GIANT最新文献

{"title":"Thermosensitive ferulic acid-modified chitosan gel coatings loaded with selenium nanoparticles for enhanced grape foliar rainfastness and selenium uptake","authors":"Songpo Duan ,&nbsp;Xin Ouyang ,&nbsp;Yingsheng Liu ,&nbsp;Dingyi Shen ,&nbsp;Zhiming Li ,&nbsp;Sijie Song ,&nbsp;Hong Shen","doi":"10.1016/j.giant.2024.100351","DOIUrl":"10.1016/j.giant.2024.100351","url":null,"abstract":"<div><div>Traditional Se (selenium) fertilizers are poorly deposited on crop leaves and are easily washed away by rain; these factors limit plant Se absorption and pose potential environmental risks. To address this issue, a thermosensitive Se nanoparticles gel (CS-FA/BP-SeNPs) based on chitosan-ferulic acid (CS-FA) and <strong>β</strong>-glycerophosphate (<strong>β</strong>-BP) was developed to increase rain-washing resistance and Se uptake in grape leaves. The CS-FA derivative was synthesized via an amide reaction between chitosan and ferulic acid_(1:2); this derivative demonstrated strong antibacterial and antioxidant activity, effectively dispersing the Se nanoparticles (SeNPs) and preventing their aggregation. <strong>β</strong>-glycerophosphate neutralized the pH value of the CS-FA/SeNPs solution, significantly increasing the stability of the SeNPs (stable for 30 days). Up to 37 °C, the solution rapidly formed a hydrogel, increasing its viscous modulus by 5.1 times and improving adhesion. Compared with SeNPs alone, CS-FA/BP-SeNPs showed superior spreading, reducing droplet splashing and retraction. In simulated rainfall experiments, the CS-FA/BP-SeNPs gel coating retained 91.1 % of the material on the leaf surface, while the corresponding value for SeNPs was 13.6 %, demonstrating excellent rainfastness in the former. In open-field cultivation trials, grape leaves treated with the CS-FA/BP-SeNPs gel coating presented a 141.3–192.7 % increase in the Se retention rate and a 51.3–62.3 % increase in Se uptake than those with SeNPs alone. Additionally, CS-FA/BP-SeNPs significantly reduced <em>Fusarium oxysporum</em> infection rates, demonstrating potential for use in challenging outdoor environments. This thermosensitive gel coating provides an effective strategy for enhancing nanoselenium utilization on crop leaves through its temperature-responsive properties and strong postgelation adhesion.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100351"},"PeriodicalIF":5.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143099038","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Ions in motion: From biological channels to engineered transport systems","authors":"Bei Wu ,&nbsp;Yifan Yan ,&nbsp;Yuting Zhu ,&nbsp;Changxing Ji ,&nbsp;Yangyang Lin ,&nbsp;Chao Lang","doi":"10.1016/j.giant.2025.100352","DOIUrl":"10.1016/j.giant.2025.100352","url":null,"abstract":"<div><div>Natural membrane proteins are molecular machines evolved over billions of years, playing crucial roles in various physiological functions by precisely mediating transmembrane transport processes. Inspired by these marvels, people have developed many artificial transport systems with structures and functions matching those of natural proteins. Compared to proteins in nature, engineered transport systems offer advantage in structural simplicity, stability, and cost-effectiveness. These artificial systems could find applications in areas ranging from medical treatment to new materials, and to biotechnologies. This review begins by examining ionic flow in nature, where the high efficiency and selectivity of protein channels have inspired engineered systems. We then explore different types of artificial transport systems, including artificial channels, transporters, and nanopores, and techniques for characterizing these systems. Applications in therapeutics, biotechnologies, separation, and energy harvesting are discussed. Finally, we offer perspectives and outlook on the further advancement of the artificial ion transport systems.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"22 ","pages":"Article 100352"},"PeriodicalIF":5.4,"publicationDate":"2025-01-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143100202","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"“Clicking” Amphiphilic Block Copolymers onto POSS Core: A General Approach for “Star-like” Polymers with Different Symmetry","authors":"Gang Li,&nbsp;Duohua Jiang,&nbsp;Panpan Ren,&nbsp;Heng Zhao,&nbsp;Kai Zhang,&nbsp;Liping Chang,&nbsp;Zhongguo Liu,&nbsp;Shouzhi Pu","doi":"10.1016/j.giant.2024.100346","DOIUrl":"10.1016/j.giant.2024.100346","url":null,"abstract":"<div><div>“<em>Star-like</em>” macromolecules have been widely studied because of their unique physical and chemical properties, which play a great role in many important application fields. In this study, a library of star-like amphiphilic block copolymers consisting of a polyhedral oligomeric silsesquioxane (POSS) core and polyethylene glycol-<em>bolck</em>-polystyrene (PEG<em>_m</em>-<em>b</em>-PS<em>_n</em>) diblock copolymer arms with an exact arm number were prepared through a robust copper-catalysed azide-alkyne cycloadditions (CuAAC) and strain-promoted azide-alkyne cycloaddition (SPAAC) click reactions. Moreover, homo- and mikto-arms star polymers with different compositions were obtained by precisely regulating the central symmetry of the POSS core. The target polymers and intermediate products were characterized by nuclear magnetic resonance (NMR), size exclusion chromatography (SEC), Fourier transform infrared (FT-IR) spectroscopy, and matrix-assisted laser desorption ionization time-of-flight (MALDI-ToF) mass spectrometry. This study demonstrates the chemical robustness of the novel POSS-based building block and establishes a general and efficient approach to prepare star-like macromolecules, especially for asymmetric heteroarm star-like macromolecules, which serve as important model compounds in the study of their bulk properties as well as self-assembling behaviors.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100346"},"PeriodicalIF":5.4,"publicationDate":"2024-11-15","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699346","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"A dynamic entanglement model for adaptive networks in amorphous polymers with pH-responsive dual-shape memory effect","authors":"Jiabin Shi ,&nbsp;Haibao Lu ,&nbsp;Tengfei Zheng ,&nbsp;Yong-Qing Fu","doi":"10.1016/j.giant.2024.100347","DOIUrl":"10.1016/j.giant.2024.100347","url":null,"abstract":"<div><div>The pH-responsive shape memory polymers (pH-SMPs) have recently attracted significant attention due to their unique and spontaneous actuation capabilities. However, there are few constitutive models developed to explore the working principles behind these complex shape memory behaviors. In this study, a dynamic entanglement model was developed for describing the pH-responsive shape memory effect (SME) in SMPs, in which the crosslinking points in polymer networks underwent reversible entanglements and disentanglements. Susceptible-Infected-Susceptible (SIS) model was firstly employed to formulate an entanglement probability function, which was used to identify the working principles for entanglements of polymer networks and shape recovery of the pH-SMPs. An entanglement free-energy function was further formulated to characterize the pH-responsive dual-SMEs based on the Flory-Huggins solution theory. Phase transition theory was then used to characterize glass transition behaviors and recovery strains of the pH-SMPs, by combining Gordon-Taylor and Kohlrausch-Williams-Watts (KWW) equations. Finally, the proposed model was verified using experimental results reported in the literature. This study provides a fundamental approach to explore the working principle and constitutive relationship between reversible entanglement and pH-responsive SME in SMPs.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100347"},"PeriodicalIF":5.4,"publicationDate":"2024-11-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699345","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Limitation and potential of lignin-assisted stabilisation of oriented liquid crystalline cellulosic mesophase","authors":"F. Robert Gleuwitz ,&nbsp;Gopakumar Sivasankarapillai ,&nbsp;Ahmed Bentaleb ,&nbsp;Nadine Kohlhuber ,&nbsp;Marie-Pierre G. Laborie","doi":"10.1016/j.giant.2024.100344","DOIUrl":"10.1016/j.giant.2024.100344","url":null,"abstract":"<div><div>This study aimed at progressing in the fundamental understanding of the lignin-assisted microstructural stabilisation observed in solution-processed materials based on the polymer blend of hydroxypropyl cellulose and hardwood organosolv lignin. Mechanical analysis, polarised infrared spectroscopy and wide-angle X-ray scattering of shear cast blend films revealed that the effect of lignin on the flow-oriented cellulosic mesophase is also valid for blends composed of ethyl cellulose as liquid crystalline matrix polymer and lignin derived oligomers from base-catalysed depolymerisation as dispersed “microstructural cementing agent”. The results underline the significant role of the solvent diffusion between the continuous cellulosic and the dispersed lignin phase, which is ascribed to polymer-/oligomer-solvent interactions. An abundance of the solvent within the lignin phase caused the disruption of the microstructural stabilisation effect. The concept of a balanced proton-donor activity was introduced linking the solvent diffusion with the lyotropic liquid crystalline phase formation, the macro- and microstructural blend morphology and aspects regarding the solution processing.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100344"},"PeriodicalIF":5.4,"publicationDate":"2024-11-12","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142699344","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Influence of activation/deactivation process on surface-initiated atom transfer radical polymerization: An in silico investigation","authors":"Zhongyan Zhang ,&nbsp;Hui Li ,&nbsp;Yuqi Guo ,&nbsp;Yao-Hong Xue ,&nbsp;Hong Liu","doi":"10.1016/j.giant.2024.100345","DOIUrl":"10.1016/j.giant.2024.100345","url":null,"abstract":"<div><div>We propose a simulation approach to explore surface-initiated atom transfer radical polymerization (SI-ATRP), in which how the chain growth is affected by activation/deactivation process could be considered explicitly. Our findings indicate that these activation and deactivation mechanisms provide all polymer chains with equal growth opportunities. This process leads to a significant increase of grafting density while concurrently reducing the dispersity of the grafted chains. The ratio of activated and dormant chains is theoretically proved to eventually reach equilibrated within the activation/deactivation process. The shorter lifetime of activation/deactivation cycle leads to an even equal opportunity and a faster “stop-continue” pace for the growth of all chains. Our study is helpful for better understanding the role of activation/deactivation process in SI-ATRP from a microscopic perspective.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100345"},"PeriodicalIF":5.4,"publicationDate":"2024-11-06","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142653876","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Homochiral “8″-shaped nanotoroids assembled from polypeptides","authors":"Ruiqi Jin,&nbsp;Yue Du,&nbsp;Jiaping Lin,&nbsp;Chunhua Cai","doi":"10.1016/j.giant.2024.100343","DOIUrl":"10.1016/j.giant.2024.100343","url":null,"abstract":"<div><div>Figure eight-shaped (“8″-shaped) nanotoroids have been observed in DNA and proteins, however, they are rarely reported in synthetic polymer systems. Reported here is the formation of homochiral “8″-shaped nanotoroids from poly(γ-benzyl glutamate) (PBG) homopolymers. The L-type and D-type PBGs, i.e., PBLG and PBDG respectively, form left-handed and right-handed “8″-shaped chiral nanotoroids. The formation of the nanotoroids is achieved in a two-step route. Nanofibers are first self-assembled by the PBG homopolymers, which, with changing solvent nature, break into short nanofibers and twist into “8″-shaped nanotoroids. In such processes, the pendant phenyl groups of PBGs change from an extended to a contract form, which generates the internal stress driving the transition of nanofibers to “8″-shaped nanotoroids. This work not only enriches the topology and preparation method of nanotoroids, but also enhances our ability in controlling polymer nanostructures.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"20 ","pages":"Article 100343"},"PeriodicalIF":5.4,"publicationDate":"2024-10-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142657154","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Small dop of comonomer, giant shift of dynamics: α-methyl-regulated viscoelasticity of poly(methacrylamide) hydrogels","authors":"Xin Guan ,&nbsp;Zhiheng Zhou ,&nbsp;Xinzhen Fan ,&nbsp;Wenchao Xu ,&nbsp;Yijie Jin ,&nbsp;Chuanzhuang Zhao","doi":"10.1016/j.giant.2024.100342","DOIUrl":"10.1016/j.giant.2024.100342","url":null,"abstract":"<div><div><em>α</em>-Methyl groups play significant roles in the regulation of water molecules within both small molecular systems and bio-macromolecular systems. Systematically studying the influence of <em>α</em>-methyl on the dynamics of water molecules within hydrogel systems is therefore worthwhile. In this study, we prepared a series of hydrogen-bonded (H-bonded) hydrogels with varying densities of <em>α</em>-methyl groups by copolymerizing methacrylamide (MAm) with its <em>α</em>-methyl-absent analogue, acrylamide (Am). Introducing a small amount of Am (≤6 mol%) into the polymer chain resulted in significant shifts in the viscoelasticity of the hydrogels. The hydrogels exhibit a “time-temperature-<em>α</em>-methyl equivalence”, meaning that introduction of <em>α</em>-methyl-absent monomer has effects similar to elevating temperature and prolonging observation time on the dynamic properties. Based on low-field nuclear magnetic resonance spectroscopy and Raman scattering, a “hydrophilic defects-assisted H-bonds dissociation” mechanism is proposed, depicting that the <em>α</em>-methyl-absent monomer can disturb the rearrangement of water molecules surrounding the polymer chain and accelerate chain dissociation. These findings enabled the copolymer hydrogels with functions such as fast self-healing and tunable interface adhesion.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"20 ","pages":"Article 100342"},"PeriodicalIF":5.4,"publicationDate":"2024-09-23","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142418054","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"Binary blends of poly(lactic acid) and poly(methyl methacrylate) for high energy density and charge/discharge efficiency capacitors","authors":"Shuo Zhao ,&nbsp;Le Zhou ,&nbsp;Junshang Zhang,&nbsp;Yang Shen,&nbsp;Ce-Wen Nan","doi":"10.1016/j.giant.2024.100340","DOIUrl":"10.1016/j.giant.2024.100340","url":null,"abstract":"<div><p>Polymer dielectrics are widely used in modern power electronics due to their high flexibility and high breakdown strength. However, the limited energy density of current polymer dielectrics limits their wider applications, and there is an urgent need to develop novel polymer dielectric materials. Poly(lactic acid) (PLA) is favored for biological applications due to its biocompatibility and biodegradability. In general, PLA has three optical isomers, namely poly(L-lactide) (PLLA), poly(D-lactide) (PDLA), and poly(DL-lactide) (PDLLA), but the investigation of their dielectric properties remains limited. In this study, a significant increase in energy storage density and charge/discharge efficiency in poly(methyl methacrylate) (PMMA) was achieved by incorporating isomers of PLA into PMMA. Experimental results indicate that the introduction of PLA creates a phase-separated structure within PMMA, and in particular, the introduction of the crystalline region significantly improved the breakdown strength (<em>E</em>_b). Finally, PLLA/PMMA 50/50 and PDLA/PMMA 50/50 exhibit the discharged energy densities of 8.55 J cm⁻³ and 8.18 J cm⁻³, respectively, with charge/discharge efficiencies of 89.6% and 90.9%. This work enables the achievement of all-organic dielectrics with high energy storage density and high efficiency through the construction of phase-separated structures and demonstrates the great potential of biodegradable polymers in electronic devices.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"20 ","pages":"Article 100340"},"PeriodicalIF":5.4,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S2666542524001048/pdfft?md5=5fdaadba5fe8c446d394f5b0099d8249&pid=1-s2.0-S2666542524001048-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142270615","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}

{"title":"The effect of dynamic cross-links and mesogenic groups on the swelling and collapse of polymer gels","authors":"Daniil E. Larin ,&nbsp;Andrey V. Shibaev ,&nbsp;Ch.-Y. Liu ,&nbsp;Alexander V. Emelyanenko","doi":"10.1016/j.giant.2024.100341","DOIUrl":"10.1016/j.giant.2024.100341","url":null,"abstract":"<div><p>The polymer gels containing dynamic cross-links and mesogenic groups are among the key candidates for the development of soft actuators and detectors, displays, sensors and other programmable and self-healing materials. In this article, firstly, the collapse of polymer networks with irreversible cross-links in the presence of a dynamic cross-linker is investigated by means of Flory-type theory. It is shown that, at not a very poor solvent quality (near the theta-conditions), the swelling ratio for a gel containing irreversible and dynamic cross-links is less than for a gel with irreversible cross-links only, whereas at poor or good solvent qualities sizes of these gels are close to each other. The number of dynamic cross-links monotonically increases with worsening the solvent quality. The gel contraction can be also achieved by increasing the dynamic cross-linker concentration, which allows one to change the transition point in a wide range of solvent conditions. Secondly, polymer networks containing irreversible and dynamic cross-links and incorporating mesogenic side groups is studied using the Maier–Saupe theory. With decreasing in the temperature, the continuous transition from a swollen to collapsed state occurs. With further increase in the temperature, the swelling ratio discontinuously decreases and the nematic order parameter sharply increases from zero to a value ​​close to one. By increasing the dynamic cross-linker concentration, the swelling-to-collapse transition and, then, the isotropic-nematic transition are observed. A phase diagram of the gel is constructed and, depending on the dynamic cross-linker concentration and temperature, the swollen gel with the zero nematic order parameter, the collapsed gel with the zero nematic order parameter, and the collapsed gel with the nematic ordering can be formed. A growth of the length of the mesogenic side group leads to an increase in the area of ​​existence of the collapsed gel with the nematic ordering in the phase diagram. The obtained theoretical results are in agreement with corresponding experimental data from the literature.</p></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"20 ","pages":"Article 100341"},"PeriodicalIF":5.4,"publicationDate":"2024-09-10","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://www.sciencedirect.com/science/article/pii/S266654252400105X/pdfft?md5=3f12b4db5dbdfa4da62fa4ae992677ca&pid=1-s2.0-S266654252400105X-main.pdf","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"142255055","PeriodicalName":null,"FirstCategoryId":null,"ListUrlMain":null,"RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":"OA","EPubDate":null,"PubModel":null,"JCR":null,"JCRName":null,"Score":null,"Total":0}