Gadenstätter, Clemens

Gratzer, Wolfgang

doi:10.1093/gmo/9781561592630.article.46780

Cited by 3 publications

(3 citation statements)

References 0 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Monomer sequences are important primary structural parameters of natural macromolecules, such as peptides, proteins, and nucleic acids, as the monomer sequence dictates the higher-order structures and thereby endows the macromolecules with special functions . In these natural macromolecules, the monomer sequences are perfectly controlled through biological synthetic processes governed by biocatalysts, such as enzymes and ribozymes.…”

Section: Introductionmentioning

confidence: 99%

Construction of Sequence-Regulated Vinyl Copolymers via Iterative Single Vinyl Monomer Additions and Subsequent Metal-Catalyzed Step-Growth Radical Polymerization

et al. 2019

View full text Add to dashboard Cite

A series of sequence-regulated vinyl copolymers with high-order and long vinyl monomer sequences were constructed via a combination of iterative single vinyl monomer additions, which were mediated by radical and cationic intermediates, and subsequent metal-catalyzed step-growth radical polymerization. The construction of vinyl monomer sequences was attained by iterative single monomer radical and cationic additions between a dichloride, having a similar substituent to that of vinyl monomers, and vinyl monomers such as styrenes, acrylates, and acrylonitrile. The resulting products were converted into sequenceregulated ab-type monomers that have embedded vinyl monomer sequences between an unconjugated CC bond and reactive C−Cl bond via selective allylation of one of the two C−Cl bonds at their terminals. The synthesized sequence-regulated ab-type monomers were polymerized via metal-catalyzed stepgrowth radical polymerization, which resulted in vinyl chloride units via repetitive intermolecular addition reactions between the CC and C−Cl terminals. Alternatively, aa-and bb-type sequence-regulated monomers, which have two unconjugated CC and two reactive C−Cl bonds, respectively, were prepared by similar iterative single monomer additions and were subsequently polymerized via metalcatalyzed step-growth radical polymerization. The repeating vinyl monomer sequence codes in the resulting polymers, such as ABCC, ABCD, ABBAC, ABDBAC, and ABDBACAEEAC, varied from 4 to 11 monomer units in which the embedded vinyl monomer units were styrenes, acrylates, acrylamides, acrylonitrile, vinyl chloride, vinylidene chloride, and ethylene.

show abstract

Section: Introductionmentioning

confidence: 99%

Construction of Sequence-Regulated Vinyl Copolymers via Iterative Single Vinyl Monomer Additions and Subsequent Metal-Catalyzed Step-Growth Radical Polymerization

et al. 2019

View full text Add to dashboard Cite

show abstract

“…This development has led to the realization that synthetic polymers are fundamental to achieve the functions of natural macromolecules bearing fully well-defined “monomer” sequences (such as in proteins and nucleic acids). However, compared to the natural macromolecules, monomer sequence regulation in synthetic polymers has been a formidable challenge. , Successful monomer sequence control in synthetic polymers may allow fine-tuning of their structures, properties, and functions, leading to promising new applications in catalysis, molecular recognition, or biodegradable materials . Alternating radical copolymerization leads to (A-B) n type copolymers suitable for application in photovoltaic devices .…”

mentioning

confidence: 99%

Nitroxide-Mediated Alternating Copolymerization of Vinyl Acetate withtert-Butyl-2-trifluoromethacrylate Using a SG1-Based Alkoxyamine

2016

View full text Add to dashboard Cite

International audienceUnique alternating copolymers based on vinylacetate (VAc) and tert-butyl-2-trifluoromethacrylate (MAFTBE,a nonhomopolymerizable monomer under radicalconditions) have been synthesized by nitroxide-mediatedpolymerization (NMP) using a SG1-based BlocBuilderalkoxyamine (MAMA-SG1) at moderate temperature (at 40°C) in dimethyl sulfoxide. First-order kinetics and linearevolutions of the molecular weight (up to 17100 g mol−1),maintaining low dispersity values (Đ ≤ 1.33), confirmed thecontrolled nature of the copolymerization. Interestingly, noneof the starting monomers could undergo homopolymerizationunder the NMP condition initiated by MAMA-SG1. Theresulting alternating copolymers were characterized by 1H, 13C, 19F, and 31P NMR spectroscopies and size exclusionchromatography (SEC). The poly(VAc-alt-MAF-TBE) copolymer is amorphous and exhibited a single glass transitiontemperature of 59 °C. This is the first report of nitroxide-mediated (co)polymerization of VAc leading to well-definedcopolymers with satisfactory yields. The results presented in this study established a new route via NMP toward the synthesis ofstrictly 1:1 alternating fluorocopolymers that can display diverse functionalities

show abstract

“…Natural macromolecules such as proteins and nucleic acids possess perfectly ordered molecular structures in terms of chain lengths, stereostructures, and monomer sequences, which are essential for their special and unique functions . Although synthetic macromolecules or polymers are widely used in our life, their primary structures are not perfectly controlled unlike natural ones.…”

Section: Introductionmentioning

confidence: 99%

Main-Chain and Side-Chain Sequence-Regulated Vinyl Copolymers by Iterative Atom Transfer Radical Additions and 1:1 or 2:1 Alternating Radical Copolymerization

2016

View full text Add to dashboard Cite

Main- and side-chain sequence-regulated vinyl copolymers were prepared by a combination of iterative atom transfer radical additions (ATRAs) of vinyl monomers for side-chain control and 1:1 or 2:1 alternating radical copolymerization of the obtained side-chain sequenced "oligomonomers" and vinyl comonomers for main-chain control. A complete set of sequence-regulated trimeric vinyl oligomers of styrene (S) and/or methyl acrylate (A) were first synthesized via iterative ATRAs of these monomers to a halide of monomeric S or A unit (X-S or X-A) under optimized conditions with appropriate ruthenium or copper catalysts, which were selected depending on the monomers and halides. The obtained halogen-capped oligomers were then converted into a series of maleimide (M)-ended oligomonomers with different monomer compositions and sequences (M-SSS, M-ASS, M-SAS, M-AAS, M-SSA, M-ASA, M-SAA, M-AAA) by a substitution reaction of the halide with furan-protected maleimide anion followed by deprotection of the furan units. These maleimide-ended oligomonomers were then radically copolymerized with styrene or limonene to enable the 1:1 or 2:1 monomer-sequence regulation in the main chain and finally result in the main- and side-chain sequence-regulated vinyl copolymers with high molecular weights in high yield. The properties of the sequence-regulated vinyl copolymers depended on not only the monomer compositions but also the monomer sequences. The solubility was highly affected by the outer monomer units in the side chains whereas the glass transition temperatures were primarily affected by the two successive monomer sequences.

show abstract

Gadenstätter, Clemens

Cited by 3 publications

References 0 publications

Construction of Sequence-Regulated Vinyl Copolymers via Iterative Single Vinyl Monomer Additions and Subsequent Metal-Catalyzed Step-Growth Radical Polymerization

Construction of Sequence-Regulated Vinyl Copolymers via Iterative Single Vinyl Monomer Additions and Subsequent Metal-Catalyzed Step-Growth Radical Polymerization

Nitroxide-Mediated Alternating Copolymerization of Vinyl Acetate withtert-Butyl-2-trifluoromethacrylate Using a SG1-Based Alkoxyamine

Main-Chain and Side-Chain Sequence-Regulated Vinyl Copolymers by Iterative Atom Transfer Radical Additions and 1:1 or 2:1 Alternating Radical Copolymerization

Contact Info

Product

Resources

About