Julian Schmidt, Anna-Lena Ziegler, Florian T Kaps, Laura J Rosenberger, Matthias Bros, Holger Frey, Robert Luxenhofer
Polyethylene glycol (PEG) plays a central role in nanomedicine, providing essential properties such as the stealth effect. However, the emergence of anti-PEG antibodies (APAs) increasingly undermines these benefits, raising concerns about safety and efficiency. This creates an urgent need for PEG alternatives. Randomized PEG (rPEG) represents a conceptually new strategy that preserves the PEG-like structure and performance while markedly reducing antigenicity. In this work, rPEG is employed as a non-antigenic A-block in ABA-type polymeric micelles (PMs). To enhance drug loading capacity beyond conventional PMs, the hydrophobic middle block is composed of poly(2-phenyl-2-oxazine) (PPheOzi). rPEG is synthesized by anionic ring-opening polymerization, PPheOzi by cationic ring-opening polymerization, and the combined rPEG-b-PPheOzi-b-rPEG triblock copolymers are linked via copper-catalyzed azide-alkyne cycloaddition. The formulations exhibit a distinct correlation between the solubilization of Efavirenz and the systematically varied rPEG composition, ranging from outstanding to moderate micelle drug loading capacities. A fundamental preclinical safety profile was established through investigations in murine fibroblasts and human peripheral blood mononuclear cells (PBMCs). Competitive enzyme-linked immunosorbent assays (ELISA) revealed a pronounced reduction in APA affinity in comparison to PEG. Taken together, the synergistic combination of rPEG and PPheOzi establishes a non-antigenic micellar platform capable of achieving high drug loadings.
{"title":"A Non-Antigenic Randomized Polyethylene Glycol/Poly(2-Phenyl-2-Oxazine)-Based Drug Delivery Platform.","authors":"Julian Schmidt, Anna-Lena Ziegler, Florian T Kaps, Laura J Rosenberger, Matthias Bros, Holger Frey, Robert Luxenhofer","doi":"10.1002/marc.202500781","DOIUrl":"https://doi.org/10.1002/marc.202500781","url":null,"abstract":"<p><p>Polyethylene glycol (PEG) plays a central role in nanomedicine, providing essential properties such as the stealth effect. However, the emergence of anti-PEG antibodies (APAs) increasingly undermines these benefits, raising concerns about safety and efficiency. This creates an urgent need for PEG alternatives. Randomized PEG (rPEG) represents a conceptually new strategy that preserves the PEG-like structure and performance while markedly reducing antigenicity. In this work, rPEG is employed as a non-antigenic A-block in ABA-type polymeric micelles (PMs). To enhance drug loading capacity beyond conventional PMs, the hydrophobic middle block is composed of poly(2-phenyl-2-oxazine) (PPheOzi). rPEG is synthesized by anionic ring-opening polymerization, PPheOzi by cationic ring-opening polymerization, and the combined rPEG-b-PPheOzi-b-rPEG triblock copolymers are linked via copper-catalyzed azide-alkyne cycloaddition. The formulations exhibit a distinct correlation between the solubilization of Efavirenz and the systematically varied rPEG composition, ranging from outstanding to moderate micelle drug loading capacities. A fundamental preclinical safety profile was established through investigations in murine fibroblasts and human peripheral blood mononuclear cells (PBMCs). Competitive enzyme-linked immunosorbent assays (ELISA) revealed a pronounced reduction in APA affinity in comparison to PEG. Taken together, the synergistic combination of rPEG and PPheOzi establishes a non-antigenic micellar platform capable of achieving high drug loadings.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00781"},"PeriodicalIF":4.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145825388","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Dalila Khlaifia, Mourad Chemek, Ahmed Said Salwa, Kamel Alimi
The development of non-fullerene acceptors (NFAs) has driven significant advancements in organic solar cells (OSCs), resulting in power conversion efficiencies (PCEs) approaching 20% and positioning OSCs for practical applications. Notably, the recently introduced fused-ring A-DA'D-A type NFAs, especially those called Y-series NFAs, have propelled the field forward due to their strong near-infrared (NIR) absorption, adaptable structural features, and efficient molecular stacking, which collectively enhance charge transfer, minimize energy losses, and improve OSC performance. This review first summarizes the progression of Y-series NFAs from Y1 to the epoch-making acceptor Y6. Recent advances in fused-ring A-DA'D-A type NFAs are then discussed, with a focus on design strategies that modify structural parameters, such as side-chains, central cores, end-capping groups, and π-spacers. The advantages of each NFA are analyzed in relation to their corresponding polymer donors. The influence of molecular structure and optoelectronic properties of NFAs on the morphology of the donor/acceptor (D/A) active layer, charge transfer dynamics, and device performance is examined. Finally, the review identifies current challenges and outlines future directions for the development of Y-series NFAs in OSCs.
非富勒烯受体(nfa)的发展推动了有机太阳能电池(OSCs)的重大进步,导致功率转换效率(pce)接近20%,为OSCs的实际应用奠定了基础。值得注意的是,最近推出的熔环A-DA'D-A型nfa,特别是y系列nfa,由于其强大的近红外(NIR)吸收,适应性强的结构特征和高效的分子堆叠,共同增强了电荷转移,最大限度地减少了能量损失,并提高了OSC性能,推动了该领域的发展。本文首先综述了y系nfa从Y1到划时代受体Y6的进展。然后讨论了融合环a - da 'D-A型nfa的最新进展,重点讨论了修改结构参数的设计策略,如侧链、中心芯、端盖群和π-间隔器。分析了每种NFA的优点及其相应的聚合物供体。研究了nfa的分子结构和光电性能对供体/受体(D/A)活性层形貌、电荷转移动力学和器件性能的影响。最后,本文确定了osc中y系列nfa的当前挑战和未来发展方向。
{"title":"Epoch-Making Design Strategies for High-Efficiency Fused-Ring A-DA'D-A Type Non-Fullerene Acceptors in Organic Solar Cells.","authors":"Dalila Khlaifia, Mourad Chemek, Ahmed Said Salwa, Kamel Alimi","doi":"10.1002/marc.202500691","DOIUrl":"https://doi.org/10.1002/marc.202500691","url":null,"abstract":"<p><p>The development of non-fullerene acceptors (NFAs) has driven significant advancements in organic solar cells (OSCs), resulting in power conversion efficiencies (PCEs) approaching 20% and positioning OSCs for practical applications. Notably, the recently introduced fused-ring A-DA'D-A type NFAs, especially those called Y-series NFAs, have propelled the field forward due to their strong near-infrared (NIR) absorption, adaptable structural features, and efficient molecular stacking, which collectively enhance charge transfer, minimize energy losses, and improve OSC performance. This review first summarizes the progression of Y-series NFAs from Y1 to the epoch-making acceptor Y6. Recent advances in fused-ring A-DA'D-A type NFAs are then discussed, with a focus on design strategies that modify structural parameters, such as side-chains, central cores, end-capping groups, and π-spacers. The advantages of each NFA are analyzed in relation to their corresponding polymer donors. The influence of molecular structure and optoelectronic properties of NFAs on the morphology of the donor/acceptor (D/A) active layer, charge transfer dynamics, and device performance is examined. Finally, the review identifies current challenges and outlines future directions for the development of Y-series NFAs in OSCs.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00691"},"PeriodicalIF":4.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145825444","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Paulo Victor Zanotto, Elizabeth Grillo Fernandes, Vitor L Martins
The development of polymer electrolytes is a promising strategy for increasing the safety and performance of lithium batteries. In particular, gel polymer electrolytes (GPEs) are closest to replacing conventional liquid electrolytes due to their properties from the incorporation of plasticizers and conductors into polymers. One family of these compounds, ionic liquids (IL), has the ideal range of properties for reducing the risk of fire, leaks, and toxic by-products. In this work, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer was used to synthesize a GPE with lithium salt and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (IL), evaluating the effect of different solvents on the final properties of the material, such as thermal stability, crystallinity, microstructure and conductivity. The addition of IL was responsible for a reduction in the crystallinity of PVDF-HFP from an average of 31% to 11%, and a diminution in its thermal stability (T2%) from 435°C to 350°C. Membrane microstructure was dependent on the solvent used, ranging from completely uniform with acetone to granular with dimethylformamide or dimethylacetamide. The dimethylacetamide electrolyte had the highest conductivity (0.43 mS cm-1), while the N-methylpyrrolidone electrolyte showed better interaction with metallic lithium.
聚合物电解质的开发是提高锂电池安全性和性能的一种很有前途的策略。特别是凝胶聚合物电解质(gpe),由于其在聚合物中掺入增塑剂和导体的特性,最接近于取代传统的液体电解质。这些化合物中的一个家族,离子液体(IL),具有理想的性能范围,可降低火灾,泄漏和有毒副产品的风险。本文以聚偏氟乙烯-共六氟丙烯(PVDF-HFP)共聚物为原料,用锂盐和1-丁基-1-甲基吡啶二(三氟甲基磺酰基)亚胺(IL)合成GPE,考察了不同溶剂对材料最终性能的影响,如热稳定性、结晶度、微观结构和电导率。IL的加入导致PVDF-HFP的结晶度从平均31%降低到11%,其热稳定性(T2%)从435℃降低到350℃。膜的微观结构取决于所使用的溶剂,从丙酮完全均匀到二甲基甲酰胺或二甲基乙酰胺颗粒状。二甲基乙酰胺电解质的电导率最高(0.43 mS cm-1),而n -甲基吡咯烷酮电解质与金属锂的相互作用更好。
{"title":"Study of Solvent Effect on PVDF-HFP Gel Polymer Electrolyte Containing Ionic Liquid Pyr<sub>1,4</sub>TFSI for Lithium Batteries Application.","authors":"Paulo Victor Zanotto, Elizabeth Grillo Fernandes, Vitor L Martins","doi":"10.1002/marc.202500767","DOIUrl":"https://doi.org/10.1002/marc.202500767","url":null,"abstract":"<p><p>The development of polymer electrolytes is a promising strategy for increasing the safety and performance of lithium batteries. In particular, gel polymer electrolytes (GPEs) are closest to replacing conventional liquid electrolytes due to their properties from the incorporation of plasticizers and conductors into polymers. One family of these compounds, ionic liquids (IL), has the ideal range of properties for reducing the risk of fire, leaks, and toxic by-products. In this work, poly(vinylidene fluoride-co-hexafluoropropylene) (PVDF-HFP) copolymer was used to synthesize a GPE with lithium salt and 1-butyl-1-methylpyrrolidinium bis(trifluoromethylsulfonyl)imide (IL), evaluating the effect of different solvents on the final properties of the material, such as thermal stability, crystallinity, microstructure and conductivity. The addition of IL was responsible for a reduction in the crystallinity of PVDF-HFP from an average of 31% to 11%, and a diminution in its thermal stability (T<sub>2%</sub>) from 435°C to 350°C. Membrane microstructure was dependent on the solvent used, ranging from completely uniform with acetone to granular with dimethylformamide or dimethylacetamide. The dimethylacetamide electrolyte had the highest conductivity (0.43 mS cm<sup>-1</sup>), while the N-methylpyrrolidone electrolyte showed better interaction with metallic lithium.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00767"},"PeriodicalIF":4.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145825397","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Redoy Gazi Shuvo, Andreas F Thünemann, Zviadi Katcharava, Anja Marinow, Richard Hoppe, Georg Woltersdorf, Mengxue Du, René Androsch, Juliana Martins de Souza E Silva, Karsten Busse, Wolfgang H Binder
Detecting nanoplastic particles in environmental samples and biological tissues remains a significant challenge, especially in view of newly emerging polymers, not yet commercially exploited. Fluorescent labeling provides a tagging strategy to overcome this limitation by reducing the detection limit of individual particles, especially for small-sized particles. We present a method for producing labeled nanoparticles (NP/MP) of poly(ethylene terephthalate) (PET) and poly(ethylene furanoate) (PEF), tagged with Alexa Fluor 633 or Alexa Fluor 647. Our preparations used mechanical grinding or solvent-based approaches (confined impinging jet mixing, ((CIJ, precipitation), generating particles with hydrodynamic diameters of 200-700 nm, displaying long-term stability in water of up to 57 days. Stable suspensions with concentrations of the particles ranging from 10 µg/mL (surfactant-free, by solvent mixing) to 5.88 mg/mL (precipitation, containing surfactant) were generated with zeta-potentials from -5 to -50 mV. Characterization of the nanoparticles by SEC, DSC, and XRD showed no significant changes in molecular weight, thermal behavior, or crystallinity via the solvent-based methods, compared to the pristine polymer, highlighting their suitability for producing standardized nanoparticle dispersions. Fluorescence spectroscopy of the Alexa-dye-labeled particles confirmed the successful incorporation of the Alexa dyes, so improving monitoring of their biological profiles of the PEF-MP/NPs. s-SNOM (near field imaging) could identify individual PEF-particles sized ∼200 nm by direct imaging.
{"title":"Generating Tagged Micro- and Nanoparticles of Poly(ethylene furanoate) and Poly(ethylene terephthalate) as Reference Materials.","authors":"Redoy Gazi Shuvo, Andreas F Thünemann, Zviadi Katcharava, Anja Marinow, Richard Hoppe, Georg Woltersdorf, Mengxue Du, René Androsch, Juliana Martins de Souza E Silva, Karsten Busse, Wolfgang H Binder","doi":"10.1002/marc.202500839","DOIUrl":"https://doi.org/10.1002/marc.202500839","url":null,"abstract":"<p><p>Detecting nanoplastic particles in environmental samples and biological tissues remains a significant challenge, especially in view of newly emerging polymers, not yet commercially exploited. Fluorescent labeling provides a tagging strategy to overcome this limitation by reducing the detection limit of individual particles, especially for small-sized particles. We present a method for producing labeled nanoparticles (NP/MP) of poly(ethylene terephthalate) (PET) and poly(ethylene furanoate) (PEF), tagged with Alexa Fluor 633 or Alexa Fluor 647. Our preparations used mechanical grinding or solvent-based approaches (confined impinging jet mixing, ((CIJ, precipitation), generating particles with hydrodynamic diameters of 200-700 nm, displaying long-term stability in water of up to 57 days. Stable suspensions with concentrations of the particles ranging from 10 µg/mL (surfactant-free, by solvent mixing) to 5.88 mg/mL (precipitation, containing surfactant) were generated with zeta-potentials from -5 to -50 mV. Characterization of the nanoparticles by SEC, DSC, and XRD showed no significant changes in molecular weight, thermal behavior, or crystallinity via the solvent-based methods, compared to the pristine polymer, highlighting their suitability for producing standardized nanoparticle dispersions. Fluorescence spectroscopy of the Alexa-dye-labeled particles confirmed the successful incorporation of the Alexa dyes, so improving monitoring of their biological profiles of the PEF-MP/NPs. s-SNOM (near field imaging) could identify individual PEF-particles sized ∼200 nm by direct imaging.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00839"},"PeriodicalIF":4.3,"publicationDate":"2025-12-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145825410","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Peng Dong, Jian-Bin Tang, Han Shang, Lei Li, Hao Lin, Gan-Ji Zhong, Zhong-Ming Li
The influence of molecular chain entanglement on the mechanical performance of polycarbonate (PC) at superhigh strain rates has been investigated, which is valuable for its safety applications like window glazing. The mechanical testing results across a wide strain rate range (0.01-100 s-1) show that toughness increases with strain rate, but significant deterioration of stiffness and toughness occurs at 100 s-1. This phenomenon is, for the first time, observed in real time using digital image correlation (DIC), revealing severe stress concentration and strain localization at 100 s-1. Nevertheless, we find this deterioration is significantly suppressed by the high entanglement density. It strengthens the strain hardening regime and dynamic mechanical analysis (DMA) is showing that both loss modulus and tan δ values increase with entanglement density in the β-relaxation region, indicating enhanced energy dissipation, which may be the underlying origin of the improved ability to resist deformation. This work is providing fundamental insights into tailoring entanglement networks to suppress energy absorption deterioration under extreme deformation conditions.
{"title":"Entanglement Network Suppresses Toughness Deterioration in Polycarbonate at Superhigh Strain Rates.","authors":"Peng Dong, Jian-Bin Tang, Han Shang, Lei Li, Hao Lin, Gan-Ji Zhong, Zhong-Ming Li","doi":"10.1002/marc.202500940","DOIUrl":"https://doi.org/10.1002/marc.202500940","url":null,"abstract":"<p><p>The influence of molecular chain entanglement on the mechanical performance of polycarbonate (PC) at superhigh strain rates has been investigated, which is valuable for its safety applications like window glazing. The mechanical testing results across a wide strain rate range (0.01-100 s<sup>-1</sup>) show that toughness increases with strain rate, but significant deterioration of stiffness and toughness occurs at 100 s<sup>-1</sup>. This phenomenon is, for the first time, observed in real time using digital image correlation (DIC), revealing severe stress concentration and strain localization at 100 s<sup>-1</sup>. Nevertheless, we find this deterioration is significantly suppressed by the high entanglement density. It strengthens the strain hardening regime and dynamic mechanical analysis (DMA) is showing that both loss modulus and tan δ values increase with entanglement density in the β-relaxation region, indicating enhanced energy dissipation, which may be the underlying origin of the improved ability to resist deformation. This work is providing fundamental insights into tailoring entanglement networks to suppress energy absorption deterioration under extreme deformation conditions.</p>","PeriodicalId":205,"journal":{"name":"Macromolecular Rapid Communications","volume":" ","pages":"e00940"},"PeriodicalIF":4.3,"publicationDate":"2025-12-22","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145809001","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}