Pub Date : 2026-03-01Epub Date: 2026-01-14DOI: 10.1016/j.giant.2026.100383
Dominik Hense , Lana Molnar , Andreas Bernkop-Schnürch , Oliver I. Strube
The blood clotting protein fibrinogen is known for its excellent biocompatibility and cell adhesion. The usual strategy to use its full potential is to create fibers and/or hydrogels out of it, most commonly enzymatically in form of fibrin. There are, however, many pathways to create fibrinogen-based materials via enzyme-free approaches. In this study, we investigate these possibilities even further and present a temperature-induced method to obtain enzyme-free fibrous hydrogels from a precursor within 30 min. The keys to create these gels are the addition of calcium salts and a defined temperature program. Successful gelation first requires an incubation period at 37 °C for approximately 10 h. This leads to the formation of a ready-to-gel precursor, which remains stable for 2.5 days when the temperature is unchanged. When lowering the temperature to 25 – 10 °C, the mixture irreversibly gels within 30 min. If the incubation period is, however, canceled earlier, the precursor will not gel at all. Additionally, this process succeeds only with Ca2+ ions; if Mg2+ is used instead, the solution remains unchanged while the addition of Sr2+ leads to amorphous precipitation over time. In this study, this remarkable process is characterized regarding optimal reaction conditions by means of scanning electron microscopy, rheology, and dynamic light scattering.
{"title":"Temperature-induced fibrillogenesis and gelation of fibrinogen mediated by calcium salts","authors":"Dominik Hense , Lana Molnar , Andreas Bernkop-Schnürch , Oliver I. Strube","doi":"10.1016/j.giant.2026.100383","DOIUrl":"10.1016/j.giant.2026.100383","url":null,"abstract":"<div><div>The blood clotting protein fibrinogen is known for its excellent biocompatibility and cell adhesion. The usual strategy to use its full potential is to create fibers and/or hydrogels out of it, most commonly enzymatically in form of fibrin. There are, however, many pathways to create fibrinogen-based materials via enzyme-free approaches. In this study, we investigate these possibilities even further and present a temperature-induced method to obtain enzyme-free fibrous hydrogels from a precursor within 30 min. The keys to create these gels are the addition of calcium salts and a defined temperature program. Successful gelation first requires an incubation period at 37 °C for approximately 10 h. This leads to the formation of a ready-to-gel precursor, which remains stable for 2.5 days when the temperature is unchanged. When lowering the temperature to 25 – 10 °C, the mixture irreversibly gels within 30 min. If the incubation period is, however, canceled earlier, the precursor will not gel at all. Additionally, this process succeeds only with Ca<sup>2+</sup> ions; if Mg<sup>2+</sup> is used instead, the solution remains unchanged while the addition of Sr<sup>2+</sup> leads to amorphous precipitation over time. In this study, this remarkable process is characterized regarding optimal reaction conditions by means of scanning electron microscopy, rheology, and dynamic light scattering.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"27 ","pages":"Article 100383"},"PeriodicalIF":4.9,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146038815","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-02-09DOI: 10.1016/j.giant.2026.100385
Yong Liu , Shi Hao Zheng , Fang Zhou , Hao Yuan
With an increasing focus worldwide on protecting the environment and developing in a sustainable way. Developing halogen-free, environmentally benign flame retardants is of critical relevance. To enhance the fire-safety performance of epoxy resins while simultaneously mitigating their environmental impacts. The bio-derived flame retardant DOPR was prepared in a single-step, one-pot process using resveratrol and DOPO as the key starting materials. The resulting product was subsequently incorporated into an epoxy matrix to obtain EP/DOPR composites. Despite encompassing only 0.35 wt % phosphorus, the EP/5DOPR composite exhibited an increased LOI of 28.19 % and secured the top-tier V-0 grade in the UL-94 flammability evaluation. Compared with neat EP, its pHRR, THR and TSP were lowered by nearly 15.65 %, 33.13 % and 9.62 %, respectively. Furthermore, the residual char yield of the composite was improved from 14.78 % to 17.88 %. The mechanical properties of the composite material were enhanced following the addition of 3wt % and 5wt % flame retardant, indicating a more favourable balance between flame retardancy efficiency and additive loading. The relevant research findings may provide a potential fundamental approach for the application of bio-based flame retardants to enhance the high performance of epoxy resins.
{"title":"Phosphorus-containing resveratrol-based flame retardants derived from esterification reactions for flame-retardant epoxy resins","authors":"Yong Liu , Shi Hao Zheng , Fang Zhou , Hao Yuan","doi":"10.1016/j.giant.2026.100385","DOIUrl":"10.1016/j.giant.2026.100385","url":null,"abstract":"<div><div>With an increasing focus worldwide on protecting the environment and developing in a sustainable way. Developing halogen-free, environmentally benign flame retardants is of critical relevance. To enhance the fire-safety performance of epoxy resins while simultaneously mitigating their environmental impacts. The bio-derived flame retardant DOPR was prepared in a single-step, one-pot process using resveratrol and DOPO as the key starting materials. The resulting product was subsequently incorporated into an epoxy matrix to obtain EP/DOPR composites. Despite encompassing only 0.35 wt % phosphorus, the EP/5DOPR composite exhibited an increased LOI of 28.19 % and secured the top-tier V-0 grade in the UL-94 flammability evaluation. Compared with neat EP, its pHRR, THR and TSP were lowered by nearly 15.65 %, 33.13 % and 9.62 %, respectively. Furthermore, the residual char yield of the composite was improved from 14.78 % to 17.88 %. The mechanical properties of the composite material were enhanced following the addition of 3wt % and 5wt % flame retardant, indicating a more favourable balance between flame retardancy efficiency and additive loading. The relevant research findings may provide a potential fundamental approach for the application of bio-based flame retardants to enhance the high performance of epoxy resins.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"27 ","pages":"Article 100385"},"PeriodicalIF":4.9,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"147397553","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2025-12-24DOI: 10.1016/j.giant.2025.100381
Tianke Chen , Yue Li , Guanchun Rui , Yuta Makita , Toshikazu Miyoshi , Eric Baer , Lei Zhu
Biaxially oriented polypropylene (BOPP) film capacitors have become the benchmark technology for DC-link and power electronic applications in electric vehicles due to their ultralow loss, high ripple current, high dielectric breakdown strength, and long operational lifetime. However, their maximum operating temperature is restricted to 85°C, a limitation that constrains performance in demanding power electronic environments (∼140°C). The origin of this temperature ceiling has remained insufficiently understood. In this work, we investigate the structure-property relationships that govern the breakdown strength and lifetime of BOPP films at elevated temperatures. Comprehensive analyses, including both structure and dielectric insulation characterizations, were performed to correlate microstructural transitions with dielectric performance. The results revealed that the αc relaxation of isotactic polypropylene around 90°C was the critical factor responsible for the deterioration of breakdown strength (and thus reduced lifetime). Because of 120° helical jumps at crystalline-amorphous interfaces, the αc relaxation lowered modulus, diminished the rigid fraction, and enhanced homocharge injection. Consequently, breakdown strength decreased sharply above 85°C. These findings provide a mechanistic explanation for the long-recognized 85°C rating of BOPP film capacitors. The insights gained not only clarify the intrinsic thermal limitation of BOPP but also point toward rational design strategies for high-temperature polymer dielectrics, such as advanced polyolefins, capable of extending the dielectric performance toward 150°C operation in next-generation electric vehicle power electronics.
{"title":"Why is the temperature rating of biaxially oriented polypropylene film capacitors limited to 85°C?","authors":"Tianke Chen , Yue Li , Guanchun Rui , Yuta Makita , Toshikazu Miyoshi , Eric Baer , Lei Zhu","doi":"10.1016/j.giant.2025.100381","DOIUrl":"10.1016/j.giant.2025.100381","url":null,"abstract":"<div><div>Biaxially oriented polypropylene (BOPP) film capacitors have become the benchmark technology for DC-link and power electronic applications in electric vehicles due to their ultralow loss, high ripple current, high dielectric breakdown strength, and long operational lifetime. However, their maximum operating temperature is restricted to 85°C, a limitation that constrains performance in demanding power electronic environments (∼140°C). The origin of this temperature ceiling has remained insufficiently understood. In this work, we investigate the structure-property relationships that govern the breakdown strength and lifetime of BOPP films at elevated temperatures. Comprehensive analyses, including both structure and dielectric insulation characterizations, were performed to correlate microstructural transitions with dielectric performance. The results revealed that the α<sub>c</sub> relaxation of isotactic polypropylene around 90°C was the critical factor responsible for the deterioration of breakdown strength (and thus reduced lifetime). Because of 120° helical jumps at crystalline-amorphous interfaces, the α<sub>c</sub> relaxation lowered modulus, diminished the rigid fraction, and enhanced homocharge injection. Consequently, breakdown strength decreased sharply above 85°C. These findings provide a mechanistic explanation for the long-recognized 85°C rating of BOPP film capacitors. The insights gained not only clarify the intrinsic thermal limitation of BOPP but also point toward rational design strategies for high-temperature polymer dielectrics, such as advanced polyolefins, capable of extending the dielectric performance toward 150°C operation in next-generation electric vehicle power electronics.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"27 ","pages":"Article 100381"},"PeriodicalIF":4.9,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145897882","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2026-01-29DOI: 10.1016/j.giant.2026.100384
Xuechun Cui , Wei Liu , Zonglin Yang , Jinman Zhou , Xianyong Lu
Multifunctional polymer microspheres are indispensable in catalysis, separation, and drug delivery, yet their scalable fabrication is often hampered by low solvent recovery, narrow synthetic scope, and poor kinetic control. These limitations not only lead to solvent wastage and environmental burdens, but also cause undesirable outcomes such as uncontrolled polymerization and broadened particle size distributions. Herein, we report a green, sustainable, and kinetically controllable precipitation polymerization strategy that couples rotary evaporation with a closed-loop solvent management system. This platform enables the efficient synthesis of polymer microspheres bearing diverse functional groups, thereby broadening their applicability across multiple application scenarios. The process achieves a solvent recovery rate of up to 95.2%, affords precise regulation of crosslinking density (0.05–0.80), and simultaneously improves both monodispersity and yield (up to 68.7% at high crosslinking degrees). Notably, the recovered acetonitrile can be directly reused without additional purification, underscoring the robustness of the solvent recycling scheme. Overall, this scalable approach integrates kinetic control, functional versatility, and solvent circularity into a unified process, providing a practical route to high-quality multifunctional polymer microspheres while minimizing solvent waste and obviating complex post-treatment steps.
{"title":"Closed-Loop green precipitation polymerization for kinetically controlled multifunctional polymer microspheres","authors":"Xuechun Cui , Wei Liu , Zonglin Yang , Jinman Zhou , Xianyong Lu","doi":"10.1016/j.giant.2026.100384","DOIUrl":"10.1016/j.giant.2026.100384","url":null,"abstract":"<div><div>Multifunctional polymer microspheres are indispensable in catalysis, separation, and drug delivery, yet their scalable fabrication is often hampered by low solvent recovery, narrow synthetic scope, and poor kinetic control. These limitations not only lead to solvent wastage and environmental burdens, but also cause undesirable outcomes such as uncontrolled polymerization and broadened particle size distributions. Herein, we report a green, sustainable, and kinetically controllable precipitation polymerization strategy that couples rotary evaporation with a closed-loop solvent management system. This platform enables the efficient synthesis of polymer microspheres bearing diverse functional groups, thereby broadening their applicability across multiple application scenarios. The process achieves a solvent recovery rate of up to 95.2%, affords precise regulation of crosslinking density (0.05–0.80), and simultaneously improves both monodispersity and yield (up to 68.7% at high crosslinking degrees). Notably, the recovered acetonitrile can be directly reused without additional purification, underscoring the robustness of the solvent recycling scheme. Overall, this scalable approach integrates kinetic control, functional versatility, and solvent circularity into a unified process, providing a practical route to high-quality multifunctional polymer microspheres while minimizing solvent waste and obviating complex post-treatment steps.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"27 ","pages":"Article 100384"},"PeriodicalIF":4.9,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"146189467","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2026-03-01Epub Date: 2025-12-31DOI: 10.1016/j.giant.2025.100382
Hangyu Wen , Yifei Zhong , Jianhua Pang , Kuanyi Wang , Guang Wei , Zhenming Yang , Songrui Wei
Two-dimensional van der Waals heterojunctions can significantly boost gas-sensing performance through interfacial synergy, surpassing the limits of individual constituents. Based on first-principles calculations, this study systematically explores the potential of a vertical heterojunction composed of novel Janus MoTeSe and InN for gas-sensing applications. Binding-energy calculations and AIMD simulations identify AB-MoIn-stacked MoTeSe/InN as the most stable configuration, and the adsorption behavior and sensing mechanism of the heterojunction toward Cl₂, NO₂, NH₃, NO, SO₂, and H₂S are investigated comprehensively. The results reveal that the heterojunction markedly enhances adsorption of Cl₂, NO₂, NO, and H₂S, with adsorption energies of -0.880 eV and -0.961 eV for Cl₂ and NO₂, respectively, accompanied by substantial charge transfer. Electronic-structure analysis elucidates the key sensing mechanisms: adsorption of NO₂ (TIn site) and NO metallizes the system, greatly increasing electrical conductivity; adsorption of Cl₂ (TN site) and SO₂ increases the bandgap by approximately 47.3 % and 49.4 %, respectively; notably, NO₂ adsorption on the TTe site also induces magnetism. Further evaluation of sensitivity and recovery time indicates that the heterojunction exhibits both high sensitivity and good reversibility toward NO₂ and Cl₂—for example, the room-temperature recovery time for NO₂ on the TTe site is only 0.36 ms. This work clarifies the atomic-scale gas-sensing mechanism of MoTeSe/InN heterostructures, especially for Cl₂ and NO₂, and provides a solid theoretical basis for their application as high-performance, recyclable gas-sensor candidates.
{"title":"MoTeSe/InN heterostructures for gas sensors: a first-principles study","authors":"Hangyu Wen , Yifei Zhong , Jianhua Pang , Kuanyi Wang , Guang Wei , Zhenming Yang , Songrui Wei","doi":"10.1016/j.giant.2025.100382","DOIUrl":"10.1016/j.giant.2025.100382","url":null,"abstract":"<div><div>Two-dimensional van der Waals heterojunctions can significantly boost gas-sensing performance through interfacial synergy, surpassing the limits of individual constituents. Based on first-principles calculations, this study systematically explores the potential of a vertical heterojunction composed of novel Janus MoTeSe and InN for gas-sensing applications. Binding-energy calculations and AIMD simulations identify AB-MoIn-stacked MoTeSe/InN as the most stable configuration, and the adsorption behavior and sensing mechanism of the heterojunction toward Cl₂, NO₂, NH₃, NO, SO₂, and H₂S are investigated comprehensively. The results reveal that the heterojunction markedly enhances adsorption of Cl₂, NO₂, NO, and H₂S, with adsorption energies of -0.880 eV and -0.961 eV for Cl₂ and NO₂, respectively, accompanied by substantial charge transfer. Electronic-structure analysis elucidates the key sensing mechanisms: adsorption of NO₂ (T<sub>In</sub> site) and NO metallizes the system, greatly increasing electrical conductivity; adsorption of Cl₂ (T<sub>N</sub> site) and SO₂ increases the bandgap by approximately 47.3 % and 49.4 %, respectively; notably, NO₂ adsorption on the T<sub>Te</sub> site also induces magnetism. Further evaluation of sensitivity and recovery time indicates that the heterojunction exhibits both high sensitivity and good reversibility toward NO₂ and Cl₂—for example, the room-temperature recovery time for NO₂ on the T<sub>Te</sub> site is only 0.36 ms. This work clarifies the atomic-scale gas-sensing mechanism of MoTeSe/InN heterostructures, especially for Cl₂ and NO₂, and provides a solid theoretical basis for their application as high-performance, recyclable gas-sensor candidates.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"27 ","pages":"Article 100382"},"PeriodicalIF":4.9,"publicationDate":"2026-03-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145979284","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-09-12DOI: 10.1016/j.giant.2025.100373
Jingnan Song , Suyan Wang , Wutong Zhao , Bonan Hao , Yecheng Zou , Xing Li , Xuefei Wu , Feng Liu , Yongming Zhang
The self-assembly behavior of short-side-chain perfluorosulfonic acid (SSC-PFSA) dispersions plays a pivotal role in governing the morphology and performance of proton exchange membranes (PEMs). We explored solvent-modulated structural transitions of SSC-PFSA dispersions using combinatory characterization techniques. It is seen that in high-dielectric environment (25 wt% ethanol), the SSC-PFSA chain adopts rigid rod-like assemblies with locally ordered alignment due to electrostatic repulsion and surface polarization. Lowering the dielectric constant (50 wt% ethanol) induces a semi-flexible configuration with approximately 20 % axial compression, and dispersing heterogeneity is observed due to inter-particle association. Upon reaching 75 wt% ethanol conditions, the rod-like assembly is elongated, loosened, and more disordered. The solvent environment plays an important role in determining the dispersion heterogeneity. More ethanol content lowers the dielectric constant, which reduces acidic dissociation and leads to localized assembly association. This work elucidates a fundamental understanding of the dynamic interplay between backbone solubility and electrostatic interactions in governing the PFSA assembly under different solvent environment. These detailed multi-length-scale nanostructures are key in determining the morphology and performance of PEM, which needs to clearly investigated before PEM fabrication.
{"title":"Elucidating the solvent-modulated self-assembly nanostructures of high ion exchange capacity short-side-chain perfluorosulfonic acid dispersions","authors":"Jingnan Song , Suyan Wang , Wutong Zhao , Bonan Hao , Yecheng Zou , Xing Li , Xuefei Wu , Feng Liu , Yongming Zhang","doi":"10.1016/j.giant.2025.100373","DOIUrl":"10.1016/j.giant.2025.100373","url":null,"abstract":"<div><div>The self-assembly behavior of short-side-chain perfluorosulfonic acid (SSC-PFSA) dispersions plays a pivotal role in governing the morphology and performance of proton exchange membranes (PEMs). We explored solvent-modulated structural transitions of SSC-PFSA dispersions using combinatory characterization techniques. It is seen that in high-dielectric environment (25 wt% ethanol), the SSC-PFSA chain adopts rigid rod-like assemblies with locally ordered alignment due to electrostatic repulsion and surface polarization. Lowering the dielectric constant (50 wt% ethanol) induces a semi-flexible configuration with approximately 20 % axial compression, and dispersing heterogeneity is observed due to inter-particle association. Upon reaching 75 wt% ethanol conditions, the rod-like assembly is elongated, loosened, and more disordered. The solvent environment plays an important role in determining the dispersion heterogeneity. More ethanol content lowers the dielectric constant, which reduces acidic dissociation and leads to localized assembly association. This work elucidates a fundamental understanding of the dynamic interplay between backbone solubility and electrostatic interactions in governing the PFSA assembly under different solvent environment. These detailed multi-length-scale nanostructures are key in determining the morphology and performance of PEM, which needs to clearly investigated before PEM fabrication.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"26 ","pages":"Article 100373"},"PeriodicalIF":4.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145158982","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-10-16DOI: 10.1016/j.giant.2025.100377
Lin Wang, Zitai Jiang
Ultrasensitive detection at the single-molecule level is crucial for advancing biomedical diagnostics, environmental monitoring, and chemical synthesis. Among various strategies, single-molecule junctions (SMJs) stand out as they convert molecular-scale events into detectable electrical signals, offering a versatile and sensitive platform for real-time, label-free, and non-destructive sensing with single-molecule resolution. This review provides an overview of the primary SMJ measurement techniques, with a particular focus on the fundamental mechanisms driving SMJ-based sensing, including the molecular chemical structure influenced by the local environment, supramolecular interactions and molecule-electrode interface. We also highlight recent progress in utilizing SMJs for monitoring chemical reactions, chiral recognition, and biomedical diagnostics. Finally, we have analyzed the current challenges in single-molecule electrical detection in terms of signal reliability, sensitivity, and selectivity, offering corresponding solutions for each to provide valuable insights for designing more effective detection systems.
{"title":"Single-molecule junctions for ultrasensitive detection: fundamental mechanisms and cross-field applications","authors":"Lin Wang, Zitai Jiang","doi":"10.1016/j.giant.2025.100377","DOIUrl":"10.1016/j.giant.2025.100377","url":null,"abstract":"<div><div>Ultrasensitive detection at the single-molecule level is crucial for advancing biomedical diagnostics, environmental monitoring, and chemical synthesis. Among various strategies, single-molecule junctions (SMJs) stand out as they convert molecular-scale events into detectable electrical signals, offering a versatile and sensitive platform for real-time, label-free, and non-destructive sensing with single-molecule resolution. This review provides an overview of the primary SMJ measurement techniques, with a particular focus on the fundamental mechanisms driving SMJ-based sensing, including the molecular chemical structure influenced by the local environment, supramolecular interactions and molecule-electrode interface. We also highlight recent progress in utilizing SMJs for monitoring chemical reactions, chiral recognition, and biomedical diagnostics. Finally, we have analyzed the current challenges in single-molecule electrical detection in terms of signal reliability, sensitivity, and selectivity, offering corresponding solutions for each to provide valuable insights for designing more effective detection systems.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"26 ","pages":"Article 100377"},"PeriodicalIF":4.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145362864","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-10-15DOI: 10.1016/j.giant.2025.100376
Hengzhi You, Weiwei Wu, Chengyang Hong, Gengxin Liu, Hao Liu
The field of polymer science has witnessed a paradigm shift from traditional polymers to giant molecules, which possess well-defined structures and discrete molecular weights. These giant molecules, constructed from precisely synthesized building blocks, offer unique opportunities to explore the relationship between molecular architecture and macroscopic properties. This study investigates the microstructure-modulated dynamics of main-chain giant molecules constructed from double-decker silsesquioxane (DDSQ) and polyhedral oligomeric silsesquioxane (POSS) building blocks. A series of giant molecules with exact chain lengths and tunable chain ends were synthesized using thiol-maleimide Michael addition reactions and an iterative "deprotection-addition" strategy. Structural and thermal analysis revealed that homopolymers and vinyl-terminated molecules exhibited amorphous features in their melt states, while carboxylic acid-terminated molecules showed evidence of microphase separation. Rheological characterization demonstrated that homopolymers and vinyl-terminated molecules exhibited unentangled, liquid-like dynamics, whereas carboxylic acid-terminated molecules displayed Zimm-like melt characteristics or pronounced elastic plateau modulus at low frequencies, indicating the formation of physically cross-linked network structures stabilized by intermolecular interactions. This research highlights that chain length and chain-end chemistry significantly govern the hierarchical assembly and viscoelastic behavior of main-chain giant molecules, offering a powerful strategy for engineering novel nanomaterials with tailored mechanical properties through precise molecular design and chain-end functionalization.
{"title":"Microstructure modulated dynamics of main-chain giant molecules with exact chain-length and tunable chemical interaction","authors":"Hengzhi You, Weiwei Wu, Chengyang Hong, Gengxin Liu, Hao Liu","doi":"10.1016/j.giant.2025.100376","DOIUrl":"10.1016/j.giant.2025.100376","url":null,"abstract":"<div><div>The field of polymer science has witnessed a paradigm shift from traditional polymers to giant molecules, which possess well-defined structures and discrete molecular weights. These giant molecules, constructed from precisely synthesized building blocks, offer unique opportunities to explore the relationship between molecular architecture and macroscopic properties. This study investigates the microstructure-modulated dynamics of main-chain giant molecules constructed from double-decker silsesquioxane (DDSQ) and polyhedral oligomeric silsesquioxane (POSS) building blocks. A series of giant molecules with exact chain lengths and tunable chain ends were synthesized using thiol-maleimide Michael addition reactions and an iterative \"deprotection-addition\" strategy. Structural and thermal analysis revealed that homopolymers and vinyl-terminated molecules exhibited amorphous features in their melt states, while carboxylic acid-terminated molecules showed evidence of microphase separation. Rheological characterization demonstrated that homopolymers and vinyl-terminated molecules exhibited unentangled, liquid-like dynamics, whereas carboxylic acid-terminated molecules displayed Zimm-like melt characteristics or pronounced elastic plateau modulus at low frequencies, indicating the formation of physically cross-linked network structures stabilized by intermolecular interactions. This research highlights that chain length and chain-end chemistry significantly govern the hierarchical assembly and viscoelastic behavior of main-chain giant molecules, offering a powerful strategy for engineering novel nanomaterials with tailored mechanical properties through precise molecular design and chain-end functionalization.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"26 ","pages":"Article 100376"},"PeriodicalIF":4.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145362865","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
The use of plant extracts for synthesizing nanoparticles has garnered significant attention due to their simplicity, environmental friendliness, and cost-effectiveness. This study synthesized titanium dioxide (titania, TiO2) nanoparticles using Aloe vera extract. Its doping with copper was also investigated to reduce the electron/hole pair recombination rate and improve the photocatalytic activity of titania. Biosynthesized titania nanoparticles were characterized by X-ray diffraction (XRD), Diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). XRD reported the formation of crystals with sizes of 4–7 nm by the Scherrer method and 5–27 nm by the Williamson-Hall method. FE-SEM and TEM analysis showed the formation of spherical particles. Spectroscopic results showed that the addition of the copper ion reduced the band gap energy from 3.10 eV to 2.89 eV. It was observed that, under light, increasing the dopant concentration from 1 % to 3 % resulted in an increase in the bacterial removal rate from 93 % to 96 % and the particulate matter removal rate from 91 % to 94 %. Therefore, Cu-TiO2 nanoparticles biosynthesized with Aloe vera extract exhibited increased photocatalytic and antibacterial activity, which can be utilized for air purification.
{"title":"Air purification and disinfection by biosynthesized Cu-doped TiO2 nanoparticles with Aloe vera extract","authors":"Niloofar Arefipour , Hassan Koohestani , Hedayat Gholami","doi":"10.1016/j.giant.2025.100375","DOIUrl":"10.1016/j.giant.2025.100375","url":null,"abstract":"<div><div>The use of plant extracts for synthesizing nanoparticles has garnered significant attention due to their simplicity, environmental friendliness, and cost-effectiveness. This study synthesized titanium dioxide (titania, TiO<sub>2</sub>) nanoparticles using Aloe vera extract. Its doping with copper was also investigated to reduce the electron/hole pair recombination rate and improve the photocatalytic activity of titania. Biosynthesized titania nanoparticles were characterized by X-ray diffraction (XRD), Diffuse reflectance spectroscopy (DRS), transmission electron microscopy (TEM), and field emission scanning electron microscopy (FE-SEM). XRD reported the formation of crystals with sizes of 4–7 nm by the Scherrer method and 5–27 nm by the Williamson-Hall method. FE-SEM and TEM analysis showed the formation of spherical particles. Spectroscopic results showed that the addition of the copper ion reduced the band gap energy from 3.10 eV to 2.89 eV. It was observed that, under light, increasing the dopant concentration from 1 % to 3 % resulted in an increase in the bacterial removal rate from 93 % to 96 % and the particulate matter removal rate from 91 % to 94 %. Therefore, Cu-TiO<sub>2</sub> nanoparticles biosynthesized with <em>Aloe vera</em> extract exhibited increased photocatalytic and antibacterial activity, which can be utilized for air purification.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"26 ","pages":"Article 100375"},"PeriodicalIF":4.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145221064","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}
Pub Date : 2025-12-01Epub Date: 2025-10-24DOI: 10.1016/j.giant.2025.100378
Jinmiao Ma , Mengmeng Han , Xusen Li , Haoying Liu , Cong Gao , Shipeng Chen , Jie Han
The research of supramolecular chiral catalyst morphology is critically important in asymmetric catalysis, yet current research predominantly focuses on helical architectures, with non-helical systems remaining underexplored. Herein, we present a new type of nanosheet (NS)-like supramolecular chiral catalyst self-assembled from l-threonine-based amphiphilie (L-ThrC16) and Cu(II), which achieves obvious asymmetric catalysis in the Diels-Alder reaction between aza-chalcone and cyclopentadiene (91% yield and 45% ee) despite its non-helical nanostructure. Compared with monomeric counterpart of l-ThrC16Cu(II) catalyst displaying racemic product, the stronger interaction between aza-chalcone and l-ThrC16NS-Cu(II) have been confirmed, which facilitates the chirality transfer from the supramolecular scaffold to aza-chalcone and thereby leading to enantioselectivity. This work not only challenges the conventional paradigm of helical dominance in chiral induction but also establishes a foundation for developing scalable, high-performance non-helical catalysts, thereby expanding the design principles for supramolecular asymmetric synthesis.
{"title":"A non-helical supramolecular chiral catalyst for the asymmetric diels-alder reaction","authors":"Jinmiao Ma , Mengmeng Han , Xusen Li , Haoying Liu , Cong Gao , Shipeng Chen , Jie Han","doi":"10.1016/j.giant.2025.100378","DOIUrl":"10.1016/j.giant.2025.100378","url":null,"abstract":"<div><div>The research of supramolecular chiral catalyst morphology is critically important in asymmetric catalysis, yet current research predominantly focuses on helical architectures, with non-helical systems remaining underexplored. Herein, we present a new type of nanosheet (NS)-like supramolecular chiral catalyst self-assembled from <em><span>l</span></em>-threonine-based amphiphilie (<em>L</em>-ThrC<sub>16</sub>) and Cu(II), which achieves obvious asymmetric catalysis in the Diels-Alder reaction between aza-chalcone and cyclopentadiene (91% yield and 45% ee) despite its non-helical nanostructure. Compared with monomeric counterpart of <em><span>l</span></em>-ThrC<sub>16<img></sub>Cu(II) catalyst displaying racemic product, the stronger interaction between aza-chalcone and <em><span>l</span></em>-ThrC<sub>16<img></sub>NS-Cu(II) have been confirmed, which facilitates the chirality transfer from the supramolecular scaffold to aza-chalcone and thereby leading to enantioselectivity. This work not only challenges the conventional paradigm of helical dominance in chiral induction but also establishes a foundation for developing scalable, high-performance non-helical catalysts, thereby expanding the design principles for supramolecular asymmetric synthesis.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"26 ","pages":"Article 100378"},"PeriodicalIF":4.9,"publicationDate":"2025-12-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"145416311","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}