Natural RAFT Polymerization: Recyclable-Catalyst-Aided, Opened-to-Air, and Sunlight-Photolyzed RAFT Polymerizations

Wang, Jie; Rivero, M.; Muñoz‐Bonilla, Alexandra; Sánchez-Marcos, J.; Xue, Wentao; Chen, Gaojian; Zhang, Weidong; Zhu, Xiulin

doi:10.1021/acsmacrolett.6b00818

Cited by 82 publications

(70 citation statements)

References 49 publications

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“…Herein, we report a novel multicomponent strategy to develop lymphoseek‐inspired adjuvants in one‐pot. First, photo‐induced reversible addition‐fragmentation chain transfer (RAFT) polymerization and photo‐activated click chemistry were employed to fabricate catechol‐containing glycopolymer, then multicomponent strategy was utilized to design desired vaccine adjuvants, where three different components, catechol‐containing glycopolymer, HAuCl 4 , and amine‐terminal CpG (CpG‐NH 2 ) can react in a single step to form hetero‐glycoadjuvant@AuNPs in one‐pot. Most notably oxidation of catechol to quinones and “catechol‐amine” reaction can be carried out simultaneously.…”

Section: Methodsmentioning

confidence: 99%

One‐Pot, Multicomponent Strategy for Designing Lymphoseek‐Inspired Hetero‐Glycoadjuvant@AuNPs

Liu

Wen

Shen

et al. 2019

Macromol. Rapid Commun.

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transported to draining lymph nodes. The second approach is based on the activation of antigen-presenting cells (APCs) to induce T cell. [9,10] Recently, inspired by the lymphoseek [11] (which is a mannose-conjugated, dextran-based LN imaging agent, acting as receptor-targeted radiotracer in breast cancer and melanoma patients), we have first developed LN-targeting adjuvant by conjugating toll-like receptor (TLR) [9] agonists, unmethylated Cytosinephosphate-Guanosine (CpG) to natural dextran. [12] Although dextran-functionalized adjuvant could not increase adjuvant internalization, they could distinctly enhance CD8 + T-cell responses, and improve cancer immunotherapy. [12] More importantly, dextran-based adjuvants could not only activate tumor-specific CTL responses, but also inhibit myeloid-derived suppressor cells (MDSCs) in tumor immune microenvironment. [13] Many works indicate that binding between C-type lectin receptors (CLRs) and carbohydrate ligands [14][15][16][17][18][19] is important not only for the induction of T-cell responses, but also for the inhibition of immunosuppressive microenvironment. [13] Therefore, lymphoseek-inspired vaccine should have advantages of promoting vaccine internalization, potentiating CD8 + T-cell responses and reducing the immunosuppressive activity, and become a promising candidate for nextgeneration cancer vaccine.Much effort has been devoted to developing new methodologies for the design and preparation of multifunctional adjuvant, which is the most challenging work. To obtain bioactive adjuvant, simple and highly efficient reaction should be used to formulate adjuvant. To date, most of the works use "grafting to" method to generate target adjuvant. [20][21][22][23] Lynn et al. attached small-molecule TLR-7/8a agonists to hydrophilic polymers to form polymer-TLR-7/8a conjugates by "grafting to" strategy. [24] Recently, inspired by quinone chemistry, we have also introduced "thiol-quinone" reaction to attach thiolated CpG to NPs for fabricating pathogen-mimetic [25][26][27] adjuvants by the "grafting to" method. [28] Besides, few works employ multicomponent strategy to design adjuvants. It is well known that onepot multicomponent strategy offers obvious advantages of simplicity and high efficiency over traditional chemical reactions. Moreover, one-pot strategy is more convenient to obtain high concentration adjuvants. Herein, we report a novel multicomponent strategy to develop lymphoseek-inspired adjuvants in one-pot. First, photo-induced reversible addition-fragmentation Glycoadjuvants Searching for vaccines (antigen and adjuvant) with easy preparation and strong T-cell response are crucial for antitumor immunity. In this work, to design lymphoseek-inspired vaccine possessing the abilities of promoting vaccine internalization and enhancing CD8 + T-cell responses, a simple multicomponent strategy is successfully utilized to fabricate lymph node and dendritic cell dual-targeting glycoadjuvant@AuNPs in one pot, where three different components, catechol-containing glycopol...

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Section: Methodsmentioning

confidence: 99%

One‐Pot, Multicomponent Strategy for Designing Lymphoseek‐Inspired Hetero‐Glycoadjuvant@AuNPs

Liu

Wen

Shen

et al. 2019

Macromol. Rapid Commun.

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“…25 Light is one of the most favoured energy sources for the temporal and spatial control of reactions, because of the straightforward nature of the processes, the mild reaction conditions and minimised side reactions. 26 One such example is photoinduced electron transfer (PET) polymerisation, which is able to precisely control the molecular weight and polydispersity of the synthesised polymers, [27][28][29] while tolerating molecular oxygen and offering compatibility to many functional monomers. 26,28 Herein we report new methods for the rapid synthesis of asymmetric miktoarm star polymers through a one-pot tandem strategy combining photo-controlled tetrazine formation chemistry, norbornene-tetrazine IEDDA chemistry and PET-atom transfer radical polymerisation (ATRP) with precise spatial and temporal control using different wavelength light.…”

Section: Introductionmentioning

confidence: 99%

“…26 One such example is photoinduced electron transfer (PET) polymerisation, which is able to precisely control the molecular weight and polydispersity of the synthesised polymers, [27][28][29] while tolerating molecular oxygen and offering compatibility to many functional monomers. 26,28 Herein we report new methods for the rapid synthesis of asymmetric miktoarm star polymers through a one-pot tandem strategy combining photo-controlled tetrazine formation chemistry, norbornene-tetrazine IEDDA chemistry and PET-atom transfer radical polymerisation (ATRP) with precise spatial and temporal control using different wavelength light. A bromine functionalised dihydrotetrazine ATRP initiator precursor was photo-oxidised aided by a photosensitiser to give a bromine functionalised tetrazine, 30 which was subsequently coupled to a norbornene-terminated polyethylene glycol (PEG) resulting in a macro-ATRP initiator, and was polymerised with an acrylamide monomer via a metal free PET-ATRP process to give the desired asymmetric star polymer.…”

Section: Introductionmentioning

confidence: 99%

Photo-controlled one-pot strategy for the synthesis of asymmetric three-arm star polymers

2019

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“…The external activation methods to RDRPs include photochemical, thermochemical, electrochemical and mechanical forces, and so on. Among them, as a more environmentally friendly external methods, visible light is the most ideal stimulus due to its low energy consumption, high performance and safe operation, it also could reversibly trigger the growth of polymer chains by simply switching the light “on” or “off.” So far, a lot of photoinduced RDRPs have been developed including atom transfer radical polymerization (ATRP), reversible addition‐fragmentation chain transfer polymerization (RAFT), ring‐opening metathesis polymerization (ROMP), iodine mediated polymerization (IMP), and cobalt mediated radical polymerization (CMRP) …”

Section: Introductionmentioning

confidence: 99%

Visible‐light induced RAFT polymerization of styrenic monomers with aromatic aldehydes as organophotoredox catalysts

Yang

Zhang

Chen

et al. 2018

J. Polym. Sci. Part A: Polym. Chem.

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A photoinduced electron transfer‐reversible addition‐fragmentation chain transfer (PET‐RAFT) polymerization of p‐methylstyrene (p‐MS) and styrene (St) with 2‐(dodecylthiocarbonothioylthio)‐2‐methylpropionic acid as the chain transfer agent (CTA) and aromatic aldehydes, including 4‐cyanobenzaldehyde (PC1), 2,4‐dimethoxy benzaldehyde, and 4‐methoxy benzaldehyde, as organic photocatalysts has been demonstrated via irradiation with 23 W compact fluorescent lamps. The kinetics of the polymerizations shows first order with respect to monomer conversions. Linear evolution of the Mn of the produced polymers with the monomer conversion is observed. Meanwhile, the as‐prepared polymers are of relatively narrow polydispersity (PDI = Mw/Mn). For instance, the polymerization of p‐MS shows living polymerization features using PC1 within a range of solvents. Especially, the Mn of PpMS increased from about 2100 to 12,700 g/mol with the monomer conversion from 8% to 52% in tetrahydrofuran. The controlled polymerization of St is also observed under optimal reaction conditions. However, the Mn discrepancy between the experimental readings and theoretical calculations is greater at the monomer conversions greater than 40% and the PDI increased gradually over the monomer conversion. This is probably because that CTA is strongly sensitive to the light irradiation with wave range around its characteristic absorption wavelength, leading to significant decomposition of CTA moieties during the RAFT polymerization. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018, 56, 2072–2079

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Natural RAFT Polymerization: Recyclable-Catalyst-Aided, Opened-to-Air, and Sunlight-Photolyzed RAFT Polymerizations

Cited by 82 publications

References 49 publications

One‐Pot, Multicomponent Strategy for Designing Lymphoseek‐Inspired Hetero‐Glycoadjuvant@AuNPs

One‐Pot, Multicomponent Strategy for Designing Lymphoseek‐Inspired Hetero‐Glycoadjuvant@AuNPs

Photo-controlled one-pot strategy for the synthesis of asymmetric three-arm star polymers

Visible‐light induced RAFT polymerization of styrenic monomers with aromatic aldehydes as organophotoredox catalysts

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