铋/锡催化L-丙交酯与乙交酯本体开环共聚

为探究金属催化剂辛酸亚锡(Sn(Oct)_(2))与次水杨酸铋(BiSS)对L-丙交酯(L-LA)与乙交酯(GA)本体开环聚合(ROP)反应过程及产物性能的影响,使用不同含量的Sn(Oct)_(2)或BiSS合成一系列聚丙交酯-乙交酯共聚物(PLGA)。通过核磁共振波谱仪、傅里叶变换红外光谱仪、凝胶渗透色谱仪对聚合物的微观结构、聚合反应动力学和相对分子质量进行了表征,借助热重分析仪和差示扫描量热仪对聚合物的热性能进行了分析。结果表明,BiSS是一种非常有吸引力的催化剂,在ROP制备PLGA共聚物中获得了与Sn(Oct)_(2)类似的结果,其催化性能可与Sn(Oct)_(2)相媲美。BiSS催化制备的PLGA的热稳定性显著提高,例如,1000×10^(-6)Bi催化制备的PLGA73在氮气氛围下的T_(5)%和T_(90)%分别为269.6℃和379.2℃,相较于Sn(Oct)_(2)分别升高了36℃和82.7℃。由BiSS催化制备的PLGA链段具有更高的随机性和更短的L-LA序列长度。BiSS可以替代商业使用的Sn(Oct)_(2)用于生产生物医学领域应用的低毒性PLGA。

Single-Molecule Confinement Induced Intrinsic Multi-Electron Redox-Activity to Enhance Supercapacitor Performance

Aggregation of polyoxometalates(POM)is largely responsible for the reduced performance of POM-based energy-storage systems.To address this challenge,here,the precise confinement of single Keggin-type POM molecule in a porous carbon(PC)of unimodal super-micropore(micro-PC)is realized.Such precise single-molecule confinement enables sufficient activity center exposure and maximum electron-transfer from micro-PC to POM,which well stabilizes the electron-accepting molecules and thoroughly activates its inherent multi-electron redox-activity.In particular,the redox-activities and electron-accepting properties of the confined POM molecule are revealed to be super-micropore pore size-dependent by experiment and spectroscopy as well as theoretical calculation.Meanwhile,the molecularly dispersed POM molecules confined steadily in the“cage”of micro-PC exhibit unprecedented large-negative-potential stability and multiple-peak redox-activity at an ultra-low loading of~11.4 wt%.As a result,the fabricated solid-state supercapacitor achieves a remarkable areal capacitance,ultrahigh energy and power density of 443 mF cm^(-2),0.12 mWh cm^(-2)and 21.1 mW cm^(-2),respectively.This work establishes a novel strategy for the precise confinement of single POM molecule,providing a versatile approach to inducing the intrinsic activity of POMs for advanced energy-storage systems.

金属钯纳米颗粒/氮化钛复合材料对水中2,4-二氯苯酚的电催化氢化脱氯（英文）

随着社会经济的快速发展,含氯有机物,特别是含氯苯系物,在农业、化工和医药等领域的使用量逐年增多,而使用过程中不合理的排放和控制致使含氯苯系物对生态环境,特别是水体环境的污染日趋严重.含氯苯系物具有高致毒致癌性,易生物富集,且很难被完全降解矿化,已被国家环保局认定为优先控制污染物.常规的废水处理工艺,如吸附、氧化及生物降解等,效率不高,且具有二次污染风险.电催化氢化脱氯技术是一种新型特别针对废水中含氯有机污染物的处理工艺,是通过在阴极电解还原水,原位生成原子态氢,以进攻苯环上C.Cl键,通过C.Cl键断裂H原子取代,使含氯苯系物完全转化为苯系物,达到去毒去害化的目的,近年来越来越受到研究者的关注.在整个电催化氢化脱氯技术中,高效稳定的电催化剂合成是关键,决定着脱氯效率、脱氯动力学、产物选择性及能量的利用率.本文报道了一种简易、无需添加任何表面活性剂的湿式还原法制备金属钯/氮化钛(Pd/TiN)和金属钯/碳(Pd/C)复合材料.在该复合材料中,金属钯颗粒具有均一的纳米尺寸(约5.0 nm)和球状形貌,且均匀分布在TiN和C载体上.作为针对水体中代表性含氯苯系物2,4-二氯苯酚的电催化氢化脱氯反应催化剂,Pd/TiN所展现的活性和稳定性均优于TiN和Pd/C,这源于TiN载体的促进作用.当TiN与Pd复合时,相应形成的Pd-TiN界面可改变Pd表面的电子结构,进一步优化Pd产活性氢及其吸附活化2,4-二氯苯酚的性能,因而其催化氢化脱氯活性增加.阴极工作电压是该催化反应中一个重要操作参数,决定了电催化氢化脱氯的效率和最终产物的构成.实验表明,.0.80 V vs Ag/AgCl是最佳操作电压,此时2,4-二氯苯酚的电催化氢化脱氯效率最高,可达到93.27%,且可实现最大程度的2,4-二氯苯酚向苯酚转化.脱氯反应路径研究发现,在Pd/TiN催化剂上2,4-二氯苯酚脱氯反应路径为2,4-二氯苯酚→对位一氯苯酚,邻位一氯苯酚→苯酚,但Pd/TiN对邻位和对位的C.Cl键断裂基本没有选择性.本文提供了一种新的有效调控Pd材料电催化氢化脱氯性能的方法,可望用于其他氢化反应体系的高效催化剂的设计合成,同时可推动电催化氢化脱氯技术在环境污染修复中的应用.

超支化聚酰胺修饰碳纳米管/环氧树脂复合材料的制备及性能

文中制备了不同支化度的超支化聚酰胺接枝碳纳米管,并对碳纳米管接枝前后的微观结构进行了表征。红外光谱和热重分析结果表明,超支化聚酰胺成功接枝到了碳纳米管表面;透射电子显微镜分析结果表明,3种支化度的超支化聚酰胺均在碳纳米管表面形成了聚合物包裹层,管径明显增加,且支化度越高,管径增加越多。进一步地,将上述所制备的超支化聚酰胺修饰碳纳米管加入环氧树脂体系,制备了不同改性环氧树脂复合材料,动态力学热分析和力学性能分析结果表明,超支化聚酰胺修饰碳纳米管/环氧树脂复合材料的储能模量、玻璃化转变温度和力学损耗峰高度均比未经修饰的碳纳米管/环氧树脂复合材料有所降低,冲击韧性明显提高,证明了超支化聚酰胺大量的分子支链对环氧树脂的增韧贡献,且支化度越高,增韧效果越明显;光学显微镜及扫描电子显微镜分析结果显示,超支化聚酰胺的加入明显改善了碳纳米管在环氧树脂中的分散性;从增韧机制来看,该体系的增韧机理属于碳纳米管拔出机制,碳纳米管的拔出物基本都是短凸棱拔出,碳纳米管大多被拉断,表明超支化聚酰胺修饰碳纳米管与环氧树脂形成了非常牢固的连接,对环氧树脂具有优异的增韧效果。

纳米二氧化硅表面接枝反应性相容剂协同增容聚苯乙烯/聚酰胺6

针对聚苯乙烯(PS)和聚酰胺6(PA6)热力学不相容引起共混物力学性能降低的问题,文中首先制得纳米SiO_(2)表面接枝苯乙烯(St)与3-异丙烯基-α,α,-二甲基苄基-异氰酸酯(TMI)共聚物为新型相容剂,并用于PS/PA6体系的反应性协同增容。扫描电镜和透射电镜分析结果表明,通过无机纳米粒子和异氰酸酯基团原位增容的协同作用可调控相容剂选择性分布,使两相界面张力减小,实现分散相PA6尺寸的降低、共混物相容性的提升。设计了不同异氰酸酯基团含量的相容剂,当添加量较少时(质量分数0.5%),拉伸强度最高增加了125.5%、断裂伸长率提升了128.1%,有效改善了PS/PA6由于热力学不相容引起的力学性能不佳的问题。

Residence time distribution of high viscosity fluids falling film flow down outside of industrial-scale vertical wavy wall: Experimental investigation and CFD prediction

The flow behavior of gravity-driven falling film of non-conductive high viscosity polymer fluids on an industrial-scale vertical wavy wall was investigated in terms of film thickness and residence time distribution by numerical simulation and experiment.Falling film flow of high viscosity fluids was found to be steady on a vertical wavy wall in the presence of the large film thickness.The comparison between numerical simulation and experiment for the film thickness both in crest and trough of wavy wall showed good agreement.The simulation results of average residence time of falling film flow with different viscous fluids were also consistent with the experimental results.This work provides the initial insights of how to evaluate and optimize the falling film flow system of polymer fluid.

An improved robust stability and robust stabilization method for linear discrete-time uncertain systems

This paper addresses the problems of the robust stability and robust stabilization of a discrete-time system with polytopic uncertainties. A new and simple method is presented to directly decouple the Lyapunov matrix and the system dynamic matrix. Combining this method with the parameter-dependent Lyapunov function approach yields new criteria that include some existing ones as special cases. A numerical example illustrates the improvement over the existing ones.

Experimental results for the vapor-liquid equilibria of 0(formaldehyde+1,3,5-trioxane+methanol+salt+water)systems and comparison with predictions

The salt effect on the vaporliquid phase equilibrium(VLE)of solvent mixtures is of significant interest in the industrial production of 1,3,5trioxane.Experimental data for the VLE of quinary systems(formaldehyde+1,3,5trioxane+methanol+salt+water)and their ternary subsystems(formaldehyde+salt+water),(1,3,5trioxane+salt+water),and(methanol+salt+water)were systematic measured under atmospheric pressure.The salts considered included KBr,NaNO_(3),and CaCl_(2).The extended UNIFAC model was used to describe the VLE of the saltcontaining reactive mixtures.The model parameters were determined from the experimental VLE data of ternary systems or obtained from the literature,and then were used to predict the VLE of systems(1,3,5trioxane+KBr+water),(methanol+KBr+water),(formaldehyde+KBr+water),and(formaldehyde+1,3,5trioxane+methanol+salt+water)with salt=KBr,NaNO_(3),and CaCl_(2).The predicted results showed good agreements with the measured results.Furthermore,the model was used to uncover the salt effect on the VLE of these multisolvent reactive systems.

Delay-dependent robust H-infinity control for discrete-time uncertain systems with time-varying state delays

This paper examines the delay-dependent H-infinity control problem for discrete-time linear systems with time-varying state delays and norm-bounded uncertainties. A new inequality for the finite sum of quadratic terms is first established. Then, some new delay-dependent criteria are derived by employing the new inequality to guarantee the robust stability of a closed-loop system with a prescribed H-infinity norm bound for all admissible uncertainties and bounded time-vary delays. A numerical example demonstrates that the proposed method is an improvement over existing ones.

Application of Microperforated-Panel Absorber in Communication Products

Base on Prof. Maa Dah-You’s general theory of the microperforated-panel (MPP) absorber, We designed a noise reduction structure-sound attenuating cabinet (SAC). It can be applied to air-cooled communication products to reduce system noise. This article introduces engineering design method of SAC and laboratory test noise reduction results of application of SAC.

Novel method for separation and screening of lubricant-degrading microorganisms and bacterial biodegradation

With the rapid increase of lubricant consumption,oil contamination becomes more serious.Biotreatment is an important method to remove oil contamination with some advantages.In this study,acclimatized oilcontaminated soil and used lubricating oil were sampled to isolate lubricant-degrading strains by several methods.51 isolates were obtained and 24-well plates were employed to assess bacterial potential in highthroughput screening.The method was noted for the prominence of oil–water two-phase system with saving chemicals,shortening cycles and lessening workloads.In order to decrease inaccuracy,subculture and resting cells were inoculated into mineral salt medium with 200 μl oil in well plates for the cultivation at 37 °C for 5and 7 days,and the biodegradation potential was characterized by the changes of oil film and cell density.With appropriate evaluation by shaking flask tests,5 isolates were retained for their potentials with the maximum biodegradation from 1500 to 2200 mg · L^(-1)and identified as Acidovorax citrulli,Pseudomonas balearica,Acinetobacter johnsonii(two isolates with different biodegradation potentials)and Acidovorax avenae using 16 S r RNA sequencing analysis.Also,lipase activity was determined using indicator titration and p-nitrophenyl palmitate(p-NPP)methods.The results indicated that only p-NPP was successful to test lipase activity with the range of 1.93–6.29 U · ml^(-1).Although these five strains could degrade 1000 mg · L^(-1)lubricating oil in158–168 h,there existed distinct difference in enzyme activity,which demonstrates that lipase activity could not be used as the criterion to evaluate microbial biodegradation potential for petroleum hydrocarbons.

Concentration of linoleic acid from cottonseed oil by starch complexation

The extraction of linoleic acid from fatty acids(FA) of the cottonseed oil using starch–FA complexes was developed for the first time. We showed that starch can form inclusion complexes of different strengths with FA and that the different strengths stem from the differences in chain length, degree of unsaturation, and position of double bonds of FA. The optimal separation conditions were determined as follows: The inclusion temperature is 69 °C, the inclusion time is 30 min, the starch/FA mass ratio is 10:1, and the ratio of the volume of methanol–water solution and the mass of FA is 18:1. Compared to urea inclusion complexation, starch complexation has milder reaction temperature and shorter reaction time. Under these conditions, linoleic acid can be concentrated from 38.9% to 70.04% by one-off extraction. Moreover, the experimental results demonstrate the almost perfect reusability of starch. These results show that starch complexation is a promising method that can be used to obtain highly concentrated linoleic acid from cottonseed oil.

Formation characteristics of Taylor bubbles in a T-junction microchannel with chemical absorption

This study focuses on the effect of chemical absorption on the formation dynamic characteristics and initial length of Taylor bubbles.The temporal evolutions of neck width and length of gaseous thread and initial length with and without chemical absorption were investigated with the Capillary number and Hatta number between 0.0010–0.0073 and 1.8–5.8 respectively.The squeezing regime with typical three stages,expansion,squeezing and pinch off is observed for both two processes.Compared with the nonabsorption process,the increase of formation time in the chemical absorption process arises mainly from the expansion stage,and the decrease of initial length is from the necking stage.In addition,the temporal length evolution satisfies the power-law scale with the same exponent but a smaller pre-exponential factor.The correlations of neck width for stage transition and initial length with Hatta number demonstrate the enhancement effect of chemical absorption on bubble formation dynamics and initial length at relatively high chemical reaction rates and long formation time.This study provides insight into the bubble formation mechanism and helps to regulate the bubble initial size with chemical absorption.

C2-phenyl-substituted benzimidazolium-based covalent organic framework as efficient catalyst for CO_(2) conversion without solvents,metals,and cocatalysts

Covalent organic frameworks(COFs) are a potential platform for carbon dioxide(CO_(2)) conversion owing to their periodic permanent porosity,adjustable structure,and chemical stability.For good catalytic performance in CO_(2) conversion,collaborative multifunctions should be strategically integrated into the catalytic system design and construction.In this study,a four-in-one high-efficiency catalyst was synthesized and tested for CO_(2) cycloaddition to form cyclic carbonate.The obtained Tp-MPB-BrCOF had a high nitrogen content,which enhanced its CO_(2) affinity through substantial Lewis acid-base or dipole-quadrupole interactions;moreover,the acid(protons transferring from oxygen(–OH) to nitrogen(–NH)),hydrogen bond donor(hydroxyl group),and Br-(nucleophile group) served as three active sites,further improving the catalyst activity.These results provide a basis for designing efficient and stable CO_(2)-conversion catalysts.

Microenvironment-responsive electrocution of tumor and bacteria by implants modified with degenerate semiconductor film

Implantable biomaterials are widely used in the curative resection and palliative treatment of various types of cancers.However,cancer residue around the implants usually leads to treatment failure with cancer reoccurrence.Postoperation chemotherapy and radiation therapy are widely applied to clear the residual cancer cells but induce serious side effects.It is urgent to develop advanced therapy to minimize systemic toxicity while maintaining efficient cancer-killing ability.Herein,we report a degenerate layered double hydroxide(LDH)film modified implant,which realizes microenvironment-responsive electrotherapy.The film can gradually transform into a nondegenerate state and release holes.When in contact with tumor cells or bacteria,the film quickly transforms into a nondegenerate state and releases holes at a high rate,rendering the“electrocution”of tumor cells and bacteria.However,when placed in normal tissue,the hole release rate of the film is much slower,thus,causing little harm to normal cells.Therefore,the constructed film can intelligently identify and meet the physiological requirements promptly.In addition,the transformation between degenerate and nondegenerate states of LDH films can be cycled by electrical charging,so their selective and dynamic physiological functions can be artificially adjusted according to demand.

MgAl-LDH强化Bi单质等离子体光催化性能的机制

通过液相超声辅助组装的方式将铋纳米球(Bi-NPs)均匀负载于层状氢氧化镁铝(MgAl-LDH)纳米片上,成功合成Bi@MgAl-LDH复合光催化剂.该催化剂在光照射下,可通过Bi单质等离子体效应连续高效氧化空气中ppb(十亿体积气体中所含污染物体积)浓度量级的NO(去除效率可稳定在56%).采用X射线衍射仪(XRD)、电子扫描显微镜(SEM)和紫外可见漫反射光谱(UV-visDRS)等手段对催化剂物相、形貌、化学组成和光学性质进行了表征分析,结合电子顺磁共振(ESR)氧化自由基捕获实验并采用原位红外光谱技术对光催化氧化NO过程进行动态监测发现,虽然MgAl-LDH作为载体没有与Bi球形成异质结结构,但其表面富含丰富的氢氧根离子,能与Bi球上光激发产生的空穴快速结合,形成·OH自由基;而光生空穴的快速消耗又能降低其与光生电子的复合,增强光电分离,促进超氧自由基形成,通过这两方面的协同作用增强了Bi球对NO的光催化氧化效果.更重要的是,LDH具有独特的水分子记忆效应,在光催化过程中被消耗的氢氧根离子可通过吸附空气中水分而不断补充,促使催化活性的稳定高效.本文的研究结果为Bi单质基等离子体直接光催化降解气相污染物性能强化提供了新的策略,同时对光催化反应机制的研究提出了新的思路.

Ag/AgCl-LaCO_3OH纳米棒可见光催化净化NO的性能增强及反应机理

采用化学沉淀法制备三元Ag/AgCl-LaCO_3OH纳米棒光催化剂.将Ag/AgCl引入LaCO_3OH(LCO)纳米棒后,可同时实现光吸收范围紫外光区拓展至可见光吸收和光生载流子的高效分离.可见光照射下,金属Ag单质等离子共振(SPR)效应诱导电荷-空穴有效分离,使其热电子传输至LCO样品缺陷能级.随后表面O_2捕获光生电子产生超氧自由基·O_2-,该自由基对氧化NO过程起主导作用.空穴可以迁移至AgCl表面与Cl^-相互作用转化Cl^0,直接参与氧化NO后再还原为Cl^-, Cl^-再与Ag^+结合生成AgCl,有效避免了AgCl的光腐蚀.优化过后的Ag/AgCl-LaCO_3OH纳米棒复合材料的可见光净化NO去除率高达54.0%,远高于纯的LCO(3.1%)和Ag/AgCl(8.0%)的可见光催化性能.利用原位红外光谱实时动态监测Ag/AgCl-LaCO_3OH光催化氧化NO的反应过程,结合自由基捕获结果,从分子层面揭示其反应机理,并提出Ag/AgCl-LaCO_3OH光催化性能增强机制.本研究结果对等离子体基半导体复合材料光催化反应机理及环境净化应用提供新的认识.

氧空位TiO2高效光催化氧化甲醛及其反应路径

通过采用一步煅烧法制备得到含大量表面氧空位的二氧化钛(TiO2),将其应用于典型空气污染物甲醛的治理.结果表明,在流动体系的测试环境中,甲醛的最大有效去除率可达95.05%,相比于本底样品(72.52%)提高了1.31倍.研究表明,含氧空位的TiO2不仅可以增强光吸收范围,还可以利用氧空位捕获光生电子,有效地抑制光生电子和空穴的复合,进而提高光催化活性.通过原位红外光谱对催化剂降解甲醛的反应过程进行实时动态监测,结合密度泛函理论(DFT)计算,表明TiO2表面的氧空位可以有效地增强甲醛分子的吸附活化,存在的大量离域电子可以注入到甲醛分子中的C=O键并使其活化断裂,从而有效地减少甲醛氧化过程中甲酸的积累,加快甲醛的高效氧化去除.本研究通过分析含氧空位TiO2对光催化甲醛氧化反应过程的影响,为光催化材料表面缺陷设计和光催化治理气相污染物提供了新的思路.

Mg-Fe LDH sealed PEO coating on magnesium for biodegradation control,antibacteria and osteogenesis

Attempt of developing bio-safety and functional layered double hydroxides(LDHs)modifed plasma electrolytic oxidation(PEO)coatings,has become a hotspot in the protection of magnesium(Mg)based biomedical implants.In the present work,Mg-Fe LDH flms with different Fe contents were fabricated on PEO coating via a novel two-step method:frstly,the Fe OOH flms were prepared by immersing PEO sample in Fe^(2+)-containing solution,and then Mg-Fe LDH flms were formed by transforming the Fe OOH flms via a hydrothermal treatment in water.The highly-oriented LDH nano-sheets could enhance the anti-corrosion performance of PEO coating,which was proved by the results of electrochemical test,hydrogen evolution and corroded morphology.PEO/Mg-Fe LDH coatings showed a low hemolysis rate(less5%)than PEO coating.In addition,PEO/Mg-Fe LDH coatings were more favorable for cell adhesion and proliferation than PEO coating.Moreover,PEO/Mg-Fe LDH coatings showed good photothermal conversion property,which demonstrated the excellent rapid antibacterial effect under NIR light.In vitro culture of rat bone marrow stem cell(r BMSC)suggested that cells cultured in the extract of PEO/Mg-Fe LDH coatings had a better osteogenic activity.In vivo subcutaneous implantation test revealed that PEO/Mg-Fe LDH coatings exhibited good anti-corrosion and histocompatibility.

Co-implantation of magnesium and zinc ions into titanium regulates the behaviors of human gingival fibroblasts

Soft tissue sealing around implants acts as a barrier between the alveolar bone and oral environment,protecting implants from the invasion of bacteria or external stimuli.In this work,magnesium(Mg)and zinc(Zn)are introduced into titanium by plasma immersed ion implantation technology,and their effects on the behaviors of human gingival fibroblasts(HGFs)as well as the underlying mechanisms are investigated.Surface characterization confirms Mg and Zn exist on the surface in metallic and oxidized states.Contact angle test suggests that surface wettability of titanium changes after ion implantation and thus influences protein adsorption of surfaces.In vitro studies disclose that HGFs on Mg ion-implanted samples exhibit better adhesion and migration while cells on Zn ion-implanted samples have higher proliferation rate and amounts.The results of immunofluorescence staining and real-time reverse-transcriptase polymerase chain reaction(RT-PCR)suggest that Mg mainly regulates the motility and adhesion of HGFs through activating the MAPK signal pathway whereas Zn influences HGFs proliferation by triggering the TGF-βsignal pathway.The synergistic effect of Mg and Zn ions ensure that HGFs cultured on co-implanted samples possessed both high proliferation rate and motility,which are critical to soft tissue sealing of implants.