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Mg-Al-hydrotalcite with alkaline sites protects Ni/KIT-6 from formation of amorphous coke in glycerol steam reforming via tailoring reaction intermediates

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Frontiers of Chemical Science and Engineering 2024年第4期18卷 25-39页

作者： Yunyu Guo Yiran wang Yuewen shao Shu Zhang Yi wang Song Hu Jun Xiang xun Hu School of Material Science and Engineering University of JinanJinan 250022China Joint International Research Laboratory of Biomass Energy and Materials College of Materials Science and EngineeringNanjing Forestry UniversityNanjing 210037China State Key Laboratory of Coal Combustion Huazhong University of Science and TechnologyWuhan 430074China

During steam reforming,the performance of a catalyst and amount/property of coke are closely related to reaction intermediates reaching surface of a catalyst.Herein,modification of reaction intermediates by placing Mg-Al-hydrotalcite above Ni/KIT-6 catalyst in steam reforming of glycerol was conducted at 300 to 600°C.The results revealed that the catalytic activity of Ni/KIT-6 in the lower bed was enhanced with either Mg1-Al5-hydrotalcite(containing more acidic sites)or Mg5-Al1-hydrotalcite(containing more alkaline sites)as upper-layer catalyst.The in situ infrared characterization of steam reforming demonstrated that Mg-Al-hydrotalcite catalyzed the deoxygenation of glycerol,facilitating the reforming of the partially deoxygenated intermediates over Ni/KIT-6.Mg-Al-hydrotalcite as protective catalyst,however,did not protect the Ni/KIT-6 from formation of more coke.Nonetheless,this did not lead to further deactivation of Ni/KIT-6 while Mg5-Al1-hydrotalcite even substantially enhanced the catalytic stability,even though the coke was much more significant than that in the use of single Ni/KIT-6(52.7%vs.28.6%).The reason beneath this was change of the property of coke from more aliphatic to more aromatic.Mg5-Al1-hydrotalcite catalyzed dehydration of glycerol,producing dominantly reaction intermediates bearing C=C,which formed the catalytic coke of with carbon nanotube as the main form with smooth outer walls as well as higher aromaticity,C/H ratio,crystallinity,crystal carbon size,thermal stability,and resistivity toward oxidation on Ni/KIT-6 in the lower bed.In comparison,the abundance of acidic sites on Mg1-Al5-hydrotalcite catalyzed the formation of more oxygen-containing species,leading to the formation of carbon nanotubes of rough surface on Ni/KIT-6.

关键词： steam reforming of glycerol Mg-Alhydrotalcite sacrificial catalyst reaction intermediates property of coke

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Aspirin in hepatocellular carcinoma:Is it an out-of-date or promising treatment?

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iLIVER 2022年第1期1卷 55-64页

作者： xun Qiu Fengqiang Gao Kai wang Zhensheng Zhang Chuxiao shao Xiao Xu Key Laboratory of Integrated Oncology and Intelligent Medicine of Zhejiang Province Department of Hepatobiliary and Pancreatic SurgeryAffiliated Hangzhou First People's HospitalZhejiang University School of MedicineHangzhou310006China Westlake Laboratory of Life Sciences and Biomedicine Hangzhou310024China NHC Key Laboratory of Combined Multi-organ Transplantation Hangzhou310003China Institute of Organ Transplantation Zhejiang UniversityHangzhou310003China Department of Hepatobiliary and Pancreatic Surgery Affiliated Lishui HospitalZhejiang University School of MedicineLishui323000China

Hepatocellular carcinoma(HCC)is one of the most aggressive human malignancies with a dismal survival rate.Few strategies can effectively prevent the occurrence of HCC.Although immunotherapy has significantly improved HCC-related survival in recent years,this systemic therapy is very expensive and lays a heavy burden on most HCC patients.Aspirin,which is currently one of the most widely used medications in analgesic and cardiovascular diseases,is reported to have anti-tumor effects on HCC.Most importantly,long-term administration of low-dose aspirin does not significantly increase the risk of gastrointestinal bleeding.Owing to its costeffectiveness and wide use,aspirin can be easily applied as an HCC treatment and is affordable for a wide range of patients.Therefore,deeper understanding and more attention are needed to extend the frontline of aspirin's preventive and therapeutic potential into cancer research and management.In this review,we discuss the preventive effect of aspirin on HCC in the context of different etiological factors,including hepatitis B or hepatitis C virus infection,non-alcoholic fatty liver disease,and alcohol-associated liver disease.The therapeutic role of aspirin in resectable or unresectable HCC management is also discussed.Furthermore,the mechanisms underlying the anti-cancer effects of aspirin on HCC are fully reviewed and discussed in the following two aspects:the effect of aspirin on multi-oncogenic signaling pathways in HCC(e.g.,AMPK,Wnt/β-catenin,NF-κB)and aspirinmediated immunometabolic responses in liver diseases.These findings indicate aspirin is a promising agent for populations at risk and HCC patients to prevent or treat HCC.

关键词： Hepatocellular carcinoma Aspirin Chemoprevention Cancer therapy Oncogenic signaling Immunometabolic response

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High-dielectric loss black silicon decorated with multi-nanostructure for wide-band mid-infrared absorption

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Rare Metals 2023年第7期42卷 2447-2456页

作者： shao-xun Zhang Jia-Chen wang Yong-Min Zhao Yu-Lu Han An-Jie Ming Feng Wei Chang-Hui Mao State Key Laboratory of Advanced Materials for Smart Sensing GRINM Group Co.LtdBeijing100088China Department of Advanced Electronic Materials GRIMAT Engineering Institute Co.LtdBeijing101407China General Research Institute for Nonferrous Metals Beijing100088China College of Bioscience and Resources Environment Beijing University of AgricultureBeijing102206China GRINM(Guangdong)Institute for Advanced Materials and Technology Foshan528051China

Because of the excellent light-trapping ability of black silicon,it has emerged as a versatile substrate for photothermic applications.In this paper,multi-nanostructured black silicon with wide-band mid-infrared absorption properties for application in pyroelectric detectors is reported.Black silicon is fabricated on a substrate surface masked by Ag nanoparticle arrays using single-step etching of C_(4)F_(8)and SF_(6)plasma.The low absorption of black silicon in the mid-infrared region is improved when a secondary nanostructure with Pt nanoparticles and SiO_(2)thin films is deposited on the surface of the prepared black silicon by microelectromechanical system(MEMS)processes.Electrons are scattered at particle boundary,resulting in dielectric loss to incident infrared(IR)region.Compared to single black silicon,the structure decorated with the multi-nanostructure can achieve higher infrared absorption,which is contributed to the high-dielectric loss properties of the Pt nanoparticles.Simulations and experiments show that the thickness of black silicon and number of layers of platinum particles contribute to mid-infrared absorption,with wavelength ranging from 2.5 to 20.0μm,and the absorption reaches~90%.The proposed absorber provides a promising solution for thermal detectors.

关键词： Surface manufacturing Mid-infrared absorption Black silicon Multi-nanostructure Single-step etching

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从“就业”到“内创业”:大学本科教学的变革逻辑与实施方略

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教育理论与实践 2023年第12期43卷 55-60页

作者：荀禹王少奇辽宁师范大学教育学院辽宁大连116029

21世纪以来,我国开展建设高质量创新型社会的矩阵行动,加快培养和造就一大批高层次创新型人才,显得更为重要和紧迫。然而,近些年出现“慢就业”“懒就业”甚至是“躺平就业”的现象,究其主要原因是就业人才缺乏创新的专业理智与情意素... 详细信息

21世纪以来,我国开展建设高质量创新型社会的矩阵行动,加快培养和造就一大批高层次创新型人才,显得更为重要和紧迫。然而,近些年出现“慢就业”“懒就业”甚至是“躺平就业”的现象,究其主要原因是就业人才缺乏创新的专业理智与情意素养。“内创业”的提出便是针对此问题所作出的价值回应,并引领大学本科教学进行反思与变革:培养具有专业理智与情意素养的“内创业者”。基于“内创业”导向的本科教学变革应以重塑大学本科教学目标为引领,再构大学本科教学价值取向为传导,转型大学本科教学范式为引擎,打造开放创新的教学生态为保障,构建“四位一体”的本科教学变革新方略。

关键词：大学本科教学 “就业” “内创业” 目标价值取向教学范式

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Competition between acidic sites and hydrogenation sites in Cu/ZrO_(2) catalysts with different crystal phases for conversion of biomass-derived organics

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Green Energy & Environment 2021年第4期6卷 557-566页

作者： Yuewen shao Tingting wang Kai Sun Zhanming Zhang Lijun Zhang Qingyin Li Shu Zhang Guangzhi Hu xun Hu School of Material Science and Engineering University of JinanJinan250022China College of Materials Science and Engineering Nanjing Forestry UniversityNanjing210037China Institute for Ecological Research and Pollution Control of Plateau Lakes School of Ecology and Environmental ScienceYunnan UniversityKunming 650504China

Oxides with different crystal phases can have important effects on the configuration of surface atoms,which can further affect the distribution of hydrogenation sites and acidic sites as well as the competitions of these varied types of catalytic sites.This could be potentially used to tailor the distribution of the products.In this study,zirconium oxides with different crystal phases supported copper catalysts were prepared for the hydrogenation of the biomass-derived furfural,vanillin,etc.The results showed that both calcination temperature and Cu species affected the shift of zirconia from tetragonal phase to the monoclinic phase.Monoclinic zirconia supported copper catalyst can effectively catalyze the hydrogenation of furfural to furfuryl alcohol via hydrogenation route due to its low amount of Brønsted acidic sites,although the surface area and the exposed metallic Cu surface area were much lower than the tetragonal zirconia supported copper catalyst.Zirconia with tetragonal or tetragonal/monoclinic phases supported copper catalysts contain abundant acidic sites and especially the Br?nsted acidic sites,which catalyzed mainly the conversion of furfural via the acid-catalyzed routes such as the acetalization,rather than the hydrogenation.The acidic sites over the Cu/ZrO_(2)catalyst played more predominant roles than the hydrogenation sites in determining the conversion of the organics like furfural and vanillin.

关键词： Zirconia supported copper catalyst Crystal phase Hydrogenation Hydrogenation sites Acidic sites

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Enhanced corrosion protection of magnesium alloy via in situ Mg-Al LDH coating modified by core-shell structured Zn-Al LDH@ZIF-8

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Rare Metals 2022年第8期41卷 2745-2758页

作者： Pu-Bo Li Yong-xun wang Ze-Xi shao Bin-Tao Wu Heng Li Mang-Mang Gao Kuan-Guan Liu Ke-Ren Shi Ningxia Key Laboratory of Photovoltaic Materials Ningxia UniversityYinchuan750021China School of Mechanical MaterialsMechatronic and Biomedical EngineeringUniversity of WollongongWollongongNSW2522Australia China Special Equipment Inspection and Research Institute Beijing100029China State Key Laboratory of High-Efficiency Utilization of Coal and Green Chemical Engineering Ningxia UniversityYinchuan750021China

The Mg-Al layered double hydroxide(LDH)conversion coatings were first synthesized in situ to modify the AZ91 D alloy through urea hydrolysis to adjust the pH values(9.4,10.4,11.2 and 11.4).The pH 11.2 Mg-Al LDH possessed the best compactness and good crystallinity compared to other in situ LDH coatings and obtained the lowest corrosion current density(i_(corr))of(2.884×10^(-6)±0.345×10^(-6))A·cm^(-2),which was attributed to the anion-exchange reaction of LDH and the physical barrier against corrosion owing to the twisted penetration pathway of the interlaced LDH sheets.Core-shell structured Zn-Al LDH@ZIF-8 powder modified with stearic acid(SA)was further wrapped with polyvinylidene fluoride(PVDF)to prepare a hydrophobic double-layered coating on the underlying pH 11.2 Mg-Al LDH(SLLZ).The water contact angle(CA)of the SLLZ coating reached 105.6°,and its i_(corr)decreased to(3.524×10^(-7)±0.214×10^(-7))A·cm^(-2)compared with a single pH 11.2 film.The SLLZ coating exhibited high durability and corrosion protection,even after15 days of immersion in NaCl solution.The PVDF,SA and ZIF-8 nano-shells contributed to good hydrophobicity,effectively forming a physical barrier.The Zn-Al LDH core and underlying in situ Mg-Al LDH were beneficial for synergistically promoting anion-exchange reaction between the intercalated anions of LDH and chlorides in corrosive media.This work provides a promising approach that combines core-shell LDH@ZIF-8 with LDH film on a Mg alloy surface to construct a hydrophobic film with excellent longterm anti-corrosion performance.

关键词： Mg alloy Layered double hydroxide Corrosion protection Coating Metal-organic frameworks

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Human trophoblast cells induced MDSCs from peripheral blood CD14＋ myelomonocytic cells via elevated levels of CCL2

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Cellular & Molecular Immunology 2016年第5期13卷 615-627页

作者： Yun Zhang Daiwei Qu Jintang Sun Lei Zhao Qingjie wang Qianqian shao Beihua Kong xun Qu Institute of Basic Medical Sciences Qilu Hospital Shandong University Jinan 250012 Shandong People's Republic of China Institute of Stomatology Qilu Hospital Shandong University Jinan 250012 Shandong People's Republic of China Department of Gynaecology and Obstetrics Qilu Hospital of Shandong University Jinan 250012 Shandong People's Republic of China The Key Laboratory of Cardiovascular Remodelling and Function Research Chinese Ministry of Education and Chinese Ministry of Health Qilu Hospital Shandong University Jinan 250012 Shandong People's Republic of China

Successful human pregnancy requires the maternal immune system to recognize and tolerate the semi-allogeneic fetus. Myeloid-derived suppressor cells （MDSCs）, which are capable of inhibiting T-cell responses, are highly increased in the early stages of pregnancy. Although recent reports indicate a role for MDSCs in fetal-maternal tolerance, little is known about the expansion of MDSCs during pregnancy. In the present study, we demonstrated that the trophoblast cell line HTR8/SVneo could instruct peripheral CD14＋ myelomonocytic cells toward a novel subpopulation of MDSCs, denoted as CD 14 ＋ H LA-DR-/=~w cells, with suppressive activity and increased expression of I DO 1, ARG- 1, a nd COX2. After interaction with HTR8/SVneo cells, CD14＋ myelomonocytic cells secrete high levels of CCL2, promoting the expression of signal transducer and activator of transcription 3. We utilized a neutralizing monoclonal antibody to reveal the prominent role of CCL2 in the induction of CD14＋HLA-DR-/low MDSCs. In combination, the results of the present study support a novel role for the cross-talk between the trophoblast cell line HTR8/SVneo and maternal CD14＋ myelomonocytic cells in initiating MDSCs induction, prompting a tolerogenic immune response to ensure a successful pregnancy.

关键词： CCL2 MDSCs tolerance in pregnancy trophoblast cells

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PNSiP/Cr(Ⅲ)/MMAO催化乙烯选择性齐聚连续化反应性能及其动力学研究

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石油学报（石油加工） 2022年第5期38卷 1102-1111页

作者：王讯邵怀启姜涛天津科技大学化工与材料学院天津300457

设计了乙烯选择性齐聚连续化反应装置,将硅胺基桥联双膦型配体铬配合物(PNSiP/CrCl_(3)(THF)_(3))、改性甲基铝氧烷(MMAO)组成催化体系,考察了其催化乙烯选择性齐聚连续化反应性能,并对该反应动力学进行研究。结果表明:当反应温度为60... 详细信息

设计了乙烯选择性齐聚连续化反应装置,将硅胺基桥联双膦型配体铬配合物(PNSiP/CrCl_(3)(THF)_(3))、改性甲基铝氧烷(MMAO)组成催化体系,考察了其催化乙烯选择性齐聚连续化反应性能,并对该反应动力学进行研究。结果表明:当反应温度为60℃、乙烯压力为5.0 MPa、氢气分压为0.2 MPa、连续化反应20 h时,该催化体系的催化活性可达46.13×10^(6)g/(mol Cr·h);产物中1-己烯和1-辛烯的总选择性最高达到88.52%,固体产物聚乙烯(PE)质量分数为0.09%。PNSiP/Cr(Ⅲ)/MMAO催化体系在乙烯选择性齐聚连续化反应中具有催化活性高、副产物(甲基环戊烷+亚甲基环戊烷)少、固体低聚物少、可实现长周期运行的优点。对PNSiP/Cr(Ⅲ)/MMAO催化乙烯选择性齐聚连续化反应动力学方程进行拟合计算,得到该反应对主催化剂浓度的反应级数为1.32、对乙烯压力的反应级数为1.92;当主催化剂摩尔浓度为7.09μmol/L、反应温度为40~60℃、压力为5.0 MPa时,该反应的表观活化能为109.7 kJ/mol。

关键词：乙烯选择性齐聚连续化反应 PNSiP/Cr配合物改性甲基铝氧烷

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Overcoming chemoresistance in non-angiogenic colorectal cancer by metformin via inhibiting endothelial apoptosis and vascular immaturity

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Journal of Pharmaceutical Analysis 2023年第3期13卷 262-275页

作者： Guang-Yue Li Shu-Jing Zhang Dong Xue Yue-Qi Feng Yan Li xun Huang Qiang Cui Bo wang Jun Feng Tao Bao Pei-Jun Liu shao-Ying Lu Ji-Chang wang Department of Science and Technology The First Affiliated Hospital of Xi'an Jiaotong UniversityXi'an710061China Department of Vascular Surgery The First Affiliated Hospital of Xi'an Jiaotong UniversityXi'an710061China Department of General Surgery The First Affiliated Hospital of Xi'an Jiaotong UniversityXi'an710061China Center for Translational Medicine The First Affiliated Hospital of Xi'an Jiaotong UniversityXi'an710061China Department of Pharmacy Xi'an Jiaotong University Health Science CenterXi'an710061China

The development of chemoresistance which results in a poor prognosis often renders current treatments for colorectal cancer(CRC).In this study,we identified reduced microvessel density(MVD)and vascular immaturity resulting from endothelial apoptosis as therapeutic targets for overcoming chemoresistance.We focused on the effect of metformin on MVD,vascular maturity,and endothelial apoptosis of CRCs with a non-angiogenic phenotype,and further investigated its effect in overcoming chemoresistance.In situ transplanted cancer models were established to compare MVD,endothelial apoptosis and vascular maturity,and function in tumors from metformin-and vehicle-treated mice.An in vitro co-culture system was used to observe the effects of metformin on tumor cell-induced endothelial apoptosis.Transcriptome sequencing was performed for genetic screening.Non-angiogenic CRC developed independently of angiogenesis and was characterized by vascular leakage,immaturity,reduced MVD,and non-hypoxia.This phenomenon had also been observed in human CRC.Furthermore,non-angiogenic CRCs showed a worse response to chemotherapeutic drugs in vivo than in vitro.By suppressing endothelial apoptosis,metformin sensitized non-angiogenic CRCs to chemo-drugs via elevation of MVD and improvement of vascular maturity.Further results showed that endothelial apoptosis was induced by tumor cells via activation of caspase signaling,which was abrogated by metformin administration.These findings provide pre-clinical evidence for the involvement of endothelial apoptosis and subsequent vascular immaturity in the chemoresistance of non-angiogenic CRC.By suppressing endothelial apoptosis,metformin restores vascular maturity and function and sensitizes CRC to chemotherapeutic drugs via a vascular mechanism.

关键词： Metformin Colorectal cancer Non-angiogenic Endothelial apoptosis Vascular immaturity

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Iptakalim ameliorates relaxation to acetylcholine in thoracic aortic rings impaired by microvesicles derived from hypoxia/reoxygenation-treated HUVECs

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中国应用生理学杂志 2016年第6期32卷 481-486页

作者： Kun-wei ZHANG Shao-Xun Wang Ye-yi LI Su WEI Man SHANG Chao LIU Miao LIU Yi-lu wang Qian ZHU Yan-na WU Jun-qiu SONG Yan-xia LIU Department of Pharmacology School of Basic Medical SciencesTianjin Medical University

Objective: To investigate the effect of Iptakalim(Ipt) preventing injury of endothelial microvesicles(EMVs) derived from hypoxia/reoxygenation(H/R)-treated HUVECs on the relaxation of rat thoracic aortic rings and explore the underlying mechanism. Methods: H/R injury model was established to release H/R-EMVs from HUVECs. H/R-EMVs from HUVECs were isolated by ultracentrifugation from the conditioned culture medium. H/R-EMVs were characterized by using Transmission Electron Microscope(TEM). Thoracic aortic rings of rats were incubated with 10^(-7)-10^(-3 )mol/L Ipt and co-cultured with 10 μg/ml H/R-EMVs for 4 hours, and their endothelium- dependent relaxation in response to acetylcholine(ACh) was recorded in vitro. The nitric oxide(NO) production of ACh-treated rat thoracic aortic rings was measured by using Griess reagent. The expression of endothelial NO synthase(e NOS), phosphorylated e NOS(p-e NOS, Ser-1177), serine/threonine kinas(Akt) and phosphorylated Akt(p-Akt, Ser-473) in the thoracic aortic rings of rats was detected by Western blotting. Results: H/R-EMVs were induced by H/R-treated HUVECs and isolated by ultracentrifugation. The isolated H/R-EMVs subjected to TEM revealed small, rounded vesicles(100–1 000 nm) surrounded by a membrane. H/R-EMVs impaired relaxation induced by ACh of rat thoracic aortic rings significantly. Compared with H/R-EMVs treatment individually, relaxation and NO production of rat thoracic aortic rings were increased by Ipt treatment in a concentration-dependent manner(P<0.05, P<0.01). The expression of total e NOS(t-e NOS) and total Akt(t-Akt) was not affected by Ipt or H/R-EMVs. However, the expression of p-e NOS and p-Akt increased after treated with Ipt(P<0.01). Conclusion: Based on H/R-EMVs treatment, ACh induced endothelium-dependent relaxation of rat thoracic aortic rings was ameliorated by Ipt in a concentration-dependent manner. The mechanisms involved the increase in NO production, p-e NOS and p-Akt expression.

关键词：人脐静脉内皮细胞主动脉丝氨酸/苏氨酸激酶复氧缺氧微泡一氧化氮合酶透射电子显微镜

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