Synthesis and depolymerization of self-immolative poly(disulfide)s with saturated aliphatic backbones

Hansen-Felby, Magnus; Sommerfeldt, Andreas; Henriksen, Martin Lahn; Pedersen, Steen Uttrup; Daasbjerg, Kim

doi:10.1039/d1py01412a

Cited by 11 publications

(7 citation statements)

References 34 publications

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“…Recently, we published that poly(dithiothreitol) (pDTT) with pendant anthraquinone (AQ) groups exhibited complete depolymerization in response to electrochemical reduction of AQ to AQ• − in what was the first use of electrochemically induced depolymerization triggering of SIPs [ 29 ]. Alternatively, dithiothreitol and base (triethylamine) can be used to initiate depolymerization [ 29 , 30 , 31 , 32 ]. An interesting aspect of the indirect electron transfer (or redox catalysis) [ 33 , 34 , 35 ] approach for carrying out reduction processes involving bond fragmentation is that it can lower significantly the electrochemical potential needed for accomplishing the process, and in a very controlled fashion.…”

Section: Introductionmentioning

confidence: 99%

Electrocatalytic Depolymerization of Self-Immolative Poly(Dithiothreitol) Derivatives

2022

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We report the use of electrogenerated anthraquinone radical anion (AQ•−) to trigger fast catalytic depolymerization of polymers derived from poly(dithiothreitol) (pDTT)—a self-immolative polymer (SIP) with a backbone of dithiothreitols connected with disulfide bonds and end-capped via disulfide bonds to pyridyl groups. The pDTT derivatives studied include polymers with simple thiohexyl end-caps or modified with AQ or methyl groups by Steglich esterification. All polymers were shown to be depolymerized using catalytic amounts of electrons delivered by AQ•−. For pDTT, as little as 0.2 electrons per polymer chain was needed to achieve complete depolymerization. We hypothesize that the reaction proceeds with AQ•− as an electron carrier (either molecularly or as a pendant group), which transfers an electron to a disulfide bond in the polymer in a dissociative manner, generating a thiyl radical and a thiolate. The rapid and catalytic depolymerization is driven by thiyl radicals attacking other disulfide bonds internally or between pDTT chains in a chain reaction. Electrochemical triggering works as a general method for initiating depolymerization of pDTT derivatives and may likely also be used for depolymerization of other disulfide polymers.

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Section: Introductionmentioning

confidence: 99%

Electrocatalytic Depolymerization of Self-Immolative Poly(Dithiothreitol) Derivatives

2022

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“…40 Furthermore, they investigated a broader range of nonfunctionalized poly(disulfide)s, prepared from monomers such as 1,4-butanedithiol, 1,5-pentanedithiol, and 1,6-hexanedithiol, to obtain poly(disulfide)s with different alkyl chain lengths. 41 The results indicated that poly(1,4-butanedithiol) and poly-(1,5-pentanedithiol) undergo head-to-tail cyclization elimination upon end-capping removal, although poly(1,5-pentanedithiol) exhibited a significantly slower degradation rate. This difference arises from the higher thermodynamic stability of the six-membered ring 1,2-dithiane produced during the degradation of poly(1,4-butanedithiol) compared to the seven-membered ring 1,2-dithiepane released during the degradation of poly (1,5-pentanedithiol).…”

Section: Architecture Of Sipmentioning

confidence: 97%

Recent Advances in Stimuli-Responsive Self-Immolative Polymers for Drug Delivery and Molecular Imaging

Li,

Liu,

et al. 2024

Chem. Mater.

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Stimuli-responsive self-immolative polymers (SIPs) represent a unique class of polymers that can undergo controlled, sequential head-to-tail depolymerization upon specific stimuli. Since their inception, they have evolved over two decades to become one of the most attractive polymer types. With their characteristic feature of "one stimulus, multiple responses", SIPs inherently possess the ability to serve as chemical amplifiers, which can amplify weak chemical or biological signals. This feature promises higher stimulus sensitivity, greater selectivity for specific microenvironments, and the potential to generate more persistent, extensive, and significant responses while consuming fewer stimuli sources. This Review summarizes the latest research advancements in stimuli-responsive SIPs for drug delivery and molecular imaging over the past five years. Regarding the structure of SIPs, we briefly overview the updates in self-immolation units, end-cap moieties, and sequence of SIPs. In terms of applications, we focus on the possible biological applications of SIPs in drug delivery for disease treatment and potential imaging methods. Finally, we provide a brief perspective of potential future directions for SIPs in these applications.

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“…Furthermore, by modifying the molecular architecture, the addition of specific compounds to trigger the depolymerization via abiotic and biotic methods is being considered. [70][71][72][73]77] The concept of self-immolative polymers referring to polymers that are designed and programmed to disassemble through a dominolike effect in response to an external stimuli has been explored. [90] The biodegradation could be accelerated by designing and adding compounds that trigger depolymerization in specific environments and conditions (Figure 7).…”

Section: Incorporation Of Additives During Processingmentioning

confidence: 99%

Boosting Degradation of Biodegradable Polymers

Bher

Cho

Auras

2023

Macromol. Rapid Commun.

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Biodegradation of polymers in composting conditions is an alternative end‐of‐life (EoL) scenario for contaminated materials collected through the municipal solid waste management system, mainly when mechanical or chemical methods cannot be used to recycle them. Compostability certification requirements are time‐consuming and expensive. Therefore, approaches to accelerate the biodegradation of these polymers in simulated composting conditions can facilitate and speed up the evaluation and selection of potential compostable polymer alternatives and inform faster methods to biodegrade these polymers in real composting. This review highlights recent trends, challenges, and future strategies to accelerate biodegradation by modifying the polymer properties/structure and the compost environment. Both abiotic and biotic methods show potential for accelerating the biodegradation of biodegradable polymers. Abiotic methods, such as the incorporation of additives, reduction of molecular weight, reduction of size and reactive blending, are potentially the most straightforward, providing a level of technology that allows for easy adoption and adaptability. Novel methods, including the concept of self‐immolative and triggering the scission of polymer chains in specific conditions, are increasingly sought. In terms of biotic methods, dispersion/encapsulation of enzymes during the processing step, biostimulation of the environment, and bioaugmentation with specific microbial strains during the biodegradation process are promising to accelerate biodegradation.

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Synthesis and depolymerization of self-immolative poly(disulfide)s with saturated aliphatic backbones

Abstract: Self-immolative polymers (SIPs) are a class of degradable stimuli-responsive polymers, which, upon removal of labile end-caps, depolymerize selectively and stepwise to small molecules.

Cited by 11 publications

References 34 publications

Electrocatalytic Depolymerization of Self-Immolative Poly(Dithiothreitol) Derivatives

Electrocatalytic Depolymerization of Self-Immolative Poly(Dithiothreitol) Derivatives

Recent Advances in Stimuli-Responsive Self-Immolative Polymers for Drug Delivery and Molecular Imaging

Boosting Degradation of Biodegradable Polymers

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