GIANT最新文献

{"title":"Giant electro-viscous effects in polar fluids with paraelectric–modulated antiferroelectric–ferroelectric phase sequence","authors":"Hiroya Nishikawa ,&nbsp;Péter Salamon ,&nbsp;Marcell Tibor Máthé ,&nbsp;Antal Jákli ,&nbsp;Fumito Araoka","doi":"10.1016/j.giant.2025.100356","DOIUrl":"10.1016/j.giant.2025.100356","url":null,"abstract":"<div><div>The recently discovered ferroelectric nematic liquid-crystal material DIO exhibits an antiferroelectric (AF) phase, characterized by a sinusoidally modulated structure between the paraelectric (P) and ferroelectric (F) nematic phases. Although these sinusoidal modulated structures associated with the P–AF–F phase sequence is commonly observed in solid ferroelectrics, their presence in soft matter systems is scarce. This study is aimed at examining the macroscopic properties of DIO, identifying unique rheological properties, such as switching between shear thinning and shear thickening behaviors at certain shear rate in the ferroelectric nematic phase. Additionally, a significant electroviscous effect is observed, with the viscosity increasing by 70 times under an ultra-low electric field of 0.15 V µm⁻¹ at the AF–F transition.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"22 ","pages":"Article 100356"},"PeriodicalIF":5.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143820456","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}

{"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":"2025-04-01","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":"3D printable colloidal dispersions demonstrating sol-to-gel transition at low silica concentrations mediated by molecular weight distribution of polypropylene glycol oligomer","authors":"Sai Wu ,&nbsp;Qingxu Zhang ,&nbsp;Shihao Xiao ,&nbsp;Li'an Zhang ,&nbsp;Chaoyi Fan ,&nbsp;Jinpeng Wang ,&nbsp;Jian Wang ,&nbsp;Yijun Shen ,&nbsp;Yihu Song ,&nbsp;Qiang Zheng","doi":"10.1016/j.giant.2025.100353","DOIUrl":"10.1016/j.giant.2025.100353","url":null,"abstract":"<div><div>Thixotropic colloidal gels composed by hydrophilic silica and polypropylene glycol (PPG) oligomer fluidize upon shear and solidify upon cease of flow, facilitating their use in 3D printing. In this study, we present a novel approach to high-fidelity 3D printing that leverages a dual-stream mixing technique within the printer nozzle for the first time. This innovative method enables the precise fabrication of colloidal objects even at low volume fractions (<em>φ</em>) of filler. The printed gels, containing a pre-stored crosslinker, can be further processed into polyurethane nanocomposites, broadening their potential applications. Rheological studies demonstrate that the sol-gel transition in these systems can be effectively controlled by adjusting the molecular weight distribution of the polydisperse PPG oligomers. This investigation has led to the creation of a comprehensive polydispersity-molecular weight-<em>φ</em> phase diagram that characterizes the behavior of the gels under different conditions. Moreover, the mechanistic studies reveal that gelation of polydisperse oligomers occurs at significantly lower <em>φ</em> compared to monodisperse systems, which is attributed to the formation of thicker glassy layers surrounding the silica nanoparticles. Our findings provide valuable insights into the design and optimization of thixotropic gels, making them promising candidates for various applications requiring precise rheological control in materials science.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"22 ","pages":"Article 100353"},"PeriodicalIF":5.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143511736","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":"Miktoarm star polymers as templates for mesoporous phenolic materials: Enhancing microphase separation and expanding phase diagrams","authors":"Ting‐Chih Chou,&nbsp;Shiao‐Wei Kuo","doi":"10.1016/j.giant.2025.100355","DOIUrl":"10.1016/j.giant.2025.100355","url":null,"abstract":"<div><div>In the field of soft matter, designing different amphiphilic chemical structures could lead to the formation of ordered microphase-separated arrangements. Unlike linear block copolymers, miktoarm star polymers have been extensively utilized and inherently enhance the conformational asymmetry value (<em>ε</em>) in the microphase separation system through their branched chemical structure, allowing control over the interfacial curvature between microphase-separated domains and facilitating the formation of unique self-assembled structures, offering the potential to expand phase diagrams. In this study, we synthesized a common linear PEO-<em>b</em>-PCL diblock copolymer via ring-opening polymerization (ROP) and also prepared an AB₃-type block copolymer, PEO-<em>b</em>-PCL₃, by linking PEO to a branched PCL₃ block through a combination of ROP and click reactions with the similar volume fraction of PEO segment. Resol-type phenolic resin was synthesized by step-growth polymerization and used as the matrix, which was mixed with different weight fractions of linear PEO-<em>b</em>-PCL and miktoarm-type PEO-<em>b</em>-PCL₃ block copolymers as templates. FT-IR analysis of these blends at room temperature revealed that, under the similar volume fraction, the miktoarm-type star polymer forms the higher fraction of intermolecular hydrogen bonds with the phenolic resin in the PCL₃ block segment, and no crystallization was observed. Variable-temperature SAXS analysis demonstrated that upon thermal cross-linking, the blends exhibited improved stability and enhanced ordered microphase-separated structures. By heating to pyrolysis temperatures to remove the template, the resulting structures were characterized by using TEM and SAXS analyses. The systems constructed by two different templates creating mesoporous materials with different ordered structures such as lamellar, hexagonal columnar, spherical, BCC packing, and even the rare short-range order Frank-Kasper phase. Through phase diagram construction, we found that even with the similar weight fraction, the ordered mesoporous structures formed using the two different type of templates displayed significant differences. Additionally, the results indicated that when the branched segment of the miktoarm-type polymer is located at the core of the micelle, the interfacial curvature decreases. Overall, this study reveals the existence of the unique short-range order Frank-Kasper phase in systems with low χ values using wet-brush blending and validates the feasibility of employing miktoarm-type polymers as templates through analysis of molecular interaction and morphological characterization. This expands the phase diagram in the direction of tuning conformational asymmetry, providing a novel approach for designing innovative or specialized ordered mesoporous materials.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"22 ","pages":"Article 100355"},"PeriodicalIF":5.4,"publicationDate":"2025-04-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143714787","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":"2025-02-01","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":"2025-02-01","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":"2025-02-01","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":"Helically deployed Au nanoparticles using block copolymer templates as chiral plasmonic monoliths","authors":"Hsiu-Wen Tsai ,&nbsp;Sheng-Wei Shao ,&nbsp;Po-Ting Chiu ,&nbsp;Cheng-Yen Chang ,&nbsp;Yu-Chuan Sung ,&nbsp;Guan-Hong Li ,&nbsp;Yi-Ching Chen ,&nbsp;Akemi Kumagai ,&nbsp;Hiroshi Jinnai ,&nbsp;Yu-Chueh Hung ,&nbsp;Jing-Cherng Tsai ,&nbsp;Rong-Ming Ho","doi":"10.1016/j.giant.2024.100350","DOIUrl":"10.1016/j.giant.2024.100350","url":null,"abstract":"<div><div>This work aims to fabricate polymeric thin films with helically deployed gold (Au) nanoparticles by using self-assembled chiral block copolymers (BCPs*) with controlled helicity as templates, giving polymeric monolith with unique optical properties as chiral plasmonic thin film. Enantiomeric polylactide-based BCPs*, polystyrene-block-poly(<em>L</em>-lactide) (PS-<em>b</em>-PLLA) and poly-styrene-block-poly(<em>D</em>-lactide) (PS-<em>b</em>-PDLA) with disulfide junction are designed and synthesized, denoted as PS-ss-PLLA and PS-ss-PDLA, respectively. The helically deployed chemical junctions of the PS-ss-PLLA and PS-ss-PDLA thin films from the self-assembly of helix-forming BCPs* can give thiol end groups preferentially arranged in a one-handed helical fashion at the inner wall of nanoporous PS after hydrolysis of polylactide followed by reducing the disulfide into thiol. Au nanoparticles (Au NPs) with a size of 2-5 nm, resulting from reduction, can associate with the thiol end groups in the nanoporous PS, forming a helical disposition of Au NPs with specific handedness. As a result, circular dichroism (CD) signals of localized surface plasmonic resonance (LSPR) originating from the helical Au NP arrays with preferred chirality can be acquired from the polymeric monolith fabricated, giving appealing applications as chiroptical devices.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100350"},"PeriodicalIF":5.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098493","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":"2025-02-01","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":"Intrinsic low-dielectric Cardo polyimide with high heat resistance, high transparency, and low birefringence","authors":"Hong Li ,&nbsp;Weiyi Jin ,&nbsp;Weiyu Zhang ,&nbsp;Jie Li ,&nbsp;Jiaqi Ji ,&nbsp;Yi Tang ,&nbsp;Tianqi Yang ,&nbsp;Shujiang Zhang ,&nbsp;Haixia Yang ,&nbsp;Chenliang Gong","doi":"10.1016/j.giant.2024.100349","DOIUrl":"10.1016/j.giant.2024.100349","url":null,"abstract":"<div><div>Low-dielectric, transparent, and high-heat-resistant polyimide (PI) films are vital for flexible electronics and high-frequency communication devices. However, balancing these properties within intrinsic polyimides remains a significant challenge. In this work, a nonplanar diamine monomer, 2,7-bis(3,5-bis(trifluoromethyl)phenyl)-9,9-bis(4-nitrophenyl)-9H-fluorene (BTFDA), containing a Cardo structure and four trifluoromethyl groups, was synthesized and copolymerized with commercial monomers to produce a series of polyimides (CPI-X). These CPI-X exhibit exceptional heat resistance, with glass transition temperatures (<em>T</em>_g) exceeding 350 °C, decomposition temperatures (<em>T</em>_{d5 %}) above 530 °C, and low thermal expansion coefficients (CTE &lt; 20.8 ppm/K). Additionally, they have excellent optical properties with over 92 % transparency at 450 nm and low birefringence (Δ<em>n</em> = 0.00042). They also demonstrate good hydrophobicity with low water absorption (<em>M</em>_a% = 0.04 %) and high-water contact angles (<em>C</em>_a = 97.6°). Most importantly, the CPI-X films show excellent dielectric properties (<em>D_k</em> = 2.25, <em>D_f</em> = 0.00365 at 1 MHz, <em>D_k</em> = 2.13, <em>D_f</em> = 0.0065 at 10 GHz). Such intrinsic PI films with low <em>D</em>_k values may be ideal candidates for next-generation interlayer media.</div></div>","PeriodicalId":34151,"journal":{"name":"GIANT","volume":"21 ","pages":"Article 100349"},"PeriodicalIF":5.4,"publicationDate":"2025-02-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143098492","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}