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211.
Sourav Adak Luke L. Daemen Monika Hartl Darrick Williams Jennifer Summerhill Heinz Nakotte 《Journal of solid state chemistry》2011,184(11):2854-2861
We present a comprehensive study of the structural properties and the thermal expansion behavior of 17 different Prussian Blue Analogs (PBAs) with compositions MII3[(M′)III(CN)6]2·nH2O and MII2[FeII(CN)6]·nH2O, where MII=Mn, Fe, Co, Ni, Cu and Zn, (M′)III=Co, Fe and n is the number of water molecules, which range from 5 to 18 for these compounds. The PBAs were synthesized via standard chemical precipitation methods, and temperature-dependent X-ray diffraction studies were performed in the temperature range between −150 °C (123 K) and room-temperature. The vast majority of the studied PBAs were found to crystallize in cubic structures of space groups Fm3?m, F4?3m and Pm3?m. The temperature dependence of the lattice parameters was taken to compute an average coefficient of linear thermal expansion in the studied temperature range. Of the 17 compounds, 9 display negative values for the average coefficient of linear thermal expansion, which can be as large as 39.7×10−6 K−1 for Co3[Co(CN)6]2·12H2O. All of the MII3[CoIII(CN)6]2·nH2O compounds show negative thermal expansion behavior, which correlates with the Irving–Williams series for metal complex stability. The thermal expansion behavior for the PBAs of the MII3[FeIII(CN)6]2·nH2O family are found to switch between positive (for M=Mn, Co, Ni) and negative (M=Cu, Zn) behavior, depending on the choice of the metal cation (M). On the other hand, all of the MII2[FeII(CN)6]·nH2O compounds show positive thermal expansion behavior. 相似文献
212.
Barbara Le?niewska Monika Kosi��ska Beata Godlewska-?y?kiewicz El?bieta Zambrzycka Agnieszka Z. Wilczewska 《Mikrochimica acta》2011,175(3-4):273-282
An ion-imprinted polymer (IIP) was obtained by copolymerization of methacrylic acid (as a functional monomer) and ethylene glycol dimethacrylate (as a crosslinking agent) in the presence of various chelators for Pt(II) ion and using 2,2??-azo-bis-isobutyronitrile as the initiator. Specifically, acetaldehyde thiosemicarbazone (AcTSn) and benzaldehyde thiosemicarbazone (BnTSn) were used as chelators. The IIPs were applied as sorbents for solid-phase extraction of Pt(II) and Pt(IV) ions from aqueous solutions. The effects of acidity and flow rate of the sample, of elution conditions and of potentially interfering ions were investigated. The imprinting effect of analyte is clearly demonstrated by the fact that only the IIP is capable of quantitative retention of Pt(II) and Pt(IV) ions. The method works best in the pH range from 0.5 to 1 and from 3.5 to 9.5. The ions can be recovered with an acidic solution of thiourea. The Pt-AcTSn polymer displays better sorption properties for the separation of analytes. The selectivity coefficients of the Pt-AcTSn and control polymers for Pt(IV) in the presence Pd(II), Rh(III), Ru(III), Al(III) and Cu(II) were calculated, and the sorbent capacity for Pt(IV) was found to be 4.56???g?g?-1. The method was successfully applied to the determination of Pt(IV) by electrothermal atomic absorption spectrometry in tap water, tunnel dust and anode slime samples. Figure
The new ion imprinted polymers based on Pt(II)-thiosemicarbazone derivative chelates were prepared and used as solid phase extraction sorbent for selective separation of platinum. The method was successfully applied to the determination of analyte in environmental samples by electrothermal atomic absorption spectrometry 相似文献
213.
A novel technique based on dynamic electrochemistry for the detection of fluoride ions was developed. It is based on its strong complexation with ferric ion. Formed fluoroferric complex is cathodically inactive at the potential of the reduction of free ferric aquo ion. The voltammetric and amperometric response of platinum comb-shaped interdigitated microelectrode array is decreased after fluoride addition. This decrease serves for the quantification of fluoride ions added to the solution. The detection limit of 4.5 × 10−5 mol dm−3 was achieved when one of the segments of interdigitated microelectrode array (IDA) was used as an indicating electrode. The detection limit is about one order of magnitude lower than in the case of conventional platinum macroelectrode. In comparison with ISE electrodes this method is faster and also avoiding large error resulting from the antilogarithmization of ISE Nerstian response. The method was applied to the analysis of toothpaste. 相似文献
214.
The replacement of fossil fuels is one of the greatest challenges that chemistry and material sciences will have to face in the near future. While hydrogen seems to be the most likely candidate for this, a material able to store the hydrogen itself is sorely needed. Intense research in the past decade has narrowed down the field of possible concepts to two materials: ammonia borane with chemically bound hydrogen atoms and metal-organic frameworks with physisorbed hydrogen molecules. Herein we want to give an overview of the strengths and weaknesses of each concept, discuss the challenges that need to be overcome, and try to compare the future capabilities of these two materials. 相似文献
215.
González-Mariño I Quintana JB Rodríguez I Schrader S Moeder M 《Analytica chimica acta》2011,684(1-2):50-57
A fully automated method for the determination of triclosan (TCS), its derivative methyl triclosan (MeTCS) and six parabens (esters of 4-hydroxybenzoic acid) including branched and linear isomers of propyl (i-PrP and n-PrP) and butyl paraben (i-BuP and n-BuP) in sewage water samples is presented. The procedure includes analytes enrichment by microextraction by packed sorbent (MEPS) coupled at-line to large volume injection-gas chromatography-mass spectrometry (LVI-GC-MS). Under optimised conditions, compounds were extracted from 2 mL samples, adjusted at pH 3, using a C18 MEPS-sorbent. Adsorbed analytes were eluted directly into the Programmable Temperature Vaporizer (PTV) injector of the chromatograph with 2×25 μL of ethyl acetate. They were quantified using standard solutions in ultrapure water submitted to the same sample enrichment process as real sewage water samples. After signal normalisation using isotopic labelled species as internal surrogates, no differences were noticed among the extraction efficiency for sewage and ultrapure water; moreover, the proposed method reported lineal calibration curves from 0.1 to 10 ng mL(-1), relative standard deviations (%RSD) between 2 and 7.1% and limits of detection (LODs) varying from 0.001 to 0.015 ng mL(-1) in ultrapure water and from 0.02 to 0.59 ng mL(-1) in the most complex sample (raw wastewater). 相似文献
216.
In this paper we present a new theory to re-examine the immobilization technique of dye doped sol-gel films, define the strength and types of possible bonds between the immobilized molecule and sol-gel glass, and show that the immobilized molecule is not free inside the pores as was previously thought. Immobilizing three different pH sensitive dyes with different size and functional groups inside the same sol-gel films revealed important information about the nature of the interaction between the doped molecule and the sol-gel matrix. The samples were characterized by means of ultraviolet-visible spectrophotometer (UV-VIS), thermal gravimetric analysis (TGA), mercury porosimetry (MP), nuclear magnetic resonance spectroscopy ((29)Si NMR) and field-emission environmental scanning electron microscopy (ESEM-FEG). It was found that the doped molecule itself has a great effect on the strength and types of the bonds. A number of factors were identified, such as number and types of the functional groups, overall charge, size, pK(a) and number of the silanol groups which surround the immobilized molecule. These results were confirmed by the successful immobilization of bromocresol green (BCG) after a completely polymerized sol-gel was made. The sol-gel consisted of 50% tetraethoxysilane (TEOS) and 50% methyltriethoxysilane (MTEOS) (w/w). Moreover, the effect of the immobilized molecule on the structure of the sol-gel was studied by means of a leaky waveguide (LW) mode for doped films made before and after polymerization of the sol-gel. 相似文献
217.
In this work we report very accurate variational calculations of the complete pure vibrational spectrum of the D(2) molecule performed within the framework where the Born-Oppenheimer (BO) approximation is not assumed. After the elimination of the center-of-mass motion, D(2) becomes a three-particle problem in this framework. As the considered states correspond to the zero total angular momentum, their wave functions are expanded in terms of all-particle, one-center, spherically symmetric explicitly correlated Gaussian functions multiplied by even non-negative powers of the internuclear distance. The nonrelativistic energies of the states obtained in the non-BO calculations are corrected for the relativistic effects of the order of α(2) (where α = 1/c is the fine structure constant) calculated as expectation values of the operators representing these effects. 相似文献
218.
Six phenolics were obtained from the leaves of Prunus padus by activity-guided isolation: isorhamnetin 3-O-β-xylopyranosyl-(1?→?2)-β-galactopyranoside (1), astragalin (2), hyperoside (3), quercetin 3-O-β-xylopyranosyl-(1?→?2)-β-galactopyranoside (4), quercetin 3-O-β-xylopyranosyl-(1?→?2)-β-glucopyranoside (5) and chlorogenic acid (6). The antioxidant potential of 70% methanolic extracts from the flowers and leaves collected over the growing season was evaluated using the 2,2-diphenyl-1-picryl hydrazyl (DPPH) radical scavenging and 2,2′-azobis-(2-amidinopropane) dihydrochloride (AAPH)-induced linoleic acid (LA) peroxidation tests in relation to the contents of the isolates 1-6, total phenolics, total proanthocyanidins and total quercetin. The IC?? values were expressed in gram dry weight per gram of DPPH or LA, respectively, and were in the range of 1.42-2.42 for the DPPH test and 1.78-4.92 for the LA peroxidation, with superior activity found for the flowers and the autumn leaves. Significant linear correlation of these values to the sum of proanthocyanidins and compounds 1-6 (R2?>?0.87) showed that the listed phenolics are synergists of the tested activity. 相似文献
219.
Mittelmaier S Fünfrocken M Fenn D Berlich R Pischetsrieder M 《Analytical and bioanalytical chemistry》2011,401(4):1183-1193
During heat sterilization of peritoneal dialysis solutions, glucose is partially transformed into glucose degradation products
(GDPs), which significantly reduce the biocompatibility of these medicinal products. Targeted α-dicarbonyl screening identified
glyoxal, methylglyoxal, 3-deoxyglucosone, 3,4-dideooxyglucosone-3-ene, glucosone, and 3-deoxygalactosone as the major six
GDPs with α-dicarbonyl structure. In the present study, an ultra-high-performance liquid chromatography method was developed
which allows the separation of all relevant α-dicarbonyl GDPs within a run time of 15 min after derivatization with o-phenylenediamine. Hyphenated diode array detection/tandem mass spectrometry detection provides very robust quantification
and, at the same time, unequivocal peak confirmation. Systematic evaluation of the derivatization process resulted in an optimal
derivatization period that provided maximal derivatization yield, minimal de novo formation (uncertainty range ±5%), and maximal
sample throughput. The limit of detection of the method ranged from 0.13 to 0.19 μM and the limit of quantification from 0.40
to 0.57 μM. Relative standard deviations were below 5%, and recovery rates ranged between 91% and 154%, dependent on the type
and concentration of the analyte (in 87 out of 90 samples, recovery rates were 100 ± 15%). The method was then applied for
the analysis of commercial peritoneal dialysis fluids (nine different product types, samples from three lots of each). 相似文献
220.
The aim of this research work was the evaluation of stir-bar sorptive extraction (SBSE) in combination with an in situ derivatization to determine parabens (methylparaben, isopropylparaben, n-propylparaben, butylparaben and benzylparaben), triclosan and methyltriclosan in soil samples. This is the first time that this approach has been applied to the determination of these compounds in soil samples, providing important advantages over conventional extraction techniques, such as minimization of sampling handling, complete elimination of the use of organic solvents and simplification of the analytical procedure with reduced time consumption. The enriched target analytes were desorbed thermally using a thermodesorption system coupled to a gas chromatograph and a mass spectrometer. The optimized derivatization and SBSE extraction conditions, as well as the analytical characteristics of the method were obtained using spiked soil samples. The proposed methodology proved to be easy to use and sensitive, with limits of detection between 80 ng/kg and 1.06 μg/kg, and reproducibility values below 13%. The accuracy of the method was evaluated at two concentration levels, obtaining apparent recoveries between 91% and 110%. The matrix composition significantly influenced the extraction procedure, and a need to adopt a standard additions protocol is apparent. The analytes assayed were determined successfully in different environmental soil samples. 相似文献