Macromolecules最新文献

{"title":"Linking the Chiral Expression of Conjugated Polymers to Their Aggregation Type","authors":"Annelien van Oosten, Karen Aerts, Yovan de Coene, Thierry Verbiest, Guy Koeckelberghs","doi":"10.1021/acs.macromol.4c02444","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02444","url":null,"abstract":"Due to their strong absorption of visible light, chirality in chiral conjugated polymers (CPs) is typically expressed by electronic circular dichroism (ECD). Unfortunately, while many chiral CPs give rise to strong ECD upon stacking, predicting and reproducing the resulting behavior has proven to be extremely difficult. Here we show that the ECD of CPs is correlated to the known types I and II aggregation. It is demonstrated that type I aggregation results in an ECD signal with an additional monosignal Cotton effect, therefore yielding an asymmetrical spectrum. In contrast, in type II aggregation, the resulting ECD signal is symmetrical. This is determined for a model chiral CP, poly(3-(3,7-(<i>S</i>)-dimethyloctyl)thiophene) in two ways. Additionally, the actual process of both aggregation types is monitored by a combination of linear and nonlinear optical techniques. Finally, the molecular structure of various CPs is correlated to the aggregation type, providing a general relationship between the molecular structure of CPs and their ECD.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"20 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050479","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":"Advancing Non-isocyanate Polyurethane Foams: exo-Vinylene Cyclic Carbonate–Amine Chemistry Enabling Room-Temperature Reactivity and Fast Self-Blowing","authors":"Maksim Makarov, Maxime Bourguignon, Bruno Grignard, Christophe Detrembleur","doi":"10.1021/acs.macromol.4c02894","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02894","url":null,"abstract":"Though widely used, polyurethane foams raise health concerns stemming from their isocyanate precursors. Nonisocyanate polyurethane foams (NIPUFs), synthesized by aminolysis of 5-membered cyclic carbonates, represent safer and more sustainable alternatives. Despite their potential, achieving efficient self-blowing NIPUFs from room temperature (RT) formulations has proven highly challenging, as previous methods rely on external heat sources, prolonged reaction times, or are based on hybrid formulations involving epoxides. In this study, we demonstrate a new concept that makes rapid the production of full NIPUFs (i.e., with exclusive urethane linkages) from RT solvent-free formulations through the incorporation of exovinylene cyclic carbonate (αCC). This approach incorporated hydroxyoxazolidone groups, i.e., cyclic hydroxyurethanes, as pendant groups of the polyhydroxyurethane backbone. We investigated the reactions occurring in this foaming system and identified optimal foaming formulations to rapidly produce the foams within 1–5 min, with a high gel content. The study explored monomer variations as amine mixtures and different αCCs. Compression tests revealed that the foam’s mechanical properties were easily tuned by adapting the formulation composition, giving access to both flexible and rigid foams with pore sizes in the range of conventional PU foams. Moreover, we highlighted the importance of the hydrophilic nature of NIPUFs on their mechanical properties, with a decrease in the Young’s modulus when exposed to increased humidity contents. While these foams, like many NIPUs, exhibit inherent hydrophilicity, this limitation may be addressed through additives or future formulation optimization. Our new concept paves the way for the rapid preparation of the next generation of full isocyanate-free polyurethane foams with modular properties.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"16 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050481","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":"How Do Solvent–Polymer–Surface Interactions Affect the Physisorption of Polymer Chains during Flow-Induced Translocation through Inorganic Oxide Nanochannels?","authors":"Yiren Wang, Jianing Zhou, Haorong Huang, Tao Zheng, Lianwei Li","doi":"10.1021/acs.macromol.4c01723","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c01723","url":null,"abstract":"This work aims to explore how polymer–surface–solvent ternary interactions play a synergistical role in affecting the physisorption of PBA_N [poly(benzyl acrylate)] chains inside 20 and 100 nm Whatman anodic aluminum oxide nanochannels in flow field by considering the Flory interaction parameter (χ_F), adsorption parameter (χ_S), solution concentration (<i>C</i>), and degree of polymerization (<i>N</i>). By using a homemade triple-pump system for in situ monitoring the transmembrane pressure during the solvent switching process, we have found: (1) a combination of χ_F and χ_S significantly impacts the adsorption and reversibility of PBA_N chains in toluene, ethyl acetate, and tetrahydrofuran, and an extremely slow kinetics process is revealed in dimethylformamide; (2) the adsorption kinetic curves for different PBA_N chain lengths are all nicely described by the dual exponential fitting including the fast and slow modes, which can be attributed to the fast approaching of whole chain and the slow reorganization of local conformation, respectively, and the conformational reorganization is found to be the most significant in dimethylformamide; (3) a universal two-regime scaling dependence <i>A</i>_occupy<i>/A</i>_total ∼ <i>N</i>^γ is observed between the cross-sectional coverage factor (<i>A</i>_occupy<i>/A</i>_total) and <i>N</i>, with γ ∼ 0.50 in the weak confinement regime when <i>A</i>_occupy<i>/A</i>_total &lt; 0.30 and γ ∼ 1.5 in the strong confinement when <i>A</i>_occupy<i>/A</i>_total &gt; 0.30, independent of pore size, chain length, and solvent type, indicating the dominant effect of the crowding effect when <i>A</i>_occupy<i>/A</i>_total &gt; 0.30; (4) the adsorption reversibility and desorption efficiency are found to increase with the solvent quality and polarity in 20 and 100 nm systems during the solvent switching process, which provides a method for the regulation of adsorption thickness; (5) an extremely weak dependence of <i>A</i>_occupy<i>/A</i>_total ∼ <i>C</i> is observed, which is consistent with Silberberg’s prediction. Our present result provides useful guidance for understanding and comparing the behavior of chain adsorption in the nonidealized and idealized membrane system.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"15 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-28","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050480","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":"Ultra-Strong, Humidity-Tolerant Thermoset Based on Dynamic Covalent Bond Integration Strategy via Boron−Nitrogen Bidentate Coordination","authors":"Wuzhuang Wei, Xiaoting Zhang, Chenyue Liang, Yu Li, Shujuan Wang, Tao Hong, Xinli Jing","doi":"10.1021/acs.macromol.4c02613","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02613","url":null,"abstract":"Dynamic covalent polymers, especially those containing boronic ester bonds, face an inherent contradiction between reversibility and robustness, as water poses a severe threat to their mechanical properties. Herein, we propose a scalable dynamic covalent chemistry, namely, interlocking imine bonds of the bis-Schiff base (Salen) and aryl boronic ester bonds to form sNCB linkages. Benefiting from the internal boron−nitrogen bidentate coordination, the sNCB linkage overcomes the inherent defect of boronic ester bonds, exhibiting strong hydrolysis/thermal stability. When we design the cross-linked network to contain merely 8 wt % of sNCB linkages, the mechanical robustness of the original polymer can be significantly enhanced, producing an ultrastrong and moisture-resistant material (PETX) with ∼102 MPa tensile strength. Moreover, PETX can still undergo multiple reprocessing and even achieve self-healing. The sNCB linkages also provide PETX with a range of structural health monitoring functions. Our work presents a promising strategy for producing high-strength, stable, and sustainable materials.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"12 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050420","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":"Reversible Thermoresponsive Host–Guest Binding of Pillar[n]arenes with Guest End-Functionalized Poly(2-n-Propyl-2-Oxazoline)s","authors":"Xinran Guan, Somdeb Jana, Takuya Tomita, Tomoki Ogoshi, Patrice Woisel, Richard Hoogenboom","doi":"10.1021/acs.macromol.4c02456","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02456","url":null,"abstract":"Host–guest based thermoresponsive supramolecular polymer assemblies have found significant interest in recent years as they provide unique opportunities for the reversible release of the guest upon thermally controlled collapse of the polymer. However, the reported systems are mostly based on polyacrylamides and polyacrylates in combination with the positively charged cyclobis(paraquat-<i>p</i>-phenylene) host. To investigate whether such thermally induced guest release can be more generally developed, here we investigated the thermoreversible host–guest association of guest-functionalized poly(2-<i>n</i>-propyl-2-oxazoline) (<b>P</b>^{<b><i>n</i></b>}<b>PrOx</b>) with various pillar[<i>n</i>]arene hosts. Two types of thermoresponsive poly(2-<i>n</i>-propyl-2-oxazoline) (<b>P</b>^{<b><i>n</i></b>}<b>PrOx</b>) consisting of a hydrophilic 4,4′-bipyridinium unit (<b>P</b>^{<b><i>n</i></b>}<b>PrOx-MV</b>) or a 5-aminopentanenitrile unit (<b>P</b>^{<b><i>n</i></b>}<b>PrOx-CN</b>; introduced as novel guest for percarboxylato pillar[5/6]arenes) as the end-group were prepared. The complexation of these guest-functionalized <b>P</b>^{<b><i>n</i></b>}<b>PrOx</b> with water-soluble pillar[5/6]arenes containing anionic carboxylate groups (<b>WP5</b> and <b>WP6</b>) or nonionic methoxytriethylene glycol (<b>TP5</b> and <b>TP6</b>) solubilizing groups was investigated in water. The 1:1 host–guest complexes, i.e., <b>WP6–P</b>^{<b><i>n</i></b>}<b>PrOx-MV</b> and <b>WP5–P</b>^{<b><i>n</i></b>}<b>PrOx-CN</b>, were formed by electrostatic interactions at 283.15 K with the association constants of (3.84 ± 0.25) × 10⁵ M^–1 and (0.96 ± 0.04) × 10⁴ M^–1, respectively. In contrast, the nonionic <b>TP5</b> and <b>TP6</b> only showed weak binding with the polymers. When heated above its cloud-point temperature, <b>P</b>^{<b><i>n</i></b>}<b>PrOx</b> collapses and precipitates due to the effect of lower critical solution temperature (LCST), which is demonstrated to lead to host–guest dissociation, providing thermal control over the complexation and decomplexation of the <b>WP6–P</b>^{<b><i>n</i></b>}<b>PrOx-MV</b> and <b>WP5–P</b>^{<b><i>n</i></b>}<b>PrOx-CN</b> host–guest complexes. The reversible, temperature-controlled threading and dethreading process suggest potential applications in sustainable separation and recovery processes, as well as in the development of smart materials with temperature-responsive functionalities.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"34 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044383","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":"Simultaneous Regulation of Molecular Weight Distribution and Composition through RDRP in a Continuous-Flow Reactor: A Kinetic Modeling","authors":"Haiyan Xue, Junpo He","doi":"10.1021/acs.macromol.4c02183","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02183","url":null,"abstract":"Regulating the molecular weight distribution (MWD) and copolymer composition is of great significance for controlling the properties of polymer materials. Combining reversible deactivation radical polymerization (RDRP) with continuous-flow synthesis techniques offers new opportunities to tailor complex MWDs. In the present work, we propose a flow-control strategy to simultaneously engineer the MWD and copolymer composition in atom transfer radical polymerization under continuous-flow conditions. A unique aspect of this approach is the intentionally designed flow rate profile, which can range from staged to quasi-continuous variations of the initiator injection flow rate. The relationship between flow rate profiles and the resulting MWD of the collected products was modeled by using Gaussian distribution mathematical equations and Monte Carlo simulations. The results show that this modeling method can not only predict the MWD from a given flow rate profile but also determine a flow rate scenario capable of producing any complex target MWD. Furthermore, we proposed a three-pump flow polymerization system capable of producing copolymers with tailored distributions and selective incorporation of comonomer units into specific product fractions. These conceptual demonstrations provide a theoretical framework for a new mode of MWD and composition regulation achieved simply by adjusting the injection flow profile of a given instrument configuration. This approach holds considerable potential for producing polymers with the desired MWDs and tailored chemical composition distributions.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"35 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050483","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":"Dynamic Viscoelastic Properties of Polystyrene Composites Reinforced with Cellulose Nanocrystals","authors":"Hiroaki NOBUOKA, Reina TANAKA, Osamu URAKAWA, Tadashi INOUE","doi":"10.1021/acs.macromol.4c03221","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03221","url":null,"abstract":"We investigated the reinforcement mechanisms of cellulose nanocrystals, CNCs, in polymer matrices by incorporating them into polystyrene, a widely used simple amorphous resin that lacks specific interactions, such as hydrogen bonding. Rheological measurements revealed that the addition of CNC induced significant reinforcement effects in the complex moduli, particularly in the rubbery state. These effects are best described using the modified Morse theory, which accounts for the molecular dynamics of semiflexible polymers in a viscoelastic medium, rather than the classical Halpin–Tsai theory traditionally applied to straight rods. Dynamic birefringence measurements, specifically the frequency dependence of the strain-induced birefringence under oscillatory deformation, provided detailed insights into the contributions of various components to viscoelastic relaxation in the composite materials. The analyses indicated that the reinforcement effects were primarily driven by the tension mode of CNCs, originating from their undulated structure caused by thermal motion.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"41 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050482","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":"Backbone Stitching in Bottlebrush Copolymer Mesodomains and the Impact of Side Chain Crystallization","authors":"Mingqiu Hu, Hong-Gyu Seong, Michael S. Dimitriyev, Weiguo Hu, Zhan Chen, Xuchen Gan, Gregory M. Grason, Todd Emrick, Thomas P. Russell","doi":"10.1021/acs.macromol.4c02589","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c02589","url":null,"abstract":"We synthesized bottlebrush statistical copolymers (BSCPs) having poly(ethylene oxide) (PEO) and poly(dimethylsiloxane) (PDMS) side chains attached to a polynorbornene backbone. Small-angle X-ray scattering analysis showed that for densely grafted BSCPs, the scattering length density gradually transitions between the PEO and PDMS domains. For loosely grafted BSCPs, the polymer backbone formed a distinct mesodomain, with a lower electron and mass density than both the PEO and PDMS domains. The bottlebrush backbone essentially “stitches” the PEO and PDMS side chains, looping back and forth from the PEO to PDMS domains with the backbone segments oriented normal to the domain interfaces. Self-consistent field theory (SCFT) calculations validated the stitching of the backbone driven by the microphase separation of PEO and PDMS, along with a strong segmental order of the side chains in the melt. The reduced birefringence upon PEO crystallization suggests the disruption of the strong segmental order by the crystallization. Both the static intrinsic and the form birefringences of the BSCPs decreased upon PEO crystallization. Solid-state NMR confirmed the rigidity of PEO crystallites and the bottlebrush backbone. Self-assembly of BSCPs containing polyhedral oligomeric silsesquioxane (POSS) pendent groups was also evaluated by X-ray scattering, showing the formation of lamellar microdomains that inhibited POSS crystallization.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"97 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044384","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":"Precision Organocatalytic Synthesis of Fluoropolyesters with Enhanced Degradability and Ionic Conductivity","authors":"Chenke Zhao, Guanchen He, Tingwei Chen, Heng Li, Junpeng Zhao","doi":"10.1021/acs.macromol.4c03117","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03117","url":null,"abstract":"Extensively as fluoropolymers are studied and utilized, the impacts of fluorinated contents on polyesters are highly under-investigated. In this study, 3,3,3-trifluoropropylene oxide (TFPO) shows significantly higher activity than non-fluorinated epoxides in organocatalytic alternating copolymerization with cyclic anhydrides, which allows synthesis of well-defined fluoropolyesters under mild conditions and one-step construction of partly fluorinated tapered block copolyesters. Thermal stability of the fluoropolyesters rivals that of the non-fluorinated counterparts, while degradation by base-catalyzed methanolysis is remarkably accelerated and shown to occur selectively through cleavage of the CF₃-neighboring ester bond to form a single product. Besides, the fluoropolyesters constitute electrolytes with notably higher Li⁺ conductivity (up to 4.5 × 10^–5 S cm^–1 at 30 °C and 4.6 × 10^–4 S cm^–1 at 80 °C) as well as excellent oxidation stability at high voltage (&gt;4.5 V). Therefore, TFPO can be harnessed to set up a special toolkit for refining the synthesis and properties of polyesters.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"30 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-27","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143050419","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":"Stepwise Grafting of Polymer Single Chains onto Nanoparticles","authors":"Yajing Yang, Jiye Yang, Fenglin Li, Dayin Sun, Jintao Zhu, Zhihong Nie, Zhenzhong Yang","doi":"10.1021/acs.macromol.4c03032","DOIUrl":"https://doi.org/10.1021/acs.macromol.4c03032","url":null,"abstract":"It is important to design hierarchically structured functional polymer/inorganic composite nanoparticles (NPs) and self-organize them toward programmable superstructures thereby. We propose the synthetic approach of stepwise grafting anionic polymer single chains onto functional nanoparticles via termination, which is ensured by the strong steric hindrance effect of the grafted chains to the target chains with a comparable size. The concept is demonstrated by the precision synthesis of NP-inserted diblock copolymer analogies of PVSt-<i>b</i>-PmSt-[Fe₃O₄@SiO₂]-PMMA-<i>b</i>-P<i>t</i>BA with two different polymer single chains at the opposite sides (PVSt-<i>b</i>-PmSt: poly(4-vinylphenyl-1-butene)-<i>block</i>-poly(4-methylstyrene), PMMA-<i>b</i>-P<i>t</i>BA: poly(methylmethacrylate)-<i>block</i>-poly(<i>tert</i>-butyl acrylate)). Both end segments of PVSt and P<i>t</i>BA are reactive to derive functional groups such as amino and carboxylic acids by the orthogonal clicking reaction and hydrolysis. The functional groups allow visualization of the composite NPs by stimulated emission depletion (STED) microscopy upon selective fluorescence dyeing and the self-organization by specific interactions toward superstructures at varied pHs. The approach is valid for the stepwise grafting of six single chains of varied compositions along the three-dimensional coordinate. The composite NPs with defined numbers and types of functional groups, and thus interaction directions, provide a huge platform for diversifying superstructures, especially under external fields.","PeriodicalId":51,"journal":{"name":"Macromolecules","volume":"48 1","pages":""},"PeriodicalIF":5.5,"publicationDate":"2025-01-26","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":null,"resultStr":null,"platform":"Semanticscholar","paperid":"143044392","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}