Polymer Chemistry最新文献

{"title":"pH-responsive polymer-supported pyrene-based fluorescent dyes for CO2 detection in aqueous environments†","authors":"David A. Londoño de la Cruz ,&nbsp;David Chappell ,&nbsp;Bilal Rashid ,&nbsp;Blaine R. Tookey ,&nbsp;Calum T. J. Ferguson ,&nbsp;Rachel K. O'Reilly","doi":"10.1039/d4py01186d","DOIUrl":"10.1039/d4py01186d","url":null,"abstract":"<div><div>Detecting fluctuations in carbon dioxide by switching ‘ON’ or ‘OFF’ fluorescence in aqueous environments has often been targeted for efficient monitoring. This switch needs to occur in a drastic and fast way that is visually observable to be effective. CO₂ dissolves in water, leading to a reduction in pH, which can be used to trigger a response. Specifically, the modification of fluorescent dyes with pH-responsive units could create a dye that responds to CO₂ and switches ‘off’ fluorescence. Here, we developed a water-soluble polymer functionalized with a CO₂-responsive pyrene dye. This functional dye contains a tertiary amine conjugated to the aromatic pyrene, which can be protonated at pH ∼ 6.5 or lower. After only 15 s of CO₂ bubbling, a significant fluorescence ‘OFF’ response was observed, with a drastic reduction in fluorescence at 480 nm as a consequence of disrupting non-covalent excimer bonds. Moreover, the exposure to atmospheric air results in a recovery of the excimer state and, therefore, the fluorescence, demonstrating its reversible nature.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 11","pages":"Pages 1265-1271"},"PeriodicalIF":4.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01186d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143055504","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Revisiting AB2 + A-R copolymerization: direct access to Janus and peripherally clickable hyperbranched polyesters†","authors":"Runa Singla ,&nbsp;E. Bhoje Gowd ,&nbsp;S. Ramakrishnan","doi":"10.1039/d4py01412j","DOIUrl":"10.1039/d4py01412j","url":null,"abstract":"<div><div>Hyperbranched polymers (HBPs) are often prepared by the self-condensation of AB₂ type monomers, which results in compact globular structures with numerous B-groups on their periphery; the number of terminal B-groups increases with the DP_<em>n</em> value of the polymer. Since the AB₂ monomer has one equivalent of B-group in excess, copolymerization with up to one equivalent of an A-R-type molecule provides direct access to HBPs whose periphery is decorated with the desired R-unit. Here, we demonstrate that direct melt condensation of a simple AB₂ monomer, dimethyl 5-(6-hydroxyhexyloxy)isophthalate (DMHHI), with MPEG-OH (A-R₁) and/or cetyl alcohol (A-R₂), generates peripherally decorated HBPs. When two different A-R molecules are used together, the relative amounts installed are controlled by the mole ratio of the two, taken during the polymerization. We show that the terminal methyl ester groups in the HBP are almost completely replaced (&gt;95%), making this a very effective and direct strategy for peripheral installation of multiple segments. Importantly, we show that when alkyl and PEG segments are co-installed, self-segregation occurs to generate a Janus structure, with evidence for this being obtained from DSC and X-ray scattering studies. Furthermore, we also demonstrate the direct synthesis of peripherally clickable HBPs using this AB₂ + A-R copolymerization strategy, wherein 10-undecen-1-ol or 10-undecyn-1-ol is used as the A-R comonomer. The terminal unsaturation is then used to install PEG segments, using radical-initiated thiol–ene or thiol–yne click reactions, to yield core–shell-type amphiphilic structures. As expected, aqueous solutions of shell-PEGylated HBPs exhibited an LCST, and the transition temperatures increased with the length of the PEG segment and its number density within the shell region. This general copolymerization approach is scalable and can readily be extended to install different types of functional motifs on the periphery of globular hyperbranched constructs, thereby providing opportunities for a variety of potential applications.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 11","pages":"Pages 1285-1296"},"PeriodicalIF":4.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143124328","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Redox-responsive micellar nanoparticles using benzothiazole-disulfide terminated polymers: employing host–guest complexation for targeted delivery of curcumin†","authors":"Salli Kocak ,&nbsp;Beyza Demirkol ,&nbsp;Ruveyda Kilic Boz ,&nbsp;Rana Sanyal ,&nbsp;Mehmet Arslan ,&nbsp;Amitav Sanyal","doi":"10.1039/d4py01086h","DOIUrl":"10.1039/d4py01086h","url":null,"abstract":"<div><div>A host–guest interaction-based redox-responsive polymeric nanoparticle system for targeted delivery of curcumin is fabricated. Host–guest interaction between a β-cyclodextrin (β-CD) terminated hydrophilic polymer and curcumin is employed to formulate stable nanosized aggregates. A redox-sensitive disulfide linkage is used to tether the CD moiety onto the polymer chain ends to obtain efficient release inside cancerous cells. For the synthesis of the β-CD terminated redox-responsive polymer, a polyethylene glycol (PEG)-based polymer containing a benzothiazole-disulfide (BDS) group at the chain end was utilized. The BDS-terminated polymers were synthesized using reversible addition–fragmentation chain transfer (RAFT) polymerization by using a BDS-containing chain-transfer agent (CTA). Initially, the post-polymerization modification abilities of these polymers were demonstrated by successful conjugation of model thiol functional compounds such as furfuryl thiol and Bodipy-SH, a fluorescent hydrophobic dye. To prepare a nanoaggregate forming polymer precursor, a thiol functional β-CD host moiety was conjugated to the BDS end groups of the reactive polymer through redox-responsive disulfide linkage formation. The other end of the β-CD-containing polymer was capped with an integrin-targeting cyclic peptide (cRGDfK). While no aggregates were observed in the aqueous medium for the BDS-containing parent polymer, the β-CD attached polymers gave nanosized aggregates with average sizes below 150 nm. Curcumin-loaded nanoaggregates were obtained through the inclusion complexation of curcumin molecules with β-CD moieties. It was shown that enhanced drug release occurred upon exposure of the nanoaggregates to the glutathione (GSH) environment. While the parent BDS functional polymers and β-CD-containing polymeric aggregates were non-toxic to healthy fibroblast cells, curcumin-loaded aggregates showed dose-dependent toxicity against the U-87 glioblastoma cancer cell line. The peptide-targeting group containing nanoparticles showed slightly higher toxicity and enhanced cellular internalization. The modular nanoparticle system disclosed here could be employed to address challenges in the delivery of hydrophobic drugs to cancer cells.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 11","pages":"Pages 1272-1284"},"PeriodicalIF":4.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143385601","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Circular polyester design by gem-heterodisubstitution: valerolactone-based polymers with high ductility and excellent strength†","authors":"Yue-Ming Pan ,&nbsp;Xin-Lei Li ,&nbsp;Wen-Da Shang ,&nbsp;Tie-Qi Xu","doi":"10.1039/d5py00022j","DOIUrl":"10.1039/d5py00022j","url":null,"abstract":"<div><div>Geminal disubstitution is a frequent focus of attention when designing monomers for the construction of recyclable polymers, but it is used for that purpose with two same substituents in cyclic monomers, which causes difficulty in producing polymers combining good strength and high elongation. Here we design a series of α,α-heterodisubstituted δ-valerolactones (δVL) with two different alkyl substituents at the α,α-position of δVL (VL^R1,R2) which, when combined with the parent δVL and <em>gem</em>-α,α-dialkyl substituted δVL with the same alkyl groups, provide a desired platform for exploring circular polymer design by focusing on the asymmetric substitution of monomers. These VL^R1,R2s allow both facile synthesis of polyester PVL^R1,R2s with strong/ductile synergistic performance in a living fashion and selective depolymerization of the PVL^R1,R2s to completely recover monomers under mild conditions (using a recyclable catalyst at 100 °C). PVL^Et,Pr is a semicrystalline, strong (ultimate strength = 39.9 MPa) and ductile (elongation at break = 331%) material. These notable mechanical properties are complemented by its superior barrier to oxygen and water-vapor permeation, relative to LDPE and PVL.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 11","pages":"Pages 1297-1304"},"PeriodicalIF":4.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143427103","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Poly(malic acid) copolymers as degradable rheology modifiers in aqueous formulations†","authors":"Christina A. R. Picken ,&nbsp;Orla Buensoz ,&nbsp;Christopher Fidge ,&nbsp;Paul Price ,&nbsp;Michael P. Shaver","doi":"10.1039/d4py01382d","DOIUrl":"10.1039/d4py01382d","url":null,"abstract":"<div><div>Polymeric rheological modifiers help tailor formulations to specific applications but many current technologies are poorly bio- or hydrolytically-degradable. This paper investigates the polycondensation of malic acid as an acid-rich branching monomer with lactic and glycolic acids to synthesise hydrophilic branched polyesters as potential formulation modifiers. The branching of the copolymers was characterised using quantitative 2D NMR spectroscopy and Mark–Houwink plots measured by gel permeation chromatography. The viscoelastic properties of the copolymers in solution were assessed within a shampoo formulation and showed increased viscosity and elastic behaviour compared to control samples. The formulations are hydrolytically degradable, with the performance of the shampoo formulations deteriorating over time.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 11","pages":"Pages 1256-1264"},"PeriodicalIF":4.1,"publicationDate":"2025-02-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01382d?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143375178","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Correction: Towards the synthesis of polythiazolines: a post-polymerization approach","authors":"Aikaterini Mathianaki, Aysha Kinjo Demeler, Adrian Dömling, Federico Ferrari, Frieda Clara M. Scheelje, Hilke Bahmann and Guillaume Delaittre","doi":"10.1039/D4PY90157F","DOIUrl":"10.1039/D4PY90157F","url":null,"abstract":"<p >Correction for ‘Towards the synthesis of polythiazolines: a post-polymerization approach’ by Aikaterini Mathianaki <em>et al.</em>, <em>Polym. Chem.</em>, 2025, https://doi.org/10.1039/d4py00930d.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 7","pages":" 913-913"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py90157f?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056353","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"In memoriam Acad. Prof. Dr Bogdan Simionescu (1948–2024)","authors":"Valentin Victor Jerca","doi":"10.1039/D4PY90155J","DOIUrl":"10.1039/D4PY90155J","url":null,"abstract":"<p >A graphical abstract is available for this content</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 7","pages":" 772-773"},"PeriodicalIF":4.1,"publicationDate":"2025-01-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143056280","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Bioderived copolymer alternatives to poly(styrene-co-maleic anhydride) via RAFT-mediated copolymerization†","authors":"Lauren Elaine Ball ,&nbsp;Michael-Phillip Smith ,&nbsp;Bert Klumperman","doi":"10.1039/d4py01227e","DOIUrl":"10.1039/d4py01227e","url":null,"abstract":"<div><div>Poly(styrene-<em>co</em>-maleic anhydride) (SMAnh) is a petroleum-based copolymer with desirable properties that afford utility in both industrial and academic fields. The reversible addition–fragmentation chain transfer (RAFT)-mediated polymerization of the bioderived comonomers, indene and itaconic anhydride, was explored using three chain transfer agents with varying activity, and generally well-controlled (<em>Đ</em> &lt; 1.40) polymerizations were observed.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 9","pages":"Pages 1019-1023"},"PeriodicalIF":4.1,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py01227e?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142987258","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Optimisation of azide–alkyne click reactions of polyacrylates using online monitoring and flow chemistry†","authors":"Despina Coursari ,&nbsp;Spyridon Efstathiou ,&nbsp;Lucas Al-Shok ,&nbsp;Mia D. Hall ,&nbsp;Ahmed M. Eissa ,&nbsp;Evelina Liarou ,&nbsp;David M. Haddleton","doi":"10.1039/d4py00984c","DOIUrl":"10.1039/d4py00984c","url":null,"abstract":"<div><div>Herein, the online and inline ¹H-NMR monitoring of azide–alkyne click reactions of polymers is investigated. The effect of the reaction solvent, ligand and temperature were investigated on small “model” molecules. Azidopropanol and 3-azidopropyl-2-bromoisobutyrate were used as the azide-containing molecules, whereas propargyl alcohol was chosen as the alkyne reactant. The optimal conditions were found to be dimethylsulfoxide (DMSO) as solvent with 2,2′ bipyridine as ligand, which were subsequently employed in the modification of different azide-functionalised polyacrylates with propargyl alcohol. From this, poly(methyl acrylate) was chosen to investigate the more complex conjugation of an alkyne monosaccharide. Finally, the “click” reaction was performed in flow leading to a successful modification in less than 1 h.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 9","pages":"Pages 1065-1071"},"PeriodicalIF":4.1,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d4py00984c?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143027102","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Stoichiometric effects on bulk stress relaxation to enhance reprocessability in covalent adaptable networks†","authors":"Jaehyun Cho ,&nbsp;Santanu Ghosh ,&nbsp;Mridula Nandi ,&nbsp;Heejoon Jeon ,&nbsp;Liang Yue ,&nbsp;H. Jerry Qi ,&nbsp;M. G. Finn ,&nbsp;Blair Brettmann","doi":"10.1039/d5py00013k","DOIUrl":"10.1039/d5py00013k","url":null,"abstract":"<div><div>Achieving maximum crosslinking density is often thought to be crucial for high performance and mechanical strength in conventional thermoset covalent adaptable networks (CANs), although some network defects can enhance properties such as toughness and reprocessability. Controlling functional group stoichiometry and crosslinking density is therefore key to better understanding and programming the properties and reprocessability of CANs. Despite efforts to systematically control CAN properties, many previous studies show inconsistent trends in stress relaxation rates, hindering a clear understanding of the factors affecting reprocessability. We show that stoichiometry is a critical factor influencing bulk stress relaxation for a dissociative type of CAN based on the aza-Michael addition reactions utilizing triacrylate monomer and two polymeric amines (Jeffamine and polyethyleneimine, PEI). Relative functional group reactivity was characterized by Fourier transform infrared spectroscopy, and four different stoichiometries were analyzed. Thermal reprocessing demonstrated the stability of mechanical properties over multiple cycles, notably in stoichiometrically balanced systems, consistent with the general principle that mechanical properties and crosslinking density reach a maximum with stoichiometric equivalence. These findings underscore the importance of careful stoichiometric design in tailoring viscoelastic properties and mechanical behavior in dissociative type CAN systems, offering insights into polymer material design for applications requiring dynamic properties and reprocessability.</div></div>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"16 9","pages":"Pages 1031-1043"},"PeriodicalIF":4.1,"publicationDate":"2025-01-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.rsc.org/en/content/articlepdf/2025/py/d5py00013k?page=search","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142992646","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}