Browse
Submit Data
Databases
API
Help

Dataset Information

0 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Glycidyl Tosylate: Polymerization of a "Non-Polymerizable" Monomer permits Universal Post-Functionalization of Polyethers.

ABSTRACT: Glycidyl tosylate appears to be a non-polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer-activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7-25 % incorporated tosylate-moieties. The microstructure of the copolymers was investigated via in situ 1 H NMR spectroscopy, and the reactivity ratios of the copolymerizations have been determined. Quantitative nucleophilic substitution of the tosylate-moiety is demonstrated for several examples. This new structure provides access to a library of functionalized polyethers that cannot be synthesized by conventional oxyanionic polymerization.

SUBMITTER: Jung P

PROVIDER: S-EPMC6771516 | biostudies-other | 2019 Sep

REPOSITORIES: biostudies-other

ACCESS DATA

Json Xml

Publications

Glycidyl Tosylate: Polymerization of a "Non-Polymerizable" Monomer permits Universal Post-Functionalization of Polyethers.

Jung Philipp P Ziegler Arthur D AD Blankenburg Jan J Frey Holger H

Angewandte Chemie (International ed. in English) 20190819 37

Glycidyl tosylate appears to be a non-polymerizable epoxide when nucleophilic initiators are used because of the excellent leaving group properties of the tosylate. However, using the monomer-activated mechanism, this unusual monomer can be copolymerized with ethylene oxide (EO) and propylene oxide (PO), respectively, yielding copolymers with 7-25 % incorporated tosylate-moieties. The microstructure of the copolymers was investigated via in situ <sup>1</sup> H NMR spectroscopy, and the reactivit ...[more]

PMID: 31339633

Similar Datasets

Selenonium Polyelectrolyte Synthesis through Post-Polymerization Modifications of Poly (Glycidyl Methacrylate) Scaffolds.

Project description:Atom transfer radical polymerization of glycidyl methacrylate monomer with poly(ethylene glycol)-based macroinitiators leads to the formation of reactive block copolymers. The epoxide side-chains of these polymers can be subjected to a regiospecific base-catalyzed nucleophilic ring-opening reaction with benzeneselenol under ambient conditions. The ß-hydroxy selenide linkages thus formed can be alkylated to access polyselenonium salts. 77Se-NMR indicates the formation of diastereomers upon alkylation. In such a manner, sequential post-polymerization modifications of poly(glycidyl methacrylate) scaffolds via selenium-epoxy and selenoether alkylation reactions furnish practical access to poly(ethylene glycol)-based cationic organoselenium copolymers.

| S-EPMC7697662 | biostudies-literature

Direct access to poly(glycidyl azide) and its copolymers through anionic (co-)polymerization of glycidyl azide.

Project description:Glycidyl azide polymer or poly(glycidyl azide) which is considered as an excellent energetic binder or plasticizer in advanced solid propellants is generally obtained by post-modification or azidation of poly(epichlorohydrin). Here we report that glycidyl azide can be directly homopolymerized through anionic ring-opening polymerization to access poly(glycidyl azide) using onium salts as initiator and triethyl borane as activator. Molar masses of poly(glycidyl azide) up to 11.0 Kg/mol are achieved in a controlled manner with a narrow polydispersity index (PDI ≤ 1.2). Similarly, alternating poly(glycidyl azide carbonate) are also prepared through alternating copolymerization of glycidyl azide with carbon dioxide. Lastly, the copolymerization of glycidyl azide with other epoxide monomers is carried out; the azido functions carried by glycidyl azide which are successfully incorporated into the backbones of polyethers and polycarbonates based on cyclohexene oxide and propylene oxide subsequently served to introduce other functions by click chemistry.

| S-EPMC6336848 | biostudies-literature

Degradable nitric oxide-releasing biomaterials via post-polymerization functionalization of cross-linked polyesters.

Project description:The synthesis of diverse nitric oxide (NO)-releasing network polyesters is described. The melt phase condensation of polyols with a calculated excess of diacid followed by thermal curing generates cross-linked polyesters containing acid end groups. Varying the composition and curing temperatures of the polyesters resulted in materials with tunable thermal and degradation properties. Glass transition temperatures for the synthesized materials range from -25.5 to 3.2 °C, while complete degradation of these polyesters occurs within a minimum of nine weeks under physiological conditions (pH 7.4, 37 °C). Post-polymerization coupling of aminothiols to terminal carboxylic acids generate thiol-containing polyesters, with thermal and degradation characteristics similar to those of the parent polyesters. After nitrosation, these materials are capable of releasing up to 0.81 μmol NO cm(-2) for up to 6 d. The utility of the polyesters as antibacterial biomaterials was indicated by an 80% reduction of Pseudomonas aeruginosa adhesion compared to unmodified controls.

| S-EPMC3070196 | biostudies-literature

Post-functionalization of drug-loaded nanoparticles prepared by polymerization-induced self-assembly (PISA) with mitochondria targeting ligands.

Project description:Herein, the postfunctionalization of different non-fouling PISA particles, prepared from either poly(oligo ethylene glycol methyl ether methacrylate) (pPEGMA) and the anticancer drug PENAO (4-(N-(S-penicillaminylacetyl)amino)phenylarsenonous acid) or zwitterionic 2-methacryloyloxyethyl phosphorylcholine (MPC) and PENAO were reported. Both PISA particles were reacted with triphenylphosphonium (TPP) as mitochondria targeting units in order to evaluate the changes in cellular uptake or the toxicity of the conjugated arsenic drug. Attachment of TPP onto the PISA particles however was found not to enhance the mitochondrial accumulation, but it did influence overall the biological activity of pMPC-based particles in 2D and 3D cultured sarcoma SW982 cells. When TPP was conjugated to the pMPC PISA particles more cellular uptake as well as better spheroid penetration were observed, while TPP on PEG-based PISA had only little effect. It was hypothesized that TPP on the micelle surface may not be accessible enough to allow mitochondria targeting, but more structural investigations are required to elucidate this.

| S-EPMC8450966 | biostudies-literature

Living supramolecular polymerization based on reversible deactivation of a monomer by using a 'dummy' monomer.

Project description:Although living supramolecular polymerization (LSP) has recently been realized, the scope of the monomer structures applicable to the existing methods is still limited. For instance, a monomer that spontaneously nucleates itself cannot be processed in a manner consistent with LSP. Herein, we report a new method for such a "reactive" monomer. We use a 'dummy' monomer which has a similar structure to the reactive monomer but is incapable of one-dimensional supramolecular polymerization. We show that in the presence of the dummy monomer, the reactive monomer is kinetically trapped in the dormant state. In this way, spontaneous nucleation of the reactive monomer is retarded; yet, addition of seeds of a supramolecular polymer can initiate the supramolecular polymerization in a chain growth manner. As a result, we obtain the supramolecular polymer of the reactive monomer with a controlled length, which is otherwise thermodynamically inaccessible. We believe that this concept will expand the scope of LSP for the synthesis of other functional supramolecular polymers, and thus lead to a variety of applications.

| S-EPMC6640193 | biostudies-literature

Chemoselective polymerization control: from mixed-monomer feedstock to copolymers.

Project description:A novel chemoselective polymerization control yields predictable (co)polymer compositions from a mixture of monomers. Using a dizinc catalyst and a mixture of caprolactone, cyclohexene oxide, and carbon dioxide enables the selective preparation of either polyesters or polycarbonates or copoly(ester-carbonates). The selectivity depends on the nature of the zinc-oxygen functionality at the growing polymer chain end, and can be controlled by the addition of exogeneous switch reagents.

| S-EPMC4232277 | biostudies-literature

The limits of precision monomer placement in chain growth polymerization.

Project description:Precise control over the location of monomers in a polymer chain has been described as the 'Holy Grail' of polymer synthesis. Controlled chain growth polymerization techniques have brought this goal closer, allowing the preparation of multiblock copolymers with ordered sequences of functional monomers. Such structures have promising applications ranging from medicine to materials engineering. Here we show, however, that the statistical nature of chain growth polymerization places strong limits on the control that can be obtained. We demonstrate that monomer locations are distributed according to surprisingly simple laws related to the Poisson or beta distributions. The degree of control is quantified in terms of the yield of the desired structure and the standard deviation of the appropriate distribution, allowing comparison between different synthetic techniques. This analysis establishes experimental requirements for the design of polymeric chains with controlled sequence of functionalities, which balance precise control of structure with simplicity of synthesis.

| S-EPMC4740409 | biostudies-literature

Polymerization driven monomer passage through monolayer chemical vapour deposition graphene.

Project description:Mass transport through graphene is receiving increasing attention due to the potential for molecular sieving. Experimental studies are mostly limited to the translocation of protons, ions, and water molecules, and results for larger molecules through graphene are rare. Here, we perform controlled radical polymerization with surface-anchored self-assembled initiator monolayer in a monomer solution with single-layer graphene separating the initiator from the monomer. We demonstrate that neutral monomers are able to pass through the graphene (via native defects) and increase the graphene defects ratio (Raman ID/IG) from ca. 0.09 to 0.22. The translocations of anionic and cationic monomers through graphene are significantly slower due to chemical interactions of monomers with the graphene defects. Interestingly, if micropatterned initiator-monolayers are used, the translocations of anionic monomers apparently cut the graphene sheet into congruent microscopic structures. The varied interactions between monomers and graphene defects are further investigated by quantum molecular dynamics simulations.

| S-EPMC6170411 | biostudies-literature

"Click handle"-modified 2'-deoxy-2'-fluoroarabino nucleic acid as a synthetic genetic polymer capable of post-polymerization functionalization.

Project description:The functions of natural nucleic acids such as DNA and RNA have transcended genetic information carriers and now encompass affinity reagents, molecular catalysts, nanostructures, data storage, and many others. However, the vulnerability of natural nucleic acids to nuclease degradation and the lack of chemical functionality have imposed a significant constraint on their ever-expanding applications. Herein, we report the synthesis and polymerase recognition of a 5-(octa-1,7-diynyl)uracil 2'-deoxy-2'-fluoroarabinonucleic acid (FANA) triphosphate. The DNA-templated, polymerase-mediated primer extension using this "click handle"-modified FANA (cmFANA) triphosphate and other FANA nucleotide triphosphates consisting of canonical nucleobases efficiently generated full-length products. The resulting cmFANA polymers exhibited excellent nuclease resistance and the ability to undergo efficient click conjugation with azide-functionalized molecules, thereby becoming a promising platform for serving as a programmable and evolvable synthetic genetic polymer capable of post-polymerization functionalization.

| S-EPMC9200136 | biostudies-literature

Designed protein multimerization and polymerization for functionalization of proteins.

Project description:Multimeric and polymeric proteins are large biomacromolecules consisting of multiple protein molecules as their monomeric units, connected through covalent or non-covalent bonds. Genetic modification and post-translational modifications (PTMs) of proteins offer alternative strategies for designing and creating multimeric and polymeric proteins. Multimeric proteins are commonly prepared by genetic modification, whereas polymeric proteins are usually created through PTMs. There are two methods that can be applied to create polymeric proteins: self-assembly and crosslinking. Self-assembly offers a spontaneous reaction without a catalyst, while the crosslinking reaction offers some catalyst options, such as chemicals and enzymes. In addition, enzymes are excellent catalysts because they provide site-specificity, rapid reaction, mild reaction conditions, and activity and functionality maintenance of protein polymers. However, only a few enzymes are applicable for the preparation of protein polymers. Most of the other enzymes are effective only for protein conjugation or labeling. Here, we review novel and applicable strategies for the preparation of multimeric proteins through genetic modification and self-assembly. We then describe the formation of protein polymers through site-selective crosslinking reactions catalyzed by enzymes, crosslinking reactions of non-natural amino acids, and protein-peptide (SpyCatcher/SpyTag) interactions. Finally, we discuss the potential applications of these protein polymers.

| S-EPMC8791688 | 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