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.     

三维大孔氮化碳材料的制备及其血液相容性

以粒径640 nm的单分散二氧化硅胶体晶体为模板,由四氯化碳和乙二胺回流加热制备出氮化碳的前驱物;将其填入模板的缝隙中,在氮气中热处理,形成氮化碳/二氧化硅的复合物;用氢氟酸除去二氧化硅模板,制备出三维大孔氮化碳材料. 通过扫描电子显微镜(SEM)、透射电子显微镜(TEM)、X射线衍射 (XRD)、选区电子衍射(SAED)、元素分析、红外光谱(FT-IR)、X射线光电子能谱(XPS),对其形貌结构、元素组成、键合状态进行了形貌和结构的表征. 采用部分凝血活酶时间(APTT)、凝血酶原时间(PT)和凝血酶时间(TT)对其体外抗凝血活性作了初步的评价,发现制备的大孔氮化碳对血液不会造成促凝,说明其可能成为一种新的血液相容性材料.     

CNTs/mesostructured silica core-shell nanowires via interfacial surfactant templating

Carbon nanotubes (CNTs)/mesostructured silica core-shell nanowires with a carbon nanotube core and controllable highly ordered periodic mesoporous silica shell are syntheiszed via the interfacial surfactant template. The core-shell nanowires are characterized by transmission electron microscope (TEM), X-ray diffraction pattern (XRD) and nitrogen sorption/desorption. The results indicate that the core-shell nanowires have highly ordered periodic mesoporous silica shell (space group p6mm), high BET surface area and narrow pore size distribution. Moreover, the morphology of core-shell nanowires can be controlled by the pH value. The core-shell nanowires have promising applications in biosensors, nanoprobes and energy storage due to their good dispersibility in polar solvents. Supported by the Australian Research Council (ARC) through Discovery Project program (DP0452461)     

Self-assembly of regular hollow icosahedra in salt-free catanionic solutions

Self-assembled structures having a regular hollow icosahedral form (such as those observed for proteins of virus capsids) can occur as a result of biomineralization processes, but are extremely rare in mineral crystallites. Compact icosahedra made from a boron oxide have been reported, but equivalent structures made of synthetic organic components such as surfactants have not hitherto been observed. It is, however, well known that lipids, as well as mixtures of anionic and cationic single chain surfactants, can readily form bilayers that can adopt a variety of distinct geometric forms: they can fold into soft vesicles or random bilayers (the so-called sponge phase) or form ordered stacks of flat or undulating membranes. Here we show that in salt-free mixtures of anionic and cationic surfactants, such bilayers can self-assemble into hollow aggregates with a regular icosahedral shape. These aggregates are stabilized by the presence of pores located at the vertices of the icosahedra. The resulting structures have a size of about one micrometre and mass of about 1010 daltons, making them larger than any known icosahedral protein assembly or virus capsid. We expect the combination of wall rigidity and holes at vertices of these icosahedral aggregates to be of practical value for controlled drug or DNA release.     

Template/surfactant free and UV light irradiation assisted fabrication of Mn-Co oxides composite nanorings: Structure and synthesis mechanism

A facile, green, cost effective, and template or surfactant free strategy via a two-step route i.e. UV irradiation followed by dissolution-growth for the controlled synthesis of Mn-Co composite nanorings at room temperature was proposed. The nanorings structures and the process were systematically studied via TEM, HRTEM, EDX and XRD. Bir-MnO_2 nanosheets first formed through the direct photolysis of KMnO_4 under UV light irradiation. This was followed by a dissolution-growth process via the dissolution of Bir-MnO_2 nanosheets by the generated H~+ from the redox reaction between the added Co(NO_3)_2 and residual KMnO_4, as well as the accompanied formation of CoOOH, and Mn-Co composite nanorings. It was found that a balance between the dissolution and growth rate was needed. Suitable pH, KMnO_4 presence and the starting nanosheets like Bir-MnO_2 were the key factors for the formation of nanorings. The obtained Mn-Co nanorings/TiO_2 showed enhanced efficiency for the catalytic oxidation of HCHO. Based on the above understandings, it is believed that the developed dissolution-growth method can be adopted for the designing and preparation of other Mn-Co composite nanostructures which can be further applied for environmental pollution remediation.     

Synthesis and Characterization of Ordered Meso-Macro-Porous Silica Membranes on a Porous Alumina Support

Macroporous silica materials with ordered three-dimensional pore structure can be easily prepared by the template-directed sol-gel process. However, it is still a challenge to prepare them in membrane form on a porous support, which limits their applications. In this work, we have demonstrated the feasibility of obtaining a three-dimensional ordered macroporous silica membrane on macroporous alumina support using poly-methyl methacrylate (PMMA) spheres as the template. PMMA spheres were packed on the top of an Anopore-alumina support by filtration of a PMMA aqueous suspension. Silica sol obtained by an acid-catalyzed sol-gel process was infiltrated into the voids among the spheres. Drying induced stress caused the membrane to crack or peel off from the top of the support. This can be minimized by annealing the PMMA template layer before the introduction of silica sol which increases the mechanical strength of the template. Calcination or solvent extraction to remove the template produced a highly ordered three-dimensional macroporous silica membrane with spherical pores connected by windows in the mesoporous range. The results show that the PMMA-templated infiltration method is effective in preparing three-dimensional ordered macroporous silica membranes on a porous support.     

MnO2/C复合纳米纤维纱线的制备及其导电性能

采用共轭静电纺丝法制备聚丙烯腈(PAN)纳米纤维纱线,并在不同温度下将PAN纳米纤维碳化得到碳纳米纤维纱线。以KMnO 4为锰源,通过水热合成法在碳纳米纤维纱线上原位生长纳米二氧化锰(MnO 2),形成MnO 2/C复合纳米纤维纱线,分别采用傅里叶变换红外光谱(FTIR)、扫描电子显微镜(SEM)、场发射扫描电子显微镜(FE-SEM)、数字万用表对碳纳米纤维纱线和MnO 2/C复合纳米纤维纱线的化学组成、表观形貌、电学性能等进行表征,并分析碳化温度对碳纳米纤维纱线的形貌和电学性能的影响,以及水热反应中盐酸浓度对纳米MnO 2形貌和MnO 2/C复合纳米纤维纱线的影响。结果表明:碳化温度越高,得到的纱线表面越光洁,石墨化程度越高,电学性能也越好,1000℃碳化工艺得到的碳纳米纤维纱线电导率最高,为31.5 S/cm;与MnO 2复合后的碳纳米纤维纱线电导率大幅下降,当盐酸与高锰酸钾摩尔浓度比为4∶1时得到的复合纳米纤维纱线的电导率最高,为0.1200 S/cm。     

稻草制浆过程中硅的形态变化

硅在稻草中主要以粒径为１５μｍ的硅晶胞形式存在于植物外层，在制浆过程中硅晶胞作为整体溶脱后再以相对小的硅晶胞附着在纤维上．在ｐＨ值、粒子粒径和反应时间几个影响硅溶出的因素中，ｐＨ值为控制因素．硅在溶液中主要以无定形形态析出，析出的硅主要附着在纤维表面，当有阳离子聚合物存在时硅沉降速度和沉降量急剧上升     

Controlled fabrication of fullerene derivative one-dimensional nanostructures via electrophoretic deposition of its clusters

Well-defined and controllable one-dimensional(ID) nanostructures of fullerene derivative have been prepared by an electrophoretic template synthesis method. The clusters of fullerene derivative formed in mixed solvents are introduced into the channels of porous alumina templates through a dc electric field. Four types of ID nanostructures(solid nanowires, solid-wall nanotubes, porous nanowires and porous-wall nanotubes) have been obtained by changing the deposition parameters. This,approach opens a new avenue to assemble fullerene derivatives, endohedral fullerenes, as well as other functional organic compounds, which can form clusters in ID nanostructure arrays for applications in chemical sensors, light energy conversion devices and nanoscale electronic and optoelectronic devices.     

Nanoscale control of silks for regular hydroxyapatite formation

The control of nanoparticle shape is still a challenge for different hydroxyapatite (HA) preparation ways.In the present study,silk fibroin with regular nanostructures was firstly prepared and then emp...     

Stability of diatomaceous silica and its geochemical implication

An experiment of stability of diatomaceous silica was performed. The results show that pH value and temperature dominantly influence the stability. The pH value concerning largely dissolving diatomaceous silica is 2-3 higher than that amorphous silica due to the buffer action of coexistent clay minerals. The solubility of diatomaceous silica rises distinctly when temperature is over 40℃, which suggests the cause of distribution of large-scale diatomite deposits in the middle to high latitude areas over the world. There is no close relationship between the solubility of diatomaceous silica and time, which shows that the content of diatomaceous silica in diatomite deposits are determined by the latest environment condition since they formed and bore no relation to the time they experienced.     

介孔二氧化硅包覆银纳米颗粒的制备及抗菌性能

首先采用次磷酸钠液相还原方法制备了纳米银溶胶;再以正硅酸乙酯为硅源,十六烷基三甲基溴化铵为模板剂,采用溶胶-凝胶法,在制备的纳米银溶胶中的银颗粒表面原位生长二氧化硅球壳;然后利用溶剂萃取法去除有机模板剂,再经超临界干燥后制备出介孔二氧化硅包覆银纳米颗粒(Ag@mSiO2)。对所得样品进行了TEM、SEM、XRD、FT-IR、N2吸附/脱附等表征,结果表明此纳米复合粒子的介孔结构有序性良好、比表面积大、呈连接的球状形貌。进一步以二倍稀释法测试了Ag@mSiO2纳米颗粒对大肠杆菌和金色葡萄球菌的最小抑菌质量浓度(均为156μg/mL)和最小杀菌质量浓度(312.5和625μg/mL),结果表明Ag@mSiO2纳米颗粒有良好的抗菌效果。     

WO_3/HMS分子筛的合成及其催化性能

以(NH4)2WO4为钨源,采用浸渍法,在不同pH值、模板剂种类、模板剂用量和硅钨比等条件下合成多相催化剂WO3/HMS,利用XRD手段对催化剂的结构进行了表征,研究了催化剂在环戊烯选择性氧化合成戊二醛反应中的催化性能.结果表明:在pH=4、硅源为正硅酸乙酯(TEOS)、模板剂为十二胺(DDA)、n(DDA)/n(TEOS)=0.20,n(Si)/n(W)=30的条件下合成的WO3/HMS分子筛催化活性最高,戊二醛的收率最高可达67%.催化剂具有较高的稳定性,可以重复使用5次,失活后的催化剂可通过高温焙烧的方式再生.     

自组装制备磁性复合微球聚集体

用部分还原法制得纳米Fe3O4,用微乳液聚合法制备聚（苯乙烯-丙烯酸）高分子微球P（St-co-AA）,再以球形P（St-co-AA）为模板与Fe3O4磁粉通过静电自组装和氢键自组装制得磁性复合微球聚集体Fe3O4／P（St-co-AA）;利用XRD、TEM、SEM、IR等对样品进行表征,采用VSM对样品进行磁性能测试．结果表明所得样品为Fe3O4单相,平均粒径约10nm．P（St-co-AA）平均尺寸为约70nm,表面含有羧基,所制磁性复合聚集体Fe3O4/P（St-co-AA）的形貌为球形、多孔、粒径约5μm,磁粉含量为29％．磁性能测试表明当外加磁场为6KOe时,磁化强度达到饱和,饱和磁化强度为69emu.g^-1．研究表明pH、搅拌等对磁性复合微球聚集体的形成有重要影响．     

模拟酶用于测定葡萄糖及免疫分析的研究

研究锰-四磺基苯卟啉(Mn-TPPS₄)络合物催化过氧化氢与邻苯二胺反应的特性,并与辣根过氧化物酶比较。与葡萄糖氧化酶的酶促反应偶联,测定血清中的葡萄糖,与试剂盒测定结果吻合。用两种方法将Mn-TPPS₄标记到牛血清白蛋白上,其免疫活性和催化活性均较好。     

Formation of a stable triplex from a single DNA strand

Homopurine.homopyrimidine DNA sequences have been shown to form triple-stranded structures readily under appropriate conditions. Interest in DNA triplexes arises from potential applications of intermolecular triplexes as antisense inhibitors of gene expression and from the possibility that intramolecular triplexes may have a role in gene expression and recombination. We recently presented NMR evidence for triplex formation from the DNA oligonucleotides d(GA)4 and d(TC)4, which showed unambiguously that the second pyrimidine strand is Hoogsteen base paired and the cytosines are protonated at N3 as required. To obtain a more well defined triplex, and to provide a model for in vivo triplex structures, we have designed and synthesized a 28-base DNA oligomer with a sequence that could potentially fold to form a triplex containing both T.A.T and C+.G.C triplets. Our NMR results indicate that the conformation at pH 5.5 is an intramolecular triplex and that a significant amount of triplex remains even at pH 8.0.     

Ag／TiO2中空纳米纤维结构材料的太阳光催化性能

利用一种模板辅助的两步法制备银修饰的TiO2中空纤维光催化纳米结构材料（Ag／TiO2）,借助于扫描电子显微镜（SEM）,X光电子能谱（XPS）,X线衍射（XRD）,uVvis光谱,Zeta电位等技术以及亚甲基蓝（MB）在不同光源条件下的降解脱色对目标材料结构、性能等进行了表征．结果表明：在空气气氛和适当温度下处理前驱材料（Ag＋-Ti4＋／CF）可以同时实现模板（CF）的去除,Ti4＋→TiO2和Ag＋→Ag的原位转化;材料的纳米纤维结构化和适量Ag（0．20％,质量分数）的引入有利于其太阳光催化性能的提高;该纤维材料易于分离,再利用．该纳米纤维结构材料良好的太阳光催化性能是众多因素协同作用的结果．     

一种新型磷酸硅铝分子筛的合成及表征

采用水热合成法,以三乙烯四胺(TETA)为模板剂,磷酸、正硅酸乙酯、乙酸镁及氢氧化铝为原料,通过调节模板剂的用量、晶化温度、晶化时间和 pH 值,合成出含镁的磷酸硅铝分子筛,原料的物质的量之比为 n(P): n(Si): n(H2O): n(Ni): n(Al): n(TETA)=1.00:0.25:0.18:0.51:30.00:0.65,晶化温度为150~170, pH ℃值为6.0,晶化时间为24 h     

晶化时间、模板剂对Si-MCM-41结构的影响

以有机硅为硅源,采用碱性水热合成制备Si-MCM-41,借助XRD,N2吸附-脱附表征手段系统研究晶化时间、模板剂对其长程有序结构的影响.结果表明:晶化过程中必须调节体系的pH,样品的六方晶相才会随晶化时间的增长而不断地生长和完善.长时间的晶化有利于孔壁增厚,对于提高Si-MCM-41的稳定性是有利的,但同时比表面积呈现下降趋势.综合考虑六方有序结构的生长和完善以及孔壁的厚度、比表面积等因素,确定晶化时间为120 h.增加模板剂(template)浓度会促进Si-MCM-41孔结构形成和排列的规整性,当模板剂为c(template)/c(SiO2)=0.7,六方有序度下降,适宜的c(template)/c(SiO2)应为0.5.     

纳米棒插接多级孔ZSM-11分子筛形貌影响因素研究

采用先低温后高温的两段晶化方法在含有四丁基溴化铵的单一模板体系中合成具有插接形貌的ZSM-11分子筛。分别从硅源、铝源、硅铝比、碱源和模板剂的种类对插接形貌形成的影响因素进行分析。结果表明:硅源、铝源以及碱源的种类主要是通过影响解聚-聚合的速率来影响体系的成核以及晶体生长的速率,从而对结晶动力学以及最终产品的晶粒尺寸产生影响,并不会对插接形貌产生大的影响;与固体硅源(硅胶小球)相比,使用液体硅源(硅溶胶和水玻璃)能够在较短时间内得到尺寸较小的分子筛产品;与无机铝源相比,采用异丙醇铝较易在短时间内获得小晶粒产品;与Li+和Na+相比,含有K+的体系中产品分子筛尺寸较大;模板剂的种类直接影响到最终结晶产物的形貌特征,四丁基铵离子的存在是这种插接形貌形成的必要条件。随着合成体系含铝量的减小,插接形貌变得不再明显,铝的存在是这种插接形貌形成的必不可少的影响因素之一。