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Production of Functional Materials Derived from Regenerated Silk Fibroin by Utilizing 3D Printing and Biomimetic Enzyme-induced Mineralization

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Chinese Journal of Polymer Science 2024年第3期42卷 299-310,I0005页

作者： Ni chen Fei-Yu Luo Gong-Wen Yang Jin-Rong Yao xin chen Zheng-zhong Shao State Key Laboratory of Molecular Engineering of Polymers Laboratory of Advanced Materials and Department of Macromolecular ScienceFudan UniversityShanghai 200433China

Critical-sized bone defects, commonly encountered in clinical orthopedic surgery, present a significant challenge. One of the promising solutions is to prepare synthetic bone substitute materials with precise structural control, mechanical compatibility, and enhanced osteogenic induction performance, nevertheless the successful preparation of such materials remains difficult. In this study, a two-step technique,integrating an extrusion-based printing process with biomimetic mineralization induced by alkaline phosphatase(ALP), was developed. Initially,a pre-cured hydrogel of regenerated silk fibroin(RSF) with a small quantity of hydroxypropyl cellulose(HPC) and ALP was prepared through heating the mixed aqueous solution. This pre-cured hydrogel demonstrated thixotropic property and could be directly extruded into predetermined structures through a 3D-printer. Subsequently, the 3D-printed RSF-based materials with ALP underwent biomimetic in situ mineralization in calcium glycerophosphate(Ca-GP) mineralizing solution, utilizing the polymer chains of RSF as templates and ALP as a trigger for cleaving phosphate bonds of Ca-GP. The resulting 3D-printed RSF-mineral composites including hydrogel and sponge possessed adjustable compression modulus of megapascal grade and variable hydroxyapatite content, which could be controlled by manipulating the duration of the mineralization process.Moreover, these 3D-printed RSF-mineral composites demonstrated non-cytotoxicity towards rat bone marrow mesenchymal stem cells. Therefore, they may hold great potential for applications involving the replacement of tissues characterized by osteoinductivity and intricate structures.

关键词： Silk protein Alkaline phosphatase Extrusion-based printing Biomineralization

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Engineering g-C_(3)N_(4)based materials for advanced photocatalysis:Recent advances

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Green Energy & Environment 2024年第2期9卷 166-197页

作者： xin-Lian Song Lei chen Li-Jiao Gao Jin-Tao Ren zhong-Yong Yuan National Institute for Advanced Materials School of Materials Science and EngineeringSmart Sensing Interdisciplinary Science CenterNankai UniversityTianjin300350China Key Laboratory of Advanced Energy Materials Chemistry(Ministry of Education) Nankai UniversityTianjin300071China

Photocatalysis driven by abundant yet intermittent solar energy has considerable potential in renewable energy generation and environmental remediation.The outstanding electronic structure and physicochemical properties of graphitic carbon nitride(g-C_(3)N_(4)),together with unique metal-free characteristic,make them ideal candidates for advanced photocatalysts construction.This review summarizes the up-to-date advances on g-C_(3)N_(4)based photocatalysts from ingenious-design strategies and diversified photocatalytic applications.Notably,the advantages,fabrication methods and limitations of each design strategy are systemically analyzed.In order to deeply comprehend the inner connection of theory–structure–performance upon g-C_(3)N_(4)based photocatalysts,structure/composition designs,corresponding photocatalytic activities and reaction mechanisms are jointly discussed,associated with introducing their photocatalytic applications toward water splitting,carbon dioxide/nitrogen reduction and pollutants degradation,etc.Finally,the current challenges and future perspectives for g-C_(3)N_(4)based materials for photocatalysis are briefly proposed.These design strategies and limitations are also instructive for constructing g-C_(3)N_(4) based materials in other energy and environment-related applications.

关键词： Graphitic carbon nitride g-C_(3)N_(4) Design strategies Photocatalysis Photocatalysts Reaction mechanism

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Spark plasma sintering of tungsten-based WTaVCr refractory high entropy alloys for nuclear fusion applications

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International Journal of Minerals,Metallurgy and Materials 2024年第1期31卷 146-154页

作者： Yongchul Yoo Xiang Zhang Fei Wang xin chen xing-zhong Li Michael Nastasi Bai Cui Department of Mechanical&Materials Engineering University of Nebraska-LincolnLincolnNE 68588USA Nebraska Center for Materials and Nanoscience University of Nebraska-LincolnLincolnNE 68588USA Department of Nuclear Engineering Texas A&M UniversityCollege StationTX 77843USA

W-based WTaVCr refractory high entropy alloys (RHEA) may be novel and promising candidate materials for plasma facing components in the first wall and diverter in fusion reactors. This alloy has been developed by a powder metallurgy process combining mechanical alloying and spark plasma sintering (SPS). The SPSed samples contained two phases, in which the matrix is RHEA with a body-centered cubic structure, while the oxide phase was most likely Ta2VO6through a combined analysis of X-ray diffraction (XRD),energy-dispersive spectroscopy (EDS), and selected area electron diffraction (SAED). The higher oxygen affinity of Ta and V may explain the preferential formation of their oxide phases based on thermodynamic calculations. Electron backscatter diffraction (EBSD) revealed an average grain size of 6.2μm. WTaVCr RHEA showed a peak compressive strength of 2997 MPa at room temperature and much higher micro-and nano-hardness than W and other W-based RHEAs in the literature. Their high Rockwell hardness can be retained to at least 1000°C.

关键词： refractory high entropy alloy plasma-facing material fusion reactor spark plasma sintering

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Design and simulation investigations on charge transport layers‑free in lead‑free three absorber layer all‑perovskite solar cells

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Frontiers of Optoelectronics 2024年第2期17卷 69-85页

作者： Guangdong Li Mingxiang Xu zhong chen School of Physics Southeast UniversityNanjing 211189China

The multiple absorber layer perovskite solar cells(PSCs)with charge transport layers-free(CTLs-free)have drawn widespread research interest due to their simplified architecture and promising photoelectric characteristics.Under the circumstances,the novel design of CTLs-free inversion PSCs with stable and nontoxic three absorber layers(triple Cs_(3)Bi_(2)I_(9),single MASnI_(3),double Cs_(2)TiBr_(6))as optical-harvester has been numerically simulated by utilizing wxAMPS simulation software and achieved high power conversion efficiency(PCE)of 14.8834%.This is owing to the innovative architecture of PSCs favors efficient transport and extraction of more holes and the slender band gap MASnI_(3)extends the absorption spectrum to the near-infrared periphery compared with the two absorber layers architecture of PSCs.Moreover,the performance of the device with p-type-Cs_(3)Bi_(2)I_(9)/p-type-MASnI_(3)/n-type-Cs_(2)TiBr_(6)architecture is superior to the one with the p-type-Cs_(3)Bi_(2)I_(9)/ntype-MASnI_(3)/n-type-Cs_(2)TiBr_(6)architecture due to less carrier recombination and higher carrier life time inside the absorber layers.The simulation results reveal that Cs_(2)TiF_(6)double perovskite material stands out as the best alternative.Additionally,an excellent PCE of 21.4530%can be obtained with the thicker MASnI_(3)absorber layer thickness(0.4μm).Lastly,the highestperformance photovoltaic devices(28.6193%)can be created with the optimized perovskite doping density of around E15 cm^(3)(Cs_(3)Bi_(2)I_(9)),E18 cm^(3)(MASnI_(3)),and 1.5E19 cm^(3)(Cs_(2)TiBr_(6)).This work manifests that the proposed CTLs-free PSCs with multi-absorber layers shall be a relevant reference for forward applications in electro-optical and optoelectronic devices.

关键词： Multiple absorber layer PSCs CTLS-free·Inverted Narrow-band gap Simulation

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A highly reduced Mo_(74) polyoxometalate featuring high proton conductivity accessed by building block strategy

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Science China Chemistry 2024年第3期67卷 862-868页

作者： Shi-Yi Liu Xue-xin Li Wei-Chao chen Kui-Zhan Shao xin-Long Wang Chao Qin zhong-Min Su Key Laboratory of Polyoxometalate and Reticular Material Chemistry of Ministry of Education Department of ChemistryNortheast Normal UniversityChangchun 130024China State Key Laboratory of Supramolecular Structure and Materials Institute of Theoretical ChemistryCollege of ChemistryJilin UniversityChangchun 130021China

Highly reduced polyoxometalates(POMs) are predicted to be used as rather high energy density materials;however,it still suffers from the limited cluster species and reduction ratio.Here we demonstrate that it is possible to employ the building block strategy to generate a highly reduced polyoxomolybdate(C_(2)H_(8)N)_(14)(NH_(4))_(4)H_(14)[Mo_(48)-ⅤMo_(26)ⅥO_(202)(OH)_(12)(SO_(4))_(6)]·46H_(2)O(Mo_(74)).The fundamental Mo-based{Mo_x}(x=4,5,and 6) building blocks,which are templated by tetra-coordinated anions{MoO_(4)}or{SO_(4)},not only lay foundation for the formation of Mo_(74) featuring an unprecedented reduction ratio of 65%,but also give rise to SBBs-mediated(secondary building blocks) supramolecular dense packing interactions among the isolated Mo_(74) clusters that are favorable for proton conduction.Remarkably,high proton conductivity(2.04×10^(-2)S cm^(-1)) had been realized at 50℃ and 90% relative humidity,revealing one of the well-known POMs-based crystalline proton conducting materials.This result highlights that this building block approach possesses great potential in producing highly reduced POM systems that can achieve controllable reduced ratio and desirable properties.

关键词： polyoxometalate building block molybdenum highly reduced state proton conduction

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Boosting thermal stability and crystallization of closed-loop-recyclable biodegradable poly(p-dioxanone) by end-group regulation

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Science China Chemistry 2024年第2期67卷 642-651页

作者： Jin Lei Zhu-xin Gui Wan-Ting Xiong Gang Wu Si-Chong chen Yu-zhong Wang The Collaborative Innovation Center for Eco-Friendly and Fire-Safety Polymeric Materials(MoE) National Engineering Laboratory of Eco-Friendly Polymeric Materials(Sichuan)State Key Laboratory of Polymer Materials EngineeringCollege of ChemistrySichuan UniversityChengdu610064China

A chemically closed-loop-recyclable biodegradable polymer,poly(p-dioxanone)(PPDO),is one of the ideal candidates for single-use plastic products due to its suitability for different application scenarios.Fascinatingly,when PPDO wastes can be collected,its monomer p-dioxanone(PDO) will be obtained through chemical recycling of these wastes;when cannot be collected,the wastes are able to be biodegraded into harmless substances.However,unsatisfied thermal stability and low crystallization rate of PPDO restrict its wider applications.Herein,based on end-group regulation,we simultaneously realized the significant enhancement of thermal stability and crystallization of PPDO through the simple melt processing with tributyl phosphite(TBP) or triphenyl phosphite(TPP).The model reactions were conducted to investigate the reaction mechanism and theoretical products during the preparation of PPDO/phosphite compounds.Two kinds of phosphites were proved to act as the end-capped reagent and chain extender in the melt processing,while TBP presented better reactivity.As a result,the activation energy of thermal decomposition was largely elevated,and the unprecedented T_(5%)(the temperature at a weight loss of 5%) and Tmax(the temperature at a maximum rate of weight loss) of PPDO were obtained,i.e.,T_(5%)of ~330 ℃ and Tmaxof ~385 ℃ in N_(2) atmosphere,T_(5%)of ~240 ℃ and Tmaxof ~317 ℃ in air atmosphere,respectively.Furthermore,the increased crystallization rate,crystallinity,crystalline orderliness,and realizable monomer recovery(yield >90%,purity >99.9%) of PPDO/phosphite compounds were confirmed.

关键词： poly(p-dioxanone) phosphite thermal stability crystallization end-group regulation

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Evaluation of water management on arsenic methylation and volatilization in arsenic-contaminated soils strengthened by bioaugmentation and biostimulation

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Journal of Environmental Sciences 2024年第3期137卷 515-526页

作者： Peng chen Yi Liu Guo-xin Sun State Key Laboratory of Urban and Regional Ecology Research Center for Eco-Environmental SciencesChinese Academy of SciencesBeijing 100085China Key Laboratory of Aquatic Botany and Watershed Ecology Wuhan Botanical GardenChinese Academy of SciencesWuhan 430074China University of Chinese Academy of Sciences Beijing 100049China

Arsenic(As) fate in paddy fields has been one of the most significant current issues due to the strong As accumulation potential of rice plants under fooded conditions. However,no attempt was done to explore As methylation and volatilization under non-fooded conditions. Herein, we investigated the effects of water management on As methylation and volatilization in three arsenic-contaminated soils enhanced by biostimulation with strawderived organic matter and bioaugmentation with genetic engineered Pseudomonas putida KT2440(GE P. putida). Under fooded conditions, the application of biochar(BC), rice straw(RS)and their combination(BC+RS) increased total As in porewater. However, these effects were greatly attenuated under non-fooded conditions. Compared with RS amendment alone, the combination of GE P. putida and RS further promoted the As methylation and volatilization,and the promotion percentage under non-fooded conditions were significantly higher than that under fooded conditions. The combined GE P. putida and RS showed the highest efficiency in As methylation(88 μg/L) and volatilization(415.4 μg/(kg·year)) in the non-fooded soil with moderate As contamination. Finally, stepwise multiple linear regression analysis presented that methylated As, DOC and p H in porewater were the most important factors contributing to As volatilization. Overall, our findings suggest that combination of bioaugmentation with GE P. putida and biostimulation with RS/BC+RS is a potential strategy for bioremediation of arsenic-contaminated soils by enhancing As methylation and volatilization under non-fooded conditions.

关键词： Arsenic methylation Arsenic volatilization Water management Straw incorporation Bioaugmentation

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An Effective Approach for the Preparation of High Performance Thermal Conductive Polymer Composites Containing Liquid Metal

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Chinese Journal of Polymer Science 2024年第7期42卷 992-1001,I0010页

作者： xin chen Xue-zhong Zhang Yi-Fei Yuan Chuan-Liang chen Lian-Hu Xiong Qiang Fu Hua Deng College of Polymer Science and Engineering State Key Laboratory of Polymer Materials EngineeringSichuan UniversityChengdu610065China Department of Materials Science and Engineering Sichuan University-Pittsburgh InstituteSichuan UniversityChengdu610065China

The preparation of high-performance thermal conductive composites containing liquid metals(LM)has attracted significant attention.However,the stable dispersion of LM within polymer solution and effective property contribution of liquid metals remains significant challenges that need to be overcome.Inspired by the properties of the dendritic structure of the tree root system in grasping the soil,“shear-induced precipitation-interfacial reset-reprotonation”processing strategy is proposed to prepare nanocomposites based on aramid micron fibers(AMFs)with hierarchical dendritic structure.Thanks to the combination of van der Waals force provided by hierarchical dendritic structure,electrostatic interaction between AMFs and LM,coordinative bonding of―NH to LM,together with interfacial re-setting and multi-step protonation,several features can be achieved through such strategy:conducive to the local filler network construction,improvement of interfacial interaction,improvement of the stability of filler dispersion in the solvent,and enhancement of mechanical and thermal properties of the films.The resulting AMFsp H=4/LM films demonstrate a thermal conductivity of 10.98 W·m^(-1)·K^(-1)at 70%filler content,improvement of 126.8%compared to ANFs/LM film;while maintaining a strength of~85.88 MPa,improvement of 77%compared to AMFs/LM film.They also possess insulation properties,enable heat dissipation for high power electronics.This work provides an effective strategy for the preparation of high performance polymer composites containing liquid metal.

关键词： Shear-induced Reprotonation AMFs LM Filler dispersion

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High cerium content(Nd-Pr-Ce)_(2)Fe_(14)B melt-spun ribbons with high coercivity

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Journal of Rare Earths 2024年第4期42卷 690-695页

作者： Yujiang zhong Junming Wang Zikai Yuan Ruijin Liu Minggang Zhu Zhe Liu xin chen Wei Li Zhaohui Guo Division of Functional Materials Central Iron and Steel Research InstituteBeijing100081China Ningbo Jinji Strong Magnetic Material Co. Ltd.Ningbo315172China Jiangxi Jiangwu Rare Metal New Material Co. Ltd.Nanchang330013China

The effects of wheel speeds on the magnetic properties and microstructures of[(Nd,Pr)_(1-x)Ce_(x)]-Fe-B meltspun ribbons were investigated.Compared to melt-spun ribbons with low cerium(Ce)content(x=0.2),amorphous formation can be suppressed at high wheel speed in the ribbons with a relatively high Ce content(x=0.8),and with the increase of the wheel speed,the magnetic properties of the ribbons with high Ce content raise continuously.At high wheel speed,the coercivity mechanism of melt-spun ribbons is mainly pinning field,and the high wheel speed introduces a large number of defects into the matrix as pinning sites.Furthermore,ribbons with high Ce content form a fine and uniform grain structure,so the grain boundary area enlarges,which further hinders the movement of domain walls.The combined effects of the above factors enable ribbons with high Ce content to have excellent magnetic properties(Hcj=0.977 T,Mr=64 m^(2) A/kg)at the wheel speed of 35 m/s.

关键词： Wheel speed Cecontent Microstructure Magnetic properties Rare earths

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Comparison of cell salvage with one and two suction devices during cesarean section in patients with placenta previa and/or accrete: a randomized controlled trial

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Chinese Medical Journal 2020年第6期133卷 638-643页

作者： Hong chen Hua Tan Pei-xin Luo Yi-Fang Shen Chang-cheng Lyu Xiao-Wei Qian xin-zhong chen Department of Anesthesia Women's HospitalZhejiang University School of MedicineHangzhouZhejiang 310006China Department of Clinical Laboratory Women's HospitalZhejiang University School of MedicineHangzhouZhejiang 310006China

Background:Cell salvage has recently been recommended for obstetric use in cases with a high risk of massive hemorrhage during cesarean section(CS).However,limited data are available to support the use of one suction device to collect lost blood.This study aimed to investigate the volume of red blood cells(RBCs)salvaged and the components of amniotic fluid(AF)in blood salvaged by one suction device or two devices during CS in patients with placenta previa and/or accrete.Methods:Thirty patients with placenta previa and/or accrete undergoing elective CS in the Women's Hospital of Zhejiang University School of Medicine were recruited for the present study from November 1,2017 to December 1,2018.The patients were randomly assigned to one of the two groups according to an Excel-generated random number sheet:Group 1(w=15),in which only one suction device was used to aspirate all blood and AF,and Group 2(w=15),in which a second suction device was mainly used to aspirate AF before the delivery of the placenta.Three samples of blood per patient(pre-wash,post-wash,and post-filtration)were collected to measure AF components.The salvaged RBC volumes were recorded.Continuous data of pre-wash,post-wash,and postfiltration samples were analyzed by using one-way analysis of variance with Tukey5s test for multiple comparisons,or Kruskal-Wallis test with Dunn test for multiple comparisons.Comparisons of continuous data between Group 1 and Group 2 were conducted using Student's t test or Mann-Whitney U test.Results:The salvaged RBC volume was significantly higher in Group 1 than that in Group 2(401.6±77.2 mL vs.330.1土53.3 mL,?=4.175,P<0.001).In both groups,squamous cells,lamellar bodies,and fat were significantly reduced by washing(all P<0.001)and squamous cells were further reduced by filtering(P<0.001).Squamous cells were found in six post-filtration samples(three from each group).Lamellar bodies and fat were completely removed by filtering.Insulin-like growth factor binding protein 1,alphafetoprotein,albumin,lactate dehydrogenase

关键词： Cell salvage Blood transfusion Placenta previa Placenta accrete Cesarean section

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