磺化聚醚醚酮与氧化石墨烯共混膜的制备以及在全钒液流电池中的应用

以浓硫酸为溶剂和磺化剂制备磺化度(DS)为65%的磺化聚醚醚酮(SPEEK),根据SPEEK和氧化石墨烯(GO)不同质量比制备一系列共混膜(S/GO).对共混膜的含水量、离子交换容量、面电阻、质子电导率、钒离子渗透率、机械强度以及耐氧化性进行研究.采用扫描电子显微镜(SEM)观察S/GO共混膜的形态;通过热重分析(TG)表征共混膜的热稳定性.结果表明随着GO引入量的增加,共混膜的含水量增加,离子交换容量(IEC)降低,质子电导率减小,钒离子渗透率减小,机械性能增强.共混膜能量效率均高于Nafion115,其中S/GO-2(GO含量2 wt%)的电池效率最佳,能量效率达到80%,相比于Nafion115提高近9%.在运行100次循环以后S/GO共混膜电池效率稳定性良好.S/GO共混膜有望在全钒液流电池中得到应用.     

对苯二胺功能化还原氧化石墨烯的结构和官能团变化

采用一步水热回流法,选取对苯二胺(PPD)对氧化石墨烯(GO)进行还原与改性处理,制备了功能化还原氧化石墨烯(GOP-X).采用傅里叶变换红外光谱(FTIR)、X射线光电子能谱(XPS)及X射线衍射(XRD)等研究了PPD与GO的反应作用类型及结构变化.结果表明,随着PPD与GO质量比的增加,GOP-X层间距(d值)先增大后减小,GOP-X共轭结构逐渐恢复,与溶剂分子作用时,层间距增幅呈减小趋势,并最终趋于恒定.PPD单体与GO反应时存在3种键合类型:(1)GO含氧官能团和PPD分子之间的氢键作用(C—OH…H2N—X);(2)质子化PPD与弱酸性GO带负电位置之间的离子键作用(—COO-H3+N—X);(3)PPD中氨基(NH2)与GO含氧官能团之间形成的共价键作用.与GO中羧基(COOH)的酰胺化反应将先于与环氧基(C—O—C)的亲核取代反应.提出了相应的作用机理.     

氧化石墨烯在氧化锌衬底上的电化学还原及其光电性能

采用阳极电泳法,在氧化锌(ZnO)衬底上沉积氧化石墨烯(GO)以形成GO-ZnO双层复合膜;采用阴极恒电位法,对复合膜上的GO进行还原。对不同还原时间的GO,通过X射线光电子能谱(XPS),傅里叶变换红外(FTIR)光谱,场发射扫描电子显微镜(FESEM)等手段对其结构变化进行表征,采用紫外-可见(UV-Vis)分光光度法和电化学测试手段对其能级演变进行考察,并对两者的对应关系进行了讨论。研究发现,当GO膜达到最大还原态后,随还原时间增加还会出现进一步的结构转变,并最终碎裂生成边缘羧基增多的小尺寸GO。GO能隙均减小至可见光范围,其能级位置及半导体极性也产生了不同的改变。由对复合膜的光电化学测试可见,除1800 s GO能级不再与ZnO匹配外,60 s到600 s GO-ZnO复合膜均可作为阳极光电极进行太阳光电转换。对光电性能差异的讨论则可得,GO膜碎裂造成叠层形貌向无序形貌的转变有利于光电转换性能的提升。     

石墨烯薄膜的光化学还原制备与表征

采用光化学还原方法制备了图案化的石墨烯薄膜.研究了光还原氧化石墨烯薄膜(PRGO)的热稳定性和发光性质.热重分析(TGA)结果表明,光化学还原主要引起氧化石墨烯(GO)氧化基团的减少,而对GO内水含量影响较小;发光(PL)测试结果表明,不同激发条件下,PRGO的发光与GO相比表现出了不同的变化规律:在波长514 nm的光激发下,PRGO的发光强度比GO明显降低,同时伴随着发光峰峰位红移;而在波长830 nm的光激发下,PRGO的发光强度比GO略有增强,并且发光峰峰位无明显变化,此结果表明不同尺寸的碳团簇局域态(sp2C团簇)的光还原反应活性不同,这与GO特殊的能带结构密切相关.     

希瓦氏菌介导制备还原氧化石墨烯薄膜及其增强的胞外电子传递

采用单室、三电极体系,通过希瓦氏菌(Shewanella)还原氧化石墨烯(GO)膜,制备了石墨烯(rGO)薄膜,并通过X射线衍射(XRD)和拉曼光谱(Raman)等手段表征了GO还原前后的结构和性质,证明了Shewanella菌可以有效将GO膜还原为rGO.以该生物还原得到的rGO薄膜为工作电极,可以有效改善Shewanella菌的胞外电子转移(EET).与空白的氧化铟锡(ITO)电极相比,rGO电极的阳极输出电流增大了13%,电量增加90%.该Shewanella还原法是一种温和制备rGO膜的方法,制得的rGO膜改善了微生物的EET效率.     

电化学法制备部分还原氧化石墨烯薄膜及其光电性能

提供了一种快速制备氧化石墨烯(GO)薄膜的方法, 并通过调节GO薄膜的含氧量来调控其能级结构.采用阳极电泳及阴极电化学还原联用的方法在F掺杂SnO₂(FTO)导电玻璃上制备出不同层数及含氧量的GO薄膜, 并通过扫描电镜(SEM)、X射线衍射(XRD)、紫外可见(UV-Vis)光谱、X射线光电子能谱(XPS)、拉曼光谱及电化学分析对样品进行表征. 用20-350 s 不同时间电泳沉积得到层数约为77-570层的GO薄膜. 经过不同时间阴极还原的GO薄膜的禁带宽度为1.0-2.7 eV, 其导带位置及费米能级也随之改变. GO作为p型半导体, 与FTO导电膜之间会形成p-n 结, 在光强为100 mW·cm^-2的模拟太阳光照射下, 电泳300 s 且电化学还原120 s时GO薄膜阳极光电流密度达到5.25×10^-8 A·cm^-2.     

聚二甲基硅氧烷封装石墨烯基柔性红外探测器的制备及其应用

采用热还原法在不同退火温度(从100到1200℃)下制备了一系列还原氧化石墨烯(r GO)薄膜,并通过X射线粉末衍射(XRD)、傅里叶变换红外光谱(FTIR)、拉曼光谱、四探针电阻仪和扫描电镜(SEM)对其进行了表征和分析.随后利用旋涂封装法制备了聚二甲基硅氧烷(PDMS)封装的石墨烯基柔性红外探测器(P-r GO-P),并成功用于红外激光、人体红外辐射、弯曲变化和压力探测.实验结果表明,采用不同温度还原的rGO薄膜封装得到的P-r GO-P柔性红外探测器在近红外(1064 nm)激光照射下均有响应,其中最高的光响应可达2.78 mA/W.此外, P-rGO-P柔性探测器对人体红外辐射和弯曲变化也具有快速、灵敏的响应,并且经过反复弯折仍能保持完整性与响应能力.     

原位无规共缩聚制备高性能石墨烯/聚酰亚胺纳米复合材料

将依次经过化学改性和还原得到的含有自由氨基的氧化石墨烯(r GO-NH2)作为共聚单体,与商品化的二胺单体和二酐单体在相关有机溶剂中进行原位无规溶液共缩聚得到前驱体溶液,然后在玻璃板上流延成膜后再进行热酰亚胺化得到一系列不同含量的还原的氧化石墨烯/聚酰亚胺(r GO/PI)纳米复合材料.通过对r GO-NH2的化学结构、组成和微观形貌的一系列测试和表征来证实上述改性和还原,以及为后续的聚合反应奠定基础.通过对所得纳米复合材料的性能进行测试后发现:当r GO-NH2的加入量为2 wt%时,其Tg、在N2和空气气氛中的T5%较PI分别升高了17.9、32.7和46.7 K,拉伸强度、拉伸模量和断裂伸长率分别增加了40.6%、16.7%和187.8%.除此之外,它的平均接触角(SCA)值增加到103.8°.与此同时,通过观察微观结构形貌来进一步了解r GO-NH2的加入量对相关性能的影响.     

系列烷基多硫化物形成的摩擦膜和热膜的XANES分析

采用X射线吸收精细结构光谱(XANES)对不同硫含量的系列烷基多硫化物与钢表面在70 ℃和150 ℃反应的热膜以及摩擦膜进行了分析. 结果表明, 在70 ℃和150 ℃下生成的热膜的主要成分是FeSO4或Fe2(SO4)3, 温度的升高会增大生成的热膜厚度; 生成的摩擦膜成分主要是铁的硫酸盐、二硫化铁和亚砜的混合物. 添加剂分子中硫含量的提高可以增大生成的热膜和摩擦膜的厚度.     

四甲基氢氧化铵改性聚偏氟乙烯接枝苯乙烯磺化膜的制备和性能

使用四甲基氢氧化铵(TMAH)甲醇溶液在液相中改性聚偏氟乙烯(PVDF),挥发溶剂得到改性聚偏氟乙烯膜(g-PVDF-M),再以过氧化苯甲酰(BPO)为引发剂,将苯乙烯接枝到g-PVDF-M膜中,磺化后制得改性聚偏氟乙烯接枝苯乙烯磺化(PVDF-g-PSSA)膜.利用傅里叶变换红外光谱(FTIR)和能谱仪的扫描电子显微镜分析了PVDF-g-PSSA膜(TMAH-25)的结构、形貌及硫元素分布情况.通过电化学工作站和气相色谱仪研究了TMAH在甲醇中的不同含量对PVDF-g-PSSA膜质子电导率和甲醇渗透率的影响.结果表明,TMAH使PVDF脱去HF生成碳碳双键,并且苯乙烯接枝到改性的聚偏氟乙烯膜中,磺化后S元素在PVDF-g-PSSA膜内部均匀分布;PVDF-g-PSSA膜的质子电导率和甲醇渗透率随TMAH在甲醇溶液中质量分数的增加而增大;TMAH的质量分数为25%时,PVDF-g-PSSA膜的电导率达1.28×10~(-2)S/cm,甲醇渗透率为4.58×10~(-7)cm~2/s.热重分析(TGA)表明,PVDF-g-PSSA膜的热稳性良好,耐热温度高达195℃,PVDF-g-PSSA膜作为电解质材料的直接甲醇燃料单电池(DMFC)功率密度达到16.45 mW/cm~2.     

应用先进光谱技术研究无机离子的环境界面化学

发生在环境界面的吸附-解吸和氧化-还原等反应对于污染物在环境介质间传输、转化以及归趋起着重要的调控作用。传统的研究方法虽然可以在实验室模拟并进而描述污染物环境界面过程,但是不能揭示界面反应机制,限制了对污染物环境界面行为的认识。近二十年来,各种谱学技术(例如X射线吸收精细结构和傅里叶红外光谱等)应用于环境界面反应的研究,推动了这一领域研究的发展,特别是在分子水平研究污染物的环境界面过程。通过现代光/波谱技术原位分析,可以实时获取界面反应的定量与结构信息,从而更准确地判断反应机制,极大促进了对污染物在多介质环境界面迁移转化规律的认识。本文将在概述环境界面化学反应的基础上,针对无机离子在环境界面的反应过程,重点介绍几种关键光/波谱技术(X射线吸收精细结构光谱、傅里叶红外光谱、拉曼光谱、核磁共振谱和穆斯堡尔谱等)在环境界面化学研究中的应用,并展望其在环境界面过程研究中的应用前景。     

ICP-MS的KED模式测定磷酸加王水复溶土壤样品中的二十种金属元素

在研究锗测定时,磷酸先溶解样品,后加入王水复溶,可同时测定锂、铍、钪、钒、铬、钴、镍、铜、锌、锗、钼、镉、钡、镧、铈、钨、铊、铅、钍和铀元素。研究ICP-MS的最佳测量模式、最佳工作状态,以铑为内标校正仪器的漂移。通过选择高、中、低几个国家一级水系沉积物和土壤标准物质随同样品一起实验溶解建立标准曲线,消除消解、分取、定容中带来的不确定误差和基体干扰,选择8个土壤标准物质为实验样本。最终结果表明,该实验方法准确度(ΔlgC)小于0.1,精密度(RSD)小于8%,该方法满足测定要求,适用于地质普通样品的多金属检测。#$NL     

Transition Metal–(μ-Cl)–Aluminum Bonding in α-Olefin and Diene Chemistry

Olefin and diene transformations, catalyzed by organoaluminum-activated metal complexes, are widely used in synthetic organic chemistry and form the basis of major petrochemical processes. However, the role of M–(μ-Cl)–Al bonding, being proven for certain >C=C< functionalization reactions, remains unclear and debated for essentially more important industrial processes such as oligomerization and polymerization of α-olefins and conjugated dienes. Numerous publications indirectly point at the significance of M–(μ-Cl)–Al bonding in Ziegler–Natta and related transformations, but only a few studies contain experimental or at least theoretical evidence of the involvement of M–(μ-Cl)–Al species into catalytic cycles. In the present review, we have compiled data on the formation of M–(μ-Cl)–Al complexes (M = Ti, Zr, V, Cr, Ni), their molecular structure, and reactivity towards olefins and dienes. The possible role of similar complexes in the functionalization, oligomerization and polymerization of α-olefins and dienes is discussed in the present review through the prism of the further development of Ziegler–Natta processes and beyond.     

中文化学名词醇醛酮醚酯之由来

1932年民国教育部颁布的《化学命名原则》为中文化学名词确立了统一的标准,并对于"元素及化合物定名取字"提出"取字应以谐声为主,会意次之,不重象形"的定名总则.它确立的中文化学名词醇、醛、酮、醚、酯是意译名,这似乎与其音译为主的命名原则相悖.本文讨论了醇、醛、酮、醚、酯的各种历史译名,并分析了它们被《原则》采纳的原因.     

Bestimmung von Fe, Co, Cu, Zn, Se, Rb und Cs in NBS-Ochsenleber, Blutplasma und Erythrocyten durch INAA und AAS

Zusammenfassung Der Gehalt von Fe, Co, Cu, Zn, Se, Rb und Cs wurde in Blutplasma und in Erythrocyten von sechs Normalpersonen mittels der instrumentellen Neutronenaktivierungsanalyse und der flammenlosen Absorptionsspektrometrie (Cu) bestimmt. Zur Überprüfung der Richtigkeit wurde der NBS-Standard 1577, Ochsenleber, verwendet. Die erhaltenen Resultate für Elemente mit höheren Gehalten (Fe, Cu, Zn) liegen weitgehend im Bereich der bisher veröffentlichten Daten. Bei Elementen mit kleineren Gehalten (Co, Se, Rb, Cs) liegen unsere Werte in dem unteren Bereich oder darunter. Für diese Elemente wurden in Blutplasma und in Erythrocyten (hier bezogen auf Trockenmasse) die folgenden Mittelwerte ermittelt: Für Co 0,22 ±0,14 ng/ml, 0,59±0,23 ng/g, für Se 103±18 ng/ml, 401±29 ng/g, für Rb 167±36 ng/ml, 12,1±2,5 g/g und für Cs 0,88±0,18 ng/ml, 13,0±5,7 ng/g.

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Determination of Fe, Co, Cu, Zn, Se, Rb and Cs in NBS Bovine Liver, blood plasma and erythrocytes by INAA and AAS

Summary The content of the above elements has been determined in blood plasma and in erythrocytes of six normal persons by instrumental neutron activation analysis and flameless atomic absorption spectrometry (Cu). The over-all accuracy of these techniques was checked by using the NBS standard 1577, Bovine Liver. The results obtained for elements of higher content (Fe, Cu, Zn) are essentially in the range of other published data. However, our results for elements occurring with lower contents (Co, Se, Rb, Cs) are in agreement with the lowest values of the published data and in some cases they are even significantly below these. For these elements, the following contents have been determined in blood plasma and in erythrocytes (here related to dry weight): for Co 0.22±0.14 ng/ml and 0.59±0.23 ng/g, for Se 103±18 ng/ml and 401±29 ng/g, for Rb 167 ±36 ng/ml and 12.1±2.5 g/g and for Cs 0.88 ±0.18 ng/ml and 13.0±5.7 ng/g, respectively.

Diese Arbeit wurde durch die Deutsche Forschungsgemeinschaft gefördert.Dem Kernforschungszentrum danken wir für den Erlaß der Bestrahlungskosten.Herrn Dr. med. K. Spenger sind wir für die Mitwirkung bei der Blutentnahme und für wertvolle Diskussion dankbar.     

Attenuation of Scopolamine-Induced Amnesia via Cholinergic Modulation in Mice by Synthetic Curcumin Analogs

Alzheimer’s disease is an emerging health disorder associated with cognitive decline and memory loss. In this study, six curcumin analogs (1a–1f) were synthesized and screened for in vitro cholinesterase inhibitory potential. On the basis of promising results, they were further investigated for in vivo analysis using elevated plus maze (EPM), Y-maze, and novel object recognition (NOR) behavioral models. The binding mode of the synthesized compounds with the active sites of cholinesterases, and the involvement of the cholinergic system in brain hippocampus was determined. The synthesized curcumin analog 1d (p < 0.001, n = 6), and 1c (p < 0.01, n = 6) showed promising results by decreasing retention time in EPM, significantly increasing % SAP in Y-maze, while significantly (p < 0.001) enhancing the % discrimination index (DI) and the time exploring the novel objects in NORT mice behavioral models. A molecular docking study using MOE software was used for validation of the inhibition of cholinesterase(s). It has been indicated from the current research work that the synthesized curcumin analogs enhanced memory functions in mice models and could be used as valuable therapeutic molecules against neurodegenerative disorders. To determine their exact mechanism of action, further studies are suggested.     

Phosphorescence of aromatic molecules in complexes with crystalline β-cyclodextrin at room temperature

The rate constants for the quenching by oxygen of triplet states of aromatic molecules (naphthalenes-d₈ and-h₈, phenanthrene) forming inclusion complexes with crystalline β-cyclodextrin in water at 290 K are equal to 900–1300 L mol⁻¹s⁻¹. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1450–1453, August, 1997.     

Direct benzylic functionalization of pyridines:Palladium-catalyzed mono-α-arylation of α-(2-pyridinyl)acetates with heteroaryl halides

Herein,we report a Pd-catalyzed mono-a-arylation reaction for pyridine benzylic functionalization.This approach serves as an efficient alternative to synthesize di-heteroaryl acetates in good yields and selectivities.Moreover,the method is applicable to heteroa ryl substrate combinations,and exhibits great functional group tolerance.A streamlined protocol also enables the rapid synthesis of diheteroaryl ketones.The synthetic value was also demonstrated by scale-up experiments.     

Unveiling Antimicrobial and Antioxidant Compositional Differences between Dukkah and Za’atar via SPME-GCMS and HPLC-DAD

Interest in plant-based diets has been on the rise in recent years owing to the potential health benefits of their individual components and the notion that plant-based diets might reduce the incidence of several diseases. Egyptian dukkah and Syrian za’atar are two of the most historic and famous Middle Eastern herbal blends used for their anti-inflammatory, hypolipidemic, and antidiabetic effects. Headspace SPME-GCMS and HPLC-DAD were adopted for characterizing the aroma profile and phenolic compounds of both herbal blends, respectively. Further, vapor-phase minimum inhibitory concentration was employed for assessing each blend’s antibacterial potential, while their antioxidant potential was estimated via in vitro antioxidant assays. SPME headspace analysis indicated the abundance of ethers and monoterpene hydrocarbons, while HPLC revealed the presence of several phenolics including rosmarinic acid, ferulic acid, and rutin. Biological investigations affirmed that vapor-phase of the tested blends exhibited antibacterial activities against Gram-positive and Gram-negative pathogens, while the antioxidant potential of the blends was investigated and expressed as Trolox (125.15 ± 5.92 to 337.26 ± 13.84 μM T eq/mg) and EDTA (18.08 ± 1.62 to 51.69 41 ± 5.33 μM EDTA eq/mg) equivalent. The presented study offers the first insight into the chemical profile and biological activities of both dukkah and za’atar.