PS-PNVP嵌段共聚物的合成及其对CaCO_3形貌的调控

采用原子转移自由基聚合(ATRP)和可逆加成-断裂链转移聚合(RAFT)两步法合成了两亲性嵌段共聚物聚苯乙烯-b-聚乙烯基吡咯烷酮(PS-PNVP).经核磁共振氢谱(1 H-NMR)、傅里叶变换红外光谱(FTIR)、凝胶渗透色谱(GPC)方法确认了PS-PNVP的结构组成、相对分子质量及相对分子质量分布.采用气相扩散法,研究了PS-PNVP胶束溶液对CaCO3晶体的矿化及调控作用.采用扫描电子显微镜(SEM)表征了矿化所得CaCO3晶体的形貌.通过调整矿化温度和改变CaCl2溶液的浓度,获得了形貌丰富的多级结构CaCO3晶体.研究表明,以PS-PNVP胶束作为模板,可制备出形貌更复杂、结构更具层次的大尺度CaCO3晶体.     

可溶性β-环糊精聚合物与芳香化合物包结比的研究

本文对可溶性β环糊精聚合物与客体分子的包结行为进行了探讨。结果表明，可溶性β环糊精聚合物与客体分子按同一包结比进行。而β环糊精体系在浓度较低时，包结比为１∶１；浓度较高时，包结比为１∶２。     

以淀粉为基质仿生合成碳酸钙材料

以淀粉为有机基质,气相扩散法仿生合成碳酸钙晶体,结果显示,淀粉的浓度对碳酸钙的形貌有重要的影响,但对碳酸钙的晶型没有影响。淀粉分子基质影响碳酸钙晶体的成核位点和生长方向。     

不同几何形状CaCO_3超微粒子的合成

用不同方法合成了纳米级链状CaCO3及微米级纺锤形、立方形、球形CaCO3粉体材料，并对各自的物理性质和结构进行了测定和表征．对不同形状CaCO3的形成机理进行了初步的探讨．     

氨基酸改性β-环糊精的合成及仿生催化Suzuki偶联反应

以β-环糊精(β-CD)磺酰化反应制得的单-(6-O-对甲苯磺酰基)-β-CD为原料,与L-丝氨酸、L-苏氨酸和L-酪氨酸发生亲核取代反应,得到了3种氨基酸改性β-环糊精衍生物单-(6-L-氨基酸-6-脱氧)-β-CD。采用核磁共振氢谱(~1H NMR)、核磁共振碳谱(~(13)C NMR)和电喷雾质谱(ESI-MS)对单-(6-L-氨基酸-6-脱氧)-β-CD进行了表征。以3种氨基酸改性β-环糊精衍生物为配体,与醋酸钯配位,水相原位合成了仿生催化Suzuki偶联反应的催化体系。考察了配体、催化剂用量、缚酸剂、反应温度及反应时间对催化产率的影响,并分析了催化反应的底物普适性。试验结果表明:以单-(6-L-丝氨酸-6-脱氧)-β-CD、单-(6-L-苏氨酸-6-脱氧)-β-CD、单-(6-L-酪氨酸-6-脱氧)-β-CD为配体,对溴甲苯和苯硼酸为底物,K_3PO_4·7H_2O为缚酸剂,催化剂物质的量分数为0.010%时,80℃反应2 h,Suzuki偶联反应产率分别可达83%、88%和94%。底物的电子效应对Suzuki偶联反应产率有一定影响,而空间位阻影响不大。     

活体水仙模板调控合成碳酸钙晶体

探讨利用一种新的天然活体植物——水仙作为模板,在室温下调控合成碳酸钙晶体,并对产物进行了SEM、XRD的分析和表征.碳酸钙的形貌随水仙的叶子、鳞茎、花部位不同而变化,分别是纺锤形、立方体、类球形,晶体大小为纳微米级,均为方解石和球霰石的混合物,但球霰石的含量随以上晶体形貌的改变而递增.这一结果充分说明水仙不同部位生物分子组成不同,因此导致对碳酸钙的调控作用不同.     

醇水体系中胰蛋白酶调控下碳酸钙的仿生合成

依据仿生矿化的基本原理,在醇水体系中以胰蛋白酶作为有机基质,CaCl2为钙源,NH4HCO3为CO2来源,采用气体扩散的方法合成了球形的碳酸钙.用XRD,SEM,FT-IR和PL等手段对所得碳酸钙进行了表征,结果发现该球形CaCO3晶体为方解石与球霞石的混合晶型,并发现在CaCO3结晶的过程中,胰蛋白酶和醇水的混合溶剂...     

L-精氨酸-β-环糊精的合成和结构表征

氨基酸修饰的环糊精用于研究分子识别、包合作用的实质和分子的自组装等,是当前环糊精化学的热点领域之一.利用L-精氨酸和单-(6-O-对甲苯磺酰基)-β-环糊精进行反应,合成了氨基酸修饰的β-环糊精.产物利用G25葡聚糖凝胶色谱过柱,然后再用水和乙醇的混合溶液重结晶进行分离和提纯.同时利用电喷雾质谱、1 H NMR、13 C NMR、红外及元素分析等手段对产物进行了表征.     

固载化环糊精的合成及其在水处理中的应用研究

将β-CD固载到聚苯乙烯上,并将固载产物应用于模拟水样和实际废水的处理.结果表明:当pH为5～7时固载化环糊精对水样中污染物的吸附率接近100%;对苯酚、苯胺、Cu2 、Pb2 、Zn2 、Cd2 的饱和吸附量分别为81.85、67.80、89.25、965.58、48.81、99.55mg·g-1,且该树脂可再生使用4次.在一定浓度范围内,处理后实际废水的Pb2 、Cu2 、Cd2 、Zn2 的浓度、CODCr和pH值都达到了污水排入城市下水道标准CJ3082-1999.     

PVP与表面活性剂混合模板对CaCO3结晶的调控作用

聚乙烯吡咯烷酮(PVP)分别与十六烷基三甲基溴化铵(CTAB)、十二烷基硫酸钠(SDS)组成混合模板,在CaCl2、Na2CO3体系中调控合成CaCO3晶体,考察结晶温度对CaCO3晶体的影响。采用电导率法确定混合模板中表面活性剂的使用浓度。通过扫描电镜(SEM)、傅里叶变换红外光谱仪(FT-IR)及X线衍射仪(XRD)对晶体的形貌和结构进行表征。结果表明:SDS与CTAB结合到PVP长链上的浓度分别为2.4和1.1 mmol/L。在PVP-CTAB模板中,5℃时为方解石的层状CaCO3聚集体,25℃时有部分球形球霰石出现,90℃时得到了棒状文石晶体。在PVP-SDS模板中,5和25℃时均为方解石型球状CaCO3聚集体,90℃时得到棒状文石晶体。     

Biomimetic synthesis of ordered silica structures mediated by block copolypeptides

In biological systems such as diatoms and sponges, the formation of solid silica structures with precisely controlled morphologies is directed by proteins and polysaccharides and occurs in water at neutral pH and ambient temperature. Laboratory methods, in contrast, have to rely on extreme pH conditions and/or surfactants to induce the condensation of silica precursors into specific morphologies or patterned structures. This contrast in processing conditions and the growing demand for benign synthesis methods that minimize adverse environmental effects have spurred much interest in biomimetic approaches in materials science. The recent demonstration that silicatein-a protein found in the silica spicules of the sponge Tethya aurantia--can hydrolyse and condense the precursor molecule tetraethoxysilane to form silica structures with controlled shapes at ambient conditions seems particularly promising in this context. Here we describe synthetic cysteine-lysine block copolypeptides that mimic the properties of silicatein: the copolypeptides self-assemble into structured aggregates that hydrolyse tetraethoxysilane while simultaneously directing the formation of ordered silica morphologies. We find that oxidation of the cysteine sulphydryl groups, which is known to affect the assembly of the block copolypeptide, allows us to produce different structures: hard silica spheres and well-defined columns of amorphous silica are produced using the fully reduced and the oxidized forms of the copolymer, respectively.     

Biomimetic synthesis for precursor of muscone

Muscone is a precious fragrant compound scarce in nature. Many attempts have been made to synthesize this unique natural product. In this work, the one- carbon unit transfer reaction of tetrahydrofolate coenzyme was initiated. Benzimidazolium salt was used as the tetrahydrofolate coenzyme model at formic acid oxidation level and di-Grignard reagent as the nucleophile to which one-carbon unit was transferred; the biomimetic synthesis of 2,15- hexade-canedione, a precursor of muscone, was successfully accomplished by using the addition-hydrolysis reaction of benzimidazolium salt with Grignard reagent. And an important useful method for the synthesis of muscone is provided.     

活体生物膜模板法诱导控制合成硫化汞纳米网状结构

利用青葱活体生物膜所具有的选择性吸收与排异、渗透与传输、诱导与控制等特殊功能,以其为模板,于室温下成功制备了网状交联结构的纳米硫化汞.该网状交联结构是由直径为80～120 nm的纳米球自组装而成的,其结构为六方相,晶格常数为a=0.414 8 nm,c=0.949 4 nm.通过紫外可见光谱和荧光光谱对产物的光学性质进行了研究,对纳米硫化汞的合成机理进行了初步探讨.     

L-赖氨酸对CaCO3晶型和形状调控

氨基酸和表面活性剂在生物矿化过程中起着重要的作用,文章研究了L-赖氨酸和十二苯基磺酸钠对CaCO3晶体结晶的协同影响,用XRD和红外光谱对合成的CaCO3晶体进行了表征,采用SEM观察分析了生成的CaCO3晶体的形貌.结果表明,在赖氨酸和十二苯基磺酸钠二元体系中,L-赖氨酸的质量浓度对CaCO3晶型和晶体形状有很大的影...     

仿生合成SiO2载体及其固定脂肪酶的条件研究

采用L-脯氨酸为模板,仿生制备用于固定脂肪酶的二氧化硅载体．SEM、IR表征得知,制备的仿生载体为粒径约3um的SiO2微球,氮气吸附表征得知,SiO2微球内部孔径大小约16．8nm．载体固定脂肪酶的实验结果表明,固定化脂肪酶的相对最佳条件：酶液质量浓度5mg／mL,反应温度40℃,反应时间7h,pH=8,最高固载率可达82．3％,酶活1067U／g载体．     

CaCO3共沉淀富集法测生活饮用水中的Zn

建立了CaCO3共沉淀富集原子吸收光谱法测定水中Zn的方法.该法消除了磷酸盐、硅酸盐、铝盐等含氧阴离子的影响,提高了测定的灵敏度,其回归方程为A=0.3527c+0.0233,相关系数r=0.9996,方法检出限为0.06μg·mL-1,精密度为0.22%～0.64%,回收率为93.4%～96.9%,结果令人满意.     

纳米聚丙烯酸酯微乳液改性纳米CaCO3研究

分别采用聚丙烯酸酯乳液和纳米级聚丙烯酸酯微乳液对纳米CaCO3进行改性,通过红外光谱分析、热重分析和扫描电镜分析研究改性纳米CaCO3的结构和性能.结果表明,改性后的纳米CaCO3由亲水疏油性变为亲油疏水性,纳米级聚丙烯酸酯微乳液与纳米CaCO3粒子表面发生了化学反应,并包覆到纳米CaCO3粒子表面.     

Biomimetic mineralization synthesis of hydroxyapatite bacterial cellulose nanocomposites

Hydroxyapatite (HAp)/bacterial cellulose (BC) nanocomposites were prepared by an optimal biomimetic mineralization synthesis approach for bone tissue engineering application. BC with ultrafine three dimensional network was negatively charged by the adsorption of polyvinylpyrrolidone (PVP) to initiate the nucleation of HAp. The HAp was grown in vitro along the nanofiber network of BC via dynamic simulated body fluid (SBF) treatment. It was found that rod-like HAp particles in the nano-scale (100–200 nm) homogeneously deposited on the surface of PVP-BC. ATR-Fourier Transform Infrared Spectroscopy (ATR-FTIR) results showed that carbonate-containing HAp crystals resembling natural bones were formed by biomimetic mineralization method. Moreover, the amount of HAp observed increased with increasing mineralization time. And the Ca/P overall ratio ranged from 1.37 to 1.59. The results from Inductively Coupled Plasma Atomic Emission Spectroscopy (ICP-AES) indicated that PVP treatment enhanced the apatite nucleation ability of BC with higher HAp deposit amount.     

Biomimetic mineralization synthesis of hydroxyapatite bacterial cellulose nanocomposites

Hydroxyapatite (HAp)/bacterial cellulose (BC) nanocomposites were prepared by an optimal biomimet ic mineralization synthesis approach for bone tissue engineering application. BC wi th ultrafine three dimensional network was negatively charged by the adsorption of polyvinylpyrrolidone (PVP) to initiate the nucl eation of HAp. The HAp was grown in vitro along the nanofiber network of BC via dynamic simulated body fluid (SBF) treatment. It was found that rod-like HAp particles in the nano-scale (100 ? 200 nm) homogeneously deposited on the surface of PVP-BC. AT R-Fourier Transform Infrared Spectroscopy (ATR-FTIR) results showed that carbonate-containing HAp crystals resembling natural bones were fo rmed by biomimetic mineralization method. Moreover, the amount of HAp observed increased with increasing mineralization time. And the Ca/P overall ratio ranged from 1.37 to 1.59. The results from Inductively Coupl ed Plasma Atomic Emission Spectroscopy (ICP-AES) indicated that PVP treatment enhanced the apatite nucleation ability of BC with higher HAp deposit amount.