Determination of styrene in olive oil by an automatic purge-and-trap system coupled to gas chromatography-mass spectrometry

Summary A new gas chromatographic method using an automatic purge-and-trap system coupled to a GC with mass selective detection to analyze styrene at the parts-per-trillions (ng kg^–1) level is described. The method shows a good sensitivity and the detection limit is 10 ng kg^–1 with a relative standard deviation (RSD) of 4.7% for 164 ng kg^–1 styrene in olive oil. This analytical method has been successfully applied to the analysis of styrene in extra-virgin olive oil from the European market.     

GS-221高速摄影测量仪测角信息的采集与处理

在GS-221高速摄影测量仪中,测角信息采集与处理速度的快慢是重要性能指标之一。本文讨论了如何在尽可能短的时间内对测角信息进行采集和处理的软件实现方法。     

Synthesis of double silylene-bridged binuclear titanium complexes and their use as catalysts for ethylene polymerization

Five new double silylene-bridged binuclear titanium complexes were synthesized by the reaction of RCpTiCl₃ and Li₂[μ,μ-(SiMe₂)₂ (C₅H₃)₂] in toluene. They were all well characterized. These complexes activated with methylaluminoxane (MAO) are highly active catalysts (2.33 × 10⁵ g PE/mol Cat h) for the polymerization of ethylene even at low Al/Ti (Al/Ti = 300). The molecular weight distribution of the polymer indicates broad or bimodal (MWD = 26.76) distribution.     

反光板(合作目标)反射率测量仪

本文介绍了反光板（合作目标）反射率测量仪的研制。仪器采用对称双光路比较测量法，给定两束相等光通量的光束，分别作为参考光束和测试光束，并用分束器实现原光路取样，从而解决了合作目标反光板入射光线与反射光线重合不能用常规测试方法来检测的难题。由于采用对称双光路的方法，入射光通量是相对恒定的，不受外界因素影响，从而使反射率测量仪达到精度高、重复性好和环境要求低的设计要求。     

Random tunneling by means of acceptance-rejection sampling for global optimization

Any global minimization algorithm is made by several local searches performed sequentially. In the classical multistart algorithm, the starting point for each new local search is selected at random uniformly in the region of interest. In the tunneling algorithm, such a starting point is required to have the same function value obtained by the last local minimization. We introduce the class of acceptance-rejection based algorithms in order to investigate intermediate procedures. A particular instance is to choose at random the new point approximately according to a Boltzmann distribution, whose temperatureT is updated during the algorithm. AsT 0, such distribution peaks around the global minima of the cost function, producing a kind of random tunneling effect. The motivation for such an approach comes from recent works on the simulated annealing approach in global optimization. The resulting algorithm has been tested on several examples proposed in the literature.     

Solution structure, mutagenesis, and NH exchange studies of the MutT enzyme–Mg-8-oxo-dGMP complex

The MutT pyrophosphohydrolase from E. coli (129 residues) catalyzes the hydrolysis of nucleoside triphosphates (NTP), including 8-oxo-dGTP, by substitution at Pβ, to yield NMP and pyrophosphate. The product, 8-oxo-dGMP is an unusually tight binding, slowly exchanging inhibitor with a K_D=52 nM, (ΔG°=−9.8 kcal/mol) which is 6.1 kcal/mol tighter than the binding of dGMP (ΔG°=−3.7 kcal/mol). The higher affinity for 8-oxo-dGMP results from a more favorable ΔH_binding (−32 kcal/mol) despite an unfavorable −TΔS°_binding (+22 kcal/mol). The solution structure of the MutT–Mg²⁺-8-oxo-dGMP complex shows a narrowed, hydrophobic nucleotide-binding cleft with Asn-119 and Arg-78 among the few polar residues. The N119A, N119D, R78K and R78A single mutations, and the R78K+N119A double mutant all showed largely intact active sites, on the basis of small changes in the kinetic parameters of dGTP hydrolysis and in ¹H–¹⁵N HSQC spectra. However, the N119A mutation profoundly weakened the active site binding of 8-oxo-dGMP by 4.3 kcal/mol (1650-fold). The N119D mutation also weakened 8-oxo-dGMP binding but only by 2.1 kcal/mol (37-fold), suggesting that Asn-119 functioned both as a hydrogen bond donor to C8=O, and a hydrogen bond acceptor from N7H of 8-oxo-dGMP, while aspartate at position −119 functioned as an acceptor of a single hydrogen bond. Much smaller weakening effects (0.3–0.4 kcal/mol) on the binding of dGMP and dAMP were found, indicating specific hydrogen bonding of Asn-119 to 8-oxo-dGMP. While formation of the wild type MutT–Mg²⁺-8-oxo-dGMP complex slowed the backbone NH exchange rates of 45 residues distributed throughout the protein, the same complex of the N119A mutant slowed the exchange rates of only 11 residues at or near the active site, indicating an increase in conformational flexibility of the N119A mutant. The R78K and R78A mutations weakened the binding of 8-oxo-dGMP by 1.7 and 1.1 kcal/mol, respectively, indicating a lesser role of Arg-78 than of Asn-119 in the selective binding of 8-oxo-dGMP, likely donating a single hydrogen bond to its C6=O. The R78K+N119A double mutant weakened the binding of 8-oxo-dGMP (K_I^slope=3.1 mM) by 6.5±0.2 kcal/mol which overlaps, within error with the sum of the effects of the two single mutants (6.0±0.3 kcal/mol). Such additive effects of the two single mutants in the double mutant are most simply explained by the independent functioning of Asn-119 and Arg-78 in the binding of 8-oxo-dGMP. Independent functioning of these two residues in nucleotide binding is consistent with their locations in the MutT–Mg²⁺-8-oxo-dGMP complex, on opposite sides of the active site cleft, with a distance of 8.4±0.5 Å between their side chain nitrogens.     

Fe/Zn双金属氰化物催化剂催化环氧丙烷聚合的活性结构研究

以氯化锌、铁氰化钾（含有整合剂）的水溶液为原料，合成了铁锌双金属氰化物（DMC）催化剂。为获得高活性的DMC催化剂，需将叔丁醇 、多元醇螯合剂螯合至其结构中，用XRD、XPS等分析手段，对铁锌DMC催化剂的结构与活性进行分析表征。实验发现，DMC催化剂的晶体结构与螯合剂密切相关，螯合剂能显著降低DMC催化剂的结晶程度，从而提高DMC催化剂的活性。同时，氯化锌过量也有利于DMC催化剂活性的提高。并表征了相关DMC催化剂的活性中心。     

高分辨双晶XRF研究酞菁化合物中硫杂质的化学态

酞菁化合物是一种大π键共轭体系的平面分子结构，它以颜色鲜艳、化学稳定性和价格便宜等特点，已在颜料工业上得到了广泛地应用．随着高科技的发展，酞菁化合物的应用进入静电复印的领域．研究中发现：酞普化合物的晶体结构直接影响它的色泽、耐热性、稳定性以及光电导性．在诸多的酸苦晶型中，β-型酞菁是比较稳定的一种，其它晶型届亚稳态型．近年来，光敏性较好的X-型用于激光印刷机感光鼓的载流子产生层［1］．用作静电复印中的酞育粗颜料，一般多为a一型，且含有大量的有机和无机杂质[2]，经高温真空升华提纯后，转变为卢一型．有趣…     

Feasibility of using solid sampling graphite furnace atomic absorption spectrometry for speciation analysis of volatile and non-volatile compounds of nickel and vanadium in crude oil

A method for the direct determination of volatile and non-volatile nickel and vanadium compounds in crude oil without previous treatment using direct solid sampling graphite furnace atomic absorption spectrometry is proposed. The crude oil samples were weighed directly onto solid sampling platforms using a microbalance and introduced into a transversely heated solid sampling graphite tube. In previous work of our group losses of volatile nickel and vanadium compounds have been detected, whereas other nickel and vanadium compounds were thermally stable up to 1300 and 1600 °C, respectively. In order to avoid this problem different chemical modifiers (conventional and permanent) have been investigated. With 400 μg of iridium as permanent modifier, the signal started to drop already after two atomization cycles, possibly because of an interaction of nickel (which is a catalyst poison) with iridium. Twenty micrograms of palladium applied in each determination was found to be optimum for both elements. The palladium was deposited on the platform and submitted to a drying step at 150 °C for 75 s. After that the sample was added onto the platform and submitted to the furnace program. The influence of sample mass on the linearity of the response and on potential measurement errors was also investigated using four samples with different nickel content. For the sample with the lowest nickel concentration the relationship between mass and integrated absorbance was found to be non-linear when a high sample mass was introduced. It was suspected that the modifier had not covered the entire platform surface, which resulted in analyte losses. This problem could be avoided by using 40 μL of 0.5 g L⁻¹ Pd with 0.05% Triton X-100. Calibration curves were established with and without modifier, with aqueous standards, oil-in-water emulsions and the certified reference material NIST SRM 1634c (trace metals in residual fuel oil). The sensitivity for aqueous standards and emulsions was close to that for SRM 1634c, making possible the use of aqueous standards for calibration. The limits of detection and quantification obtained for nickel and vanadium under this condition were found to be 0.02 and 0.06 μg g⁻¹, respectively, for both elements, based on 10 mg of sample. Nickel and vanadium were determined in the samples with (total Ni and V) and without the use of Pd (thermally stable compounds), and the concentration of volatile compounds was calculated by difference. The results were compared with those obtained by high-resolution continuum source graphite furnace atomic absorption spectrometry by emulsion technique; no significant differences were found for total Ni and V at the 95% confidence level according to a Student's t-test.     

Sampling and local models for multivariate image analysis

Local models are a very important concept for microscopic and macroscopic imaging. Different methods of sub-sampling a multivariate image are described both in general and for three examples. The need for sub-sampling and its influence on multivariate image analysis and visualization are studied. Examples from MRI (256 × 256), satellite imaging (7 × 512 × 512) and biofuel studies (6 × 512 × 512) are used to illustrate some of the principles involved.