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1.
Endogenous ligands for cannabinoid receptors (“endocannabinoids”) include the lipid transmitters anandamide and 2-arachidonoylglycerol (2-AG). Endocannabinoids modulate a diverse set of physiological processes and are tightly regulated by enzymatic biosynthesis and degradation. Termination of anandamide signaling by fatty acid amide hydrolase (FAAH) is well characterized, but less is known about the inactivation of 2-AG, which can be hydrolyzed by multiple enzymes in vitro, including FAAH and monoacylglycerol lipase (MAGL). Here, we have taken a functional proteomic approach to comprehensively map 2-AG hydrolases in the mouse brain. Our data reveal that 85% of brain 2-AG hydrolase activity can be ascribed to MAGL, and that the remaining 15% is mostly catalyzed by two uncharacterized enzymes, ABHD6 and ABHD12. Interestingly, MAGL, ABHD6, and ABHD12 display distinct subcellular distributions, suggesting that they may control different pools of 2-AG in the nervous system.  相似文献   

2.
The active site of recombinant hexa-histidine-tagged human monoacylglycerol lipase (hMGL) is characterized by mass spectrometry using the inhibitors 5-((biphenyl-4-yl)methyl)-N,N-dimethyl-2H-tetrazole-2-carboxamide (AM6701), and N-arachidonylmaleimide (NAM) as probes. Carbamylation of Ser(129) by AM6701 in the putative hMGL catalytic triad demonstrates this residue's essential role in catalysis. Partial NAM alkylation of hMGL cysteine residues 215 and/or 249 was sufficient to achieve approximately 80% enzyme inhibition. Although Cys(215) and/or Cys(249) mutations to alanine(s) did not affect hMGL hydrolytic activity as compared with nonmutated hMGL, the C215A displayed heightened NAM sensitivity, whereas the C249A evidenced reduced NAM sensitivity. These data conclusively demonstrate a sulfhydryl-based mechanism for NAM inhibition of hMGL in which Cys(249) is of paramount importance. Identification of amino acids critical to the catalytic activity and pharmacological modulation of hMGL informs the design of selective MGL inhibitors as potential drugs.  相似文献   

3.
Compared with oligomeric proanthocyanidins, highly polymeric proanthocyanidins have more difficulty to analyze the molecular sizes and the mode of interflavan linkages of flavan-3-ol units through doubly linked A-type bonds and single B-type bonds. Recently, we have shown that seed shells of the Japanese horse chestnut contain highly polymeric proanthocyanidins as dominant polyphenolics that can be separated into two fractions according to the difference in the molecular sizes. Here, we tried to perform the structural characterization of them in terms of the molecular sizes and the proportions of A-type linkages relative to B-type linkages. The results were compared with those of the corresponding preparations with variations in the sizes from fruits of blueberry and cranberry. Gel permeation chromatography revealed that the molecular sizes of them were higher in the order of blueberry > cranberry > seed shells of the Japanese horse chestnut when they are compared between the respective fractions. For the analysis of terminal and extension units of those proanthocyanidins, the isolated fractions were subjected to the thiolytic cleavage of the B-type linkages using 1-dodecanethiol, and the resulting degradation products were identified by ultra-performance liquid chromatography electrospray-ionization mass spectrometry (UPLC-ESI/MS). These analyses provided fast and good resolution of the degradation products and revealed higher proportions of A-type linkages compared with B-type linkages in the both isolated fractions in the order of the seed shells > cranberry > blueberry. Moreover, the isolated fractions with higher molecular sizes and those more abundant in the proportions of A-type linkages were found to be more effective in the inhibition of pancreatic lipase activity. The results suggest that higher molecular sizes and more abundance of A-type bonds in polymeric proanthocyanidins are promising key factors for the attenuation of lipid digestion as dietary supplements.  相似文献   

4.
As the important parts of advanced oxidation processes (AOPs), photocatalysis and electrocatalysis technologies have a good applicative promising in the removal of micropollutants from water. But it is unpractical for photocatalysis with the catalytic reaction rate, the immobilization of catalyst, and the stability aspects, etc.[1—3]. One of the vital faults for the application of electrocatalysis for removal organics is electrode fouling [4]. The anodic direct electrons transfer reactions p…  相似文献   

5.
The phosphoramidite monomer of the C-nucleoside 2'-aminoethoxy-2-amino-3-methylpyridine (AE-MAP) has been synthesized for the first time and incorporated into triplex-forming oligonucleotides (TFOs). Ultraviolet melting and DNase I footprinting studies show that AE-MAP is a potent triplex-stabilizing monomer that is selective for GC base pairs. TFOs containing AE-MAP bind with high affinity to duplexes but only weakly to single stranded DNA. In addition, AE-MAP confers high nuclease resistance on oligonucleotides. TFOs containing AE-MAP have potential for gene knock-out and gene expression studies.  相似文献   

6.
We investigated the influence of temperature, pressure, exposure time, and decompression rate on lipase activity in high-pressure CO2 medium. A high-pressure, variable-volume view cell was employed in the experiments, varying the temperature from 30 to 70°C in the pressure range of 70–250 bar at various high-pressure exposure times (60–360 min) and adopting several decompression rates (10–200 kg/[m3·min]). The results obtained show that an increase in temperature and density led to an enhancement of enzyme activity losses while the decompression rates had a weak influence on enzyme inactivation.  相似文献   

7.
Using a set of three isotactic polypropylene samples that had been individually labeled with carbon-13 at each of the three positions in the monomer unit, we conducted experiments to determine the position of origin of carbon monoxide and carbon dioxide that arise during thermal oxidation of this polymer. By GC-mass-spectral analysis, we find that 2/3 of the CO2 derives from the C(1) [methylene] carbon and the remaining 1/3 comes from the C(2) [tertiary] carbon, with none coming from the C(3) [methyl group] carbon. The CO also comes mainly from the C(1) [methylene] carbon (≥80%). This is in contrast to the solid-phase oxidation products, which have been found (by C-13 NMR on these same labeled PP materials) to originate predominantly (80-85%) from oxidation at the C(2) [tertiary] carbon. These results can be understood in terms of the free-radical reactions that underlie the polypropylene oxidation chemistry.  相似文献   

8.
The degradation of 1,2 and 1,4 polybutadienes by heating in inert atmosphere was characterized by FTIR, NMR and TGA/TCT/GC/MS for the volatile organic compounds. Two distinct mass change stages in the thermogravimetric analysis indicated different temperature ranges of degradation. Below 300 °C, the predominant reactions depend on the chemical structure of PBs. Thus, M1 and M2 formation by heating 1,4-PB at 260 °C allows us to prove crosslinking reaction. On the other hand, heating 1,2-PB at 260 °C leads to decahydronaphthalene and methyl formation by cycloaddition and rearrangement. At about 300 °C, only radical scission occurs for 1,2-PB whereas Diels Alder and proton transfer mechanisms are described for 1,4-PB. The products of reaction are respectively conjugated diene, cyclic and linear unsaturated compounds sometimes with methyl groups. Above 400 °C, the main process is aromatisation for both PBs.  相似文献   

9.
对近年发展的Ti基TiO2纳米管阵列改性的方法及其在光催化降解有机污染物方面应用的研究进展进行了全面的综述,分析了当前存在的问题,并对TiO2纳米管阵列材料研究的发展趋势进行了展望.  相似文献   

10.
Organic substances (toluene, asphaltene dissolved in toluene) poorly soluble in water were solubilized by sodium dodecylsulfate (SDS) and the organic pollutants were mineralized together with the surfactants in diluted TiO2 suspension by UV light. In concentrated aqueous suspension, crude oil was photodegraded on the surface of Na-bentonite and the photocatalyst TiO2. Experiments have been carried out with Na-bentonite contaminated with crude oil mixed in a ratio of 1:1 with TiO2 as well. The photooxidation processes were followed by total organic carbon content (TOC) and diffuse reflection infrared spectroscopy (DRIFT) measurements.  相似文献   

11.
In this study, a series of hybrid Ag2CO3/ZnO composites were synthesised via a simple precipitation route and investigated for discolouration-degradation of Methylene Blue and disinfection of Escherichia coli in natural sunlight. It was observed that the photonic efficiency of discolouration was more than 6 times that of the conventionally popular TiO2, under experimental conditions; 100% Total Organic Carbon reduction was observed in 30 ?min and 32% disinfection in an hour. This upswing in the performance is attributed to favourable modulation of the dynamics of charge transfer. The photocatalysts were characterized by X-Ray Diffraction, Scanning Electron Microscopy, Transmission Electron Microscopy, Brunauer, Emmett and Teller and Ultraviolet–Visible-Near-InfraRed Spectroscopy. An equitable photocatalyst functional mechanism has also been proposed on the basis of Tauc plot and scavenging experiments. The effect of influencing parameters has also been investigated and reported in terms of photonic efficiency. Since the entire study is carried out in direct sunlight, it inherently supports realizable solar energy applications in wastewater treatment.  相似文献   

12.
半导体光催化剂作为一种可再生和可持续降解有机污染物的材料被广泛研究.K2Ti4O9由于无毒、低成本、稳定的物理化学性质和独特的光电性能被应用于光催化反应.但是,K2Ti4O9只能被紫外光所激发(因为其带隙能为3.2-3.4 eV),所以大量工作致力于研究如何降低其带隙能,从而使其可以被太阳光中的可见光激发,扩大其应用范围.其中N元素掺杂K2Ti4O9 (N-K2Ti4O9)是最常见的方法之一.单纯的N-K2Ti4O9虽然具有光催化能力,但其吸附容量太小,不能有效地将溶液中的有机物吸附至其表面,因而催化降解有机物效果不显著.UiO-66-NH2是一种Zr基金属-有机骨架化合物,它对阳离子染料具有良好的吸附性能,且具有一些常规无机半导体光催化材料所没有的性质.本文将UiO-66-NH2和N-K2Ti4O9经高温焙烧制备了N-K2Ti4O9/UiO-66-NH2复合材料,发现该复合材料不仅具有UiO-66-NH2优良的吸附性能,还因为复合提高了其光电性能,从而大大提高了光催化性能,当N-K2Ti4O9/ZrCl4质量比为3∶7时光催化性能最佳.为了考察N-K2Ti4O9/UiO-66-NH2复合材料的微观形貌、复合结构及光生电子-空穴分离效率,首先通过场发射透射电镜分析N-K2Ti4O9,UiO-66-NH2和N-K2Ti4O9/UiO-66-NH2(3∶7)复合材料的形貌,然后采用能量散射谱测定复合材料的元素分布,并利用N-K2Ti4O9和UiO-66-NH2中代表性元素K,Ti和Zr的分布判断复合材料的复合结构,最后运用高分辨电镜观察复合材料中N-K2Ti4O9和UiO-66-NH2的异质结界面,确定了两者是通过自组装复合在一起,而不是简单的物理混合.X射线衍射结果表明,复合材料具有N-K2Ti4O9和UiO-66-NH2两者的特征衍射峰,仅在强度和位置上略有变化.这可能是N-K2Ti4O9/UiO46-NH2异质结构所致.通过UiO-66-NH2和N-K2Ti4O9的紫外-可见吸收光谱,用公式计算出它们的带隙能分别是2.645和3.195 eV,与文献结果基本一致.由于光催化剂的光生载流子迁移速率同样影响光催化性能,因此我们在CHI-660D电化学工作站上控制光源反复开关数次,同时记录N-K2Ti4O9,UiO-66-NH2和N-K2Ti4O9/UiO-66-NH2(3∶7)的光响应电流,发现N-K2Ti4O9/UiO-66-NH2(3∶7)复合材料展现出最高的光响应电流强度,表明其具有最高的光生载流子迁移速率和最低的光生载流子复合速率.可见,N-K2Ti4O9和UiO-66-NH2复合有利于光生载流子迁移,这可能是由于N-K2Ti4O9/UiO-66-NH2异质结界面有利于光生载流子在两种材料之间迁移所致.测试了N-K2Ti4O9/UiO-66-NH2(3∶7)复合材料对不同染料的光催化降解性能.结果发现,该材料对阳离子型染料(罗丹明B和亚甲基蓝)的光催化性能远远高于对阴离子型染料(甲基橙和刚果红).这是由于它对阳离子型染料的吸附性能远高于对阴离子型染料,因此N-K2Ti4O9/UiO-66-NH2复合材料对阳离子型染料具有选择性光催化.  相似文献   

13.
Adsorption and photo-Fenton processes were used as handy tools to ascertain the capability of natural clays to remove cadmium (Cd) and 2-chlorophenol (2-CP) from aqueous solution. Natural Fe-rich clay collected from Tejera-Esghira in Medenine area, south Tunisia, was used as a catalyst in the heterogeneous photo-Fenton oxidation of 2-CP in aqueous solution. Clay samples were acid activated to improve their adsorptive capacity for the removal of Cd. Experimental results indicated that the adsorption of Cd ions onto natural red clay of Tejera-Esghira followed the pseudo-second-order kinetic model. Langmuir model was found to describe the equilibrium data with the calculated maximum adsorption capacity of 23.59 mg g?1 for acid-activated clay. Photo-Fenton experiments proved high activity of the natural clay catalyst, which was able to completely degrade the phenol present in the treated solution after 30 min and in the presence of ultraviolet light C (UV-C). Total organic carbon and gas chromatography analysis confirmed a 2-CP degradation mechanism toward an almost complete mineralization of the organic compound.  相似文献   

14.
This paper describes a simple and rapid way of monitoring a photocatalytic degradation of phenol in aqueous suspensions of TiO2. A three-way analytical methodology based on fluorescence excitation-emission matrix (EEM) and parallel factor analysis (PARAFAC) was developed to resolve the species present in the reaction mixture and quantify the concentration of phenol and its principal degradation products throughout the degradation. Parameters such as core consistency, fit% and correlation coefficients between recovered and pure spectra were used to determine the appropriate number of factors for the PARAFAC model. The accuracy of the model was evaluated by the root mean square error of prediction (RMSEP). Using a four-factors PARAFAC model, phenol, hydroquinone, resorcinol and catechol, were satisfactorily determined. The proposed method is an interesting alternative to the traditional techniques normally used for monitoring degradation reactions.  相似文献   

15.
Wei Zhang  Georgia Pugh 《Tetrahedron》2003,59(24):4237-4247
A straightforward 2-step parallel synthesis for structurally diversified spiro compounds is developed. 2-Bromobenzoic acids are used as common building blocks to couple with a series of conjugated enoles or enamines. Sequential intramolecular free radical Michael additions lead to formation of spirobenzolactones, spirobenzolactams, spirobenzolactone-lactams, spiorbenzolactone-thiolactones, spiordilactones, and bridged-spirolactones.  相似文献   

16.
武慧中  王佳栋  陈瑞敏  袁潮苇  张锦  张育新  盛剑平  董帆 《催化学报》2021,42(7):1195-1204,中插66-中插70
室内家具和工业生产排放的挥发性有机化合物(VOCs)是典型的空气污染物,对环境和人类健康造成严重威胁.然而,目前广泛应用的二氧化钛(P25)光催化剂在降解VOCs,尤其是降解芳香烃的过程中,存在光催化转化率低,失活快等问题.因此,开发具有高效和稳定性的新型光催化剂来降解VOCs,并将其实际应用是重要的科学问题.SnO2是一种稳定无毒的半导体光催化剂,但电子和空穴的复合率较高.掺杂过渡金属离子后可以提供缺陷态来抑制催化剂电子空穴对的快速复合,促进界面电荷转移.相比其他金属离子,Zn2+与Sn4+的离子半径非常相近,因此Zn2+会很容易掺杂到SnO2晶格中.并且用Zn2+取代Sn4+会形成表面修饰,即形成更多的氧空位(SOVs)来补偿正电荷.氧空位的存在不仅会产生缺陷能级,而且还可以促进大量局域电子的累积.SnO2上氧空位和Zn掺杂结构的协同作用可以弥补单一的外源离子掺杂或产生氧空位的不足.因此,本文采用一种简便的一步法合成催化剂Zn-SnO2,即在SnO2上同时实现Zn掺杂和形成SOVs,利用两者对SnO2的协同作用提高电荷转移和分离效率,使其在低或高相对湿度条件下均表现出高效、稳定的光催化降解甲苯性能.采用低温固态电子顺磁共振(EPR)检测了催化剂中的氧空位,在纯SnO2中仅检测到弱的EPR信号,而Zn-SnO2上的EPR信号非常强,表明Zn2+的掺杂诱导产生了大量的氧空位.扫描电镜和透射电镜结果表明,掺杂Zn2+可以有效抑制SnO2纳米粒子的晶体生长和相变,使得掺杂Zn2+的SnO2粒子的粒径显著减小,从而导致SOVs含量增加,此外粒径的减小有利于增大其比表面积,增加活性吸附位点.紫外可见漫反射结果表明,Zn-SnO2拓宽了光吸收范围,这归因于锌掺杂和氧空位的协同作用.在紫外光照射下,Zn-SnO2的光催化降解甲苯性能优于纯SnO2和P25,降解率达到77.5%.ESR光谱结果表明,Zn-SnO2上的电子自旋共振信号强度均强于纯SnO2和P25,说明Zn-SnO2具有较好的氧化能力,也与DFT计算O2和H2O的吸附能结果相吻合,表明了锌掺杂和SOVs对SnO2的协同作用可以显著提高电荷转移和分离效率.最后,通过原位红外光谱和DFT计算方法对甲苯降解的机理进行了研究.结果表明,甲苯的苯环在纯SnO2表面倾向于在苯甲酸阶段打开,在Zn-SnO2表面更倾向于在苯甲醛阶段选择性地开环.可见,Zn-SnO2光催化剂缩短了甲苯的降解路径,并能显著抑制中间毒副产物产生.综上,本工作提供了一种安全,高效和可持续的降解VOCs的光催化剂.  相似文献   

17.
The behaviour of allylbutyltin dichloride in water, water–ethanol and water–hexane media, under either homogeneous or heterogeneous conditions, has been studied. 1,3-Diallyl-1,3-dibutyl-1,3-dichlorodistannoxane, butyltin di(hydroxy)chloride and butyltin trichloride arise from the solvolytic, acid–base and degradation processes. The degradation process involving the cleavage of the tin–carbon allyl bond has been interpreted to occur via an intramolecular reaction at the expense of the cation [Bu(CH2=CHCH2)Sn(OH)(H2O)n]+. The mechanistic pathway is ascribable to an internal interaction of the electrophilic cation with a bonded water molecule. This mechanistic proposal may be of some help with understanding of the chemical degradation of diorganotin derivatives in aquatic environments.  相似文献   

18.
在低温(200℃)下采用一步水热分解CoFe2O4纳米粒子表面的镉二硫代氨基甲酸酯配合物制备了磁性CoFe2O4/CdS纳米复合物,运用X射线衍射、红外光谱、扫描电镜、X射线能量散射谱、紫外-可见光谱、透射电镜(TEM)、N2吸附-脱附、X射线光电子能谱和振动样品磁强计对所制样品进行了表征.TEM结果表明,CoFe2O4/CdS纳米复合物由几乎均一的约20nm球形纳米粒子组成.光吸收谱显示该样品的带隙为2.24 eV,很适合用于声/光催化降解有机污染物.在紫外光照射下评价了CoFe2O4/CdS纳米复合物的声催化H2O2辅助降解甲基蓝、罗丹明B和甲基橙反应活性.结果表明,该纳米复合物对这3种染料均表现出很好的声催化活性(5-9 min内完全降解).另外,比较实验结果表明,CoFe2O4/CdS纳米复合物是一个比纯CdS更高效的声催化剂.因此,纳米复合是一种非常好的提高CdS声催化活性的手段.该CoFe2O4/CdS纳米复合物表现出的磁性使其很容易从反应混合物中分离出来而重复使用.  相似文献   

19.
近年来,半导体光催化在环境净化和有机合成领域的研究引起了广泛的重视.其中,在有机合成领域中,光催化技术已经应用在醇类、环己烷以及芳香族化合物的选择性氧化研究.而另一类具有特殊结构的有机物——N-杂环芳烃,在药物化学和材料科学中具有重要意义.而传统用于合成N-杂化芳烃的脱氢催化氧化反应通常需要高温高压的苛刻环境,传统方法通常还需要使用贵金属催化剂,这也增加了N-杂化芳烃的合成成本;另外,如果合成是均相催化过程,则催化剂难以实现回收利用.因此,开发室温常压条件下的非贵金属多相光催化技术具有巨大的应用前景.本文以能够被可见光驱动的钼酸铋半导体为催化剂,利用氧缺陷策略来提升钼酸铋的光催化氧化性能.不同于传统氧缺陷制备方法(氢气还原热处理、离子掺杂等),本文采用一种低成本的乙二醛辅助溶剂热的方法合成具有可调控的含氧空位Bi2MoO6催化剂(OVBMO).通过X射线粉末衍射(XRD)、扫描电镜、透射电镜、紫外可见漫反射吸收光谱、氮气物理吸附脱附、X射线光电子能谱(XPS)、电子自旋共振光谱、光致发光光谱及电化学测试等技术对制备的OVBMO材料进行了物理化学性质及能带研究.XPS,XRD,Raman和FT-IR结果表明,氧空位存在于[Bi2O2]2+和MoO6八面体的层间.紫外可见漫反射结果表明,随着氧空位的引入,Bi2MoO6的光吸收范围扩大,带隙变窄.结合莫特肖特基和VBXPS分析获得OVBMO的能带位置,发现氧空位的存在不仅会导致禁带中出现缺陷带能级,还会导致价带顶位置上移,促进光生空穴的迁移.PL和电化学结果表明,氧空位的存在使得载流子浓度、载流子的分离能力与界面电荷迁移能力都有较大提升,这是因为氧空位引入的缺陷能级可以浅势捕获电子,抑制光催化剂中的电子与空穴的复合,改变化学反应的速率.同时,氧空位有助于捕获分子氧,分子氧与捕获的光生电子发生反应,产生更多的超氧自由基(·O2)和空穴(h+),从而极大地提升光催化剂的氧化性能.因此,OVBMO在1,2,3,4-四氢喹啉脱氢氧化产生喹啉及系列抗生素(环丙沙星、四环素、盐酸土霉素)的降解反应中,表现出较好的光催化氧化性能.结合多种表征分析,本文还进一步阐明了OVBMO催化剂将1,2,3,4-四氢喹啉脱氢氧化为喹啉的自由基参与的多相催化反应机理.  相似文献   

20.
Nanosized pure TiO2 particles with high crystallinity and large surface area were prepared by hydrolysis of tetrabutyl titanate in water/Triton X-100/isooctane reverse micelle solutions as reaction media followed by hydrothermal treatment to improve crystallinity. The prepared TiO2 nanoparticles were characterized by XRD, BET, TGA, FT-IR and TEM. The size of ultrafine particles was controlled by changing the water content of the reverse micelle solution. The TiO2 particles showed monodispersity, large surface area and high degrees of crystallinity and thermostability. The photocatalytic activity of the TiO2 particles was evaluated by decomposition of toluene in the gas phase. The activity of the TiO2 nanoparticles was higher than that of commercially available anatase fine particles, such as ST-01, which is one of the most active photocatalysts for degradation of organic compounds in the gas phase.  相似文献   

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