Computational Evaluation of the Sulfonyl Radical as a Universal Leaving Group for RAFT Polymerisation

2013 ◽  
Vol 66 (3) ◽  
pp. 308 ◽  
Author(s):  
Ganna Gryn'ova ◽  
Tamaz Guliashvili ◽  
Krzysztof Matyjaszewski ◽  
Michelle L. Coote
Keyword(s):  
Chain Transfer ◽  
Superior Performance ◽  
Experimental Conditions ◽  
Computational Evaluation ◽  
Reversible Addition ◽  
Wide Range ◽  
Leaving Group ◽  
Radical Polymerisation ◽  
Synthetic Routes ◽  
High Level

The present study investigates the performance of the sulfonyl radical, i.e. •SO2Ph, as a universal leaving group in reversible addition–fragmentation chain-transfer (RAFT) polymerisation. The sulfonyl radical is widely used as a radical initiator and has already been proved successful as a leaving group in an atom-transfer radical polymerisation. Our results, obtained using high-level ab initio computational methodology under relevant experimental conditions, indicate superior performance of the sulfonyl compared with a reference cyanoisopropyl group in controlling RAFT of a wide range of monomers. Importantly, the presence of sulfonyl chain ends in the polymers so formed opens attractive possibilities for further functionalisation. Potential synthetic routes to the R-sulfonyl RAFT agents are discussed.

scholarly journals Redox-Initiated Reversible Addition–Fragmentation Chain Transfer (RAFT) Polymerization

2019 ◽  
Vol 72 (7) ◽  
pp. 479 ◽  
Author(s):  
Amin Reyhani ◽  
Thomas G. McKenzie ◽  
Qiang Fu ◽  
Greg G. Qiao
Keyword(s):  
Redox Reactions ◽  
Chain Transfer ◽  
Raft Polymerization ◽  
Molecular Structures ◽  
Biologically Relevant ◽  
Molecular Weights ◽  
Polymeric Biomaterials ◽  
Reversible Addition ◽  
Wide Range ◽  
Metal Catalyzed

Reversible addition–fragmentation chain transfer (RAFT) polymerization initiated by a radical-forming redox reaction between a reducing and an oxidizing agent (i.e. ‘redox RAFT’) represents a simple, versatile, and highly useful platform for controlled polymer synthesis. Herein, the potency of a wide range of redox initiation systems including enzyme-mediated redox reactions, the Fenton reaction, peroxide-based reactions, and metal-catalyzed redox reactions, and their application in initiating RAFT polymerization, are reviewed. These redox-RAFT polymerization methods have been widely studied for synthesizing a broad range of homo- and co-polymers with tailored molecular weights, compositions, and (macro)molecular structures. It has been demonstrated that redox-RAFT polymerization holds particular promise due to its excellent performance under mild conditions, typically operating at room temperature. Redox-RAFT polymerization is therefore an important and core part of the RAFT methodology handbook and may be of particular importance going forward for the fabrication of polymeric biomaterials under biologically relevant conditions or in biological systems, in which naturally occurring redox reactions are prevalent.

A Detailed investigation of the experimental conditions for the reversible addition fragmentation chain transfer-mediated copolymerization of acrylonitrile and butadiene

2011 ◽  
Vol 50 (1) ◽  
pp. 174-180 ◽  
Author(s):  
Christoph J. Dürr ◽  
Sebastian G. J. Emmerling ◽  
Andreas Kaiser ◽  
Sven Brandau ◽  
Axel K. T. Habicht ◽  
...  
Keyword(s):  
Chain Transfer ◽  
Experimental Conditions ◽  
Reversible Addition

General Cyclopropane Assembly via Enantioselective Redox-Active Carbene Transfer to Aliphatic Olefins

2018 ◽  
Author(s):  
Marc Montesinos-Magraner ◽  
Matteo Costantini ◽  
Rodrigo Ramirez-Contreras ◽  
Michael E. Muratore ◽  
Magnus J. Johansson ◽  
...  
Keyword(s):  
Total Synthesis ◽  
Asymmetric Synthesis ◽  
Chemical Space ◽  
Synthetic Approach ◽  
Asymmetric Cyclopropanation ◽  
Redox Active ◽  
Wide Range ◽  
Leaving Group ◽  
Stereoelectronic Properties ◽  
Carbene Transfer

Asymmetric cyclopropane synthesis currently requires bespoke strategies, methods, substrates and reagents, even when targeting similar compounds. This limits the speed and chemical space available for discovery campaigns. Here we introduce a practical and versatile diazocompound, and we demonstrate its performance in the first unified asymmetric synthesis of functionalized cyclopropanes. We found that the redox-active leaving group in this reagent enhances the reactivity and selectivity of geminal carbene transfer. This effect enabled the asymmetric cyclopropanation of a wide range of olefins including unactivated aliphatic alkenes, enabling the 3-step total synthesis of (–)-dictyopterene A. This unified synthetic approach delivers high enantioselectivities that are independent of the stereoelectronic properties of the functional groups transferred. Our results demonstrate that orthogonally-differentiated diazocompounds are viable and advantageous equivalents of single-carbon chirons<i>.</i>

Strongly Coupled Redox-Linked Conformational Switching at the Active Site of the Non-Heme Iron-Dependent Dioxygenase, TauD

2019 ◽  
Author(s):  
Christopher John ◽  
Greg M. Swain ◽  
Robert P. Hausinger ◽  
Denis A. Proshlyakov
Keyword(s):  
Active Site ◽  
Structural Model ◽  
Heme Iron ◽  
Chemical Transformations ◽  
Experimental Conditions ◽  
Strongly Coupled ◽  
Non Heme Iron ◽  
Reversible Redox ◽  
Wide Range ◽  
Complex Structural

2-Oxoglutarate (2OG)-dependent dioxygenases catalyze C-H activation while performing a wide range of chemical transformations. In contrast to their heme analogues, non-heme iron centers afford greater structural flexibility with important implications for their diverse catalytic mechanisms. We characterize an <i>in situ</i> structural model of the putative transient ferric intermediate of 2OG:taurine dioxygenase (TauD) by using a combination of spectroelectrochemical and semi-empirical computational methods, demonstrating that the Fe (III/II) transition involves a substantial, fully reversible, redox-linked conformational change at the active site. This rearrangement alters the apparent redox potential of the active site between -127 mV for reduction of the ferric state and 171 mV for oxidation of the ferrous state of the 2OG-Fe-TauD complex. Structural perturbations exhibit limited sensitivity to mediator concentrations and potential pulse duration. Similar changes were observed in the Fe-TauD and taurine-2OG-Fe-TauD complexes, thus attributing the reorganization to the protein moiety rather than the cosubstrates. Redox difference infrared spectra indicate a reorganization of the protein backbone in addition to the involvement of carboxylate and histidine ligands. Quantitative modeling of the transient redox response using two alternative reaction schemes across a variety of experimental conditions strongly supports the proposal for intrinsic protein reorganization as the origin of the experimental observations.

The way of value of Correlation of genomic DNA microsatellite loci and live weight of Chukchi reindeer

2020 ◽  
pp. 27-32
Author(s):  
V. Dodokhov ◽  
N. Pavlova ◽  
T. Rumyantseva ◽  
L. Kalashnikova
Keyword(s):  
Microsatellite Markers ◽  
Agricultural Production ◽  
Live Weight ◽  
Biodiversity Loss ◽  
Tribal Community ◽  
High Germination ◽  
Wide Range ◽  
The Mean ◽  
High Level ◽  
Dna Microsatellite

The article presents the genetic characteristic of the Chukchi reindeer breed. The object of the study was of the Chukchi reindeer. In recent years, the number of reindeer of the Chukchi breed has declined sharply. Reduced reindeer numbers could lead to biodiversity loss. The Chukchi breed of deer has good meat qualities, has high germination viability and is adapted in adverse tundra conditions of Yakutia. Herding of the Chukchi breed of deer in Yakutia are engaged only in the Nizhnekolymsky district. There are four generic communities and the largest of which is the agricultural production cooperative of nomadic tribal community «Turvaurgin», which was chosen to assess the genetic processes of breed using microsatellite markers: Rt6, BMS1788, Rt 30, Rt1, Rt9, FCB193, Rt7, BMS745, C 143, Rt24, OheQ, C217, C32, NVHRT16, T40, C276. It was found that microsatellite markers have a wide range of alleles and generally have a high informative value for identifying of genetic differences between animals and groups of animal. The number of identified alleles is one of the indicators of the genetic diversity of the population. The total number of detected alleles was 127. The Chukchi breed of deer is characterized by a high level of heterozygosity, and the random crossing system prevails over inbreeding in the population. On average, there were 7.9 alleles (Na) per locus, and the mean number of effective alleles (Ne) was 4.1. The index of fixation averaged 0.001. The polymorphism index (PIC) ranged from 0.217 to 0.946, with an average of 0.695.

COVID-19 Outbreak Prediction with Machine Learning

2020 ◽  
Author(s):  
Sina Faizollahzadeh Ardabili ◽  
Amir Mosavi ◽  
Pedram Ghamisi ◽  
Filip Ferdinand ◽  
Annamaria R. Varkonyi-Koczy ◽  
...  
Keyword(s):  
Machine Learning ◽  
Prediction Models ◽  
Fuzzy Inference ◽  
Control Measures ◽  
Future Research ◽  
Complex Nature ◽  
Inference System ◽  
Wide Range ◽  
Standard Models ◽  
High Level

Several outbreak prediction models for COVID-19 are being used by officials around the world to make informed-decisions and enforce relevant control measures. Among the standard models for COVID-19 global pandemic prediction, simple epidemiological and statistical models have received more attention by authorities, and they are popular in the media. Due to a high level of uncertainty and lack of essential data, standard models have shown low accuracy for long-term prediction. Although the literature includes several attempts to address this issue, the essential generalization and robustness abilities of existing models needs to be improved. This paper presents a comparative analysis of machine learning and soft computing models to predict the COVID-19 outbreak as an alternative to SIR and SEIR models. Among a wide range of machine learning models investigated, two models showed promising results (i.e., multi-layered perceptron, MLP, and adaptive network-based fuzzy inference system, ANFIS). Based on the results reported here, and due to the highly complex nature of the COVID-19 outbreak and variation in its behavior from nation-to-nation, this study suggests machine learning as an effective tool to model the outbreak. This paper provides an initial benchmarking to demonstrate the potential of machine learning for future research. Paper further suggests that real novelty in outbreak prediction can be realized through integrating machine learning and SEIR models.

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