Mechanistic Limitations in the Synthesis of Polyesters by Lipase-Catalyzed Ring-Opening Polymerization (Record no. 45337)

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control field MX-MdCICY
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control field 20250625140644.0
040 ## - CATALOGING SOURCE
Transcribing agency CICY
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Classification number (OCLC) (R) ; Classification number, CALL (RLIN) (NR) B-11110
008 - FIXED-LENGTH DATA ELEMENTS--GENERAL INFORMATION
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245 10 - TITLE STATEMENT
Title Mechanistic Limitations in the Synthesis of Polyesters by Lipase-Catalyzed Ring-Opening Polymerization
490 0# - SERIES STATEMENT
Volume/sequential designation Biotechnology and BioEngineering, 84(1), p.103-113, 2003
520 3# - SUMMARY, ETC.
Summary, etc. Lipase-catalyzed polymerization of caprolactone (CL)in toluene with methoxy-poly(ethylene glycol)(MPEG)and water as initiators was characterized in detail for mechanistic insight. 1H NMR analysis of polycaprolactone chains (PCL), dicaprolactone, degree of esterification of MPEG, and fractions of PCL chains initiated by MPEG and water were used to follow the reactions. The data were analyzed with the kinetic scheme involving formation of the acylenzyme and its consequent reaction with MPEG, water, or PCL to yield the MPEG- or waterinitiated PCL chains, or increase in PCL length. A limit for MPEG initiator esterification in lipase-catalyzed CL polymerization was observed and was explained by preferential reaction of PCL propagation over MPEG esterification at long reaction times and low MPEG concentrations. Slower monomer conversion in concentrated monomer solutions was explained by decreased partitioning of PCL between the solvent and the enzyme. This effect resulted in inhibition of the lipase by the reaction product, PCL chains, and/or insufficient diffusion of monomer to the enzyme active site. High monomer/ initiators ratio in these solutions did not yield longer polymer chains due to decreased monomer conversion and the corresponding decrease in product yields; lower yields were also observed for chain initiation by MPEG and water. A shift in the reaction rate-limiting step from formation of acylenzyme in dilute CL solutions to its deacylation in concentrated CL solutions yielded higher PCL polydispersity due to increased initiation by water. Enhanced intramolecular cyclization was also observed. Endgroup composition of PCL chains was influenced by the concentration of monomer, ratio of initiators (MPEG and water), and reaction time, yielding PCL chains initiated exclusively by MPEG at "infinite reaction times.
650 14 - SUBJECT ADDED ENTRY--TOPICAL TERM
Topical term or geographic name entry element LIPASE
650 14 - SUBJECT ADDED ENTRY--TOPICAL TERM
Topical term or geographic name entry element POLYESTER
650 14 - SUBJECT ADDED ENTRY--TOPICAL TERM
Topical term or geographic name entry element RING-OPENING
650 14 - SUBJECT ADDED ENTRY--TOPICAL TERM
Topical term or geographic name entry element POLYMERIZATION
650 14 - SUBJECT ADDED ENTRY--TOPICAL TERM
Topical term or geographic name entry element POLYETHYLENE GLYCOL
650 14 - SUBJECT ADDED ENTRY--TOPICAL TERM
Topical term or geographic name entry element INITIATORS
700 12 - ADDED ENTRY--PERSONAL NAME
Personal name Panova, A.A.
700 12 - ADDED ENTRY--PERSONAL NAME
Personal name Kaplan, D.L.
856 40 - ELECTRONIC LOCATION AND ACCESS
Uniform Resource Identifier <a href="https://drive.google.com/file/d/1zvwO-kkbSgMO-ujSnCPGPqnZfWhau3Hx/view?usp=drivesdk">https://drive.google.com/file/d/1zvwO-kkbSgMO-ujSnCPGPqnZfWhau3Hx/view?usp=drivesdk</a>
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Source of classification or shelving scheme Clasificación local
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  Clasificación local     Ref1 CICY CICY Documento préstamo interbibliotecario 25.06.2025   B-11110 25.06.2025 25.06.2025 Documentos solicitados