Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.

Influence of glycol ether additive with low molecular weight on the interactions between CO_(2) and oil: Applications for enhanced shale oil recovery

The high-efficient development of shale oil is one of the urgent problems in the petroleum industry. The technology of CO_(2) enhanced oil recovery(EOR) has shown significant effects in developing shale oil. The effects of several glycol ether additives with low molecular weight on the interactions between CO_(2) and oil were investigated here. The solubility of glycol ether additive in CO_(2) was firstly characterized. Then,the effects of glycol ether additives on the interfacial tension(IFT) between CO_(2) and hexadecane and the volume expansion and extraction performance between CO_(2) and hexadecane under different pressures was investigated. The experimental results show that diethylene glycol dimethyl ether(DEG), triethylene glycol dimethyl ether(TEG), and tetraethylene glycol dimethyl ether(TTEG) all have low cloud point pressure and high affinity with CO_(2). Under the same mass fraction, DGE has the best effect to reduce the IFT between hexadecane and CO_(2) by more than 30.0%, while an overall reduction of 20.0%-30.0% for TEG and 10.0%-20.0% for TTEG. A new method to measure the extraction and expansion rates has been established and can calculate the swelling factor accurately. After adding 1.0% DEG, the expansion and extraction amounts of CO_(2) for hexadecane are respectively increased to 1.75 times and 2.25 times. The results show that glycol ether additives assisted CO_(2) have potential application for EOR. This study can provide theoretical guidance for the optimization of CO_(2) composite systems for oil displacement.

Interfacial engineering through lead binding using crown ethers in perovskite solar cells

In the domain of perovskite solar cells(PSCs),the imperative to reconcile impressive photovoltaic performance with lead-related issue and environmental stability has driven innovative solutions.This study pioneers an approach that not only rectifies lead leakage but also places paramount importance on the attainment of rigorous interfacial passivation.Crown ethers,notably benzo-18-crown-6-ether(B18C6),were strategically integrated at the perovskite-hole transport material interface.Crown ethers exhibit a dual role:efficiently sequestering and immobilizing Pb^(2+)ions through host-guest complexation and simultaneously establishing a robust interfacial passivation layer.Selected crown ether candidates,guided by density functional theory(DFT)calculations,demonstrated proficiency in binding Pb2+ions and optimizing interfacial energetics.Photovoltaic devices incorporating these materials achieved exceptional power conversion efficiency(PCE),notably 21.7%for B18C6,underscoring their efficacy in lead binding and interfacial passivation.Analytical techniques,including time-of-flight secondary ion mass spectrometry(ToF-SIMS),ultraviolet photoelectron spectroscopy(UPS),time-resolved photoluminescence(TRPL),and transient absorption spectroscopy(TAS),unequivocally affirmed Pb^(2+)ion capture and suppression of non-radiative recombination.Notably,these PSCs maintained efficiency even after enduring 300 h of exposure to 85%relative humidity.This research underscores the transformative potential of crown ethers,simultaneously addressing lead binding and stringent interfacial passivation for sustainable PSCs poised to commercialize and advance renewable energy applications.

The effect of salt anion in ether‐based electrolyte for electrochemical performance of sodium‐ion batteries:A case study of hard carbon

Compared with the extensively used ester‐based electrolyte,the hard carbon(HC)electrode is more compatible with the ether‐based counterpart in sodium‐ion batteries,which can lead to improved cycling stability and robust rate capability.However,the impact of salt anion on the electrochemical performance of HC electrodes has yet to be fully understood.In this study,the anionic chemistry in regulating the stability of electrolytes and the performance of sodium‐ion batteries have been systematically investigated.This work shows discrepancies in the reductive stability of the anionic group,redox kinetics,and component/structure of solid electrolyte interface(SEI)with different salts(NaBF_(4),NaPF_(6),and NaSO_(3)CF_(3))in the typical ether solvent(diglyme).Particularly,the density functional theory calculation manifests the preferred decomposition of PF_(6)−due to the reduced reductive stability of anions in the solvation structure,thus leading to the formation of NaF‐rich SEI.Further investigation on redox kinetics reveals that the NaPF_(6)/diglyme can induce the fast ionic diffusion dynamic and low charge transfer barrier for HC electrode,thus resulting in superior sodium storage performance in terms of rate capability and cycling life,which outperforms those of NaBF_(4)/diglyme and NaSO_(3)CF_(3)/diglyme.Importantly,this work offers valuable insights for optimizing the electrochemical behaviors of electrode materials by regulating the anionic group in the electrolyte.

TLC Identification and Extraction Process of Rubiasin-1-methyl Ether from Yao Medicine Chuanlianzhu

[Objectives]To establish a thin-layer chromatography(TLC)method for the determination of rubiadin-1-methyl ether in Yao Medicine Chuanlianzhu(Damnacanthus giganteus).[Methods]A silica gel G thin-layer plate was adopted for TLC.Petroleum ether(60-90℃)-chloroform-methanol-water(7:15:3:1)was used as the developing solvent and inspected under ultraviolet lamp(365 nm).The content was determined by Inertsil ODS-3 C 18 column(4.60 mm×250 mm,5μm),mobile phase:acetonitrile-0.2%phosphoric acid gradient elution,detection wavelength 277 nm,flow rate 1.0 mL/min,column temperature 30℃,injection volume 10μL.[Results]The spots of 10 Chuanlianzhu samples from different origins showed the same color at the same position as the control,and the spots were clear and specific.The injection volume of rubiadin-1-methyl ether showed a good linear relationship in the range of 2.90-145μg(R=0.9996).The average recovery rate of rubiadin-1-methyl ether in the low,medium and high dose groups of Yao Medicine Chuanlianzhu was 98.72%,and RSD=1.78%.[Conclusions]This method can effectively identify Yao Medicine Chuanlianzhu medicinal materials and accurately determine the content of rubiadin-1-methyl ether in the medicinal materials.It provides a scientific basis for the development and utilization of Yao Medicine Chuanlianzhu medicinal resources.

骨形成肽1和聚多巴胺复合涂层修饰提高聚醚醚酮表面活性

背景:聚醚醚酮具有与人体皮质骨相近的弹性模量及良好的射线透射性、化学稳定性和生物相容性等优点,有望应用于口腔种植领域,然而其具有生物惰性,难以与周围组织形成骨结合,因此如何提高聚醚醚酮的表面活性是目前的主要问题。目的:分析聚醚醚酮表面骨形成肽1和聚多巴胺复合涂层的促成骨和成血管作用。方法:将聚醚醚酮片浸泡于多巴胺溶液中24 h,制备聚醚醚酮-聚多巴胺材料;将聚醚醚酮-聚多巴胺材料浸泡于骨形成肽1溶液中24 h,制备聚醚醚酮-聚多巴胺-骨形成肽1材料,表征材料的微观形貌、亲水性与元素组成。将骨髓间充质干细胞分别接种于聚醚醚酮、聚醚醚酮-聚多巴胺、聚醚醚酮-聚多巴胺-骨形成肽1材料表面,通过活死细胞染色和细胞骨架染色评估细胞活性与黏附状态,茜素红和骨钙素免疫荧光染色检测细胞成骨分化能力。将人脐静脉内皮细胞分别接种于3组材料表面,通过活死细胞染色和细胞骨架/血管内皮生长因子免疫荧光染色评估细胞活性及成血管水平。结果与结论:①扫描电镜下可见聚醚醚酮材料表面光滑,聚醚醚酮-聚多巴胺材料表面出现凹凸不平的沉积物,聚醚醚酮-聚多巴胺-骨形成肽1材料表面有小颗粒突起;接触角测试结果显示,聚醚醚酮-聚多巴胺-骨形成肽1材料的亲水性优于其他两种材料;X射线光电子能谱测试结果显示,骨形成肽1成功修饰于聚醚醚酮材料表面;②活死细胞染色和细胞骨架染色显示,相较于其他两种材料,聚醚醚酮-聚多巴胺-骨形成肽1材料可提高骨髓间充质干细胞的活性与黏附;茜素红和骨钙素免疫荧光染色显示,相较于其他两种材料,聚醚醚酮-聚多巴胺-骨形成肽1材料可促进骨髓间充质干细胞的成骨分化;③活死细胞染色和免疫荧光染色显示,相较于其他两种材料,聚醚醚酮-聚多巴胺-骨形成肽1材料可提高人脐静脉内皮细胞的活性与黏附及血管内皮生长因子蛋白的表达;④结果表明,骨形成肽1和聚多巴胺复合涂层可提高聚醚醚酮表面的促成骨和成血管活性。

在Windows平台下开发Ethereal插件的方法与实现

Ethereal是一个UNIX和类UNIX操作系统下的基于图形用户接口库GTK+和包捕获、过滤库Libpcap(W indows平台下使用W inpcap库)的网络协议分析器或嗅探器。它具有很好的跨平台捕获性能,且支持第三方插件。详细阐述了在W indows平台下开发Ethereal插件的方法,并结合CORBA协议解析器的生成实例介绍了其实现技术。

基于Ethereal的协议分析实验设计

目前高校计算机网络课程中在教学过程中,普遍存在学生感觉协议的学习枯燥无味、难于理解,无法对协议的工作做到眼见为实。为此,设计了基于协议分析工具Ethereal的网络协议分析实验,帮助学生有效地了解协议的工作过程、掌握协议的工作原理、提高理论课程的教学质量和效果。

基于Ethereal的CORBA通信协议解析功能扩展的方法与实现

Ethereal是一个基于libpcap的开放源代码的网络监听和协议解析工具。介绍了Linux的网络捕获体系结构,详细阐述了在Linux平台下为Ethereal添加CORBA通信协议解析功能的方法及实现技术。结合CORBA实例,对生成的CORBA协议解析器进行了实验验证。

HMME-PDT对CNE-2细胞增殖的抑制作用

目的探讨血卟啉单甲醚介导的光动力学疗法(HMME-PDT)对鼻咽癌CNE-2细胞的抑制作用。方法以血卟啉单甲醚为光敏剂,532nm激光为激发光源的光动力学疗法作用于鼻咽癌CNE-2细胞。细胞用5、10、20!g/ml浓度的光敏剂孵育2h后,用0.6、1.2、2.4、4.8、9.6J/cm2剂量的激光照射;激光功率密度为10mW/cm2。MTT法检测在HMME和激光两种变量下PDT对细胞活性的抑制作用;光镜观察PDT作用后细胞形态的变化;免疫组化法检测PCNA的表达。结果在HMME剂量为5!g/ml、10!g/ml及20!g/ml时,细胞的抑制率随着激光剂量从0.6J/cm2增加至9.6J/cm2而逐渐增加;并且和HMME及激光剂量密切相关;光镜观察结果表明PDT组与对照组相比细胞密度明显减少,细胞核浓聚、碎裂。免疫组化结果显示PDT作用后PCNA表达减少。结论HMME-PDT对CNE-2细胞的增殖有明显的抑制作用。

Synthesis of Methyl Acetate by Dimethyl Ether Carbonylation over Cu/HMOR： Effect of Catalyst Preparation Method

Dimethyl ether carbonylation to methyl acetate was comparatively investigated over mor- denite supported copper （Cu/HMOR） catalysts prepared by different methods including evaporation, urea hydrolysis, incipient wetness impregnation and ion-exchange. The results showed that Cu/HMOR prepared via iron-exchange method exhibited the highest catalytic activity due to the synergistic effect of active-site metal and acidic molecular sieve support. Conversion of 95.3% and methyl acetate selectivity of 94.9% were achieved under conditions of 210℃, 1.5 MPa, and GSHV of 4883 h-1. The catalysts were characterized by nitrogen absorption, X-ray diffraction, NH3 temperature program desorption, and CO temperature program desorption techniques. It was found that Cu/HMOR prepared by ion-exchange method possessed high surface area, moderate strong acid centers, and CO adsorption centers, which improved catalytic performance for the reaction of CO insertion to dimethyl ether.

Effect of Calcination Temperature on Catalytic Activity and Textual Property of Cu/HMOR Catalysts in Dimethyl Ether Carbonylation Reaction

The effect of calcination temperature on the catalytic activity for the dimethyl ether （DME） carbonylation into methyl acetate （MA） was investigated over mordenite supported copper （Cu/HMOR） prepared by ion-exchange process. The results showed that the catalytic activity was obviously affected by the calcination temperature. The maximal DME conversion of 97.2% and the MA selectivity of 97.9% were obtained over the Cu/HMOR calcined at 430 ℃ under conditions of 210 ℃, 1.5 MPa, and GSHV of 4883 h^-1. The obtained Cu/HMOR catalysts were characterized by powder X-ray diffraction, N2 absorption, NH3 temperature program desorption, CO temperature program desorption, and Raman techniques. Proper calcination temperature was effective to promote copper ions migration and diffusion, and led the support HMOR to possess more acid activity sites, which exhibited the complete decomposing of copper nitrate, large surface area and optimum micropore structure, more amount of CO adsorption site and proper amount of weak acid centers.

以532nm激光为光源的HMME-PDT对人类乳腺癌细胞的杀伤作用

目的:探讨532nm激光不同光剂量参数及血卟啉单甲醚(HMME)不同浓度参数对体外培养的乳腺癌细胞(MCF-7)的光动力学杀伤作用。方法:MCF-7细胞用浓度分别为5μg/m l、10μg/m l、20μg/m l的HMME孵育2h后,以532nm半导体激光照射,能量密度分别为0.3J/cm 2、0.6J/cm 2、1.2J/cm 2、2.4J/cm 2、4.8J/cm 2,24h后用CCK-8检测细胞存活率,并在光镜及电镜下观察细胞的形态变化。结果:随着激光剂量的增大,在一定的范围内,细胞的抑制率呈现上升趋势;能量密度为2.4J/cm 2,HM M E浓度为20μg/m l时,达到最大的抑制率为55.5%;并且细胞的抑制率也和H M M E浓度呈剂量依赖型;光镜下可观察到细胞坏死和凋亡样改变。结论:以532nm激光为光源的H M M E-PDT对M CF-7细胞有明显的杀伤作用,并在一定范围内呈光剂量和H M M E浓度剂量依赖型。

基于EtherCAT技术的多轴运动控制系统

以EtherCAT通信技术为基础,设计了一种基于ARM和FPGA双核的EtherCAT总线式多轴运动控制系统。提出了STM32作为系统管理芯片,通过SPI通信控制ET1200从站控制芯片实现EtherCAT总线从站通信功能的解决方案;并采用FPGA作为协处理器,完成运动控制算法的实现和执行。完成了运动控制系统的硬件电路设计和软件开发,并制作了样机。经试验测试,实现了EtherCAT总线通信功能,采用TwinCAT完成了闭环运动控制,并且可以独立工作实现运动规划,满足工业控制工程中的应用要求。

HMME介导的光动力对兔血管平滑肌细胞生长抑制及诱导细胞凋亡的作用

目的:观察原代培养的兔血管平滑肌细胞在HMME-PDT作用下生长的变化及其死亡方式。方法:常规台盼兰染色观察HMME-PDT作用后6h和24 h对细胞的杀伤作用,HMME的浓度为10μg/ml,激光剂量为2.4～9.6 J/cm2;HE染色法观察PDT后24 h细胞形态的变化;流式细胞仪AnnexinⅤ/PI双染法检测细胞死亡方式;共聚焦显微镜观察HMME在线粒体的定位。结果:台盼兰法检测结果显示随着PDT能量密度的增加细胞的存活率逐渐下降,光镜下可见大部分细胞呈死亡或凋亡样改变,AnnexinⅤ/PI法检测显示PDT 24 h后凋亡率可达50.5%,共聚焦显微镜观察到HMME在线粒体内有分布。结论:HMME-PDT能显著抑制兔血管平滑肌细胞的生长,并使其发生明显的凋亡。

基于EtherCAT的双机器人协作系统设计

提出了一种基于Ether CAT的双机器人协作系统解决方案。首先,针对机器人协作分拣系统,提出了一种多机器人协作联控的整体解决方案。并对系统的硬件结构、软件架构、流程进行详细说明。其次,针对多机器人协作系统的实时通讯问题,提出了一种基于Ether CAT总线协议的解决方案。最后,将该方案用到机器人系统进行验证,测试结果表明,构建Ether CAT的多机器人总线通讯系统能够满足多机器人协作的同步性要求。

Production of Light Olefins from Biosyngas by Two-stage Catalytic Conversion Process via Dimethyl Ether

NiSAPO-34 and NiSAPO-34/HZSM-5 were prepared and evaluated for the performance of dimethyl ether （DME） conversion to light olefins （DTO）. The processes of two-stage light olefin production, DME synthesis and the following DTO, were also investigated using biosyngas as feed gas over Cu/Zn/A1/HZSM-5 and the optimized 2%NiSAPO-34/HZSM- 5. The results indicated that adding 2%Ni to SAPO-34 did not change its topology structure, but resulted in the forming of the moderately strong acidity with decreasing acid amounts, which slightly enhanced DME conversion activity and C2=-C3= selectiw ity. Mechanically mixing 2%NiSAPO-34 with HZSM-5 at the weight ratio of 3.0 further prolonged DME conversion activity to be more than 3 h, which was due to the stable acid sites from HZSM-5. The highest selectivity to light olefins of 90.8% was achieved at 2 h time on stream. The application of the optimized 2%NiSAPO-34/HZSM-5 in the second-stage reactor for DTO reaction showed that the catalytic activity was steady for more than 5 h and light olefin yield was as high as 84.6 g/m3syngas when the biosyngas （H2/CO/CO2/N2/CH4=41.5/26.9/14.2/14.6/2.89, vol%） with low H/C ratio of 1.0 was used as feed gas.

HMME—PDT联合氟制剂预防龋病的动物实验研究

目的:在构建龋病动物模型基础上观察HMME-PDT联合氟制剂预防龋病的效果。方法:选取断奶21d SPF-Wista大鼠80只,种植变形链球菌构建致龋模型后分为蒸馏水、HMME-PDT、氟化钠、以及HMME-PDT+氟化钠组4组,连续8周给大鼠进行口腔处理,采集大鼠唾液培养,记录变形链球菌水平及观察实验组大鼠口内变形链球菌生长繁殖的影响并评估Keyes记分抑制龋损形成的效果。结果:与蒸馏水组相比,其余各组变形链球菌水平和龋齿Keyes记分均有不同程度的降低,其中HMME-PDT显示对窝沟面龋和光滑面龋有较好的防治效果(P<0.05),但均低于氟化钠组;HMME-PDT+氟化钠组未见明显的协同抑龋作用。结论:HMME-PDT能有效抑制口腔变链菌繁殖,降低龋齿的发生率。

影响HMME在不同溶液中光漂白速率的主要因素分析

目的分析在不同溶液体系中,影响国产光敏剂血卟啉单甲醚(HMME)光漂白速率的主要因素。方法首先从理论上,根据光漂白速率方程分析了可能影响光漂白速率的主要因素。然后测定不同溶液中不同浓度HMME的光漂白(充氧),通过绘制光漂白曲线(HMME浓度-照光时间)比较HMME漂白速率。结合理论推导结果与实验结果分析各因素对漂白速率的影响。结果HMME的光漂白速率在白蛋白悬液中快于DMSO中,DMSO中快于细胞悬液和PBS中,后两种溶液中HMME的光漂白速率相近。HMME对532nm光的摩尔消光系数:εDMSO>εcells-suspension>εalbumin-buffer>εPBS。结论光敏剂溶液条件会影响光敏剂光漂白速率。其中摩尔消光系数、光敏剂浓度、溶液微环境对光漂白速率影响较大。摩尔消光系数增加HMME光漂白速率,蛋白、DMSO的存在可以加速HMME的光漂白。

光动力治癌新药血卟啉单甲醚(HMME)的研究

本文报道了一种单体卟啉血卟啉单甲醚的合成及其光敏化力、人癌细胞光灭活作用、动物移植瘤光动力疗效和有关的临床前药理毒理学研究资料。实验结果表明,与临床应用的混合卟啉制剂血卟啉衍生物(HpD)相比,HMME具有光敏化力强、肿瘤选择性摄入率高、光动力效应强、毒性低、无致突变和致畸胎作用等优点,是一种较理想的光动力治癌新药。