Polymer Chemistry最新文献

{"title":"Dibenzobarrelene-derived Pd-NHCs: efficient precatalysts for the Suzuki–Miyaura polycondensations of dichloroarene monomers†","authors":"Yuman Guo, Hao Wu, Meng-Jiao Zhang and Feng-Shou Liu","doi":"10.1039/D4PY01026D","DOIUrl":"10.1039/D4PY01026D","url":null,"abstract":"<p >Pd-catalyzed Suzuki–Miyaura polycondensations (SMPs) have emerged as a powerful method for synthesizing conjugated polymers (CPs). While numerous reports have utilized dibromoarene and diiodoarene derivatives as monomers, there has been less research on the use of the deactive dichloroarenes due to harsh conditions and low efficiency. In this study, aiming to overcome these challenges and develop robust palladium precatalysts, a series of dibenzobarrelene-derived palladium N-heterocyclic carbenes (Pd-NHCs) were designed and synthesized. It was observed that the “large-but-flexible” nature of these Pd-IPr<small>^DBB</small> complexes as well as the “throw-away” ligands facilitated the stability of Pd(0) species and the polymerization process. Additionally, optimization of polycondensation conditions such as choice of base, solvent, and temperature was conducted. This work presents an efficient protocol for synthesizing conjugated polymers with high yields and high molecular weights, demonstrating a broad monomer scope and outperforming conventional palladium phosphine-based catalytic systems.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 4962-4971"},"PeriodicalIF":4.1,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142599998","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":"Axial-phenyl-constrained bis(imino)acenaphthene-nickel precatalysts enhance ethylene polymerization†","authors":"Quanchao Wang, Qiuyue Zhang, Yizhou Wang, Song Zou, Yanping Ma, Tongling Liang and Wen-Hua Sun","doi":"10.1039/D4PY01110D","DOIUrl":"10.1039/D4PY01110D","url":null,"abstract":"<p >To enhance the performance of the bis(imino)acenaphthene-nickel precatalyst, an axial phenyl group was introduced on the acenaphthenyl backbone, and five analogues were formed: bis(aryl)imino-5-phenylacenaphthene nickel bromides (aryl: 2,6-dimethylphenyl, <strong>Ni1</strong>; 2,6-diethylphenyl, <strong>Ni2</strong>; 2,6-diisopropylphenyl, <strong>Ni3</strong>; 2,4,6-trimethylphenyl, <strong>Ni4</strong>; and 2,6-diethyl-4-methylphenyl, <strong>Ni5</strong>). The molecular structures of mononuclear <strong>Ni2</strong> and dinuclear <strong>Ni3</strong> were confirmed as distorted tetrahedron and square-pyramidal geometries around the nickel core, respectively. All five precatalysts achieved better activity as well as thermostability for ethylene polymerization and delivered polyethylene elastomer with higher molecular weight and more branches than the benchmark nickel precatalyst proposed by Brookhart. Specifically, <strong>Ni2</strong>/EASC maintained a catalytic activity of 4.52 × 10<small>⁶</small> g PE per mol (Ni) per h even at 100 °C. More importantly, the resultant polyethylenes exhibited excellent mechanical properties with high strain (&gt;1000%) and stress (&gt;10 MPa) values observed during tensile stress–strain tests. Topographic steric maps showed that there is sufficient space around the nickel center for ethylene to conduct coordination and facilitate polymeric propagation. The introduction of an axial phenyl group into the backbone of nickel complexes not only elevates the catalytic performance, but also provides these polyethylene elastomers with attractive properties.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 4993-5006"},"PeriodicalIF":4.1,"publicationDate":"2024-11-11","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142598351","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":"Sequence-defined structural transitions by calcium-responsive proteins†","authors":"Marina P. Chang, Winnie Huang, Gatha M. Shambharkar, Kenny M. Hernandez and Danielle J. Mai","doi":"10.1039/D4PY00907J","DOIUrl":"10.1039/D4PY00907J","url":null,"abstract":"<p >Biopolymer sequences dictate their functions, and protein-based polymers are a promising platform to establish sequence–function relationships for novel biopolymers. To efficiently explore vast sequence spaces of natural proteins, sequence repetition is a common strategy to tune and amplify specific functions. This strategy is applied to repeats-in-toxin (RTX) proteins with calcium-responsive folding behavior, which stems from tandem repeats of the nonapeptide GGXGXDXUX in which X can be any amino acid and U is a hydrophobic amino acid. To determine the functional range of this nonapeptide, we modified a naturally occurring RTX protein that forms β-roll structures in the presence of calcium. Sequence modifications focused on calcium-binding turns within the repetitive region, including either global substitution of nonconserved residues or complete replacement with tandem repeats of a consensus nonapeptide GGAGXDTLY. Some sequence modifications disrupted the typical transition from intrinsically disordered random coils to folded β rolls, despite conservation of the underlying nonapeptide sequence. Proteins enriched with smaller, hydrophobic amino acids adopted secondary structures in the absence of calcium and underwent structural rearrangements in calcium-rich environments. In contrast, proteins with bulkier, hydrophilic amino acids maintained intrinsic disorder in the absence of calcium. These results indicate a significant role of nonconserved amino acids in calcium-responsive folding, thereby revealing a strategy to leverage sequences in the design of tunable, calcium-responsive biopolymers.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 47","pages":" 4864-4874"},"PeriodicalIF":4.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597633","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":"Reducing agent-triggered templated synthesis of a dynamic covalent poly(disulfide)s nanonetwork: remarkable tuning in noncovalent encapsulation stabilities and cargo release†","authors":"Arun Mondal, Sk Sujauddin, Dhiman Mondal, Soumya Kolay, Shuvajyoti Sarkar and Mijanur Rahaman Molla","doi":"10.1039/D4PY01109K","DOIUrl":"10.1039/D4PY01109K","url":null,"abstract":"<p >We demonstrated a new methodology for the templated synthesis of a crosslinked poly(disulfide)s-based dynamic covalent nanonetwork as a highly stable potential delivery vehicle for chemotherapeutic applications. The synthesis was carried out by treatment of a nanoaggregate of a biomass-derived lipoic acid-based amphiphilic monomer with a reducing agent at room temperature in open air and aqueous medium. The hydrodynamic diameter of the naoaggregate was ∼130 nm as probed by dynamic light scattering. Control over the crosslinking density was achieved by varying the ratio of monomer : reducing agent. The crosslinking percentage varied from ∼13% to ∼100%. This provided the opportunity of fine-tuning the stability of the nanocarrier, noncovalent encapsulation stabilities and kinetics of cargo release, which are highly relevant in drug-delivery applications. For a highly crosslinked nanonetwork, in the simulated redox condition of cancer cells, ∼80% release of the guest molecule was noted from the nanonetwork in a sustained manner. Controlled depolymerization of the polymer was accomplished by use of specific mol% of the same reducing agent. Finally, the reversibility and recyclability of the poly(disulfide)s to the monomeric form was achieved by treatment of the polymer with an external thiol in the presence of an organic base.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 48","pages":" 5007-5015"},"PeriodicalIF":4.1,"publicationDate":"2024-11-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142597636","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":"Alternating radical copolymerization of α-styrylboronic acid pinacol ester with electron-deficient olefins†","authors":"Yiyang Xiao, Zepeng Zhang, Yan Xu and Jianbo Wang","doi":"10.1039/D4PY00976B","DOIUrl":"10.1039/D4PY00976B","url":null,"abstract":"<p >Here, α-styrylboronic acid pinacol ester (<strong>StBpin</strong>) has been found to undergo alternating radical copolymerization with electron-deficient olefin comonomers, including <em>n</em>-butyl acrylate, <em>N</em>,<em>N</em>-dimethylacrylamide, acrylonitrile, and <em>N</em>-ethylmaleimide. Compared with styrene, which also copolymerizes with these electron-deficient olefins in an alternating manner, <strong>StBpin</strong> resulted in the formation of copolymers with higher alternating selectivity, but lower yields and low molecular weights due to its diminished reactivity.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 47","pages":" 4835-4841"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594261","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":"Mesomorphic and photochromic luminescent behaviour of side-chain liquid crystalline polymers containing di-substituted cyanostilbene groups with different numbers of alkyl tail chains†","authors":"Juan Luo, Juan Wang, Junde Zhang, Huizi Cao and Xiaofang Chen","doi":"10.1039/D4PY00889H","DOIUrl":"10.1039/D4PY00889H","url":null,"abstract":"<p >In this work, side-chain luminescent liquid crystalline polymers (SCLLCPs) that contain di-substituted cyanostilbene (CS) groups with different numbers of substituted terminal alkyl chains, namely <strong>PNB-Z-4</strong>, <strong>PNB-Z-34</strong>, and <strong>PNB-Z-345</strong>, were synthesized. Their mesomorphic structure, luminescence properties and photochromic luminescent behaviour were investigated. <strong>PNB-Z-4</strong> containing one alkyl chain in each mesogen possesses a supramolecular oblique columnar (Col<small>_ob</small>) phase with large lattice parameters, which can transform into a lamellar structure at high temperature. <strong>PNB-Z-34</strong> and <strong>PNB-Z-345</strong> with two and three alkyl tails exhibit a hexagonal columnar phase (Col<small>_h</small>) structure. Their fluorescence quantum yields (<em>Φ</em><small>_F</small>) in the solid state are improved by increasing the number of alkyl tails as well. <strong>PNB-Z-34</strong> and <strong>PNB-Z-345</strong> exhibit aggregation-induced emission (AIE) properties, while <strong>PNB-Z-4</strong> shows weak fluorescence. Furthermore, their photochromic fluorescence responses are quite different. <strong>PNB-Z-4</strong> exhibits an obvious “turn-on” photo-responsive behaviour with <em>Φ</em><small>_F</small> increasing from 0.70% to 7.73% after UV irradiation with the existence of [2 + 2] cycloaddition, while <strong>PNB-Z-34</strong> and <strong>PNB-Z-345</strong> show <em>Z</em>/<em>E</em> isomerization induced blueshift fluorescence response.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 47","pages":" 4842-4851"},"PeriodicalIF":4.1,"publicationDate":"2024-11-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142594316","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":"Bisbenzothieno[b]-fused BODIPYs in panchromatic photoinitiation for free radical and cationic photopolymerization and application in 3D printing†","authors":"Yangyang Xu, Wenlong Tang, Hui Deng, Jianjun Zhang, Zhongquan Zhu, Changjiang Yu, Haiguang Zhu, Ke Sun, Jiazhu Li and Jacques Lalevée","doi":"10.1039/D4PY00926F","DOIUrl":"10.1039/D4PY00926F","url":null,"abstract":"<p >Polymerization reactions induced by light are gaining increasing importance in the field of polymer synthesis; however, effective photopolymerization under visible light emitting diodes (LEDs), as opposed to UV light, remains limited and warrants further research and development. In this work, a family of bisbenzothieno[<em>b</em>]-fused boron dipyrromethene (BODIPY) derivatives, which have not been previously tested for photopolymerization, were designed. They contain seven fused aromatic rings with broad absorption properties and were introduced with amine and iodonium salt to form three-component photoinitiating systems (PISs) for the first time. Remarkably, under visible light irradiation, <em>e.g.</em> LED@405 nm and LED@660 nm, these PISs were able to initiate the free radical polymerization of acrylate monomers and cationic polymerization of epoxy monomers at room temperature, displaying different photopolymerization kinetics. This excellent initiation ability at both ends of the visible spectrum (<em>i.e.</em> the highest and lowest photon energy) indicated a remarkable panchromatic initiation ability. The exceptional photochemical reactivity of these BODIPY dyes and the underlying photoinitiation mechanisms of the PISs were thoroughly investigated through steady-state photolysis, fluorescence quenching experiments, and theoretical calculations. Finally, three-dimensional patterns with excellent spatial resolution were successfully printed using the BODIPY dye with the highest photoinitiation efficiency <em>via</em> direct laser writing, highlighting its significant potential for 3D printing applications.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 47","pages":" 4875-4887"},"PeriodicalIF":4.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580723","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":"Fully bio-based acetal diepoxy monomer with high modulus, good thermal stability and readily degradability†","authors":"Zidie Song, Li Liu, Pengbo Zhang, Kangle Xue, Zibo Hua, Tao You, Yiqi Wu, Hong Cui, Zhen Hu and Yudong Huang","doi":"10.1039/D4PY01038H","DOIUrl":"10.1039/D4PY01038H","url":null,"abstract":"<p >Degradable epoxy resins are designed to address the environmental pollution caused by traditional epoxy resins. However, incorporating the degradability of dynamic covalent bonds in the design of degradable resins often compromises the rigidity and heat resistance of the material, rendering it less suitable for high-temperature applications, such as those used in deep space exploration. This paper presents the creation of an innovative, entirely bio-based epoxy monomer. Its cyclic rigid dynamic bonds confer a high tensile modulus (4.06 GPa), glass transition temperature (<em>T</em><small>_g</small> = 240 °C), notable creep resistance with full shape recovery at 180 °C, and remarkable degradability, dissolving entirely in a 1 M HCl solution in just 60 minutes at 50 °C. The preparation of the diacetal was accomplished by reacting vanillin with xylitol under acidic conditions. This was followed by a reaction with bio-derived epichlorohydrin to produce bio-based, multifunctional epoxy monomers featuring hydroxyl groups and bicyclic acetal structures, representing a new strategy for eco-friendly polymer synthesis. This monomer was then cured with a hardener to create an epoxy crosslinked network. The eco-friendly raw materials are easily obtainable, and the synthesized cross-linked network structure is exceptionally high-performing. This makes it a potential material for use in deep space exploration and other tough environments, and it provides a benchmark for synthesizing chemically degradable epoxy resins suitable for extreme conditions.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 47","pages":" 4824-4834"},"PeriodicalIF":4.1,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142589014","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":"Aromatic vs. aliphatic linkers: impact on dye loading and stability in oligoglycerol-derived dendronized polymersomes†","authors":"Raj Kumar Roy, Trisha Samanta, Supriyo Saha, Aparna Ramesh, Naznin Ara Begum, Goutam Ghosh and Pradip Dey","doi":"10.1039/D4PY01028K","DOIUrl":"10.1039/D4PY01028K","url":null,"abstract":"<p >Nanocarriers protect the payload from degradation and enable specific targeting of the diseased tissue, thus reducing systemic toxicity. So, it is crucial and desirable to design a nanocarrier with specific nano-architectures that possess those essential characteristics. Considering the above aspects, we report the one-pot synthesis and self-assembly of oligoglycerol-based amphiphilic dendronized polythiourethanes consisting of an aliphatic or aromatic linker. During the ring opening of cyclodithiocarbonate, the generated thiols were utilized to conjugate first or zeroth-generation oligoglycerol dendrons (containing four or two hydroxyl groups) in one pot. Among them, the aromatic linker containing polymer ARM-PTU-G<small>₁</small>-OH had a higher encapsulation ability for hydrophobic dyes (pyrene and Nile red) than the other aliphatic linker containing polymer ALP-PTU-G<small>₁</small>-OH. Both the polymers had hydrodynamic diameters of 167 nm with PDI = 0.314–0.326. In addition, AFM results showed that ALP-PTU-G<small>₁</small>-OH and ARM-PTU-G<small>₁</small>-OH formed spherical aggregates with diameters of 136 ± 28 nm and 161 ± 35 nm, respectively. The formation of polymersomes was probed by encapsulating the hydrophilic dye calcein. Both the polymers were able to encapsulate calcein. Among them, the aromatic linker-containing polymer had 31% encapsulation efficiency, whereas the aliphatic linker-containing polymer had 14% encapsulation efficiency. To understand the stability of the polymersomes, a FRET study was performed by encapsulating DiO and DiI dyes individually in both the polymersomes, and then mixing and studying the evolution of FRET with time. The results showed that the mechanism of dye exchange was different for both polymers, and the aromatic linker containing polymersome had better stability during dye exchange. A few parameters were calculated by fitting the change in donor emission intensity with time, and it showed that in ARM-PTU-G<small>₁</small>-OH dye exchange occurred <em>via</em> a slow merging and splitting mechanism. In contrast, in ALP-PTU-G<small>₁</small>-OH, a fast expulsion and insertion mechanism was mainly operative.</p>","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":" 1","pages":" 27-36"},"PeriodicalIF":4.1,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142574348","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":"Increase of Spatiotemporal Resolution and Reproducible Layer Thicknesses in Cationic Vat Photopolymerization","authors":"Emile Goldbach, Xavier Allonas, Christian Ley, Lucile Halbardier, Céline Croutxe-Barghorn","doi":"10.1039/d4py01046a","DOIUrl":"https://doi.org/10.1039/d4py01046a","url":null,"abstract":"In this paper, the 3D DLP printing of an epoxy-based material controlled by pyridine derivatives was investigated. The impact of the pyridine structure and concentration on the cationic polymerization kinetic was explored. An increase of the inhibition time and a decrease of the heat flow were observed and attributed to the trapping of the initiating species and the stabilization of the growing chains. This allows for the confinement of the polymerization process and limits the presence of lateral defects around the printed objects. Furthermore, the validity of the Jacobs law was discussed. Due to the photoinitiator photolysis, an increase in the penetration depth was observed in relation with the solidification delay. A model was developped to relate the change of printed layer thickness with the applied light dose, taking this phenomenon into account. This led to a more precise determination of the critical energy.","PeriodicalId":100,"journal":{"name":"Polymer Chemistry","volume":"59 1","pages":""},"PeriodicalIF":4.6,"publicationDate":"2024-11-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142580566","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}