Molecular studies of hydroxamate siderophore interactions with aqueous and solid phase iron
- 出版日期：2004.
- 页数：1 v. :
- 第一责任说明：David Charles Edwards.
- 分类号：a155 ; a270
- ISBN：0496999893(ebk.) :
MARC全文
02h0029527 20131113150426.0 cr un||||||||| 120621s2004 xx ||||f|||d||||||||eng | 3164943 0496999893(ebk.) : CNY371.35 NGL NGL NGL a155 ; a270 Edwards, David Charles. Molecular studies of hydroxamate siderophore interactions with aqueous and solid phase iron [electronic resource] / David Charles Edwards. 2004. 1 v. : digital, PDF file. Adviser: Myneni, Satish C. B. ; Spiro, Thomas G. Thesis (Ph.D.)--Princeton University, 2004. This dissertation explores the functional group and dissolution properties of hydroxamate siderophores in aqueous solution. Microbially produced siderophores in soil and aqueous systems obtain (by complexation or iron oxide dissolution) ferric iron in limiting environments to sustain cellular growth in bacteria and fungi. For this reason, siderophores play a role in controlling the free ferric iron flux in the environment. Infrared (IR), ultra-violet/visible (UV/vis), and X-ray absorption (XA) spectroscopic techniques were used to probe the molecular structure of desferrioxamine B (desB (C25H48O 8N6)； a hydroxamate siderophore) and acetohydroxamic acid (aHa (CH3CONHOH)； model monohydroxamic acid) as a function of pH in aqueous solutions. These experimental methods were complemented with calculated model compounds to correctly assign infrared and X-ray transitions. Infrared results from alla were difficult to apply to desB because of the large amount of coupling between the hydroxamate functional group and long chain methylene groups in the molecule. However, XA spectra of aHa greatly aided in the interpretation of desB. Upon deprotonation of the hydroxamate group (primarily an O-acid), the (C＝O)NO core electronic charge is highly delocalized, with most of the negative charge drawn towards the two oxygen atoms. Calculated transitions in the pre-edge region of the XA spectra indicate that 2p-orbitals from all atoms in the hydroxamate core interact with the 3d-orbitals from ferric iron. The large amount of delocalization in the hydroxamate core is the likely cause for the strong binding constants of hydroxamate siderophores. Iron oxide dissolution studies with aHa and desB were conducted with inductively coupled plasma - atomic emission spectrometry (ICP-AES). The results indicate that siderophores preferentially dissolve disordered iron oxide phases rather than coarse-grained goethite, the most ubiquitous iron oxide phase in soil systems. This work is directly applicable to research that requires an advanced understanding of the functional group chemistry of siderophores in a wide pH range. This includes, but is not limited to, contaminant transport, actinide remediation at Superfund sites, and cellular dissociation mechanisms. Chemistry ; Geochemistry Analysis. ; Analysis. Electronic dissertations. aeBook. aCN bNGL http://pqdt.bjzhongke.com.cn/Detail.aspx?pid=h4IrhplDN60%3d NGL Bs1583 rCNY371.35 ; h1 bs1204