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Biomimetic titanium mineralization.

机译:仿生钛矿化。

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摘要

While many industrial processes to form nanostructured metal-oxides require extreme temperatures, pressures, and caustic chemicals, Nature is able to form such structures under ambient conditions. The use of these inorganic structures by organisms is known as biomineralization. A deeper understanding of biomineralization, particularly the chemistry underlying these processes, offers potential for the development of biomimetic methods in materials chemistry. The work presented in this thesis investigates both the use and the biomimetic formation of mineralized titanium oxide structures.;Two organisms were studied for their apparent affinity towards titanium dioxide. The foraminiferan Bathysiphon argenteus was found to incorporate needles of rutile TiO2 into its shell. These needles were presumed to be detrital and collected from the environment. The Gram-positive bacteria Rhodococcus ruber was found to have three dominant cell-surface proteins that adhered strongly to TiO2. Preliminary experiments identified them as Elongation Factor G, dihydrolipoamide dehydrogenase, and Elongation Factor EF1A.;The R5 peptide, poly(allylamine), spennidine, and spermine were used to study the formation of micro- and nanostructured titanium oxide at the molecular level. All of the biomolecules studied induced the formation of micro- and nanostructured titanium oxide. The solid formed with poly(allylamine) was a titanium phosphate solid, while the solids formed with the R5 peptide, spermidine, and spermine were titanium dioxide. The green fluorescent protein was encapsulated in the solid precipitated with poly(allylamine) only. The effects of temperature and pH were studied in all cases. The kinetics and the mechanism of reaction were studied for the reactions with spermidine and spermine.;Titanium mineralization was also investigated using the iron-storage protein, ferritin. Oxidative and hydrolytic mineralization reactions were studied by the direct addition of Ti(III) and Ti(IV) precursors to ferritin. The reactions were monitored by using transmission electron microscopy, UV-Vis spectroscopy, mass spectrometry, and competition experiments. Preliminary results from a photoreductive method revealed a shift associated with a change in molecular weight upon mineralization as evidenced by using analytical ultracentrifugation.;Finally, the photoreduction of high-valent titanium precursors was studied. The photoreduction of Ti(IV) citrate was evidenced by the formation of a purple color due to a ligand-to-metal charge transfer. The citrate ligand was oxidatively decarboxylated to form acetone dicarboxylic acid, which spontaneously decarboxylated to form acetoacetic acid and, ultimately, acetone. These photoproducts were detected by using nuclear magnetic resonance. The photoreduction of TiBALDH was evidenced by the formation of a bright blue color, although no photoproducts were detected.
机译:虽然形成纳米结构金属氧化物的许多工业过程都需要极高的温度,压力和腐蚀性化学物质,但大自然能够在环境条件下形成这种结构。生物对这些无机结构的使用被称为生物矿化。对生物矿化特别是这些过程背后的化学的更深入的了解为材料化学中仿生方法的发展提供了潜力。本文研究的工作既研究了矿化二氧化钛结构的用途,又探讨了其仿生形成的方法。研究了两种生物对二氧化钛的表观亲和力。发现有孔虫Bathysiphon argenteus将金红石型TiO2的针状物掺入其壳中。这些针被认为是有害的,是从环境中收集的。发现革兰氏阳性菌红球菌具有三种主要的细胞表面蛋白,它们与TiO2牢固粘附。初步实验将其鉴定为延伸因子G,二氢脂酰胺脱氢酶和延伸因子EF1A.R5肽,聚烯丙胺,斯潘定和精胺用于研究分子水平上的微纳米结构二氧化钛的形成。所有研究的生物分子都诱导了微结构和纳米结构的氧化钛的形成。由聚(烯丙胺)形成的固体是磷酸钛固体,而由R5肽,亚精胺和亚精胺形成的固体是二氧化钛。将绿色荧光蛋白封装在仅用聚烯丙胺沉淀的固体中。在所有情况下都研究了温度和pH的影响。研究了亚精胺和亚精胺反应的动力学和反应机理。还使用铁存储蛋白铁蛋白研究了钛的矿化作用。通过将Ti(III)和Ti(IV)前体直接添加到铁蛋白中来研究氧化和水解矿化反应。通过使用透射电子显微镜,紫外-可见光谱,质谱和竞争实验监测反应。光还原法的初步结果表明,通过分析超速离心法可以证明矿化过程中分子量变化的相关变化。最后,研究了高价钛前体的光还原。柠檬酸Ti(IV)的光还原反应是由于配体向金属的电荷转移而形成紫色而证明的。将柠檬酸酯配体氧化脱羧以形成丙酮二羧酸,然后将其自发脱羧以形成乙酰乙酸,最终形成丙酮。这些光产物通过核磁共振检测。 TiBALDH的光还原反应由亮蓝色形成,尽管未检测到光产物。

著录项

  • 作者

    Cole, Kathryn Elizabeth.;

  • 作者单位

    Yale University.;

  • 授予单位 Yale University.;
  • 学科 Chemistry Biochemistry.;Chemistry Inorganic.
  • 学位 Ph.D.
  • 年度 2009
  • 页码 131 p.
  • 总页数 131
  • 原文格式 PDF
  • 正文语种 eng
  • 中图分类 生物化学;无机化学;
  • 关键词

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