Thiol coupling based synthesis of temperature-sensitive polymer–peptide conjugates with controlled architecture.

2012 ◽  
Vol 1418 ◽  
Author(s):  
Jean-Baptiste Guilbaud ◽  
Aline F. Miller ◽  
Alberto Saiani
Keyword(s):  
Phase Transition ◽  
Molecular Weight ◽  
Low Temperature ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Temperature Sensitive ◽  
Thermoresponsive Polymer ◽  
Peptide Conjugates ◽  
Synthetic Strategy ◽  
Self Assembling

ABSTRACTA synthetic strategy to couple selectively an ionic complementary thiol modified octapeptide, that is able to gel at low temperature, to the thermoresponsive polymer poly(N-isopropylacrylamide) (pNIPAAm) with controlled molecular weight and narrow polydispersity is described. The polymer was synthesized by atom transfer radical polymerization (ATRP) affording halogen functionalized chain ends. This allowed subsequent coupling to a thiol terminated ionic complementary octapeptide via nucleophile substitution. Results indicated that the peptide was covalently attached to the polymer and that both the coil-globule phase transition of pNIPAAm and the gelation properties of the peptide were retained in the conjugated product. This method provides a versatile route for the synthesis of a range of bioconjugate materials with controlled architecture and dual self-assembling and thermoresponsive behavior.

Application of novel ionic liquids for reverse atom transfer radical polymerization of methacrylonitrile without any additional ligand

2009 ◽  
Vol 24 (5) ◽  
pp. 1880-1885 ◽  
Author(s):  
Hou Chen ◽  
Yanfeng Meng ◽  
Ying Liang ◽  
Zixuan Lu ◽  
Pingli Lv
Keyword(s):  
Molecular Weight ◽  
Ionic Liquids ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Reaction Rate ◽  
Atom Transfer ◽  
Additional Ligand ◽  
Rapid Reaction ◽  
Living Nature ◽  
First Time

Reverse atom transfer radical polymerization of methacrylonitrile (MAN) initiated by azobisisobutyronitrile (AIBN) was approached for the first time in the absence of any ligand in four novel ionic liquids, 1-methylimidazolium acetate ([mim][AT]), 1-methylimidazolium butyrate ([mim][BT]), 1-methylimidazolium caproate ([mim][CT]), and 1-methylimidazolium heptylate ([mim][HT]). The polymerization in [mim][AT] not only showed the best control of molecular weight and its distribution but also provided a more rapid reaction rate with the ratio of [MAN]:[FeCl3]:[AIBN] at 300:2:1. The block copolymer PMAN-b-PSt was obtained via a conventional ATRP process in [mim][AT] by using the resulting PMAN as a macroinitiator. After simple purification, [mim][AT] and FeCl3 could be easily recycled and reused and had no effect on the living nature of reverse atom transfer radical polymerization of MAN.

scholarly journals Tuning the molecular weight distribution from atom transfer radical polymerization using deep reinforcement learning

2018 ◽  
Vol 3 (3) ◽  
pp. 496-508 ◽  
Author(s):  
Haichen Li ◽  
Christopher R. Collins ◽  
Thomas G. Ribelli ◽  
Krzysztof Matyjaszewski ◽  
Geoffrey J. Gordon ◽  
...  
Keyword(s):  
Molecular Weight ◽  
Reinforcement Learning ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Weight Distribution ◽  
In Silico ◽  
Atom Transfer ◽  
Polymer Molecular Weight ◽  
Molecular Weight Distributions ◽  
Weight Distributions

Combination of deep reinforcement learning and atom transfer radical polymerization gives precise in silico control on polymer molecular weight distributions.

scholarly journals Synthesis of Well-Defined Three-Arm Star-Branched Polystyrene through Arm-First Coupling Approach by Atom Transfer Radical Polymerization

2015 ◽  
Vol 2015 ◽  
pp. 1-7 ◽  
Author(s):  
Syed Shahabuddin ◽  
Fatem Hamime Ismail ◽  
Sharifah Mohamad ◽  
Norazilawati Muhamad Sarih
Keyword(s):  
Molecular Weight ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Polymeric Chain ◽  
Atom Transfer ◽  
Simple Route ◽  
Coupling Strategy ◽  
Coupling Approach ◽  
Branched Polystyrene ◽  
Williamson Reaction

Here we describe a simple route to synthesize three-arm star-branched polystyrene. Atom transfer radical polymerization technique has been utilized to yield branched polystyrene involving Williamson coupling strategy. Initially a linear polymeric chain of predetermined molecular weight has been synthesized which is further end-functionalized into a primary alkyl bromide moiety, a prime requisition for Williamson reaction. The end-functionalized polymer is then coupled using 1,1,1-tris(4-hydroxyphenyl)ethane, a trifunctional core molecule, to give well-defined triple-arm star-branched polystyrene.

Polystyrene–organoclay nanocomposites produced by in situ activators regenerated by electron transfer for atom transfer radical polymerization

2012 ◽  
Vol 32 (4-5) ◽  
pp. 235-243 ◽  
Author(s):  
Khezrollah Khezri ◽  
Vahid Haddadi-Asl ◽  
Hossein Roghani-Mamaqani ◽  
Mehdi Salami-Kalajahi
Keyword(s):  
Molecular Weight ◽  
Electron Transfer ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Polymer Matrix ◽  
Clay Content ◽  
Xrd Analysis ◽  
Size Exclusion ◽  
Atom Transfer ◽  
Scanning Calorimetry

Abstract A newly developed initiation system, activators regenerated by electron transfer (ARGET), was employed to synthesize polystyrene-organoclay nanocomposites via atom transfer radical polymerization (ATRP). ARGET ATRP was applied since it is carried out at significantly low concentrations of the catalyst and environmentally acceptable reducing agents. Conversion and molecular weight evaluations were performed using gravimetry and size exclusion chromatography (SEC), respectively. According to the findings, addition of clay content resulted in a decrease in conversion and molecular weight of nanocomposites. However, an increase of polydispersity index is observed by increasing nanoclay loading. The living nature of the polymerization is revealed by 1H NMR spectroscopy and extracted data from the SEC traces. X-ray diffraction (XRD) analysis shows that organoclay layers are disordered and delaminated in the polymer matrix and exfoliated morphology is obtained. Thermogravimetric analysis (TGA) shows that thermal stability of the nanocomposites is higher than the neat polystyrene. A decrease in glass transition temperature of the samples by increasing organoclay content is observed by differential scanning calorimetry (DSC). Transmission electron microscopy (TEM) reveals that clay layers are partially exfoliated in the polymer matrix containing 2 wt% of organomodified montmorillonite (PSON 2) and a dispersion of partially exfoliated clay stacks is formed.

Synthesis of acrylic hot-melt adhesive based on poly(methyl methacrylate)-b-poly(2-ethylhexyl acrylate) copolymer using atom transfer radical polymerization for a nylon fabric bonding system

2019 ◽  
Vol 89 (23-24) ◽  
pp. 5177-5186
Author(s):  
Chung-Feng Jeffrey Kuo ◽  
Jiong-Bo Chen ◽  
Po-Yen Chen ◽  
Garuda Raka Satria Dewangga
Keyword(s):  
Molecular Weight ◽  
Block Copolymer ◽  
Methyl Methacrylate ◽  
Atom Transfer Radical Polymerization ◽  
Radical Polymerization ◽  
Atom Transfer ◽  
Poly Methyl Methacrylate ◽  
Bonding System ◽  
Nylon Fabric ◽  
Hot Melt

Adhesives, such as hot-melt adhesives (HMAs), are widely used in the textile industry for bonding layers of materials and have replaced traditional sewing methods. The block copolymer is a common type of HMA that provides excellent physical features and mechanical properties compared with others. Acrylate-based monomers, methyl methacrylate (MMA), and 2-ethylhexyl acrylate (2-EHA) were used as ingredients to form a linear block copolymer using atom transfer radical polymerization. MMA provides excellent cohesive strength, while 2-EHA provides good adhesion properties. An end-brominated poly(methyl methacrylate) (PMMA-Br) macroinitiator was synthesized from a MMA monomer and initiator, with the best composition obtained by the addition of a 0.6 mol initiator. The macroinitiator had the lowest molecular weight with highest conversion (97%). The addition of a 0.3 mol macroinitiator showed the lowest molecular weight with the highest conversion of acrylic copolymer PMMA- b-poly(2-ethylhexyl acrylate) (PEHA). The glass transition temperature increased with the addition of the macroinitiator concentration, from −43.7℃ to −37.6℃. The thermal stability was reduced with the addition of macroinitiator content, from 332.37℃ to 286.81℃. The shear strength and peel strength of the PMMA- b-PEHA HMAs on nylon fabrics were enhanced from 11.24 to 16.92 kg cm−2 and from 0.29 to 0.61 kg cm−1, respectively, and did not change significantly after being washed 50 times and then kept in low-temperature storage, with the addition of the macroinitiator concentration. The block copolymer PMMA- b-PEHA prepared in this study could be used as a HMA for nylon fabric bonding systems.

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