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Electron transfer reactions in elect...
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Kumar, Satish.
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Electron transfer reactions in electrostatic polypeptide-based assemblies.
紀錄類型:
書目-電子資源 : Monograph/item
正題名/作者:
Electron transfer reactions in electrostatic polypeptide-based assemblies./
作者:
Kumar, Satish.
面頁冊數:
228 p.
附註:
Source: Dissertation Abstracts International, Volume: 64-03, Section: B, page: 1263.
Contained By:
Dissertation Abstracts International64-03B.
標題:
Chemistry, Physical. -
電子資源:
http://pqdd.sinica.edu.tw/twdaoapp/servlet/advanced?query=3084835
Electron transfer reactions in electrostatic polypeptide-based assemblies.
Kumar, Satish.
Electron transfer reactions in electrostatic polypeptide-based assemblies.
- 228 p.
Source: Dissertation Abstracts International, Volume: 64-03, Section: B, page: 1263.
Thesis (Ph.D.)--Boston University, 2003.
Fundamental hydrophobic and electrostatic (charge-charge) interactions are common structural or mechanistic elements deployed in molecular recognition. In this dissertation, the interaction of selected synthetic polypeptides with small molecules that provide counter charges and/or hydrophobic contacts have been examined. One purpose of the work has to do with the building of self-assembled biomolecular scaffolds that organize electron donors and acceptors in such a way as to observe long range light-induced electron transfer or charge transport, thus attempting artificial photosynthesis. Another aspect of the work has to do with the development of a simple, rapid assay for polyelectrolytes (negatively charged biopolymers) using the partitioning of a fluorescent dye marker that is based on electrostatic recognition.Subjects--Topical Terms:
560527
Chemistry, Physical.
Electron transfer reactions in electrostatic polypeptide-based assemblies.
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Source: Dissertation Abstracts International, Volume: 64-03, Section: B, page: 1263.
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Fundamental hydrophobic and electrostatic (charge-charge) interactions are common structural or mechanistic elements deployed in molecular recognition. In this dissertation, the interaction of selected synthetic polypeptides with small molecules that provide counter charges and/or hydrophobic contacts have been examined. One purpose of the work has to do with the building of self-assembled biomolecular scaffolds that organize electron donors and acceptors in such a way as to observe long range light-induced electron transfer or charge transport, thus attempting artificial photosynthesis. Another aspect of the work has to do with the development of a simple, rapid assay for polyelectrolytes (negatively charged biopolymers) using the partitioning of a fluorescent dye marker that is based on electrostatic recognition.
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Polypeptides were prepared that contain charged and hydrophobic residues at appropriate locations to provide binding sites for photoactive dyes. The PCB(+), a net positively charged carbazole (electron donor)-containing polypeptide (28 residues), binds very efficiently with eosin Y (EY<super>2−</super>), an electron acceptor, via electrostatic interactions. The time-resolved absorption and emission data suggest a rapid forward and back electron transfer (<10 ns) between dye and peptide bound carbazole. A similar but negatively charged polypeptide, PCB(−), participates in an electron transfer process with a di-cationic electron acceptor, heptyl viologen. In an additional system, an aggregate of a mono-1,8-naphthalimide-spermine derivative (MNS) on a poly(glutamic acid) template is recruited as an electron donor.
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Absorption and emission spectra for another charged photochemical agent bis-1,8-naphthalimide-spermine (BNS) revealed a ground state intramolecular complexation of the two naphthalimide chromophores, particularly for aqueous media. Observation of a lower fluorescence quantum yield for BNS and the appearance of the radical anion intermediate on ns laser flash photolysis suggest a mechanism of intramolecular electron transfer involving two naphthalimide chromophores.
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The polycationic fluorescent probe, MNS, forms electrostatic aggregates in the presence of negatively charged polymers such as poly(glutamate) and poly(acrylic acid). The MNS monomeric emission (394 nm) has been used to provide a simple spectrophotometnc assay for trace quantities (sub ppm) of negatively charged polyelectrolytes.
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