On-line delta(18)O measurement of organic and inorganic substances

A method for the automated sample conversion and on-line oxygen isotope ratio (delta(18)O) determination for organic and inorganic substances is presented. The samples are pyrolytically decomposed at 1400 degrees C in the presence of nickelized graphite. With the system presented organic as well as inorganic samples such as nitrates, sulphates and phosphates of 50-100 &mgr;g O can be analyzed for their delta(18)O values with a standard deviation usually better than 0.5 per thousand. Additionally, carbon isotope ratios of organic substances and nitrogen isotope ratios of inorganic nitrogenous compounds are available in the same sample run. Data for international and some inter-laboratory reference materials are presented to show the accuracy and reliability of the method. The effect of some additives on the CO yield was checked for substances which do not pyrolyze completely. Copyright 1999 John Wiley & Sons, Ltd.     

地球化学样品中有机碳的光谱分析

有机碳已成为多目标地球化学调查、土地质量地球化学调查等项目研究的必测指标,对有机碳的准确定量是地球化学调查工作的重要内容,准确测定有机碳含量具有重要意义。然而传统的重量法、容量法流程长、速度慢,已经不能满足大批量及快速测定地球化学样品的要求。采用稀盐酸去除样品中的无机碳,应用高频红外碳硫分析仪对不同类型地球化学样品中有机碳的测定进行了研究,着重从称样量、酸的选择、最佳浓度及用量、助熔剂的选择和最佳加入量进行对比实验,优化出适合分析地球化学样品中有机碳含量的条件,并采用国家一级地球化学标准物质建立校准曲线,建立盐酸预处理-红外吸收光谱法测定地球化学样品中有机碳含量的分析方法。结果表明：陶瓷坩埚经1 200 ℃灼烧处理可以有效降低碳空白,减小对分析结果的影响;选择50.0～70.0 mg称样量,测试准确度高且样品熔融时不易喷溅;0.40～0.60 mL稀盐酸（1+7）除尽样品中的无机碳同时减少有机碳流失损失;0.40～0.50 g纯铁屑和1.50～1.70 g钨粒作为助熔剂,助熔效果稳定;采用国家一级地球化学标准物质建立校准曲线,校准曲线线性良好（R2=0.998 5）。该方法的检出限为69 μg·g-1,测定结果的相对标准偏差（RSD,n=12）均小于8%。经63个不同类型国家一级地球化学标准物质（土壤、岩石、水系沉积物）验证,测定结果与标准值相符。本方法操作简便,检出限低,灵敏度高,结果准确可靠,适用于地球化学样品中有机碳含量的测定。     

微波消解/ICP-MS法测定二色补血草中27种元素

采用微波消解及ICP-MS,建立了一种测定二色补血草中Be,B,Na,Al,Mg,P,K,Ca,V,Cr,Mn,Fe,Co,Ni,Cu, Zn,Ga,As,Se,Sr,Mo,Cd,Ba,La,Hg,Pb和Th共27种元素的方法.实验采用国家一级标准物质茶叶(GBW-07605)评价了方法的准确性,通过在线加入Ge,In和Bi三种元素内标液的方法来校正由于基体效应和信号漂移对测量所造成的影响.方法的回收率为92.4%～107.2%,相对标准偏差为1.5%～9.7%,检出限为0.002～0.081 μg·L-2,元素的测定结果表明:二色补血草中含有丰富的Na,K,Ca,Mg和P等常量元素,Fe,Mn,Zn,Cr和Cu等微量元素.实验结果为深入研究二色补血草无机元素与药效的相关性提供了参考数据.     

Organic optoelectronic device fabrication using standard UV photolithography

The fabrication of organic optoelectronic devices requires patterning techniques that are compatible with organic semiconductor materials. Photolithography represents, by far, the dominant patterning approach for inorganic electronics and optoelectronics. High speed, parallel patterning capability, high resolution, and the availability of standard equipment make this technology also very attractive for applications in the field of organic semiconductor technology. In the present paper we present a successful implementation of photolithography to fabricate organic diodes. This process provides the basis for a future high‐resolution monolithic integration of organic optoelectronic and photonic devices into one photonic circuit. (© 2008 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Determination of Trace Elements in High‐Purity Palladium by Inductively Coupled Plasma Mass Spectrometry Using an Internal Standard Method

Method validation of inductively coupled plasma mass spectrometry analyses for trace impurities in high‐purity materials is often limited not only by the lack of suitable reference materials with the same matrix composition but also by the lack of a significant number of certified trace element concentrations in the available reference materials. This paper demonstrates a new and simple method for the direct determination of 44 trace elements in high‐purity palladium using inductively coupled plasma mass spectrometry and an internal standard method. Sc and In were employed as internal standards to effectively eliminate nonspectral interferences from the Pd matrix. The detection limits of the 44 trace impurities were from 0.00078 to 0.46 µg/mL and the relative standard deviations (n=6) were below 3.5%. The method was further validated using a palladium standard material (Aldrich palladium standard material, CAS no. 7440053). The analytical results are in good agreement with the certified values.     

Thin film optimization design of organic–inorganic hybrids for waveguide high‐rejection optical filters

We report the fabrication of transparent, low surface roughness (<0.1 nm), and low‐loss (1.5 ± 0.2 dB cm^–1, 532 nm) thin films of organic–inorganic hybrids with controlled refractive index values stable under aging. High‐rejection optical filters based on first‐order Bragg gratings inscribed in channel waveguides were fabricated using UV‐laser writing. Their high‐rejection figure of merit (～24 dB) is the best value found until now for organic–inorganic hybrids reinforcing the potential of sol–gel technology in the integration of optoelectronic components based on hybrid materials, namely in the fabrication of cost‐effective integrated optics devices. (© 2011 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Electroluminescence from hybrid organic–inorganic LEDs based on thermally evaporated CdS thin films

Hybrid organic–inorganic light emitting devices combine the color purity and durability of inorganic light emitting diodes (LEDs) with high efficiency, flexibility and low processing cost of organic LEDs (OLEDs). A significant challenge is to incorporate inorganic nanocrystals inside the OLED structure. In the present work, thin films of CdS were successfully incorporated inside standard OLED structure using vacuum thermal evaporation technique. For the characterization of these films, they were deposited on plain glass plates at room temperature and studied using structural (XRD and TEM), morphological (SEM and AFM) and optical (UV and PL) techniques. The films were found to be composed of nanocrystals of CdS in which the size of the crystals increased with the increase in film thickness. The hybrid organic–inorganic LEDs showed improved luminance and efficiency as compared to the organic LED without CdS layers.     

有机酸在电感耦合等离子体质谱中基体效应的研究

研究了乙二酸、乳酸、酒石酸和柠檬酸等有机试剂对不同质量和不同电离电位元素电感耦合等离子体质谱信号的影响。结果表明,随着雾化气流速的调节,低浓度有机酸介质对所分析元素具有增强效应,尤其是对电离电位在9～11 eV的Be,Zn,As,Se,Sb和Hg等高电离电位元素的影响。酒石酸的增强效应显著大于乙二酸、乳酸、柠檬酸。探讨了有机酸的增强机理。利用酒石酸对Be,Zn,As,Se,Sb和Hg等的增强特性,测定了水标准物质SRM 1640中的Be,Zn,As,Se,Sb和SRM 1641d中Hg,其测定结果与标准样品提供的标准值基本一致。     

粉末压片-X射线荧光光谱法在地球化学标准物质均匀性检验中的应用研究

均匀性是标准物质三大特性之一。X射线荧光光谱法（XRF）,精密度高,可实现多元素同时分析,是地球化学标准物质均匀性检验重要方法之一。目前,应用XRF对标准物质进行均匀性检验还存在争议。由于均匀性检验要求称样量为最小取样量,一般地球化学标准物质的最小取样量为0.1 g,而采用粉末压片-XRF进行均匀性检验时称样量为4 g左右,得到的结果在理论上不足以支撑样品在最小取样量条件下是否均匀。本研究改变了以往压片模具的大小,采用0.1 g样品粉末压片法制样,在对仪器条件进行优化的基础上,选取了3个土壤（GBW07425,GBW07428,GBW07388）和3个水系沉积物（GBW07375,GBW07378,GBW07379）标准物质,每个标准物质取15瓶,每瓶取样2份,共制样片30个,对SiO₂,Al₂O₃,TFe₂O₃,MgO,CaO,Na₂O,K₂O,Mn,Ti和P共10个主量组分进行了均匀性检验,根据单因素方差分析的F值、测定值的标准偏差（s）和相对标准偏差（RSD）综合判定样品的均匀性。通过理论计算,在样品照射半径为5 mm的条件下,所测10个主量组分的最小取样量小于0.1 g。0.1 g压片测定结果表明,本研究中的方法准确度高,相对误差小于16%,精密度高,相对标准偏差不超过4.3%,F值小于临界值,标准物质的均匀性良好。在最小取样量为0.1 g的条件下,应用X-射线荧光光谱法进行均匀性检验,不仅能够解决地球化学标准物质均匀性检验中长期存在的争议问题,还可为X-射线荧光光谱法在其他领域的应用提供技术支持。     

Organic–inorganic polymer hybrids prepared by the sol-gel method

This review focuses on some aspects of organic-inorganic hybrid materials prepared by the sol-gel method. This field has been studied worldwide as one of the nanotechnologies, and is now of current interest for both organic and inorganic scientists. The elaboration of organic–inorganic polymer hybrid materials using the sol-gel process can be accomplished by various approaches. The simplest method is increasing the compatibility by using physical interactions, covalent bonding and compatibilizer between organic polymer and silica gel. Other novel approaches, such as an in-situ method, NHSG (Non- Hydrolysis Sol-Gel) process, and use of reactive polymer hybrids resulted in the preparation of novel transparent organic–inorganic polymer hybrid materials. Stimulus responsive polymer hybrids are also mentioned. Furthermore, nano-structured organic–inorganic polymer hybrids are created by using supermolecular and self-assembly of organic molecules or polymers recently. The obtained nano-structured hybrid materials showed unique properties that could not be found in amorphous hybrid materials. The possibilities and applications of organic–inorganic polymer hybrid materials are also described in this review.     

无机纳米氧化铝/聚酰亚胺复合膜的表征

研究无机纳米掺杂有机复合薄膜力学性能、热学性能、电学性能变化规律的关键在于快速、准确地掌握复合膜中纳米无机物的掺入量及其颗粒大小和分布状态。文章通过X射线荧光光谱、红外光谱、扫描电子显微镜、原子力显微镜等测试方法对无机纳米氧化铝/聚酰亚胺复合薄膜的三氧化二铝掺入量、化学结构及表面形貌进行了表征分析(该材料为本研究室制备的)。结果表明:聚酰亚胺有机相与三氧化二铝无机相之间形成了键联型复合杂化体系;三氧化二铝粒子呈纳米级均匀地分散在聚酰亚胺基体中,颗粒直径均在50nm以下;利用X射线荧光光谱法测定出三氧化二铝的质量含量为7·9%,利用该方法定性、定量分析无机纳米掺杂有机复合薄膜材料中的无机组分具有样品不需要预处理、不需要加载电荷(可用于分析绝缘材料)、非接触性、非破坏性、速度快、准确度高等优点。     

超声波辅助溶剂萃取-电感耦合等离子体质谱法测定生物样品中的总汞和甲基汞

建立了超声波辅助溶剂萃取联用电感耦合等离子体质谱法(ICP-MS)测定生物样品中总汞(T-Hg)和甲基汞(MeHg)的分析方法。实验优化了萃取溶剂种类,溶剂浓度,各种辅助方法和超声波振荡时间等各种萃取条件。选择6 mol·L-1 HCl作为溶剂,超声2 h, 以有机溶剂萃取,再以水反萃,稀释后直接进行测量MeHg的含量。此方法可用于同时测定T-Hg和MeHg, 检出限为0.01 ng·mL-1,相对标准偏差为3.44％,线性范围为1～50 ng·mL-1,加标回收率为80%～97%。在此条件下测定了5种不同类型生物标准参考物质的T-Hg和MeHg,测定值与标准值吻合。该法综合了超声波辅助萃取和溶剂微萃取以及ICP-MS的优点,操作简便快速,灵敏度高,适合于各种生物样品中痕量MeHg快速萃取分离和分析。     

Organic-inorganic nanocomposite materials prepared by the sol-gel route as new ionic conductors in quasi solid state electrolytes

Nanocomposite organic/inorganic materials made through sol-gel method exhibit high values of ionic conductivity when they were impregnated with the redox couple I ₃ ⁻ /I⁻ Two different kinds of nanocomposite materials, depending on the different interactions between silica and poly(ethylene)oxide or poly(propylene)oxide blends, were prepared by the sol-gel technique in room temperature. Gels, for both nanocomposite materials, were obtained by acetic acid catalyzed solvolysis and were regulated by formation of intermediate products, such as silicon ester and -Si-O-Si-oligomers. Time-resolved fluorescence techniques and conductivity measurements were performed in order to define the parameters which allow maximum probe mobility and minimum confinement conditions with the aim to apply these materials in quasi solid state electrolytes. Paper presented at the Patras Conference on Solid State Ionics — Transport Properties, Patras, Greece, Sept. 14 – 18, 2004.     

弱碱性阴离子交换树脂富集ICP-AES测定环境水体中Cr(Ⅵ)和有机态Cr(Ⅲ)的研究

选用331弱碱性阴离子交换树脂,对微污染水体中的Cr(Ⅵ)和有机态Cr(Ⅲ)进行了分离富集作用研究,考察了酸度、富集时间、洗脱液类型、洗脱液浓度及溶液中共存离子对分离富集过程的影响。研究表明,分别用1.0 mol·L-1 HCl和2.0 mol·L-1 NH₄NO₃＋0.5 mol·L-1 NH₃·H₂O可以很好分步洗脱有机态Cr(Ⅲ)和Cr(Ⅵ),利用ICP-AES测定, 该方法对Cr(Ⅲ)和Cr(Ⅵ)的检出限分别为1.1和 1.4 μg·L-1,相应的相对标准偏差RSD(n＝6)平均值分别为3.8％和5.6％。该方法适用于自来水、地下水、地表水及生活污水中痕量Cr(Ⅵ)和有机态Cr(Ⅲ)的分离富集及测定。     

Ultrafast laser processing of drug particles in water for pharmaceutical discovery

The laser fragmentation technique has been extensively used to produce inorganic nanoparticles, but its practice on organic materials, especially on drugs, is less common. Here, we briefly review the recent advances in laser micro-/nanonization of organic materials and the rationale of using laser fragmentation for drug discovery. We present our case studies of two drug models: fenofibrate and naproxen. Both drugs were fragmented in water with femtosecond (fs) laser and characterized in terms of particle size distribution and physicochemical properties. Effects of fs laser fragmentation were also compared with nanosecond (ns) laser fragmentation and with conventional media milling technique. Fs laser was more suitable to produce sub-micron size drug particles than ns laser, but degradation of drugs after nanonization was also more pronounced than micronization. Physicochemical transformations such as oxidation, hydration and amorphisation might occur during the laser–material interactions. Laser nanonization showed improved dissolution kinetics, similar to media milling. Unlike the conventional milling techniques, laser fragmentation enabled the treatment of minute amount (as small as several milligrams) of drugs with high efficiency, thus is a useful tool for particle size reduction during the early phases of drug discovery.     

无机/有机稀土配合物杂化发光材料研究进展

近年来材料的发展趋势是功能互补,性能优化。稀土配合物发光强度大、单色性好,缺点是光稳定性和热稳定性较差,因此须将其掺入一定基质中,这样所得到的有机 /无机杂化发光材料,兼备了有机、无机材料的优点。根据杂化材料中稀土配合物与基质之间作用力不同,可分为第一类杂化材料(两相间以弱键如氢键等结合)和第二类杂化材料(两相间以强键如共价键等结合)。对这两类杂化材料近年来国内外的研究情况作了综合评述,并展望了其发展趋势。     

Preparation and atomic oxygen erosion resistance of silica film formed on silicon rubber by sol-gel method

Based on the characteristic that silicon coupling agents have the capability to develop ‘molecular bridge’ in the interface of organic materials and inorganic materials, silica films were prepared on the surface of flexible silicon rubber by sol-gel method and the optical transmittance of the sample before and after atomic oxygen irradiation was tested. The surface morphology and structure of silica films were investigated by scanning electronic microscope (SEM) and Fourier transformed infrared spectroscopy (FTIR). The results indicated that the silica sol could easily form a uniform thin film on the surface of silicon rubber pretreated by high concentration silicon coupling agents, and the inorganic silica films could combine with organic silicon rubber without obvious delamination on the interface.     

Diffusivity control in nanoporous membrane through organic-inorganic hybridization

Nanoporous inorganic materials have attracted great interest due to their potential application as nanofilters, drug delivery carriers and adsorbents. In order to control the molecular passage through nanopores, we have modified the pore channel of inorganic materials with organic moieties and investigated the diffusion pattern of small molecules. The surface was modified by octyltriethoxysilane (OTS) by refluxing in toluene for 12 h. The water contact angle of OTS modified zirconia membrane was observed ∼110° showing hydrophobic surface. Contact angles to various solvents were also examined to verify the self-assembled monolayer of octyl chains on the inorganic membrane. The molecular passage patterns of both pristine and modified nanoporous membrane were evaluated by means of the diffusivity of small dye molecule, azobenzene. The diffusion coefficients of azobenzene on both membranes were measured in various solvents on the basis of Fick’s diffusion law. The diffusivities in various solvents for pristine and its modified zirconia membrane were determined. The diffusivity was observed to be influenced by surface energy of both membrane and solvent as well as the polarity of solvents.     

双叔丁基苯并噁唑噻酚在多孔二氧化硅中发光的研究

利用溶胶凝胶法制备了用有机荧光染料2,5-双（5-叔丁基-1,3-苯并噁唑-2-基）噻酚（2,5-bis（5-tert-butyl-2-benzoxazolyl）thiophene, BBOT）的高浓度掺杂的纳米多孔二氧化硅固态薄膜,该薄膜呈现明亮的蓝色发光。通过紫外-可见光谱、瞬态-稳态荧光光谱、光学显微镜技术的研究表明：（1）在掺杂浓度低于6&#215;10^-3 mol&#183;L^-1时,薄膜中荧光染料BBOT的光强比值随浓度呈线性增加;（2）在掺杂浓度低于6&#215;10^-3 mol&#183;L-1时,显微镜观察可见薄膜发光均匀、没有相分离产生;（3）固体薄膜中分子的荧光寿命比在1,4二氧六环稀溶液中的1.957 ns延长。在掺杂浓度为6&#215;10^-3 mol&#183;L^-1的样品中随着凝胶化程度逐渐升高荧光寿命从固化温度为50 ℃样品的2.45 ns提高到固化温度为90 ℃样品的3.04 ns。在掺杂浓度高达6&#215;10^-3 mol&#183;L^-1时,该体系并不产生分子荧光的浓度猝灭。通过对比固态掺杂体系中和相同浓度下1,4二氧六环溶液中BBOT的荧光寿命随浓度和二氧化硅体系凝胶化程度变化的规律,发现多纳米孔二氧化硅基质可以有效地抑制BBOT荧光的浓度猝灭,获得了具有稳定荧光的有机无机杂化材料。     

基于元素对研究激光剥蚀-电感耦合等离子体质谱分析硫化物矿物的基体效应

基体效应是影响LA-ICP-MS分析结果准确性的主要因素之一,但目前却没有一种量化基体效应研究的方法。提出了一种以分析元素与内标元素的强度比(I_i/I_is)为纵坐标、浓度比(c_i/c_is)为横坐标绘制I_i/I_is-c_i/c_is图,以元素对I_i/I_is-c_i/c_is图的线性相关系数ｒ量化基体效应的思路。以Fe为内标,考察了13个常用玻璃标准物质与2个硫化物标准及多个硫化物矿物中6个元素对的基体效应,结果显示Cu/Fe和Zn/Fe的线性相关系数r都小于0.99,而痕量元素对Mn/Fe,Co/Fe,Ga/Fe,Pb/Fe的线性相关系数r都大于0.999;以S为内标,考察了2个硫化物标准与多个硫化物矿物中三个主量元素对Fe/S,Cu/S和Zn/S的基体效应,结果显示其线性相关系数r都小于0.999。无论是以Fe为内标结合玻璃标准为外标,还是以S为内标结合硫化物标准为外标分析硫化物矿物,主量元素大多数分析结果的误差大于10%;而以Fe为内标时,绝大多数玻璃标准获得的痕量元素分析结果与MASS-1较为一致,误差小于15%。研究表明,玻璃标准及硫化物矿物标准均与硫化物矿物存在一定的基体效应差异,而采用元素对I_i/I_is-c_i/c_is图的线性相关系数r量化基体效应具有一定的合理性与实用性。研究也表明了以Fe为内标,采用非基体匹配的玻璃标准可用于定量分析硫化物矿物中的痕量元素,尤其是具有较高痕量元素含量的NIST610。