Spectroscopic studies of the secondary structure of small peptides containing 4-(2-aminoethyl)-6-dibenzofuranpropanoic acid and synthesis of phosphomonoesters and phosphodiesters derived from the photohydrolysis of 2-methoxy-5-nitrophenyl substituted phosphotriesters /

Simple amides and peptides containing the

Bibliographic Details
Main Author: Graciani, Nilsa Raquel, 1966-
Format: Thesis Book
Language:English
Published: [Place of publication not identified] : [publisher not identified] ; 1994.
Subjects:
Online Access:http://proxy.library.tamu.edu/login?url=http://proquest.umi.com/pqdweb?did=741965341&sid=1&Fmt=2&clientId=2945&RQT=309&VName=PQD

MARC

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037 |a 95-20367  |b UMI 
040 |a TXA  |c TXA  |d UtOrBLW 
049 |a TXAM  |a TXAR 
099 |a 1994  |a Dissertation  |a G731 
100 1 |a Graciani, Nilsa Raquel,  |d 1966- 
245 1 0 |a Spectroscopic studies of the secondary structure of small peptides containing 4-(2-aminoethyl)-6-dibenzofuranpropanoic acid and synthesis of phosphomonoesters and phosphodiesters derived from the photohydrolysis of 2-methoxy-5-nitrophenyl substituted phosphotriesters /  |c by Nilsa Raquel Graciani. 
264 1 |a [Place of publication not identified] :  |b [publisher not identified] ;  |c 1994. 
300 |a xvi, 158 leaves :  |b illustrations ;  |c 28 cm. 
336 |a text  |b txt  |2 rdacontent 
337 |a unmediated  |b n  |2 rdamedia 
338 |a volume  |b nc  |2 rdacarrier 
504 |a Includes bibliographical references. 
500 |a Vita. 
502 |b Ph. D.  |c Texas A&M University  |d 1994. 
500 |a "Major Subject: Chemistry". 
530 |a Issued also on microfiche from University Microfilms Inc. 
520 |a Simple amides and peptides containing the  
520 |a conformationally restricted unnatural amino acids 4-(2- 
520 |a arninomethyl)-6-dibenzoftiranethanoic acid (2) and 4- 
520 |a amino-6-dibenzofuranmethanoic acid (3) were studied by  
520 |a NMR and FT-IR to ascertain their hydrogen bonding and 0- 
520 |a sheet nucleation capabilities as well as to compare them  
520 |a to the nucleator 4-(2-aminoethyl)-6- 
520 |a dibenzofuranpropanoic acid (1). Neither 2 nor 3 are  
520 |a effective P-sheet nucleators. Water soluble peptides  
520 |a containing I were studied using CD, I D- and 2D-NMR  
520 |a techniques to determine the mechanism by which residue 1  
520 |a nucleates P-sheet structure formation. In solution, at  
520 |a pH 4-5, peptides containing hydrophobic residues or  
520 |a histidine in the i and i+3 positions exhibit a well- 
520 |a defined P-tum structure with the dibenzofuran ring of 1  
520 |a adopting a perpendicular conformation with respect to  
520 |a the plane of the strands. The dibenzofuran portion of 1  
520 |a interacts with either the hydrophobic side chains or the  
520 |a charged imidazole ring flanking it through a hydrophobic  
520 |a or 7E-cation-like interaction, thus forming a well- 
520 |a defined P-tum mimetic capable of propagating P-sheet  
520 |a structure through a portion of the attached peptide  
520 |a strands. This hydrophobic cluster also promotes the  
520 |a formation of a 15-membered ring hydrogen bonded  
520 |a conformation necessary for P-sheet nucleation. A  
520 |a potential photocleavable protecting group for the  
520 |a synthesis of 
520 |a phosphopeptides containing 1 was developed. Phosphotriesters  
520 |a composed of one or two 2-methoxy-5-nitrophenyl group(s) can  
520 |a be quantitatively photohydrolyzed in aqueous acetonitrile to  
520 |a yield the desired phosphodiester or phosphomonoester,  
520 |a respectively. Photohydrolysis occurs by attack of hydroxide  
520 |a at both the phosphoryl phoSDhorus and at the ipso-carbon in  
520 |a the triplet exited state of the 2-methoxy-5riitrophenyl  
520 |a substituted phosphoesters. 
650 4 |a Major chemistry. 
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952 f f |a Texas A&M University  |b College Station  |c Electronic Resources  |s www_evans  |d Available Online  |t 0  |e 1994 Dissertation G731  |h Other scheme 
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