Browse
Submit Data
Databases
API
Help

Dataset Information

7 Views

0 Connections

0 Citations

0 Reanalyses

0 Downloads

Omics score: 0

Metal-Free Addition/Head-to-Tail Polymerization of Transient Phosphinoboranes, RPH-BH2: A Route to Poly(alkylphosphinoboranes).

ABSTRACT: Mild thermolysis of Lewis base stabilized phosphinoborane monomers R(1)R(2)P-BH2?NMe3 (R(1),R(2)=H, Ph, or tBu/H) at room temperature to 100?°C provides a convenient new route to oligo- and polyphosphinoboranes [R(1)R(2)P-BH2]n. The polymerization appears to proceed via the addition/head-to-tail polymerization of short-lived free phosphinoborane monomers, R(1)R(2)P-BH2. This method offers access to high molar mass materials, as exemplified by poly(tert-butylphosphinoborane), that are currently inaccessible using other routes (e.g. catalytic dehydrocoupling).

SUBMITTER: Marquardt C

PROVIDER: S-EPMC4648028 | biostudies-literature | 2015 Nov

REPOSITORIES: biostudies-literature

ACCESS DATA

Json Xml

Publications

Metal-Free Addition/Head-to-Tail Polymerization of Transient Phosphinoboranes, RPH-BH2: A Route to Poly(alkylphosphinoboranes).

Marquardt Christian C Jurca Titel T Schwan Karl-Christian KC Stauber Andreas A Virovets Alexander V AV Whittell George R GR Manners Ian I Scheer Manfred M

Angewandte Chemie (International ed. in English) 20151002 46

Mild thermolysis of Lewis base stabilized phosphinoborane monomers R(1)R(2)P-BH2⋅NMe3 (R(1),R(2)=H, Ph, or tBu/H) at room temperature to 100 °C provides a convenient new route to oligo- and polyphosphinoboranes [R(1)R(2)P-BH2]n. The polymerization appears to proceed via the addition/head-to-tail polymerization of short-lived free phosphinoborane monomers, R(1)R(2)P-BH2. This method offers access to high molar mass materials, as exemplified by poly(tert-butylphosphinoborane), that are currently i ...[more]

PMID: 26427911

Similar Datasets

Transition-metal-free controlled polymerization for poly(<i>p</i>-aryleneethynylene)s.

Project description:A transition-metal-free controlled polymerization for the attainment of poly(p-aryleneethynylene)s is developed. The polymerization of 1-pentafluorophenyl-4-[(trimethylsilyl)ethynyl]benzene with a catalytic amount of fluoride anions proceeds in a chain-growth-like manner to afford polymers with controlled molecular weights and low polydispersity indexes. The mechanism involves a pentacoordinated fluorosilicate as a key intermediate. The anionic "living" nature of this process is applied to block copolymerization and also surface-terminated polymerization.

| S-EPMC5592747 | biostudies-literature

Non-metal with metal behavior: metal-free coordination-insertion ring-opening polymerization.

Project description:The "coordination-insertion" ring-opening polymerization (ROP) mechanism has so far been the monopoly of metal catalysts. In this work, we present a metal-free "coordination-insertion" ROP of trimethylene carbonate (TMC) and ε-caprolactone (ε-CL), as well as their sequential block copolymerization, with N-trimethylsilyl-bis (trifluoromethanesulfonyl)imide (TMSNTf2) as the non-metallic initiator/catalyst. TMSNTf2 was proposed to work through an unprecedented metal-free "coordination-insertion" mechanism, which involves the coordination of monomer to the Si atom of TMSNTf2, the nucleophilic attack of the -NTf2 group on the coordinated monomer, and the cleavage of the acyl-oxygen bond of the monomer. The proposed metal-free "coordination-insertion" ROP was studied by NMR, SEC, and MALDI-TOF analyses. In addition, the TMSNTf2-mediated ROP of TMC and ε-CL led to linear and cyclic polymers following two-stage first-order polymerization processes, as evidenced by structural analyses and kinetics study, which further demonstrated the metal-free "coordination-insertion" mechanism.

| S-EPMC8372312 | biostudies-literature

Ubiquitination of the Dishevelled DIX domain blocks its head-to-tail polymerization.

Project description:Dishevelled relays Wnt signals from the plasma membrane to different cytoplasmic effectors. Its signalling activity depends on its DIX domain, which undergoes head-to-tail polymerization to assemble signalosomes. The DIX domain is ubiquitinated in vivo at multiple lysines, which can be antagonized by various deubiquitinases (DUBs) including the CYLD tumour suppressor that attenuates Wnt signalling. Here, we generate milligram quantities of pure human Dvl2 DIX domain mono-ubiquitinated at two lysines (K54 and K58) by genetically encoded orthogonal protection with activated ligation (GOPAL), to investigate their effect on DIX polymerization. We show that the ubiquitination of DIX at K54 blocks its polymerization in solution, whereas DIX58-Ub remains oligomerization-competent. DUB profiling identified 28 DUBs that cleave DIX-ubiquitin conjugates, half of which prefer, or are specific for, DIX54-Ub, including Cezanne and CYLD. These DUBs thus have the potential to promote Dvl polymerization and signalosome formation, rather than antagonize it as previously thought for CYLD.

| S-EPMC4423210 | biostudies-literature

Synthesis of poly(acrylic acid) coated magnetic nanospheres via a multiple polymerization route.

Project description:Magnetic nanospheres are versatile candidates for both fundamental and practical applications. Before they are applied in more complicated fields, their surface must be modified by several functionalities. However, the surface modification can be affected by the magnetic nanoparticles (MNP) embedded in the polymer matrix. Herein, the synthesis of poly(acrylic acid) coated magnetic nanospheres via a multiple polymerization route is described. During the synthesis process, seed emulsion polymerization was applied to redistribute the MNP in the polymer matrix, and the relationship between the structure of magnetic nanospheres and the thickness of the grafted poly(acrylic acid) layer was investigated. The development of size, morphology and magnetic properties of the nanospheres were characterized by transmission electron microscopy, dynamic light scattering, thermogravimetric analysis, X-ray diffraction and vibrating sample magnetometry. This work would pave the way to design and preparation of new structure of functional magnetic nanospheres with precise surface modification.

| S-EPMC6689630 | biostudies-literature

Metal-Free Regiodivergent Addition of Carbon Nucleophiles to ?,?-Unsaturated Electrophiles.

Project description:A mild and metal-free regiodivergent addition of carbon nucleophiles to ?,?-unsaturated electrophiles was developed. Total 1,2-regioselectivity was observed in the addition of nitrobenzyl chloride derivative 1 to ?,?-unsaturated aldehydes 2 in the presence of TDAE. Moreover, the reaction between p-nitrobenzyl chloride 1a and ?,?-unsaturated iminium salts 4 led to the formation of the 1,4-adduct with total regioselectivity.

| S-EPMC6152382 | biostudies-literature

Metal-free atom transfer radical polymerization with ppm catalyst loading under sunlight.

Project description:Organocatalytic atom transfer radical polymerization (O-ATRP) is recently emerging as an appealing method for the synthesis of metal-free polymer materials with well-defined microstructures and architectures. However, the development of highly effective catalysts that can be employed at a practical low loading are still a challenging task. Herein, we introduce a catalyst design logic based on heteroatom-doping of polycyclic arenes, which leads to the discovery of oxygen-doped anthanthrene (ODA) as highly effective organic photoredox catalysts for O-ATRP. In comparison with known organocatalysts, ODAs feature strong visible-light absorption together with high molar extinction coefficient (ε455nm up to 23,950 M-1 cm-1), which allow for the establishment of a controlled polymerization under sunlight at low ppm levels of catalyst loading.

| S-EPMC7814125 | biostudies-literature

Biodegradable Multiblock Poly[N-(2-hydroxypropyl)methacrylamide] via Reversible Addition-Fragmentation Chain Transfer Polymerization and Click Chemistry.

Project description:A new bifunctional chain transfer agent (CTA) containing alkyne end groups was designed, synthesized and used for direct synthesis of clickable telechelic polymers. Good control of reversible addition-fragmentation chain transfer (RAFT) polymerization of N-(2-hydroxypropyl)methacrylamide (HPMA) was achieved by using the new CTA, as indicated by a linear increase of number average molecular weight (Mn) with conversion and low polydispersity (PDI) (<1.1). In particular, enzymatically degradable multiblock HPMA polymers were readily prepared by subsequent reaction with ??, -diazido oligopeptide (GFLG) sequence via Cu(I) catalyzed alkyne-azide cycloaddition. Upon exposure of high molecular weight fractions of multiblock polyHPMA to papain or cathepsin B, the polymer was degraded into segments of molecular weight and narrow polydispersity similar to those of the initial telechelic polyHPMA.

| S-EPMC3086388 | biostudies-literature

An electrochemical study of frustrated Lewis pairs: a metal-free route to hydrogen oxidation.

Project description:Frustrated Lewis pairs have found many applications in the heterolytic activation of H2 and subsequent hydrogenation of small molecules through delivery of the resulting proton and hydride equivalents. Herein, we describe how H2 can be preactivated using classical frustrated Lewis pair chemistry and combined with in situ nonaqueous electrochemical oxidation of the resulting borohydride. Our approach allows hydrogen to be cleanly converted into two protons and two electrons in situ, and reduces the potential (the required energetic driving force) for nonaqueous H2 oxidation by 610 mV (117.7 kJ mol(-1)). This significant energy reduction opens routes to the development of nonaqueous hydrogen energy technology.

| S-EPMC4148919 | biostudies-literature

Transient structural distortion of metal-free Cu/Zn superoxide dismutase triggers aberrant oligomerization.

Project description:Amyotrophic lateral sclerosis (ALS) is a neurodegenerative disease linked to the misfolding of Cu/Zn superoxide dismutase (SOD1). ALS-related defects in SOD1 result in a gain of toxic function that coincides with aberrant oligomerization. The structural events triggering oligomerization have remained enigmatic, however, as is the case in other protein-misfolding diseases. Here, we target the critical conformational change that defines the earliest step toward aggregation. Using nuclear spin relaxation dispersion experiments, we identified a short-lived (0.4 ms) and weakly populated (0.7%) conformation of metal-depleted SOD1 that triggers aberrant oligomerization. This excited state emanates from the folded ground state and is suppressed by metal binding, but is present in both the disulfide-oxidized and disulfide-reduced forms of the protein. Our results pinpoint a perturbed region of the excited-state structure that forms intermolecular contacts in the earliest nonnative dimer/oligomer. The conformational transition that triggers oligomerization is a common feature of WT SOD1 and ALS-associated mutants that have widely different physicochemical properties. But compared with WT SOD1, the mutants have enhanced structural distortions in their excited states, and in some cases slightly higher excited-state populations and lower kinetic barriers, implying increased susceptibility to oligomerization. Our results provide a unified picture that highlights both (i) a common denominator among different SOD1 variants that may explain why diverse mutations cause the same disease, and (ii) a structural basis that may aid in understanding how different mutations affect disease propensity and progression.

| S-EPMC2775296 | biostudies-literature

Oxonitriles: a grignard addition-acylation route to enamides.

Project description:[reaction: see text] Sequential addition of three different Grignard reagents and pivaloyl chloride to 3-oxo-1-cyclohexene-1-carbonitrile installs four new bonds to generate a diverse array of cyclic enamides. Remarkably, formation of the C-magnesiated nitrile intermediate is followed by preferential acylation by pivaloyl chloride rather than consumption by an in situ Grignard reagent. Rapid N-acylation of the C-magnesiated nitrile generates an acyl ketenimine that reacts readily with Grignard reagents or a trialkylzincate, effectively assembling highly substituted, cyclic enamides.

| S-EPMC2518779 | biostudies-literature

OmicsDI is part of the ELIXIR infrastructure

OmicsDI is an Elixir interoperability service. Learn more ›

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