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91.
Katharina Uhlir Michele Gironda Luca Bombelli Michael Eder Nicola Aresi Gabriele Groschner Martina Griesser 《X射线光谱测定》2019,48(4):293-302
Rembrandt's painting Old Woman Praying, 1629/30, is the most valuable and exceptional work of art of the Residenzgalerie Salzburg (RGS). It is painted on a gilded copper plate with dimensions of only approximately 15 × 12 cm. The painting probably belongs to a series of three small-scale tronies, all executed on gilded copper plates. This particular picture preparation, which represents a special feature in Rembrandt's work, is quite unusual in the history of art. Previous investigations on the comparable paintings The Laughing Man, 1629/30, in the Mauritshuis, The Hague and the Self Portrait, 1630, in the National Museum, Stockholm showed that the gilding of the copper plate was applied over a lead white ground. To characterize the painting in the RGS, X-ray fluorescence (XRF) mapping was performed in a collaboration between the Research Office Residenzgalerie, Land Salzburg, the XGLab S.R.L, Milan, and the Conservation Science Department of the Kunsthistorische Museum Vienna (KHM). The results indicate a different structure for this painting than that used for The Laughing Man and the Self Portrait. The gilding was applied directly onto the copper plate, but with three areas with the gilding missing. It seems likely that in these sections, the gold was purposely removed to provide a different darker effect. XRF mapping yielded valuable insights into the structure of the painting and its technique as well as the principal pigments used for its composition. 相似文献
92.
93.
Analysis of polycyclic aromatic hydrocarbons (PAHs) in environmental samples: a critical review of gas chromatographic (GC) methods 总被引:1,自引:0,他引:1
Polycyclic aromatic hydrocarbons (PAHs) are frequently measured in the atmosphere for air quality assessment, in biological
tissues for health-effects monitoring, in sediments and mollusks for environmental monitoring, and in foodstuffs for safety
reasons. In contemporary analysis of these complex matrices, gas chromatography (GC), rather than liquid chromatography (LC),
is often the preferred approach for separation, identification, and quantification of PAHs, largely because GC generally affords
greater selectivity, resolution, and sensitivity than LC. This article reviews modern-day GC and state-of-the-art GC techniques
used for the determination of PAHs in environmental samples. Standard test methods are discussed. GC separations of PAHs on
a variety of capillary columns are examined, and the properties and uses of selected mass spectrometric (MS) techniques are
presented. PAH literature on GC with MS techniques, including chemical ionization, ion-trap MS, time-of-flight MS (TOF-MS),
and isotope-ratio mass spectrometry (IRMS), is reviewed. Enhancements to GC, for example large-volume injection, thermal desorption,
fast GC, and coupling of GC to LC, are also discussed with regard to the determination of PAHs in an effort to demonstrate
the vigor and robustness GC continues to achieve in the analytical sciences. 相似文献
94.
Barone V Casarin M Forrer D Pavone M Sambi M Vittadini A 《Journal of computational chemistry》2009,30(6):934-939
A semiempirical addition of dispersive forces to conventional density functionals (DFT-D) has been implemented into a pseudopotential plane-wave code. Test calculations on the benzene dimer reproduced the results obtained by using localized basis set, provided that the latter are corrected for the basis set superposition error. By applying the DFT-D/plane-wave approach a substantial agreement with experiments is found for the structure and energetics of polyethylene and graphite, two typical solids that are badly described by standard local and semilocal density functionals. 相似文献
95.
Prof. Domenico C. M. Albanese Dr. Michele Penso 《European journal of organic chemistry》2023,26(19):e202300224
Phase Transfer Catalysis (PTC) is a powerful tool to perform reactions in a practical fashion, both in laboratory and industrial scale. Significant cost savings and major process improvements can be achieved in reactions performed under PTC conditions. In the last few years remarkable results in stereoselective reactions were achieved using chiral, non-racemic quaternary ammonium salts. Moreover, the use of bulky, chiral phosphate anions paired with achiral cations to generate lipophilic ion pairs allowed to design new avenues for the stereoselective construction of important building blocks. Hydrogen bond interactions were also shown to provide new pathways for asymmetric nucleophilic substitutions using insoluble reagents under PTC conditions. This Review will focus on recent advances in developing practical synthetic routes to construct molecules in a stereoselective fashion under PTC conditions. 相似文献
96.
Michael R. Smith Clare B. Martin Sonia Arumuganainar Ari Gilman Bruce E. Koel Michele L. Sarazen 《Angewandte Chemie (International ed. in English)》2023,62(8):e202218208
Immobilization of porphyrin complexes into crystalline metal–organic frameworks (MOFs) enables high exposure of porphyrin active sites for CO2 electroreduction. Herein, well-dispersed iron-porphyrin-based MOF (PCN-222(Fe)) on carbon-based electrodes revealed optimal turnover frequencies for CO2 electroreduction to CO at 1 wt.% catalyst loading, beyond which the intrinsic catalyst activity declined due to CO2 mass transport limitations. In situ Raman suggested that PCN-222(Fe) maintained its structure under electrochemical bias, permitting mechanistic investigations. These revealed a stepwise electron transfer-proton transfer mechanism for CO2 electroreduction on PCN-222(Fe) electrodes, which followed a shift from a rate-limiting electron transfer to CO2 mass transfer as the potential increased from −0.6 V to −1.0 V vs. RHE. Our results demonstrate how intrinsic catalytic investigations and in situ spectroscopy are needed to elucidate CO2 electroreduction mechanisms on PCN-222(Fe) MOFs. 相似文献
97.
A new algorithm for density-functional-theory-based ab initio molecular dynamics simulations is presented. The Kohn–Sham
orbitals are expanded in Gaussian-type functions and an augmented-plane-wave-type approach is used to represent the electronic
density. This extends previous work of ours where the density was expanded only in plane waves. We describe the total density
in a smooth extended part which we represent in plane waves as in our previous work and parts localised close to the nuclei
which are expanded in Gaussians. Using this representation of the charge we show how the localised and extended part can be
treated separately, achieving a computational cost for the calculation of the Kohn–Sham matrix that scales with the system
size N as O(NlogN). Furthermore, we are able to reduce drastically the size of the plane-wave basis. In addition, we introduce a multiple-cutoff
method that improves considerably the performance of this approach. Finally, we demonstrate with a series of numerical examples
the accuracy and efficiency of the new algorithm, both for electronic structure calculations and for ab initio molecular dynamics
simulations.
Received: 15 December 1998 /Accepted: 18 February 1999 /Published online: 14 July 1999 相似文献
98.
Dattilo D Armelao L Maggini M Fois G Mistura G 《Langmuir : the ACS journal of surfaces and colloids》2006,22(21):8764-8769
We report the immobilization of a fulleropyrrolidine, bearing a dec-9-ynyl functionality, on silicon surfaces through a thermal hydrosilylation protocol. Contact angle measurements on porous silicon (PS) surfaces reveal an unusual dependence of the angle with the PS roughness that apparently contradicts Wenzel's formula. This result has been explained by an extension of Wenzel's model in which the critical angle, which discriminates between the hydrophilic/hydrophobic character of a solid material, is substantially reduced below 90 degrees by surface roughness. 相似文献
99.
The field of application of solid-state NMR to the study of supramolecular systems is growing rapidly, with many research groups involved in the development of techniques for the study of crystalline and amorphous phases. This Feature Article aims to provide an overview of the recent contributions of our research group to this field, paying particular attention to the study of the weak interactions such as hydrogen bonds in supramolecular systems through solid-state NMR investigations. The structure and dynamic behaviour of selected host-guest systems will be also discussed. 相似文献
100.
The AOAC Use-Dilution methods do not provide procedures to enumerate the test microbe on stainless steel carriers (penicylinders) or guidance on the expected target populations of the test microbe (i.e., a performance standard). This report describes the procedures used by the U.S. Environmental Protection Agency to enumerate the test microbe (carrier counts) associated with conducting the Use-Dilution method with Staphylococcus aureus (Method 955.15) and Pseudomonas aeruginosa (Method 964.02) and the examination of historical data. The carrier count procedure involves the random selection of carriers, shearing bacterial cells from the carrier surface through sonication, and plating of serially diluted inoculum on trypticase soy agar. For each Use-Dilution test conducted, the official AOAC method was strictly followed for carrier preparation, culture initiation, test culture preparation, and carrier inoculation steps. Carrier count data from 78 Use-Dilution tests conducted over a 6-year period were compiled and analyzed. A mean carrier count of 6.6 logs (approximately 4.0 x 10(6) colony-forming units/carrier) was calculated for both S. aureus and P. aeruginosa. Of the mean values, 95% fell within +/- 2 repeatability standard deviations. The enumeration procedure and target carrier counts are desirable for standardizing the Use-Dilution methods, increasing their reproducibility, and ensuring the quality of the data. 相似文献