New Polymers Possessing a Disulfide Bond in a Unique Environment

Graf, Tyler A.; Yoo, Jun; Brummett, Adam B.; Lin, Ran; Wohlgenannt, M.; Quinn, Daniel M.; Bowden, Ned B.

doi:10.1021/ma3017103

Cited by 20 publications

(22 citation statements)

References 69 publications

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“…4d), and rate of S 8 consumption was observed to dominate in the initial stages over vinylic polymerization [51]. More recently Bowden et al developed a new class of sulfur containing polymers based upon poly(aminosulfides) [52][53][54].…”

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confidence: 99%

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Polymerizations with elemental sulfur: A novel route to high sulfur content polymers for sustainability, energy and defense

Griebel

Glass

Char

et al. 2016

Progress in Polymer Science

375

254

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Recent developments in the polymerizations of elemental sulfur (S 8 ) to prepare high sulfur content polymers are reviewed. While the homopolymerization of S 8 via ring-opening processes to prepare high molar mass polymeric sulfur has long been known, this form of polymeric sulfur is chemically unstable and depolymerizes back to S 8 . In the current report, we discuss the background into the production of sulfur via petroleum refining and the challenges associated with utilizing S 8 as a chemical reagent for materials synthesis. To circumvent these long standing challenges in working with sulfur, the use of S 8 as a reaction medium and comonomer in a process termed, inverse vulcanization, was developed to prepare chemically stable and processable sulfur copolymers. Furthermore, access to polymeric materials with a very high content of sulfur-sulfur (S-S) bonds enabled for the first time the creation of materials with useful (electro)chemical and optical properties which are reviewed for use in Li-S batteries, IR imaging technology and self-healing materials.

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Section: Insert Figure 4 and Figure 4 Captionmentioning

confidence: 99%

“…(Fig. 30a) [53,[334][335][336], radical mediated addition-fragmentation chain transfer reactions ( Fig. 30b) [337][338][339][340][341][342][343][344][345], alkoxyamine exchange reactions (Fig.…”

Section: Insertmentioning

confidence: 99%

Polymerizations with elemental sulfur: A novel route to high sulfur content polymers for sustainability, energy and defense

Griebel

Glass

Char

et al. 2016

Progress in Polymer Science

375

254

View full text Add to dashboard Cite

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“…2a ). Dialkoxydisulfide 28 , 29 and diaminodisulfide 30 – 32 have been investigated as sulfur transfer reagents since 1970s. However, unsymmetrical polysulfidation with disulfanyl motif has never been achieved owing to the sharp contradiction raised by sequential and selective cleavage of dual S-O(N) bonds.…”

Section: Introductionmentioning

confidence: 99%

Unsymmetrical polysulfidation via designed bilateral disulfurating reagents

Xue

Jiang

2020

Nat Commun

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Sulfur-sulfur motifs widely occur in vital function and drug design, which yearns for polysulfide construction in an efficient manner. However, it is a great challenge to install desired functional groups on both sides of sulfur-sulfur bonds at liberty. Herein, we designed a mesocyclic bilateral disulfurating reagent for sequential assembly and modular installation of polysulfides. Based on SO bond dissociation energy imparity (mesocyclic compared to linear imparity is at least 5.34 kcal mol −1 higher), diverse types of functional molecules can be bridged via sulfur-sulfur bonds distinctly. With these stable reagents, excellent reactivities with nucleophiles including C, N and S are comprehensively demonstrated, sequentially installing on both sides of sulfur-sulfur motif with various substituents to afford six species of unsymmetrical polysulfides including di-, tri-and even tetra-sulfides. Life-related molecules, natural products and pharmaceuticals can be successively cross-linked with sulfur-sulfur bond. Remarkably, the cyclization of tri-and tetra-peptides affords 15-and 18-membered cyclic disulfide peptides with this reagent, respectively.

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“…The synthesis of sulfur‐containing oligomers and polymers has been studied by several authors because of their interesting properties such as high melting temperature, thermal stability, biodegradability, optical activity, conductivity and photoconductivity . These properties are due to the high polarizability and high reactivity of sulfur atoms, as well as the flexibility of S–S and C–S bonds .…”

Section: Introductionmentioning

confidence: 99%

Chemoenzymatic synthesis of poly(phenylene disulfides) with insulating properties and resistant to high temperatures

Sierra¹,

Miranda-Molina²,

Castillo³

et al. 2017

J of Chemical Tech & Biotech

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BACKGROUND: Cyclic aromatic disulfides (CAD) can be used as cross-linking agents or precursors for the synthesis of high temperature resistant polymers such as poly(phenylene disulfides) (PPD). Chemical synthesis of CAD relies on the use of corrosive agents, detrimental for the environment. This paper reports an environment friendly chemoenzymatic procedure to obtain PPD starting from simple aromatic dithiols. RESULTS:The enzymatic reaction was carried out in an aqueous mixture with acetonitrile as co-solvent, using 1,4-and 1,3-benzenedithiol as monomers and a fungal laccase (EC 1.10.3.2) as catalyst. The products obtained were identified as mainly cyclic aromatic disulfides. Thermal analysis suggested that the enzymatically-synthesized CAD display thermal stability and are amenable precursors of high molecular weight sulfur-containing polymers through solvent-free, melt ring opening polymerization (mROP). After mROP, polymeric molecules around 12.8 kDa were obtained and identified as PPD. The resultant PPD shows uniform size, resistance to temperatures up to 400 ∘ C and electrical insulating properties. CONCLUSION: Laccase-catalyzed synthesis of CAD represents a novel reaction, not previously described elsewhere for oxidoreductases. A 100% substrate conversion was achieved under mild reaction conditions and no over-oxidation of CAD was observed, representing an advantage over chemical synthesis. The CAD products precipitated completely from the reaction medium, thus simplifying the purification process.

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New Polymers Possessing a Disulfide Bond in a Unique Environment

Cited by 20 publications

References 69 publications

Polymerizations with elemental sulfur: A novel route to high sulfur content polymers for sustainability, energy and defense

Polymerizations with elemental sulfur: A novel route to high sulfur content polymers for sustainability, energy and defense

Unsymmetrical polysulfidation via designed bilateral disulfurating reagents

Chemoenzymatic synthesis of poly(phenylene disulfides) with insulating properties and resistant to high temperatures

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