective recovery of Ni,Cu, and Co from low-nickel matte via a hydrometallurgical process

Low-nickel matte was intensively characterized, and Ni, Cu, and Co were determined to exist mainly as (Fe,Ni)₉S₈ and FeNi₃, Cu₅FeS₄, and (Fe,Ni)₉S₈ and Fe₃O₄ (in isomorphic form), respectively. The efficient and selective extraction of Ni, Cu, and Co from the low-nickel matte in an (NH₄)₂S₂O₈/NH₃·H₂O solution system was studied. The effects of (NH₄)₂S₂O₈ and NH₃·H₂O concentrations, leaching time, and leaching temperature on the metal extraction efficiency were systematically investigated. During the oxidative ammonia leaching process, the metal extraction efficiencies of Ni 81.07%, Cu 93.81%, and Co 71.74% were obtained under the optimal conditions. The relatively low leaching efficiency of Ni was mainly ascribed to NiFe alloy deactivation in ammonia solution. By introducing an acid pre-leaching process into the oxidative ammonia leaching process, we achieved the high extraction efficiencies of 98.03%, 99.13%, and 85.60% for the valuable metals Ni, Cu, and Co, respectively, from the low-nickel matte.     

季铵盐阳离子的Waugh型化合物的合成与表征

以(NH₄)₆［MnMo₉O₃₂］为前体原料,采用常规的水溶液法与四甲(乙)氯化铵反应制备了2种含有混合阳离子的Waugh型钼酸盐(NH₄)₄［N(CH₃)₄］₂［MnMo₉O₃₂］·9H₂O(化合物1)和(NH₄)₄［N(CH₂CH₃)₄］₂［MnMo₉O₃₂］·7H₂O(化合物2),用元素分析、红外光谱、热重分析对其进行了表征,并对化合物1进行了单晶结构测定,化合物1属于单斜晶系,C2/c空间群,a=2.379(11)nm,b=1.186(5)nm,c=1.600(7)nm,β=102.308(4)°,V=4.413(3)nm³,Z=4,Dc=2.460 g/cm³,R₁=0.041 8,wR₂=0.117 5(I>2σ),GOF=1.058.对化合物的形成规律探索发现:季铵盐与(NH₄)₆MnMo₉O₃₂的物质的量之比为3∶1,易形成单晶.对化合物1和2光催化降解亚甲基蓝模拟废水进行了探索,光催化90 min和180 min时脱色率分别达到95.96%和85.64%,表明化合物1和2对亚甲基蓝染料废水均具有良好的光催化活性.     

低温热处理制备立方相纳米(ZrO2)0.9-(CaO)0.1粉末

以ZrOCl₂,Ca(NO₃)₂和NH₃·H₂O为原料,用液相化学共沉淀法制备（ZrO₂ ）_0.9-（CaO）_0.1粉末,经过600 ℃热处理,用TEM观察形貌,BET测定粒子尺寸,XRD和Raman光谱分析相结构.结果表明：粉末样品的粒径为8.9　nm,晶粒表现为0.5　nm的立方相结构.     

B型Anderson结构Cr-Mo杂多化合物的合成、晶体结构及性质

在水溶液中合成了一个Ｂ型Anderson结构Cr-Mo杂多阴离子的二甲亚砜溶剂化合物,其分子式为： （NH₄）_３Ｈ_３（CrMo₆O₂₄H₆）₂（C₂H₆SO）₆. X射线单晶分析表明, 该化合物属三斜晶系, P1空间群, 主要晶胞参数为： a=1.428 9(3)　nm, b=1.429 5(3)　nm, c=1.626　3(3)　nm, α=63.93(3)°, β=90.00(3)°, γ=60.05(3)°, R=0.039 8. TG曲线表明, 化合物失重分三步进行, 化合物最后分解温度在494.41 ℃.     

磷酸铵强化硫化蓝铜矿及其对浮选的影响

蓝铜矿是一种重要的氧化铜矿物,采用常规的硫化–黄药浮选法回收蓝铜矿时浮选效果不理想。本研究通过微浮选试验、飞行时间二次离子质谱(ToF-SIMS)、X射线光电子能谱(XPS)、Zeta电位、接触角、傅里叶变换红外(FT-IR)光谱和紫外–可见光(UV–Vis)光谱检测研究了(NH₄)₃PO₄和Na₂S对蓝铜矿表面的强化硫化效果。微浮选试验表明,(NH₄)₃PO₄和Na₂S同时加入可提高蓝铜矿的可浮性;ToF-SIMS和XPS分析表明,与蓝铜矿–Na₂S体系相比,(NH₄)₃PO₄和Na₂S处理后的蓝铜矿表面硫组分含量较高,Cu(I)组分含量也得到增加;硫化前采用(NH₄)₃PO₄预处理后,蓝铜矿表面Zeta电位呈负偏移,且矿物表面的接触角增大,即(NH₄)₃PO₄的加入增强了蓝铜矿表面的硫化,促进了黄药的吸附;FT-IR和UV–Vis分析表明,在蓝铜矿浮选过程中,(NH₄)₃PO₄的加入增加了矿物表面黄药的有效吸附量,降低了黄药的使用量。因此,(NH₄)₃PO₄有利于蓝铜矿的硫化浮选。     

原位光反应法合成过氧桥连草酸铀酰配合物

在室温和实验室灯光照射条件下, 通过原位光化学反应, 分别以乙二胺和二亚乙基三胺为模板, 合成3种过氧桥连的草酸铀酰配合物[NH₃(CH₂)₂NH₃]₃[(UO₂)₂O₂(C₂O₄)₄]·4H₂O (1), [NH₃(CH₂)₂NH₂(CH₂)₂NH₃]₂[(UO₂)₂O₂(C₂O₄)₄]·2H₂O (2)和[NH₃(CH₂)₂NH₂(CH₂)₂NH₃]₂[(UO₂)₂O₂(C₂O₄)₄] (3)。借助单晶X射线衍射、拉曼光谱(Raman)、粉末X射线衍射(PXRD)和热重分析(TGA), 对配合物的结构及其性质进行表征和分析。1和2中U-O₂-U二面角为180°, 而通常过氧配合物的过氧二面角小于180°。2和3中过氧键的键长比正常的过氧键长短, 其中2更接近超氧键的键长, 但价态和拉曼图谱都表明其为过氧键。     

Recycling of Spent Nickel-Cadmium Batteries

A technique for recycling spent nickel-cadmium batteries, which makes separaion of cadmium and nickel possible, is developed by laboratory-scale experiments. NH₃-H₂CO₃ aqueous solution was used in this leaching technique. Since neutralization and/or solvent extraction were not required in the separation procedure of nickel and cadmium, the closed systemizaion of the process becomes possible. Experimental results show that, (1) if the NH₃ concentraion of leaching solution is sufficiently high and the ratio of H₂CO₃ to NH₃ is properly adjusted, both Ni(OH)₂ and Cd(OH)₂ react with NH, and quickly dissolve into leaching solution, and (2) Ni(OH)₂ can be converted into insoluble NiO by calcination at 500℃, and CdO from Cd(OH)₂ by calcination maintains good solubility in NH₃-H₂CO₃ aqueous solution. As a conclusion, the recycling technique characterized by two step leaching can be developed based on such changes in dissolution behavior by calcination. Meanwhile, the yields of 99.8% for nickel and 97.6% for cadmium are obtained, and the purities of recovered nickel and cadmium are 99.9% and 98.6%, respectively.     

含5-氟尿嘧啶稀土磷钨酸盐诱导细胞凋亡作用研究

 多金属氧酸盐作为一种无机金属-氧簇化合物,在抗肿瘤、抗病毒等药物化学领域引起广泛关注。研究了以下5种含5-氟尿嘧啶稀土磷钨酸盐K₉（C₄H₄FN₂O₂）₂La（PW₁₁O₃₉）₂·18H₂O,K₉（C₄H₄FN₂O₂）₂Ce（PW₁₁O₃₉）₂·23H₂O,K₉（C₄H₄FN₂O₂）₂Nd（PW₁₁O₃₉）₂·25H₂O,K₉（C₄H₄FN₂O₂）₂Sm（PW₁₁O₃₉）₂·11H₂O和K₉H（C₄H₄FN₂O₂）Eu（PW₁₁O₃₉）₂·11H₂O（FLnPW,Ln=La、Ce、Nd、Sm、Eu）对HeLa细胞凋亡和周期的影响,以5-氟尿嘧啶为阴性对照,同时比较了含5-氟尿嘧啶磷钨酸盐K11C₄H₄FN₂O₂（PW₁₁O₃₉）·7H₂O（FPW）及磷钨酸H₃PW₁₂O₄₀（PW）的生物活性。细胞形态检测表明,化合物作用于HeLa细胞后均出现明显凋亡形态特征,细胞核染色质呈高度浓缩和边缘化现象（PW除外）。流式细胞周期检测表明,化合物作用后HeLa细胞均出现S期阻滞,与5-氟尿嘧啶相比,FPW作用后S期阻滞增强,而FCePW、FNdPW和FEuPW组同时出现S期和G₂/M期阻滞。流式细胞检测表明,化合物诱导HeLa细胞发生凋亡（PW除外）,且诱导凋亡活性顺序为FLnPW > FPW > 5-氟尿嘧啶。Caspase 3检测表明,化合物作用后Caspase 3活性增强（PW除外）,活性顺序与凋亡活性顺序相同,其中FCePW组和FEuPW组Caspase 3相对活性显著增强。实验结果表明,所考查化合物（PW除外）能诱导细胞周期阻滞、诱导凋亡活性以及激活Caspase 3,且FLnPW的活性均高于FPW和5-氟尿嘧啶,而PW只能使肿瘤细胞发生坏死,说明5-氟尿嘧啶和稀土元素对化合物的抗肿瘤活性发挥关键作用,FLnPW可能是通过诱导细胞周期阻滞以及激活Cas-pase 3细胞凋亡通路,实现显著抑制HeLa细胞增殖。     

SrFeO3-δ纳/微米纤维的制备及其磁性

利用静电纺丝法与溶胶 凝胶技术, 制备PVP/Sr(OOCCH₃)₂·0.5H₂OC₁₅H₂₁FeO₆复合纳米纤维, 热处理后得到了SrFeO_3-δ纳/微米纤维, 并采用X射线衍射（XRD）、 扫描电镜（SEM）、 透射电镜（TEM）和超导量子干涉仪磁强计（SQUID）研究纤维样品的晶体结构、 微观形貌及其磁性. 实验结果表明： PVP/Sr(OOCCH₃)₂·0.5H₂OC₁₅H₂₁FeO₆复合纤维表面光滑, 长直连续, 平均直径约为500 nm; 在空气气氛下, 经800 ℃焙烧2 h后得到的SrFeO_3-δ纳/微米纤维均为较纯的立方钙钛矿型结构, 平均晶粒尺寸约为32 nm, 纤维直径为260~480 nm, 平均直径约为400 nm, 具有较大长径比; 当温度为175 ℃时, SrFeO_3-δ纤维样品的磁化率有极大值, 磁性纳米效应的影响及SrFeO_3-δ中螺旋反铁磁有序性、 顺磁性和铁磁性的共同作用使得纤维样品与块体样品的磁学性能不同, 其Neel温度与Curie温度均升高.     

细胞粘附肽Arg-Gly-Asp的合成与生物活性检测

采用固相多肽合成法合成Ag-G ly-Asp(RGD)三肽,以天门冬氨酸计RGD三肽收率为75%,采用MTT法进行合成肽RGD抑制人纤维肉瘤细胞HT1080转移机理方面的研究,证实了人工合成的RGD肽能抑制人纤维肉瘤细胞HT1080与纤维连接蛋白(FN)的粘附。     

RGD peptides induce apoptosis by direct caspase-3 activation

Synthetic peptides containing the arginine-glycine-aspartate (RGD) motif have been used extensively as inhibitors of integrin-ligand interactions in studies of cell adhesion, migration, growth and differentiation, because the RGD motif is an integrin-recognition motif found in many ligands. Here we report that RGD-containing peptides are able to directly induce apoptosis without any requirement for integrin-mediated cell clustering or signals. We show that RGD-containing peptides enter cells and directly induce autoprocessing and enzymatic activity of procaspase-3, a pro-apoptotic protein. Using the breast carcinoma cell line MCF-7, which has a functional deletion of the caspase-3 gene, we confirm that caspase-3 is required for RGD-mediated cell death. In addition to an RGD motif, pro-caspase-3 also contains a potential RGD-binding motif, aspartate-aspartate-methionine (DDM), near the site of processing to produce the p12 and p17 subunits. On the basis of the ability of RGD-DDX interactions to trigger integrin activation, we suggest that RGD peptides induce apoptosis by triggering conformational changes that promote pro-caspase-3 autoprocessing and activation. These findings provide an alternative molecular explanation for the potent proapoptotic properties of RGD peptides in models of angiogenesis, inflammation and cancer metastasis.     

纳米银对体外培养细胞附着形态及膜功能的影响

通过研究纳米银的急性细胞毒性及其对体外培养的人脐静脉内皮细胞(HUVEC)和人脐动脉平滑肌细胞(HUASMC)附着形态、膜流动性和膜完整性的影响,初步探讨了纳米银的生物安全性.实验结果表明:浓度为0.003 9~0.5mg/mL的纳米银没有急性细胞毒性,但会影响细胞的附着形态,使细胞变小变圆,附着性变差;纳米银聚集沉积在细胞膜周围,影响细胞膜的流动性和细胞膜的完整性,从而产生一定的细胞毒性.     

Functionalization of PCL fibrous membrane with RGD peptide by a naturally occurring condensation reaction

Poly(e-caprolactone)(PCL)is widely adopted as an ingredient for tissue engineering scaffolds.To improve its cell affinity,in this study,we developed a new method to introduce bioactive RGD peptides onto the surface of PCL via condensation reaction between 2-cyanobenzothiazole(CBT)and D-cysteine.The PCL fibrous membranes were prepared by electrospinning,and RGD functionalization was characterized by fluorescence microscopy,scanning electron microscopy(SEM),X-ray photoelectron spectroscopy(XPS)and water contact angle(WCA).As expected,our results demonstrated the successful RGD immobilization on the surface of PCL.RGD modification improved the hydrophilicity of PCL,changing their WCA from 112.20°to38.35°.Cell adhesion,spreading and proliferation of 3T3fibroblasts were also enhanced.We therefore believe that the methods reported in this study was facile and effective for functional modification of the hydrophobic PCL scaffolds.The moderate reaction conditions are also suitable for covalent immobilization of bioactive molecules onto PCL.     

纤维粘连蛋白在人滋养上皮的不同定位与功能

从正常人不同发育时期,不明原因流产,增殖型和侵蚀型葡萄胎滋养细胞角度,用免疫组织化学方法观察纤维粘连蛋白（FN）的显微定位,比较研究其不同定位与滋养上皮增殖,生长，分化,凋亡，迁移和浸润的关系。结果显示 正常人不同发育时期,FN在早孕合体滋养细胞基底膜和绒毛外滋养细胞膜呈阳性着色,在中期非合体结处的滋养细胞质呈免疫反应阳性,在足月滋养细胞呈阴性着色; 不明原因流产,FN在合体滋养细胞核内呈阳性着色; FN在增殖型葡萄胎滋养细胞膜和绒毛外滋养细胞质呈强阳性着色;FN在侵蚀型葡萄胎滋养细胞质呈阳性着色。提示FN胞质定位与滋养上皮迁移和侵蚀密切相关,FN基底膜定位与滋养细胞分化密切相关,FN胞膜定位与滋养细胞增殖相关,FN的阴性着色与滋养细胞衰老,FN胞核转位与滋养细胞凋亡可能相关。     

Peptides containing the cell-attachment recognition signal Arg-Gly-Asp prevent gastrulation in Drosophila embryos

It has recently been suggested that the Arg-Gly-Asp sequence (RGD) forms part of a widespread cell-extracellular matrix recognition system. Analysis of the cell binding sites of vertebrate fibronectin and other extracellular proteins that interact with cell surfaces implicate the same amino acid triplet. Peptides containing this sequence inhibit certain developmental events such as cell-matrix adhesion or cellular migration in vitro and in vivo. The RGD-sequence is also part of the cellular recognition site of the aggregation protein discoidin I in Dictyostelium suggesting that the RGD-recognition system could be universally used. In Drosophila, despite its advanced genetics, very little is known about the extracellular components that are involved in cell movements and morphogenesis. We report here that peptides containing the RGD-sequence prevent gastrulation of Drosophila embryos. The phenotypic effect is similar to that observed in the dorsal-group mutants: no ventral furrow is formed and the embryos lack dorsal-ventral polarity. The specificity of the inhibiting action suggests that the RGD-sequence may also be used by invertebrates to mediate cell-attachment phenomena.     

Expression, distribution and function of the focal adhesion kinase (pp125FAK) during murine ectoplacental cone outgrowthin vitro

Mouse embryo implantation is a complex process that includes trophoblast cells derived from ectoplacental cone (EPC) adhesion to and migration through the extracellular matrix (ECM) of uterine endometrium and invasion into the decidua. At the time of implantation, fibronectin (FN) is abundant in the decidua and is distributed pericellularly around each individual stromal cell, and its receptor (integrin α-5β-1) expression on trophoblast populations is up-regulated. The focal adhesion kinase, a 125 ku protein tyrosine kinase (pp125 FAK), is tyrosine phosphorylated upon integrin engagement with its ECM ligand, and its tyrosine phosphorylation sites then serve as the binding sites which couple it with cellular proteins that contain Src SH2 or SH3 domains. Through these linkages, pp125 FAK may integrate multiple signals triggered by integrins. The model of EPC culture %in vitro% was used to study the expression, distribution and function of pp125 FAK during EPC outgrowth on FN. Results indicated that, pp125 FAK primarily expressed and distributed in cellular focal adhesions of the front edge of trophoblast outgrowth from EPC, and was localized in the peripheral region of the individual migrating trophblast cell; antibody or antisense oligodeoxynucleotide to pp125 FAK inhibited EPC attachment and outgrowth, as well as trophoblast cells spreading and migration. This experiment demonstrated that pp125 FAK as an integrin-mediated signaling molecule was involved in EPC outgrowth %in vitro%, and played an important role during trophoblast cells interaction with FN.     

ICAM, an adhesion ligand of LFA-1, is homologous to the neural cell adhesion molecule NCAM

Antigen-specific cell contacts in the immune system are strengthened by antigen-nonspecific interactions, mediated in part by lymphocyte-function associated (LFA) antigens. The LFA-1 antigen is widely expressed on cells of haematopoietic origin and is a major receptor of T cells, B cells and granulocytes. LFA-1 mediates the leukocyte adhesion reactions underlying cytolytic conjugate formation, helper T-cell interactions, and antibody-dependent killing by natural killer cells and granulocytes. Recently, ICAM-1 (intercellular adhesion molecule-1) has been defined as a ligand for LFA-1. Monoclonal antibodies to ICAM-1 block T lymphocyte adhesion to fibroblasts and endothelial cells and disrupt the interaction between cytotoxic T cells and target cells. In addition, purified ICAM-1 reconstituted into artificial membranes binds LFA-1+ cells. ICAM-1 is found on leukocytes, fibroblasts, epithelial cells and endothelial cells and its expression is regulated by inflammatory cytokines. LFA-1 has been placed in the integrin family of cell surface receptors by virtue of the high sequence similarity between the LFA-1 and integrin beta chains. The adhesion ligands of the integrin family are glycoproteins bearing the Arg-Gly-Asp (RGD) sequence motif, for example, fibronectin, fibrinogen, vitronectin and von Willebrand factor. Here we show that a complementary DNA clone ICAM-1 contains no RGD motifs, but instead is homologous to the neural cell adhesion molecule NCAM.     

Rapid neutrophil adhesion to activated endothelium mediated by GMP-140.

Granule membrane protein-140 (GMP-140), a membrane glycoprotein of platelet and endothelial cell secretory granules, is rapidly redistributed to the plasma membrane during cellular activation and degranulation. Also known as PADGEM protein, GMP-140 is structurally related to two molecules involved in leukocyte adhesion to vascular endothelium: ELAM-1, a cytokine-inducible endothelial cell receptor for neutrophils, and the MEL-14 lymphocyte homing receptor. These three proteins define a new gene family, termed selectins, each of which contains an N-terminal lectin domain, followed by an epidermal growth factor-like module, a variable number of repeating units related to those in complement-binding proteins, a transmembrane domain, and a short cytoplasmic tail. Here we demonstrate that GMP-140 can mediate leukocyte adhesion, thus establishing a functional similarity with the other selectins. Human neutrophils and promyelocytic HL-60 cells bind specifically to COS cells transfected with GMP-140 complementary DNA and to microtitre wells coated with purified GMP-140. Cell binding does not require active neutrophil metabolism but is dependent on extracellular Ca2+. Within minutes after stimulation with phorbol esters or histamine, human endothelial cells become adhesive for neutrophils; this interaction is inhibited by antibodies to GMP-140. Thus, GMP-140 expressed by activated endothelium might promote rapid neutrophil targeting to sites of acute inflammation.