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Polyphosphoester-modified Cellulose Nanocrystals for Stabilizing Pickering Emulsion Polymerization of Styrene

Chinese Journal of Polymer Science 2020年第9期38卷 921-931,I0005页

作者： Kun-Ming Che Ming-Zu Zhang jin-lin he Pei-Hong Ni College of Chemistry Chemical Engineering and Materials ScienceState and Local Joint Engineering Laboratory for Novel Functional Polymeric MaterialsJiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSuzhou Key Laboratory of Macromolecular Design and Precision SynthesisSoochow UniversitySuzhou 215123China

The structure and properties of functional nanoparticles are important for stabilizing Pickering emulsion polymerization.Recently,cellulose nanocrystals(CNCs)are increasingly favored as a bio-based stabilizer for Pickering emulsions.In this study,we reported a novel functionalized polyphosphoester-grafted CNCs for the stabilization of oil-in-water Pickering emulsions and the emulsion polymerization of styrene.First,polyphosphoester containing an amino group at one end of the chain,abbreviated as PBYP-NH2,was prepared by ring-opening polymerization(ROP)and hydrolysis reaction,wherein PBYP represents poly[2-(but-3-yn-1-yloxy)-2-oxo-1,3,2-dioxaphospholane].Subsequently,CNC-COOH was obtained via 2,2,6,6-tetramethylpiperidine-1-oxyl(TEMPO)oxidation of CNCs.The functionalized nanocrystals CNC-PBYP-COOH with carboxyl groups and polyphosphoester on the surface were obtained by the amidation reaction of PBYP-NH2 with CNC-COOH.Finally,we used CNC-PBYP-COOH as sole particle emulsifiers to stabilize styrene-in-water Pickering emulsions and studied its effects on the emulsions in details by using dynamic light scattering(DLS).The results indicated that the properties of these emulsions depended on the concentration of hydrophobically modified CNCs,volume ratios of oil to water,and pH values.The modified CNCs had higher ability to stabilize the styrene-in-water emulsions relative to the unmodified CNCs,and a stable oil-in-water(o/w)Pickering emulsion with diameter of hundreds of nanometers could be obtained.The resulting emulsions could be polymerized to yield nanosized latexes.The polyphosphoester-modified CNCs as green particle emulsifiers can efficiently stabilize nanoemulsions and latexes,which would promote the development of novel environmentally friendly materials.

关键词： Cellulose nanocrystals(CNCs) Polyphosphoesters(PPEs) Pickering emulsion Emulsion polymerization

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Effect of Sequence Structure on Wetting Behaviors of Fluorinated Methacrylate Polymers Based on Perfluorohexylethyl Methacrylate and Stearyl Acrylate

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Chinese Journal of Polymer Science 2017年第9期35卷 1061-1072页

作者： zi-xu gu jun cheng ming-zu zhang jin-lin he 倪沛红 College of Chemistry Chemical Engineering and Materials Science State and Local Joint Engineering Laboratory for Novel Functional Polymeric Materials Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Suzhou Key Laboratory of Macromolecular Design and Precision Synthesis Soochow University Suzhou 215123 China

Due to the non-crystalline properties of short chain perfluoroalkyl groups, using short chain perfluoroalkyl to stabilize low surface free energy polymers has been a challenging task. In this study, we prepare a series of random copolymers poly（perfluorohexylethyl methacrylate）-co-poly（stearyl acrylate）（P13FMA-co-PSA） and block copolymers poly（perfluorohexylethyl methacrylate）-b-poly（stearyl acrylate）（P13FMA-b-PSA）, and systematically investigate the effects of the sequence structure and the content of 13FMA of the fluorinated copolymers on surface free energy and surface reorganization. Static/dynamic contact angle goniometry and water/oil repellency analyses demonstrate that the random polymer P13FMA-co-PSA could not achieve low surface free energy and low surface reorganization at the same time. In contrast, for the block copolymer P13FMA-b-PSA, both low surface free energy and low surface reorganization are acquired simultaneously. The results of X-ray photoelectron spectroscopy （XPS）, dynamic contact angle goniometry and differential scanning calorimetry （DSC） reveal the above-mentioned properties. The consecutive 13FMA segments improve the surface fluorine density, while the consecutive SA chains enhance the crystallinity of the SA segments, and further hinder the surface reorganization of the perfluoroalkyl groups. Therefore, P13FMA-b-PSA exhibits a higher utilization efficiency of fluorine atoms and a better structural stability than P13FMA-co-PSA.

关键词： Surface free energy Surface reorganization Perfluorohexylethyl methacrylate （13FMA） Stearyl acrylate （SA） Water/oil repellency

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SYNTheSIS OF pH-RESPONSIVE AMPHIPHILIC DIBLOCK COPOLYMERS CONTAINING POLYISOBUTYLENE via OXYANION-INITIATED POLYMERIZATION AND TheIR MULTIPLE SELF-ASSEMBLY MORPHOLOGIES

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Chinese Journal of Polymer Science 2013年第2期31卷 218-231页

作者： Huai-chao Wang Ming-zu Zhang 倪沛红 jin-lin he Ying Hao Yi-xian Wu College of Chemistry Chemical Engineering and Materials Science Soochow University Jiangsu Key Laboratory of Advanced Functional Polymer Design and Application Soochow University State Key Lab of Chemical Resource Engineering Beijing University of Chemical Technology

Two pH-responsive amphiphilic diblock copolymers, namely polyisobutylene-block-poly[2-（N,N- dimethylamino）ethyl methaerylate] （PIB-b-PDMAEMA） and polyisobutylene-block-poly（metharylic acid）（PIB-b-PMAA）, were synthesized via oxyanion-initiated polymerization, and their multiple self-assembly behaviors have been studied. An exo-01efin-terminated highly reactive polyisobutylene （HRPIB） was first changed to hydroxyl-terminated PIB （PIB-OH） via hydroboration-oxidation of C =C double bond in the chain end, and then reacted with KH to yield a potassium alcoholate of PIB （PIB-O-K＋）. PIB-O-K＋ was immediately used as a macroinitiator to polymerize DMAEMA monomer, resulting in a cationic diblock copolymer PIB-b-PDMAEMA. With the similar synthesis procedure, the anionic diblock copolymer PIB-b- PMAA could be prepared via a combination of oxyanion-initiated polymerization of tert-butyl methacrylate （tBMA） and subsequent hydrolysis of tert-butyl ester groups in PtBMA block. The functional PIB and block copolymers have been fully characterized by 1H-NMR, FT-IR spectroscopy, and gel permeation chromatography （GPC）. These samples allowed us to systematically investigate the effects of block composition on the pH responsivity and various self-assembled morphologies of the copolymers in THF/water mixed solvent. Transmission electron microscopy （TEM） images revealed that these diblock copolymers containing small amount of original PIB without exo-olefin-terminated group are able to self-assemble into micelles, vesicles with different particle sizes and cylindrical aggregates, depending on various factors including block copolymer composition, solvent polarity and pH value.

关键词： Oxyanion-initiated polymerization Polyisobutylene Stimuli responsivity Amphiphilic copolymer Self- assembly.

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Monoclonal Antibody-conjugated Polyphosphoester-hyd-DOX Prodrug Nanoparticles for Targeted Chemotherapy of Liver Cancer Cells

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Chinese Journal of Polymer Science 2021年第11期39卷 1392-1402页

作者： Ya-Kui Huang Hong-Rui Tian Ming-Zu Zhang jin-lin he Jian Liu Pei-Hong Ni College of Chemistry Chemical Engineering and Materials ScienceState and Local Joint Engineering Laboratory for Novel Functional Polymeric MaterialsJiangsu Key Laboratory of Advanced Functional Polymer Design and ApplicationSuzhou Key Laboratory of Macromolecular Design and Precision SynthesisSoochow UniversitySuzhou 215123China Institute of Functional Nano and Soft Materials(FUNSOM) Soochow UniversitySuzhou 215123China

In order to overcome the limitation of traditional active nano-therapeutic drugs on tumor targeting efficiency which cannot reach the receptor/target in sufficient amount in the body,in this work,we developed a monoclonal antibody(mAb)and a polymer-hyd-doxorubicin prodrug conjugate,which enables the self-assembled nanoparticles to have precise targeting,tumor tissue aggregation and pH-sensitive drug release.We first prepared an amphiphilic polymer prodrug,abbreviated as H2N-PEEP-b-PBYP-hyd-DOX,via a combination of ring-opening polymerization(ROP)and"click"chemistry,in which PEEP and PBYP represent two kinds of phosphoester segmemts,-hyd-is hydrazone bond.After self-assembly into prodrug nanoparticles(PDNPs)with a diameter of about 93 nm,CD147 mAb was conjugated onto the PDNPs by EDC/NHS chemistry to form mAb-PDNPs.For the PDNPs and mAb-PDNPs,we also investigated their stability,in vitro drug release behavior and cellular uptake.The results showed that the pH-responsive PDNPs can remain relatively stable under the condition of PB 7.4 buffer solution.However,under acidic conditions or in the presence of phosphodiesterase I(PDE I),both the amount and rate of DOX release increased at the same incubation period.Cytotoxicity assay showed that mAb-PDNPs exhibited higher cytotoxicity(IC50:1.12 mg·L^(-1))against hepG2 cells than PDNPs(IC50:2.62 mg·L^(-1))without monoclonal antibody.The nanoparticles with antibodies mAb-PDNPs have relatively better stability and can directly achieve the targeting drug delivery through CD147 mAb.

关键词： Monoclonal antibody Polymeric prodrug Polyphosphoester Drug delivery Targeted therapy

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Spin effect on redox acceleration and regioselectivity in Fe-catalyzed alkyne hydrosilylation

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National Science Review 2024年第2期11卷 155-167页

作者： Peng he Meng-Yang Hu jin-Hong Li Tian-Zhang Qiao Yi-lin Lu Shou-Fei Zhu Frontiers Science Center for New Organic Matter State Key Laboratory and Institute of Elemento-Organic Chemistry Nankai University

Iron catalysts are ideal transition metal catalysts because of the Earths abundant, cheap, biocompatible features of iron salts. Iron catalysts often have unique open-shell structures that easily undergo spin crossover in chemical transformations, a feature rarely found in noble metal catalysts. Unfortunately, little is known currently about how the open-shell structure and spin crossover affect the reactivity and selectivity of iron catalysts, which makes the development of iron catalysts a low efficient trial-and-error program. In this paper, a combination of experiments and theoretical calculations revealed that the iron-catalyzed hydrosilylation of alkynes is typical spin-crossover catalysis. Deep insight into the electronic structures of a set of well-defined open-shell active formal Fe(0) catalysts revealed that the spin-delocalization between the iron center and the 1,10-phenanthroline ligand effectively regulates the iron center's spin and oxidation state to meet the opposite electrostatic requirements of oxidative addition and reductive elimination, respectively,and the spin crossover is essential for this electron transfer process. The triplet transition state was essential for achieving high regioselectivity through tuning the nonbonding interactions. These findings provide an important reference for understanding the effect of catalyst spin state on reaction. It is inspiring for the development of iron catalysts and other Earth-abundant metal catalysts, especially from the point of view of ligand development.

关键词： spin effect spin-delocalization spin crossover iron-catalysis alkyne hydrosilylation

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Construction of algal-bacterial consortia using green microalgae Chlorella vulgaris and As(Ⅲ)-oxidizing bacteria:As tolerance and metabolomic profiling

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Journal of Environmental Sciences 2024年第5期139卷 258-266页

作者： Xiaoman he Guobing lin Jiayuan Zeng Zhaoguang Yang lin Wang College of Chemistry and Chemical Engineering Central South UniversityChangsha 410083China Key Laboratory of Hunan Province for Water Environment and Agriculture Product Safety Central South UniversityChangsha 410083China

Bioremediation became a promising technology to resolve arsenic(As)contamination in aquatic environment.Since monoculture such as microalgae or bacteria was sensitive to environmental disturbance and vulnerable to contamination,green microalgae Chlorella vulgaris and arsenite(As(Ⅲ))-oxidizing bacteria Pseudomonas sp.SMS11 were co-cultured to construct algal-bacterial consortia in the current study.The effects of algae-bacteria(A:B)ratio and exposure As(Ⅲ)concentration on algal growth,As speciation and metabolomic profile were investigated.Algal growth arrested when treated with 100 mg/L As(Ⅲ)without the co-cultured bacteria.By contrast,co-cultured with strain SMS11 significantly enhanced As tolerance in C.vulgaris especially with A:B ratio of 1:10.All the As(Ⅲ)in culture media of the consortia were oxidized into As(Ⅴ)on day 7.Methylation of As was observed on day 14.Over 1% and 0.5% of total As were converted into dimethylarsinic acid(DMA)after 21days cultivation when the initial concentrations of As(Ⅲ)were 1 and 10 mg/L,respectively.Metabolomic analysis was further performed to reveal the response of consortia metabolites to external As(Ⅲ).The enriched metabolomic pathways were associated with carbohydrate,amino acid and energy metabolisms.Tricarboxylic acid cycle and glyoxylate and dicarboxylate metabolism were upregulated under As stress due to their biological functions on alleviating oxidative stress and protecting cells.Both carbohydrate and amino acid metabolisms provided precursors and potential substrates for energy production and cell protection under abiotic stress.Alterations of the pathways relevant to carbohydrate or amino acid metabolism were triggered by energy requirement.

关键词： Microalgae Algal-bacterial consortia As(Ⅲ)-oxidizing bacteria Metabolomics Energy metabolism

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Emerging role of lncRNAs as mechanical signaling molecules in mechanotransduction and their association with Hippo-YAP signaling:a review

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Journal of Zhejiang University-Science B(Biomedicine & Biotechnology) 2024年第4期25卷 280-292页

作者： Siyi lin Xinyu he Ying WANG Yu CheN Aifu lin College of Medicine Zhejiang UniversityHangzhou 310058China College of Life Sciences Zhejiang UniversityHangzhou 310058China Cancer Center Zhejiang UniversityHangzhou 310058China Key Laboratory for Cell and Gene Engineering of Zhejiang Province Hangzhou 310058China International School of Medicine International Institutes of Medicinethe Fourth Affiliated Hospital of Zhejiang University School of MedicineYiwu 322000China Key Laboratory of Cancer Prevention and Intervention China National Ministry of EducationHangzhou 310058China Future health Laboratory Innovation Center of Yangtze River DeltaZhejiang UniversityJiaxing 314100China

Cells within tissues are subject to various mechanical forces,including hydrostatic pressure,shear stress,compression,and tension.These mechanical stimuli can be converted into biochemical signals through mechanoreceptors or cytoskeleton-dependent response processes,shaping the microenvironment and maintaining cellular physiological balance.Several studies have demonstrated the roles of Yes-associated protein(YAP)and its homolog transcriptional coactivator with PDZ-binding motif(TAZ)as mechanotransducers,exerting dynamic influence on cellular phenotypes including differentiation and disease pathogenesis.This regulatory function entails the involvement of the cytoskeleton,nucleoskeleton,integrin,focal adhesions(FAs),and the integration of multiple signaling pathways,including extracellular signal-regulated kinase(ERK),wingless/integrated(WNT),and Hippo signaling.Furthermore,emerging evidence substantiates the implication of long non-coding RNAs(lncRNAs)as mechanosensitive molecules in cellular mechanotransduction.In this review,we discuss the mechanisms through which YAP/TAZ and lncRNAs serve as effectors in responding to mechanical stimuli.Additionally,we summarize and elaborate on the crucial signal molecules involved in mechanotransduction.

关键词： YAP/TAZ Long non-coding RNA(lncRNA) Mechanotransduction F-actin

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Mitigating gut immune adverse effects in CTLA-4 blockade for antitumor efficacy

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Science China(Life Sciences) 2024年第7期67卷 1539-1541页

作者： Shijun he Jianping Zuo Zemin lin Laboratory of Immunopharmacology State Key Laboratory of Drug ResearchShanghai Institute of Materia MedicaChinese Academy of SciencesShanghai 201203China Innovation Research Institute of Traditional Chinese Medicine Shanghai University of Traditional Chinese MedicineShanghai 201203China School of Pharmacy University of Chinese Academy of SciencesBeijing 100049China

By creating an immune checkpoint blockade-induced colitis model,Lo et al.(2024)have suggested a strategy for alleviating gastrointestinal immune-related adverse events while preserving the antitumor stimulatory effect... 详细信息

关键词： al. immune gastrointestinal

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Study of primordial deuterium abundance in Big Bang nucleosynthesis

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Nuclear Science and Techniques 2024年第3期35卷 208-215页

作者： Zhi-lin Shen Jian-Jun he Key Laboratory of Beam Technology of Ministry of Education College of Nuclear Science and TechnologyBeijing Normal UniversityBeijing 100875China Institute of Radiation Technology Beijing Academy of Science and TechnologyBeijing 100875China

Big Bang nucleosynthesis(BBN)theory predicts the primordial abundances of the light elements^(2) H(referred to as deuterium,or D for short),^(3)he,^(4)he,and^(7) Li produced in the early universe.Among these,deuterium,the first nuclide produced by BBN,is a key primordial material for subsequent reactions.To date,the uncertainty in predicted deuterium abundance(D/H)remains larger than the observational precision.In this study,the Monte Carlo simulation code PRIMAT was used to investigate the sensitivity of 11 important BBN reactions to deuterium abundance.We found that the reaction rate uncertainties of the four reactions d(d,n)^(3)he,d(d,p)t,d(p,γ)^(3)he,and p(n,γ)d had the largest influence on the calculated D/H uncertainty.Currently,the calculated D/H uncertainty cannot reach observational precision even with the recent LUNA precise d(p,γ)^(3) he rate.From the nuclear physics aspect,there is still room to largely reduce the reaction-rate uncertainties;hence,further measurements of the important reactions involved in BBN are still necessary.A photodisintegration experiment will be conducted at the Shanghai Laser Electron Gamma Source Facility to precisely study the deuterium production reaction of p(n,γ)d.

关键词： Big Bang nucleosynthesis Abundance of deuterium Reaction cross section Reaction rate Monte Carlo method

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Clinical efficacy and gene chip expression analysis of Shenzhu Guanxin recipe granules(参术冠心方颗粒) in patients with intermediate coronary lesions

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Journal of Traditional Chinese Medicine 2024年第3期44卷 545-553页

作者： jin Xiao WU Bingxin lin Miaoyang ZHONG Biying lin Luoqi XU Danping Department of Traditional Chinese Medicine the First Affiliated Hospital of Jinan UniversityJinan University Department of Cardiology Second Clinical College of Guangzhou University of Chinese Medicine Department of Traditional Chinese Medicine the Eighth Affiliated HospitalSun Yat-Sen University

OBJECTIVE: To evaluate the clinical efficacy and safety of Shenzhu Guanxin recipe granules(参术冠心颗粒, SGR) in treating patients with intermediate coronary lesions(ICL), and to investigate the potential mechanism though a transcriptome sequencing approach. METHODS: ICL patients with Qi deficiency and phlegm stasis were adopted and randomly assigned to a case group or a control by random number generator in a 1∶1 randomization ratio to evaluate the clinical efficacy. RESULTS: There was no significant difference between the two groups in coronary computed tomography angiography related indexes in the two groups before and after intervention. Through the gene chip expression analysis, it is finally concluded that there are 355 differential mRNAs(190 up-regulated genes and 165 down regulated genes) when compared the SGR group and placebo group. Through protein-protein interaction network analysis of differentially expressed genes, 10 hub genes were finally obtained: CACNA2D2, CACNA2D3, DNAJC6, FGF12, SGSM2, CACNA1G, LRP6, KIF25, OXTR, UPB1. CONCLUSIONS: SGR combined with Western Medicine can be safely used to treat ICL patients with Qi deficiency and phlegm stasis. The possible mechanism of action and relevant gene loci and pathway were proposed.

关键词： Shenzhu Guanxin recipe granules deficiency and phlegm stasis gene expression profiling intermediate coronary lesions

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