环氢化邻苯二甲酸二异壬酯的开发与应用进展

介绍了环氢化邻苯二甲酸二异壬酯的性能、生产的主要技术路线与最佳的操作条件及有关进展情况。对现工业化运行的主要环氢化邻苯二甲酸二异壬酯生产工艺的技术特点进行了具体的分析和总结。并探讨了扩大应用范围等的前景与市场需求。

环氢化邻苯二甲酸二异壬酯的开发与应用进展

全文介绍了环氢化邻苯二甲酸二异壬酯的性能、生产的主要技术路线与最佳的操作条件及有关进展情况。对现工业化运行的主要环氢化邻苯二甲酸二异壬酯生产工艺的技术特点进行了具体的分析和总结,并探讨了扩大应用范围等的前景与市场需求。

环氢化偏苯三酸三酯的开发与应用进展

介绍了环氢化偏苯三酸三酯的性能，生产的主要技术路线与最佳的操作条件及有关进展情况。对现工业化运行的环氢化偏苯三酸三酯生产工艺的技术特点进行了具体的分析和总结，阐述了国内外研究开发的现状与发展趋势。并探讨了扩大应用范围等的前景与市场需求。

环氢化邻苯二甲酸二（12～13）酯的开发与应用进展

介绍了环氢化邻苯二甲酸二（12～13）酯的性能，生产的主要技术路线与最佳的操作条件及有关进展情况。对现工业化运行的主要环氢化邻苯二甲酸二（12～13）酯生产工艺的技术特点进行了具体的分析和总结，阐述了国内外研究开发的现状与发展趋势。并探讨了扩大应用范围等的前景与市场需求。

氢化环氧树脂体系形状记忆效应的研究

将顺丁烯二酸酐(MA)与不同比例的氢化环氧树脂、聚丙二醇二缩水甘油醚(PPGDGE)共混,经完全固化制备出一种新型的形状记忆氢化环氧树脂体系。利用DMA,DSC、弯曲测试和U型形状记忆测试系统研究了该固化体系的动态力学性能、力学性能和形状记忆性能,结果表明:该固化体系交联点之间存在较长的柔性链段,导致部分结晶现象的出现;固化体系的玻璃化转变温度(Tg)最高达124℃,并且Tg随PPGDGE含量的增加而线性降低;该形状记忆氢化环氧固化体系具有优良的形状记忆性能,经过5次形状记忆测试,变形的试样均能在数分钟内完全恢复到变形前的状态,形变恢复率达100%。

四脚氧化锌晶须/氢化环氧树脂形状记忆复合材料的制备与性能

采用不同比例的四脚氧化锌晶须(T-ZnOw)与氢化环氧树脂(H-EP)共混,在聚丙二醇二缩水甘油醚(PPGDGE)和异佛尔酮二胺用量不变的前提下,经完全固化制备出一种新型的复合材料。通过动态力学性能测试、力学测试、红外光谱、扫描电子显微镜和U型形状记忆测试系统地研究了该体系的力学性能和形状记忆性能。实验结果表明,该体系复合材料的玻璃化转变温度最高可达到61.5℃,其力学性能比纯环氧树脂提高了15.87%。该试样具有良好的形状记忆性能,变形的试样几乎可以完全回复。

环氢化邻苯二甲酸二异壬酯的开发与应用进展

全文介绍了环氢化邻苯二甲酸二异壬酯的性能，生产的主要技术路线与最佳的操作条件及有关进展情况。对现工业化运行的主要环氢化邻苯二甲酸二异壬酯生产工艺的技术特点进行了具体的分析和总结，阐述了国内外研究开发的现状与发展趋势。并探讨了扩大应用范围等的前景与市场需求。

盐酸多西环素氢化合成研究

在盐酸多西环素的氢化合成生产中采用可回收的以硅胶固定的均相铑催化剂,在反应温度90℃,压力294kPa,反应时间6h,m(催化剂)∶m(助催化剂)∶m(脱水物)=0.02∶0.05∶1的最佳条件下,收率可达85%以上,催化剂可套用10多次,该工艺提高了产品立体选择性和收率,降低了贵金属消耗,有较大的工业价值。

Pt(Ⅱ)催化炔基氮丙啶合成环戊烷吡咯机理的密度泛函理论研究

用量子化学密度泛函理论B3LYP方法在6-311G(d,p)的计算水平上对Pt Cl2催化2-炔基-1-氮杂环己烷合成1,4,5,6-四氢化环戊烷吡咯的反应,进行了计算,找到两条主要的反应通道,最优势反应路径包括炔基的活化、氮丙啶的氮与炔基间的环化反应、环异构化、质子转移和催化剂解离5个步骤。Pt Cl_2催化作用的本质在于Pt^(2+)与炔基配位,能降低炔基反键轨道π*_(C1-C2)的能级,降低炔基反键轨道π*_(C1-C2)与氮丙啶的氮原子孤电子占据轨道LP-(2p)_N的能级差,使丙啶氮原子与炔基之间的环化反应势垒下降。

Damage effect and mechanisms of cyclophosphamide to human neuroblastoma SH-SY5Y cells

OBJECTIVE To investigate the damage effect and mechanisms of cyclophosphamide(CTX)and its active metabolite derivative 4-hydroperoxycyclophosphamide(4-HC)to human neuroblas⁃toma SH-SY5Y cells.METHODS SH-SY5Y cells were treated with CTX[0(cell control),0.01,0.1,1,5,10,20,40 and 80 mmol·L^(-1)]and 4-HC[0(cell control),0.01,0.1,1,5,10,20,40 and 80μmol·L^(-1)]for 48 h.Cell confluence and morphology were observed by the IncuCyte ZOOM system.Cell viability was assessed by CCK-8 assay.Lactate dehydrogenase(LDH)release was measured by LDH assay kit.SH-SY5Y cells were treated with CTX(0,1,5,10 and 20 mmol·L^(-1))and 4-HC(0,1,5,10 and 20μmol·L^(-1))for 48 h before cell proliferation was analyzed by 5-ethynyl-2′-deoxyuridine(EdU)staining assay.Immunofluorescence was employed to assess the levels of the DNA double-strand break markerγ-H2AX and to evaluate changes in mitochondrial membrane potential.SH-SY5Y cells were treated with CTX(0,1,5 and 10 mmol·L^(-1))and 4-HC(0,1,5 and 10μmol·L^(-1))for 48 h,and the alterations in glycolysis and oxidative phosphorylation levels were analyzed using the Seahorse XFe96 Analyzer.RESULTS Compared with the cell control group,cell confluence and cell viability were significantly reduced in the CTX and 4-HC groups(P<0.01),and the half-maximal inhibitory concentrations(IC50)for CTX and 4-HC were 4.44 mmol·L^(-1) and 4.78μmol·L^(-1),respectively.The release rate of LDH was signif⁃icantly increased while the percentage of EdU+cells was significantly reduced in the CTX and 4-HC groups(P<0.01).The percentage ofγ-H2AX+cells was significantly increased and mitochondrial membrane potential significantly decreased in the CTX and 4-HC group(P<0.05).Treatment with CTX and 4-HC resulted in reduced levels of maximum glycolytic capacity,glycolytic reserve,maximal respi⁃ration,and ATP production(P<0.05).CONCLUSION CTX and 4-HC exert significant cytotoxic effects on SH-SY5Y cells by disrupting cell membrane structure,impeding cell proliferation,and reducing cell viability.The mechanisms underlying these effects may involve intracellular DNA damage,disturbance of energy metabolism and mitochondrial dysfunction.

由三氯戊烯酮合成氢化吡唑环和氢化异恶唑环

二氯丁烯酮①可看成“隐”乙酰乙酸乙酯,前者比后者容易合成得多。后者是杂环合成的重要原料,许多实验证明,前者①也是杂环合成的良好原料。①在形成杂环时,利用了羰基及β-氯的活性。使①在甲基上氯甲基化,得三氯戊烯酮②。由于②具有更活泼的饱和β-氯,应是更活泼的杂环合成原料。利用这点,合成了吡啶酮环。本文报道氢化吡唑环和氢化异恶唑环的合成。反应式如下:

Pyrrolidine dithiocarbamate reduces ischemia-reperfusion injury of the small intestine

AIM： To evaluate whether pyrrolidine dithiocarbamate （PDTC）, an enhancer of HO production, attenuates intestinal IR injury. METHODS： Eighteen male rats were randomly allocated into three groups： （a） sham; （b） IR, consisting of 30 min of intestinal ischemia, followed by 2-h period of reperfusion; and （c） PDTC treatment before IR. Intestinal microvascular perfusion （IMP） was monitored continuously by laser Doppler flowmetry. At the end of the reperfusion, serum samples for lactate dehydrogenase （LDH） levels and biopsies of ileum were obtained. HO activity in the ileum was assessed at the end of the reperfusion period. RESULTS： At the end of the reperfusion in the IR group, IMP recovered partially to 42.5% of baseline （P〈0.05 vs sham）, whereas PDTC improved IMP to 67.3% of baseline （P〈0.01 vs IR）. There was a twofold increase in HO activity in PDTC group （2 062.66±106.11） as compared to IR （842.3±85.12） （P〈0.001）. LDH was significantly reduced （P〈0.001） in PDTC group （585.6±102.4） as compared to IR group （1 973.8±306.5）. Histological examination showed that the ileal mucosa was significantly less injured in PDTC group as compared with IR group. CONCLUSION： Our study demonstrates that PDTC improves the IMP and attenuates IR injury of the intestine possibly via HO production. Additional studies are warranted to evaluate the clinical efficacy of PDTC in the prevention of IR injury of the small intestine.

Electrocatalytic H_(2)O_(2)generation for disinfection

Epidemics are threatening public health and social development.Emerging as a green disinfectant,H_(2)O_(2)can prevent the breakout of epidemics in migration.Electrochemical H_(2)O_(2)production powered by renewable electricity provides a clean and decentralized solution for on-site disinfection.This review firstly discussed the efficacy of H_(2)O_(2)in disinfection.Then necessary fundamental principles are summarized to gain insight into electrochemical H_(2)O_(2)production.The focus is on exploring pathways to realize a highly efficient H_(2)O_(2)production.Progress in advanced electrocatalysts,typically single-atom catalysts for the two-electron oxygen reduction reaction(2e−ORR),are highlighted to provide high H_(2)O_(2)selectivity design strategies.Finally,a rational design of electrode and electrolytic cells is outlined to realize the on-site disinfection.Overall,this critical review contributes to exploiting the potentials and constraints of electrochemical H_(2)O_(2)generation in disinfection and pinpoints future research directions required for implementation.

Differential generation of hydrogen peroxide upon exposure to zinc and cadmium in the hyperaccumulating plant specie(Sedum alfredii Hance)

Sedum alfredii Hance has been identified as zinc(Zn) and cadmium(Cd) co-hyperaccumulator.In this paper the relationships of Zn or Cd hyperaccumulation to the generation and the role of H2O2 in Sedum alfredii H.were examined.The results show that Zn and Cd contents in the shoots of Sedum alfredii H.treated with 1000 μmol/L Zn2+ and/or 200 μmol/L Cd2+ increased linearly within 15 d.Contents of total S,glutathione(GSH) and H2O2 in shoots also increased within 15 d,and then decreased.Total S and GSH contents in shoots were higher under Cd2+ treatment than under Zn2+ treatment.However,reverse trends of H2O2 content in shoots were obtained,in which much higher H2O2 content was observed in Zn2+-treated shoots than in Cd2+-treated shoots.Similarly,the microscopic imaging of H2O2 accumulation in leaves using H2O2 probe technique showed that much higher H2O2 accumulation was observed in the Zn2+-treated leaf than in the Cd2+-treated one.These results suggest that there are different responses in the generation of H2O2 upon exposure to Zn2+ and Cd2+ for the hyperaccumulator Sedum alfredii H.And this is the first report that the generation of H2O2 may play an important role in Zn hyperaccumulation in the leaves.Our results also imply that GSH may play an important role in the detoxification of dissociated Zn/Cd and the generation of H2O2.

Synthesis of ε-Caprolactone by Oxidation of Cyclohexanone with Monoperoxysuccinic Acid

In the absence of catalyst,70%hydrogen peroxide was used to oxidize succinic anhydride to solid monoperoxysuccinic acid(PSA).Then PSA was applied to synthesis ofε-caprolactone(ε-CL)by oxidation of cyclohexanone in the heterogeneous system.In order to achieve material recycle,solid precipitated in the process of synthesizingε-CL was dehydrated via reactive distillation followed by recrystallization to prepare succinic anhydride,which was characterized by IR(infrared spectra)and1HNMR(1H nuclear magnetic resonance).Effects of molar ratio of PSA to cyclohexanone,acetic acid dosage,reaction temperature,reaction time on conversion of cyclohexanone,yield and selectivity ofε-CL were investigated respectively.The results indicated that conversion of cyclohexanone,yield and selectivity ofε-CL were upto 98.1%,97.5%and 99.4%respectively under the optimal conditions.In addition,in the process of synthesizing succinic anhydride,the optimal yield of succinic anhydride reached 67.4%.

Highly efficient Rh(Ⅰ)/tris-H_8-binaphthyl monophosphite catalysts for hydroformylation of dicyclopentadiene to dialdehydes

Novel catalytic systems for the Rh‐catalyzed hydroformylation of dicyclopentadiene have been developed using tris‐H8‐binaphthyl monophosphite as ligands containing different ester substituents at the 2’‐binaphthyl position(OCOMe,OCOPh,OCOAdamantyl and OCOPhCl).The catalysts exhibited high activity(S/C=4000,TON=3286)with good to excellent selectivity towards dialdehydes.Remarkably,the Rh(I)complex bearing the ligands with chlorophenyl ester substituents led to 99.9%conversion and 98.7%selectivity for dialdehydes under relatively mild conditions(6 MPa,120°C).

Purification of Sulfuric and Hydriodic Acids Phases in the Iodine-sulfur Process

Iodine-sulfur （IS） thermochemical water-splitting cycle is the most promising massive hydrogen production process. To avoid the undesirable side reactions between hydriodic acid（HI） and sulfuric acid （H2SO4）, it is necessary to purify the two phases formed by the Bunsen reaction. The purification process could be achieved by reverse reaction of the Bunsen reaction. In this study, the purification of the H2SO4 and HI Phases was studied. The purification proceeded in both batches and the continuous mode, the influences of operational parameters, including the reaction temperature, the flow rate of nitrogen gas, and the composition of the raw material solutions, on the purification effect, were investigated. Results showed that the purification of the H2SO4 phase was dominantly-affected by the reaction temperature, and iodine ion in the sulfuric acid phase could be removed completely when the temperature was above 130℃; although, the purification effect of the HI phase improved with increasing of both the flow rate of nitrogen gas and temperature.

Performance of Ni-based, Fe-based and Co-based Oxygen Carriers in Chemical-Looping Hydrogen Generation

Ni-based, Fe-based and Co-based oxygen carriers with perovskite oxides used as the supports were prepared by citric acid complexation method, The oxygen carriers were characterized by thermal analysis, H2-temperature-programmed reduction and X-ray diffraction methods. Performance tests were evaluated through Chemical-Looping Hydrogen Genera- tion in a fixed-bed reactor operating at atmospheric pressure. The characterization results showed that all samples were composed of metal oxides and perovskite oxides. Performance results indicated that CH4 conversion over the oxygen car- riers decreased in the lbllowing order： NiO/LaNiO3〉Co203/LaCoO3〉Fe203/LaFeO3. The ability of NiO/LaNiO3 and F%O3/ LaFeO3 to decompose water was stronger than that of Co203/LaCoO3 as evidenced by our experiments. H2 amounting to 80 mL upon reacting on methane in every cycle could be completely oxidized by NiO/LaNiO3 at 900℃ in the period from the third cycle to the eighth cycle.

Green and efficient epoxidation of methyl oleate over hierarchical TS-1

The epoxidation of methyl oleate(MO)was conducted in the presence of aqueous H2O2 as the oxidant and hierarchical TS-1(HTS-1)as the catalyst;the catalyst was synthesized using polyquaternium-6 as the mesopore template.The effects of various parameters,i.e.,H2O2/C=C molar ratio,oxidant concentration,amount of the catalyst,reaction temperature,and time,were systematically studied.Furthermore,response surface methodology(RSM)was used to optimize the conditions to maximize the yield of epoxy MO and to evaluate the significance and interplay of the factors affecting the epoxy MO production.The H2O2/C=C molar ratio and catalyst amount were the determining factors for MO epoxidation,wherein the maximum yield of epoxy MO reached 94.9%over HTS-1 under the optimal conditions.

ACCESSING HIGH THERMAL EFFICIENCY POWER GENERATION USING FLUID PHASE CHEMICAL LOOPING

In order to burn a hydrocarbon fuel efficiently using conventional cycles,very high temperatures are required.Chemical looping combustion（CLC）offers an alternative cycle for large scale power production.In CLC a carrier molecule is used to transport oxygen between two redox reactions,one where the carrier is oxidised and another where it is reduced by reaction with a fuel.Separation of the oxygen carrier from fuel ash can be aided by means of phase difference and this is a key advantage of fluid phase CLC where the carrier medium proposed is sodium,potassium or zinc.The principle exploited in fluid phase CLC is the recirculation of both energy and entropy.High thermal efficiencies,circa 75% at 35 bar are theoretically achievable taking into account component efficiencies,with separation of nitrogen and carbon dioxide,in combination with the water shift gas reaction,as an inherent part of the cycle if air is used as the oxygen source.