Dynamic polythioesters via ring-opening polymerization of 1,4-thiazine-2,5-diones

Ura, Yasuyuki; Al‐Sayah, Mohammad H.; Montenegro, Javier; Beierle, John M.; Leman, Luke J.; Ghadiri, Mojtaba

doi:10.1039/b903612a

Cited by 43 publications

(32 citation statements)

References 51 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…The concentration of thiol, [R″SH], was arbitrarily set to 1 mM constructive processes from all three of these classifications. Monomers functionalized with both thiols and thioesters can polymerize into macromolecules (Ura, et al 2009). Reactions coupled to the hydrolysis of thioesters (e.g., formation of phosphoanhydrides via acylphosphate intermediates) can be used to store energy (de Duve 1991;Wächtershäuser 1992).…”

Section: Implications For Thioesters In the Origin Of Lifementioning

confidence: 99%

The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water

Bracher

Snyder

Bohall

et al. 2011

Orig Life Evol Biosph

155

158

View full text Add to dashboard Cite

This article reports rate constants for thiol-thioester exchange (k (ex)), and for acid-mediated (k (a)), base-mediated (k (b)), and pH-independent (k (w)) hydrolysis of S-methyl thioacetate and S-phenyl 5-dimethylamino-5-oxo-thiopentanoate-model alkyl and aryl thioalkanoates, respectively-in water. Reactions such as thiol-thioester exchange or aminolysis could have generated molecular complexity on early Earth, but for thioesters to have played important roles in the origin of life, constructive reactions would have needed to compete effectively with hydrolysis under prebiotic conditions. Knowledge of the kinetics of competition between exchange and hydrolysis is also useful in the optimization of systems where exchange is used in applications such as self-assembly or reversible binding. For the alkyl thioester S-methyl thioacetate, which has been synthesized in simulated prebiotic hydrothermal vents, k (a) = 1.5 × 10(-5) M(-1) s(-1), k (b) = 1.6 × 10(-1) M(-1) s(-1), and k (w) = 3.6 × 10(-8) s(-1). At pH 7 and 23°C, the half-life for hydrolysis is 155 days. The second-order rate constant for thiol-thioester exchange between S-methyl thioacetate and 2-sulfonatoethanethiolate is k (ex) = 1.7 M(-1) s(-1). At pH 7 and 23°C, with [R″S(H)] = 1 mM, the half-life of the exchange reaction is 38 h. These results confirm that conditions (pH, temperature, pK (a) of the thiol) exist where prebiotically relevant thioesters can survive hydrolysis in water for long periods of time and rates of thiol-thioester exchange exceed those of hydrolysis by several orders of magnitude.

show abstract

Section: Implications For Thioesters In the Origin Of Lifementioning

confidence: 99%

The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water

Bracher

Snyder

Bohall

et al. 2011

Orig Life Evol Biosph

155

158

View full text Add to dashboard Cite

show abstract

“…Generally, the synthesis of polythioesters is achieved either by: i) polyaddition of dithiol acids to unconjugated diolefins; ii) polycondensation reaction of dithiols with diacids (or activated derivatives of diacids); iii) polyaddition of biscyclic thioethers (e.g., thiiranes) with activated diacid derivatives; v) ring‐opening polymerization of thioanhydrides, thioglycolides or thiolactides; or v) microbial synthesis …”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

278

220

View full text Add to dashboard Cite

The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

show abstract

“…Sidechain modification of polymers is of general interest to avoid tedious optimization of polymerization conditions with every structural modification and to produce comparable functional systems with identical scaffold [4 – 6][12] [15 – 21]. Synthetic strategies that in part have been applied previously to synthetic transport systems include the formation of hydrazones,[4][15][16] sulfonium cations,[6] boronate esters,[17] amides,[12] thioesters,[18] disulfides,[19] diselenides,[20] triazoles,[5][21] and so on. In the following, we introduce a general method for sidechain modification of CPDs to secure synthetic access to comparable systems.…”

Section: Introductionmentioning

confidence: 99%

Sidechain Engineering in Cell‐Penetrating Poly(disulfide)s

Morelli

Matile

2017

Helvetica Chimica Acta

View full text Add to dashboard Cite

Cell‐penetrating poly(disulfide)s (CPDs) have been introduced recently to explore new ways to enter into cells. In this report, we disclose a general method to covalently modify the sidechains of CPDs. Compatibility of copper‐catalyzed alkyne‐azide cycloaddition (CuAAC) with the addition of either strained cyclic disulfides of varied ring tension or increasing numbers of guanidinium and phosphonium cations is demonstrated. Reloading CPDs with disulfide ring tension results in an at least 20‐fold increase in activity with preserved sensitivity toward inhibition with the Ellman's reagent. The cumulation of permanent positive charges by sidechain engineering affords Ellman‐insensitive CPDs with similarly increased activity. Co‐localization experiments indicate that the CPDs reach endosomes, cytosol and nucleus, depending on their nature and their concentration. Supported by pertinent controls, these trends confirm that CPDs operate with combination of counterion‐ and thiol‐mediated uptake, and that the balance between the two can be rationally controlled. For the most active CPDs, uptake can be observed at substrate (fluorophore) concentrations as low as 5 nm.

show abstract

Dynamic polythioesters via ring-opening polymerization of 1,4-thiazine-2,5-diones

Cited by 43 publications

References 51 publications

The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water

The Relative Rates of Thiol–Thioester Exchange and Hydrolysis for Alkyl and Aryl Thioalkanoates in Water

Sulfur Chemistry in Polymer and Materials Science

Sidechain Engineering in Cell‐Penetrating Poly(disulfide)s

Contact Info

Product

Resources

About