Search results for " Polymer"

Probing the Folding of Peptide–Polymer Conjugates Using the π-Dimerization of Viologen End-Groups

2020

The synthesis of a foldable viologen-functionalized peptide–polymer conjugate is presented. The ABA-type triblock conjugate with a PEG polymer was capped with a FHFHF pentapeptide sequence and further modified with a viologen building block at both chain ends. The pH-responsive peptide domains fold into an intermediate structure inducing close proximity of the viologen units, which upon a reduction step form π-dimers of the radical cation. Overall the intramolecular folding and intermolecular self-assembly process leads to the formation of supramolecular nanorods. Mixing of viologen-peptide–polymer conjugates with unfunctionalized conjugates leads to crosslinking of the nanorods and hydroge…

Cationic Au Nanoparticle Binding with Plasma Membrane-like Lipid Bilayers: Potential Mechanism for Spontaneous Permeation to Cells Revealed by Atomis…

2014

Despite being chemically inert as a bulk material, nanoscale gold can pose harmful side effects to living organisms. In particular, cationic Au nanoparticles (AuNP+) of 2 nm diameter or less permeate readily through plasma membranes and induce cell death. We report atomistic simulations of cationic Au nanoparticles interacting with realistic membranes and explicit solvent using a model system that comprises two cellular compartments, extracellular and cytosolic, divided by two asymmetric lipid bilayers. The membrane-AuNP+ binding and membrane reorganization processes are discovered to be governed by cooperative effects where AuNP+, counterions, water, and the two membrane leaflets all contr…

Polymerization of methyl and phenyl oxazoline initiated with alkyl chloroformates

2010

It has been shown that alkyl chloroformates are capable of initiating the polymerization of oxazolines. Esters itself initiate rather slowly and the polymerization proceeds via covalent growing species. Exchange of counter ions with triflate or iodide anions leads to faster initiation and higher reaction rates. The polymerization is of living character.

1980

1974

1978

A newly designed automatically controlled stirred reactor suitable for kinetic measurements of reactions with half lives ≥2s has been applied to follow the anionic polymerization of methyl methacrylate in THF with Na+ as a counter ion in the presence of an excess of NaB(C6H5)4. As initiators were used: benzylsodium reacted with α-methylstyrene (I), fluorenylsodium (II), and 9-methylfluorenylsodium (III). With I the initiation is fast as compared with the polymerization reaction which is first order in monomer concentration. Within the range of −50°C to −100°C an almost unperturbed “living” polymerization is observed. The Arrhenius plot of the rate constants results in a straight line with a…

1984

The decomposition reactions of the lithiated dimer, trimer, and tetramer of methyl methacrylate (MMA) in THF at 25°C were investigated. The decomposition of the lithiated dimer proceeds via depolymerization to lithiated monomer and MMA, addition of MMA to residual lithiated dimer, resulting the trimer (“disproportionation” of the dimer), and subsequent autocondensation of the products. The lithiated trimer almost exclusively undergoes cyclo-autocondensation, whereas for the lithiated tetramer both reactions proceed simultaneously to a remarkable degree. It is shown that the relative rate of autocondensation, which is highly dependent on the degree of polymerization of the oligomer, controls…

Theoretische analyse der bei einem zweiwegwachstumsmechanismus auftretenden molekulargewichtsverteilungen und ihre anwendung auf die anionische polym…

1967

Es werden mittels der Momentmethode die fur einen abbruchfreien Zweiwegwachstumsmechanismus zu erwartenden Molekulargewichtsverteilungen und ihr Zusammenhang mit dem kinetischen Ablauf theoretisch abgeleitet. Die ermittelten Bezichungen werden auf das Polymerisationssystem Styrol in Cumylmethylather mit Cumylnatrium als Initiator angewandt. Durch Einsetzen der vorher experimentell ermittelten kinetischen Daten in die theoretisch abgeleitete Gleichung werden die Molekulargewichtsverteilungen des untersuchten Systems berechnet und mit den experimentell ermittelten verglichen. Die gute Ubereinstimmung zwischen Theorie und Experiment stellt einen schlussigen Beweis fur das Vorliegen eines Zweiw…

Kinetics of Group Transfer Polymerization

1987

The group transfer polymerization (GTP) of methyl methacrylate (MMA) and tert.-butyl methacrylate (TBMA), catalyzed by bifluoride, is of first order with respect to monomer and catalyst concentrations. A slightly negative order with respect to initiator concentration is observed, indicating an inhibitive function of the initiator. Termination reactions occur at lower catalyst concentrations. They are very pronounced for TBMA and result in incomplete conversions. For MMA, at lower catalyst and higher initiator concentrations, induction periods are observed which increase when lowering the temperature. This is related with the formation of active chains. The Arrhenius plots for the propagatio…

Herstellung, charakterisierung und lösungseigenschaften von einheitlichen styrol-α-methylstyrol block-copolymeren

1977

An improved anionic polymerization technique for the preparation of highly uniform styrene/α-methylstyrene linear two-block copolymers is described. Three sets of samples with molecular weights M were prepared under equal experimental conditions, namely polystyrenes (2 · 105 < M < 3 · 106), poly(α-methylstyrene)s (7 · 104 < M < 4 · 106), and block copolymers (2 · 105 < M < 2,5 · 106). Ultracentrifugation in a density-gradient does not show any chemical heterogeneities in the block copolymers. The molecular polydispersity U = Mw/Mn–1 is U = 0,03 or less as estimated from GPC-measurements. The high molecular and chemical homogeneity of the block copolymers and the optical similarity of the tw…