NDLI: Ring-opening polymerization of L-lactide using N-heterocyclic molecules: mechanistic, kinetics and DFT studies

Please wait, while we are loading the content...

Hydrolysable polylactide–polyphosphazene block copolymers for biomedical applications: synthesis, characterization, and composites with poly(lactic-co-glycolic acid)

Iodine-containing radio-opaque polyphosphazenes

One-pot synthesis of polymeric nanomaterials via RAFT dispersion polymerization induced self-assembly and re-organization

Polymer micelles decorated by gadolinium complexes as MRI blood contrast agents: design, synthesis and properties

Ring-opening polymerization of L-lactide using N-heterocyclic molecules: mechanistic, kinetics and DFT studies

Efficient synthesis of photoresponsive azobenzene-containing side-chain liquid crystalline polymers with high molecular weights by click chemistry

Rapid preparation of polymersomes by a water addition/solvent evaporation method

Back cover

Polymer Chemistry Vol - 1 Issue - 8

Polymer Chemistry Vol - 1 Issue - 7

Polymer Chemistry Vol - 1 Issue - 6

Polymer Chemistry Vol - 1 Issue - 5

Polymer Chemistry Vol - 1 Issue - 4

Polymer Chemistry Vol - 1 Issue - 3

Polymer Chemistry Vol - 1 Issue - 2

Ring-opening polymerization of L-lactide using N-heterocyclic molecules: mechanistic, kinetics and DFT studies

Content Provider	Royal Society of Chemistry (RSC)
Author	Katiyar, Vimal Nanavati, Hemant
Copyright Year	2010
Abstract	We report here our investigations of the mechanism and kinetics of N-heterocyclic molecules as initiators for PLA synthesis. This is a step towards employing life saving drugs based on N-heterocyclic functional groups, to generate carrier-drug complexes in situ, via ring opening polymerization (ROP) of L-lactide. During administration, the drug may be released with well-defined release rate kinetics. With this motivation, five and six membered N-heterocyclic molecules such as 4-pyrrolidino-pyridine (PDP), 2-methyl-pyridine, pyridine, pyrrole and imidazole, are examined as initiators of bulk ROP of L-lactide, to yield metal-free poly(L-lactide) (PLA). NMR, IR and MALDI-TOF MS analyses, establish the reacting species in the polymerization. Side reactions such as formation of macrocycles, occur when permitted by lack of steric hindrance, as when polymerization is initiated by PDP + benzyl alcohol or by imidazole. Accordingly, we propose a PDP-based anionic polymerization mechanism, and then examine the effect of reaction parameters. The kinetics studies indicate an overall first order reaction with lactide, and low activation energy. Density functional theory (DFT) calculations of the initiators' proton affinities, provide a fundamental understanding, to enable selection of more efficient various N-heterocyclic drug molecules, which can be utilized as initiators, to generate PLA chains as carriers for drug administration. We find that PDP has the highest proton affinity, and that the order of the calculated proton affinities correlates broadly with the resulting PLA molecular weights. We also find that PDP appears to the most effective initiator, yielding Mw ∼28,000 Da in 90 min, which is in line with the correlation between initiator effectiveness and proton affinities, of the investigated five and six member N-heterocyclic molecules.
Starting Page	1491
Ending Page	1500
Page Count	10
File Format	HTM / HTML PDF
ISSN	17599954
Volume Number	1
Issue Number	9
Journal	Polymer Chemistry
DOI	10.1039/c0py00125b
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Proton affinity PLA Ring-opening polymerization Polymerization Steric effects Benzyl alcohol Reaction rate Lactide Pyridine Ionization Imidazole Pyrrole Anionic addition polymerization Density functional theory Nuclear magnetic resonance Molar mass distribution PDP Activation energy
Content Type	Text
Resource Type	Article
Subject	Organic Chemistry Biochemistry Bioengineering Biomedical Engineering Polymers and Plastics

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

Macromolecular Dyes by Chromophore-Initiated Ring Opening Polymerization of L-Lactide

Single site catalysts for stereoselective ring-opening polymerization of lactides

Modification of proline‐based 2,5‐diketopiperazines by anionic ring‐opening polymerization

Initiators for the stereoselective ring-opening polymerization of meso-lactide

Polymerization of cyclic esters using N-heterocyclic carbene carboxylate catalysts

Lipase-Catalyzed Ring-Opening Polymerization of Benzyl Malolactonate: An Unusual Mechanism?

Anionic ring-opening polymerization of N -glycidylphthalimide: Combination of phosphazene base and activated monomer mechanism

o-Benzenedisulfonimide as a recyclable cationic organocatalyst for the controlled/living ring-opening polymerization of δ-valerolactone and ε-caprolactone

Reactivity Ratios and Mechanistic Insight for Anionic Ring-Opening

Ring-opening polymerization of L-lactide using N-heterocyclic molecules: mechanistic, kinetics and DFT studies

Similar Documents

Macromolecular Dyes by Chromophore-Initiated Ring Opening Polymerization of L-Lactide

Single site catalysts for stereoselective ring-opening polymerization of lactides

Modification of proline‐based 2,5‐diketopiperazines by anionic ring‐opening polymerization

Initiators for the stereoselective ring-opening polymerization of meso-lactide

Polymerization of cyclic esters using N-heterocyclic carbene carboxylate catalysts

Lipase-Catalyzed Ring-Opening Polymerization of Benzyl Malolactonate: An Unusual Mechanism?

Anionic ring-opening polymerization of N -glycidylphthalimide: Combination of phosphazene base and activated monomer mechanism

o-Benzenedisulfonimide as a recyclable cationic organocatalyst for the controlled/living ring-opening polymerization of δ-valerolactone and ε-caprolactone

Reactivity Ratios and Mechanistic Insight for Anionic Ring-Opening

Ring-opening polymerization of L-lactide using N-heterocyclic molecules: mechanistic, kinetics and DFT studies