顶空固相微萃取-气相色谱-质谱法同时测定饮用水源水中24种VOCs

建立了同时测定饮用水源水中24种挥发性有机物(VOCs)的顶空固相微萃取-气相色谱-质谱法.用75 μm CarboxenTM-Polydimethylsiloxane(CAR-PDMS)固相微萃取柱顶空萃取水样中的VOCs,VOCs用气相色谱-质谱联用仪检测,采用内标法定量.对萃取柱涂层、样品盐度、萃取温度和萃取时间等样品前处理条件进行了优化,VOCs的检出限在0.03～0.31 μg/L之间,线性相关系数r＞0.996(二氯甲烷和三氯甲烷除外).对饮用水源水实际水样0.50μg/L和1.00 μg/L两个加标浓度水平的回收率进行了测定,三氯甲烷回收率均值分别为104％和142％,其余VOCs回收率分别为90.0％～120％和88.0％～110％,除二氯甲烷和三氯甲烷外,其余VOCs测定结果的相对标准偏差均小于15.0％(n=6).该方法适用于饮用水源水中挥发性有机物的监测分析.     

Does cytotoxicity of metallointercalators correlate with cellular uptake or DNA affinity?

The cytotoxicity of the metallointercalators, [Pt(5,6-dimethyl-1,10-phenanthroline)(trans-1R,2R-diaminocyclohexane)](2+) ([56MERR]) and [Pt(5,6-dimethyl-1,10-phenanthroline)(trans-1S,2S-diaminocyclohexane)](2+) ([56MESS]), towards A549 human lung cancer cells was examined using the 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) assay. The IC(50) value obtained following exposure of A549 cells to [56MESS] for 4 h was approximately three times smaller than that obtained when [56MERR] was administered under the same conditions, indicating that the former complex displayed greater cytotoxicity. Both IC(50) values were greater than that obtained after exposure of A549 cells to cisplatin, demonstrating that the latter compound was the most cytotoxic of the three examined. Microprobe synchrotron radiation X-ray fluorescence (SR-XRF) analyses of metallointercalator-treated A549 cells showed that platinum became localised in DNA-rich regions of the nucleus. In contrast, when the same cells were treated with cisplatin the metal became distributed throughout the cell. Determination of the maximum concentration of platinum present inside the cells using graphite furnace atomic absorption spectrophotometry (GFAAS) of platinum-treated cells suggested that there was greater uptake of [56MERR] compared to [56MESS] by the A549 cells, and that platinum uptake did not account for the greater toxicity of [56MESS], as assessed by the MTT assay. Electrospray ionization mass spectrometric (ESI-MS) and circular dichroism (CD) spectroscopic studies of solutions containing either [56MERR] or [56MESS], and a duplex hexadecamer molecule, showed the two metallointercalators displayed very similar affinity towards the nucleic acid. Overall these results indicate that the difference in cytotoxicity of the two platinum metallointercalators is probably the result of variations in their interactions with other cellular components.     

Photophysical and electrochemical properties of platinum(II) complexes bearing a chromophore-acceptor dyad and their photocatalytic hydrogen evolution

A series of platinum(II) complexes bearing a chromophore-acceptor dyad obtained by reacting 4-(p-bromomethylphenyl)-6-phenyl-2,2'-bipyridine or 4'-(p-bromomethylphenyl)-2,2':6',2'-terpyridine with pyridine, 4-phenylpyridine, 4,4'-bipyridine, 1-methyl-4-(pyridin-4'-yl)pyridinium hexafluorophosphate respectively, were synthesized. Their photophysical properties, emission quenching studies by Pt nanoparticles and methyl viologen, electrochemical properties and photoinduced electron-transfer reactions in a photocatalytic hydrogen-generating system containing triethanolamine and colloidal Pt without an extra electron relay, were investigated. A comparison of the rates of hydrogen production for the two photocatalytic systems, one containing a metal-organic dyad and the other comprising a 1:1 mixture of the parental platinum(II) complexes and the corresponding electron relay, showed that intramolecular electron transfer improves the photocatalytic efficiency. Compared with cyclometalated platinum(II) complexes, the related platinum(II) terpyridyl complexes exhibited poor performance for photocatalytic hydrogen evolution. An investigation into the amount of hydrogen generated by three platinum(II) complexes containing cyclometalated ligands with methyl groups located on different phenyl rings revealed that the efficiency of hydrogen evolution was affected by a subtle change of functional group on ligand, and the hydrogen-generating efficiency in the presence or absence of methyl viologen is comparable, indicating electron transfer from the excited [Pt(C^N^N)] chromophore to colloidal Pt. (1)H NMR spectroscopy of the metal-organic dyads in an aqueous solution in the presence of excess triethanolamine revealed that the dyad with a viologen unit was unstable, and a chemical reaction in the compound occurred prior to irradiation by visible light under basic conditions.     

Simple replacement reaction for the preparation of ternary Fe(1-x)PtRu(x) nanocrystals with superior catalytic activity in methanol oxidation reaction

The finding of new metal alloyed nanocrystals (NCs) with high catalytic activity and low cost to replace PtRu NCs is a critical step toward the commercialization of fuel cells. In this work, a simple cation replacement reaction was utilized to synthesize a new type of ternary Fe(1-x)PtRu(x) NCs from binary FePt NCs. The detailed structural transformation from binary FePt NCs to ternary Fe(1-x)PtRu(x) NCs was analyzed by X-ray absorption spectroscopy (XAS). Ternary Fe(35)Pt(40)Ru(25), Fe(31)Pt(40)Ru(29), and Fe(17)Pt(40)Ru(43) NCs exhibit superior catalytic ability to withstand CO poisoning in methanol oxidation reaction (MOR) than do binary NCs (FePt and J-M PtRu). Also, the Fe(31)Pt(40)Ru(29) NCs had the highest alloying extent and the lowest onset potential among the ternary NCs. Furthermore, the origin for the superior CO resistance of ternary Fe(1-x)PtRu(x) NCs was investigated by determining the adsorption energy of CO on the NCs' surfaces and the charge transfer from Fe/Ru to Pt using a simulation based on density functional theory. The simulation results suggested that by introducing a new metal into binary PtRu/PtFe NCs, the anti-CO poisoning ability of ternary Fe(1-x)PtRu(x) NCs was greatly enhanced because the bonding of CO-Pt on the NCs' surface was weakened. Overall, our experimental and simulation results have indicated a simple route for the discovery of new metal alloyed catalysts with superior anti-CO poisoning ability and low usage of Pt and Ru for fuel cell applications.     

Conformity and precision of CO2 densimetry in CO2 inclusions: microthermometry versus Raman microspectroscopic densimetry

To assess the ability of densimetry for CO₂ fluid in CO₂ inclusions, we compare two methods, microthermometry and Raman microspectroscopic densimetry for CO₂. The comparative experiment was performed for nine CO₂ inclusions in three mantle xenoliths. The results are as follows: (1) microthermometry precisely determines CO₂ density with the range of 0.65 to 1.18 g/cm³ compared with Raman microspectroscopic densimetry; (2) CO₂ density obtained by Raman microspectroscopic densimetry is fairly consistent with that by microthermometry; (3) it is hard to determine CO₂ density in CO₂ inclusion with diameter of less than around 3 µm using microthermometry; and (4) microthermometry can be applied only to the CO₂ inclusion whose CO₂ density ranges from around 0.65 to 1.18 g/cm³, whereas the Raman microspectroscopic densimetry is applicable to CO₂ density ranging from 0.1 to 1.24 g/cm³. The above features carry the potential for estimation of depth origin of mantle‐derived rocks. The depth where the rocks were trapped by host magma can be estimated using both geothermometric data and CO₂ fluid density in CO₂ inclusions in the rocks. Typical precisions of density of CO₂ in CO₂ inclusions obtained by the Raman microspectroscopic densimetry (~0.01 g/cm³) and by the microthermometry (< 0.001 g/cm³) correspond to uncertainties in the depth origin of 2.4 km and < 1.7 km, respectively, at 1000 ± 50 °C. In case of the mantle under 750–1250 °C and 1 GPa, the CO₂ fluid has a density ranging from 1.06 g/cm³ to 1.21 g/cm³, which are well measured by the Raman microspectroscopic densimetry. Combination of both densimetries for CO₂ in mantle minerals elucidates the deep structure of the Earth. Copyright © 2012 John Wiley & Sons, Ltd.     

Multi-armed spirals and multi-pairs antispirals in spatial rock–paper–scissors games

We study the formation of multi-armed spirals and multi-pairs antispirals in spatial rock–paper–scissors games with mobile individuals. We discover a set of seed distributions of species, which is able to produce multi-armed spirals and multi-pairs antispirals with a finite number of arms and pairs based on stochastic processes. The joint spiral waves are also predicted by a theoretical model based on partial differential equations associated with specific initial conditions. The spatial entropy of patterns is introduced to differentiate the multi-armed spirals and multi-pairs antispirals. For the given mobility, the spatial entropy of multi-armed spirals is higher than that of single armed spirals. The stability of the waves is explored with respect to individual mobility. Particularly, we find that both two armed spirals and one pair antispirals transform to the single armed spirals. Furthermore, multi-armed spirals and multi-pairs antispirals are relatively stable for intermediate mobility. The joint spirals with lower numbers of arms and pairs are relatively more stable than those with higher numbers of arms and pairs. In addition, comparing to large amount of previous work, we employ the no flux boundary conditions which enables quantitative studies of pattern formation and stability in the system of stochastic interactions in the absence of excitable media.     

A three‐dimensional surface‐enhanced Raman scattering substrate: Au nanoparticle supramolecular self‐assembly in anodic aluminum oxide template

A three‐dimensional surface‐enhanced Raman scattering (SERS) substrate via the self‐assembly of properly sized Au nanoparticles in anodic aluminum oxide templates was designed and prepared. Au nanoparticles first underwent hydrophobic surface modification. Then, the hydrophobic Au nanoparticles self‐assembled, aggregated and formed many hot spots in the anodic aluminum oxide templates through a supramolecular interaction. We chose thiophenol as a probe molecule to evaluate the SERS enhancement ability of this three‐dimensional substrate. The enhancement factor was calculated to be 4.6 × 10⁶ under the radiation of a 785‐nm laser. By further comparing SERS signals from different points on the same substrate, we confirmed that this substrate possessed good reproducibility and could be applied for SERS detection. Copyright © 2011 John Wiley & Sons, Ltd.