Browse
Submit Data
Databases
API
Help

Dataset Information

24 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Chain-end-functionalized polyphosphazenes via a one-pot phosphine-mediated living polymerization.

ABSTRACT: A simple polymerization of trichlorophosphoranimine (Cl3 P = N-SiMe3 ) mediated by functionalized triphenylphosphines is presented. In situ initiator formation and the subsequent polymerization progress are investigated by (31) P NMR spectroscopy, demonstrating a living cationic polymerization mechanism. The polymer chain lengths and molecular weights of the resulting substituted poly(organo)phosphazenes are further studied by (1) H NMR spectroscopy and size exclusion chromatography. This strategy facilitates the preparation of polyphosphazenes with controlled molecular weights and specific functional groups at the α-chain end. Such well-defined, mono-end-functionalized polymers have great potential use in bioconjugation, surface modification, and as building blocks for complex macromolecular constructs.

SUBMITTER: Wilfert S

PROVIDER: S-EPMC4115175 | biostudies-literature |

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Similar Datasets

Hetero and homo α,ω-chain-end functionalized polyphosphazenes.

Project description:The control of chain-ends is fundamental in modern macromolecular chemistry for directed one-to-one bioconjugation and the synthesis of advanced architectures such as block copolymers or bottlebrush polymers and the preparation of advanced soft materials. Polyphosphazenes are of growing importance as elastomers, biodegradable materials and in biomedical drug delivery due to their synthetic versatility. While controlled polymerization methods have been known for some time, controlling both chain-ends with high fidelity has proven difficult. We demonstrate a robust synthetic route to hetero and homo α,ω-chain-end functionalized polyphosphazenes via end-capping with easily accessible, functionalized triphenylphosphine-based phosphoranimines. A versatile thiol-ene "click"-reaction approach then allows for subsequent conversion of the end-capped polymers with various functional groups. Finally, we demonstrate the utility of this system to prepare gels based on homo α,ω-chain-end functionalized polyphosphazenes. This development will enhance their progress in various applications, particularly in soft materials and as degradable polymers.

| S-EPMC9325445 | biostudies-literature

Isothiourea-mediated one-pot synthesis of functionalized pyridines.

Project description:Acids to bases: The synthesis of 2,4,6-trisubstituted pyridines from (phenylthio)acetic acid and a range of α,β-unsaturated ketimines is reported. This process proceeds by intermolecular Michael addition/lactamization, thiophenol elimination, and N- to O-sulfonyl migration, giving 2-sulfonate-substituted pyridines which are readily derivatized to generate structural diversity.

| S-EPMC4065352 | biostudies-literature

Novel Chain-End Modification of Polymer Iodides via Reversible Complexation-Mediated Polymerization with Functionalized Radical Generation Agents.

Project description:The modification of polymer chain ends is important in order to produce highly functional polymers. A novel chain-end modification of polymer iodides (Polymer-I) via reversible complexation-mediated polymerization (RCMP) with different functionalized radical generation agents, such as azo compounds and organic peroxides, was developed. This reaction was comprehensively studied for three different polymers, i.e., poly (methyl methacrylate), polystyrene and poly (n-butyl acrylate) (PBA), two different functional azo compounds with aliphatic alkyl and carboxy groups, three different functional diacyl peroxides with aliphatic alkyl, aromatic, and carboxy groups, and one peroxydicarbonate with an aliphatic alkyl group. The reaction mechanism was probed using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS). The combination of PBA-I, iodine abstraction catalyst and different functional diacyl peroxides enabled higher chain-end modification to desired moieties from the diacyl peroxide. The dominant key factors for efficiency in this chain-end modification mechanism were the combination rate constant and the amount of radicals generated per unit of time.

| S-EPMC10305694 | biostudies-literature

One-pot phosphine-catalyzed syntheses of quinolines.

Project description:In this study we developed an efficient one-pot procedure for the preparation of 3-substituted and 3,4-disubstituted quinolines from stable starting materials (activated acetylenes reacting with o-tosylamidobenzaldehydes and o-tosylamidophenones, respectively) under mild conditions. The reaction appears to operate under a general base catalysis mechanism, instigated by the β-phosphonium enoate α-vinyl anion generated in situ through nucleophilic addition of PPh(3) to the activated alkyne. Michael addition of the deprotonated tosylamides to the activated alkynes and subsequent rapid aldol cyclization led to the formation of labile N-tosyldihydroquinoline intermediates. Driven by aromatization, detosylation of the dihydroquinoline intermediates occurred readily in the presence of dilute aqueous HCl to give the final quinoline products.

| S-EPMC3459651 | biostudies-literature

Sequence-encoded bioactive protein-multiblock polymer conjugates via quantitative one-pot iterative living polymerization.

Project description:Protein therapeutics are essential in treating various diseases, but their inherent biological instability and short circulatory half-lives in vivo pose challenges. Herein, a quantitative one-pot iterative living polymerization technique is reported towards precision control over the molecular structure and monomer sequence of protein-polymer conjugates, aiming to maximize physicochemical properties and biological functions of proteins. Using this quantitative one-pot iterative living polymerization technique, we successfully develop a series of sequence-controlled protein-multiblock polymer conjugates, enhancing their biostability, pharmacokinetics, cellular uptake, and in vivo biodistribution. All-atom molecular dynamics simulations are performed to disclose the definite sequence-function relationship of the bioconjugates, further demonstrating their sequence-encoded cellular uptake behavior and in vivo biodistribution in mice. Overall, this work provides a robust approach for creating precision protein-polymer conjugates with defined sequences and advanced functions as a promising candidate in disease treatment.

| S-EPMC11306232 | biostudies-literature

Catechol End-Functionalized Polylactide by Organocatalyzed Ring-Opening Polymerization.

Project description:There is a great interest in incorporating catechol moieties into polymers in a controlled manner due to their interesting properties, such as the promotion of adhesion, redox activity or bioactivity. One possibility is to incorporate the catechol as end-group in a polymer chain using a functional initiator by means of controlled polymerization strategies. Nevertheless, the instability of catechol moieties under oxygen and basic pH requires tedious protection and deprotection steps to perform the polymerization in a controlled fashion. In the present work, we explore the organocatalyzed synthesis of catechol end-functional, semi-telechelic polylactide (PLLA) using non-protected dopamine, catechol molecule containing a primary amine, as initiator. NMR and SEC-IR results showed that in the presence of a weak organic base such as triethylamine, the ring-opening polymerization (ROP) of lactide takes place in a controlled manner without need of protecting the cathechol units. To further confirm the end-group fidelity the catechol containing PLLA was characterized by Cyclic Voltammetry and MALDI-TOF confirming the absence of side reaction during the polymerization. In order to exploit the potential of catechol moieties, catechol end-group of PLLA was oxidized to quinone and further reacted with aliphatic amines. In addition, we also confirmed the ability of catechol functionalized PLLA to reduce metal ions to metal nanoparticles to obtain well distributed silver nanoparticles. It is expected that this new route of preparing catechol-PLLA polymers without protection will increase the accessibility of catechol containing biodegradable polymers by ROP.

| S-EPMC6415175 | biostudies-literature

Diblock dialternating terpolymers by one-step/one-pot highly selective organocatalytic multimonomer polymerization.

Project description:The synthesis of well-defined block copolymers from a mixture of monomers without additional actions ("one-pot/one-step") is an ideal and industrially valuable method. In addition, the presence of controlled alternating sequences in one or both blocks increases the structural diversity of polymeric materials, but, at the same time, the synthetic difficulty. Here we show that the "one-pot/one-step" ring-opening terpolymerization of a mixture of three monomers (N-sulfonyl aziridines; cyclic anhydrides and epoxides), with tert-butylimino-tris(dimethylamino)phosphorene (t-BuP1) as a catalyst, results in perfect diblock dialternating terpolymers having a sharp junction between the two blocks, with highly-controllable molecular weights and narrow molecular weight distributions (Ð < 1.08). The organocatalyst switches between two distinct polymerization cycles without any external stimulus, showing high monomer selectivity and kinetic control. The proposed mechanism is based on NMR, in-situ FTIR, SEC, MALDI-ToF, reactivity ratios, and kinetics studies.

| S-EPMC8655074 | biostudies-literature

One-Pot Synthesis of Charged Amphiphilic Diblock and Triblock Copolymers Via High-Throughput Cu(0)-Mediated Polymerization.

Project description:Block copolymers containing functionalized monomers, for example those containing charged groups, can be used for many purposes, one of which is the design of polymeric supramolecular materials based on electrostatic interactions. In this paper the synthesis of diblock copolymers and ABA-triblock copolymers containing poly(n-butyl acrylate) as a first or middle block and poly(2-(dimethylamino)ethyl acrylate), poly(1-ethoxyethyl acrylate) and poly(1-ethoxyethyl-2-carboxyethyl acrylate) as second or outer blocks, resulting in block copolymers that can contain positive or negative charges, is reported. The polymerizations were performed and optimized via one-pot sequential monomer addition reactions via Cu(0)-mediated polymerization using an automated parallel synthesizer. Different initiators, monomer concentrations and polymerization times were tested. While a bromide-containing initiator led to the best results for most monomers, when polymerizing 2-(dimethylamino)ethyl acrylate the use of a chloride-containing initiator was necessary. Due to the slower polymerization using this initiator, a longer polymerization time was needed before addition of the second monomer. Using the optimized conditions, the diblock and triblock copolymers could be synthesized with good control over molecular weight and dispersities around 1.1 were obtained.

| S-EPMC6418976 | biostudies-literature

Coordinative Chain Transfer Polymerization of Butadiene with Functionalized Aluminum Reagents.

Project description:Functionalized aluminum alkyls enable effective coordinative chain transfer polymerization with selective chain initiation by the functionalized alkyl. (ω-Aminoalkyl)diisobutylaluminum reagents (12 examples studied) obtained by hydroalumination of α-amino-ω-enes with diisobutylaluminum hydride promote the stereoselective catalytic chain growth of butadiene on aluminum in the presence of Nd(versatate)3 , Cp*2 Nd(allyl), or Cp*2 Gd(allyl) precatalysts and [PhNMe2 H+ ]/[B(C6 F5 )4 - ]. Carbazolyl- and indolylaluminum reagents result in efficient molecular weight control and chain initiation by the aminoalkyl rather than the isobutyl substituent bound to aluminum. As confirmed for (3-(9H-carbazol-9-yl)propyl)-initiated polybutadiene (PBD), for example, by deuterium quenching studies, polymer chain transfer by β-hydride transfer is negligible in comparison to back-transfer to aluminum.

| S-EPMC6899983 | biostudies-literature

One-Pot Tandem Approach to Functionalized 3-Hydroxy-2-furanyl-acrylamides.

Project description:A novel one-pot tandem process involving Knoevenagel condensation, Michael addition, selective amidation, and Paal-Knorr cyclization to diverse functionalized 3-hydroxy-2-furanyl-acrylamides from simple 2-oxoaldehydes and aroylacetonitriles was presented. Attempts were also made to expand the scope of the reaction to different 2-heteroarylfurans. The packing diagram of the molecules viewed down along the α-axis of the unit cell showed a characteristic intramolecular classical O-H···O hydrogen bond between hydroxyl and carbonyl O atoms leading to self-associated (Z)-2-furanyl-acrylamides.

| S-EPMC6641926 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

Tweets

OmicsDI Databases

PRIDE
PeptideAtlas
MassIVE
JPOST Repository
Physiome Model Repository

EGA
EVA
ENA
LINCS
PAXDB
Cell Collective

MetaboLights
Metabolomics Workbench
MetabolomeExpress
GNPS
BioModels
FAIRDOMHub

ArrayExpress
dbGaP
ExpressionAtlas
GEO
NODE

Information

Databases
Help
API
Contact us
Code on GitHub
Terms of use
Submit Data