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41.
Dr. Rebecca L. Greenaway Dr. Valentina Santolini Dr. Filip T. Szczypiński Dr. Michael J. Bennison Dr. Marc A. Little Andrew Marsh Dr. Kim E. Jelfs Prof. Andrew I. Cooper 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(17):3718-3722
Molecular dumbbells with organic cage capping units were synthesised via a multi-component imine condensation between a tri-topic amine and di- and tetra-topic aldehydes. This is an example of self-sorting, which can be rationalised by computational modelling. 相似文献
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The Ramanujan Journal - Let $$D_h$$ , $$E_k$$ and $$F_{\alpha }$$ be sets of size $$h,k,\alpha $$ respectively, with $$k \le h$$ . We define a strongly widened derangement to be a permutation of... 相似文献
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Rosário Monteiro Gil Faria Manuela Meireles Luísa Correia‐Sá Diana Teixeira Ana Faria Conceição Calhau Valentina F. Domingues Cristina Delerue‐Matos 《Biomedical chromatography : BMC》2012,26(12):1494-1501
Scientific evidence has shown an association between organochlorine compounds (OCC) exposure and human health hazards. Concerning this, OCC detection in human adipose samples has to be considered a public health priority. This study evaluated the efficacy of various solid‐phase extraction (SPE) and cleanup methods for OCC determination in human adipose tissue. Octadecylsilyl endcapped (C18‐E), benzenesulfonic acid modified silica cation exchanger (SA), poly(styrene‐divinylbenzene (EN) and EN/RP18 SPE sorbents were evaluated. The relative sample cleanup provided by these SPE columns was evaluated using gas chromatography with electron capture detection (GC–ECD). The C18‐E columns with strong homogenization were found to provide the most effective cleanup, removing the greatest amount of interfering substance, and simultaneously ensuring good analyte recoveries higher than 70%. Recoveries > 70% with standard deviations (SD) < 15% were obtained for all compounds under the selected conditions. Method detection limits were in the 0.003–0.009 mg/kg range. The positive samples were confirmed by gas chromatography coupled with tandem mass spectrometry (GC‐MS/MS). The highest percentage found of the OCC in real samples corresponded to HCB, o,p′‐DDT and methoxychlor, which were detected in 80 and 95% of samples analyzed respectively. Copyright © 2012 John Wiley & Sons, Ltd. 相似文献
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Mikhail I. Smushkin Valentina G. Kharchenko Boris I. Drevko 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):621-624
It is shown using 1H NMR spectroscopy that 2,4,6-triphenyl-4H-seleno(thio)pyrans can be isomerized into 2H-isomers by the action of lithium perchlorate or lithium chloride in DMF or only by DMF. The reaction time is found to depend on the Lewis acidity of used salt. It is supposed that isomerization in presence of Lewis acids proceeds as endocyclic 1,3-proton transfer or as a series of two 1,2-hydride shifts. 相似文献
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Valeria van Axel Castelli Antonella Dalla Cort Luigi Mandolini Valentina Pinto David N. Reinhoudt Fabrizio Ribaudo 《Supramolecular chemistry》2013,25(2-3):211-219
The complexation of the salophen-uranyl metallocleft 2 and of its half-cleft analogue 3 with enones and other carbonyl compounds was assessed in chloroform by UV-Vis titration and, occasionally, by FT-IR measurements. Complexes with receptors 2 and 3 are in all cases more stable than those with the control unsubstituted uranyl-salophen 1 , showing that in addition to the primary binding force provided by coordination of the carbonyl oxygen to the uranium, a significant driving force for complexation, typically in the range of 2-3 kcal/mol, results from van der Waals interactions of the guest with the aromatic walls. Replacement of the phenyl group in 3 with larger aromatic residues to give 4 and 5 , led to enhanced complex stabilities, due to more extended contact surfaces between host and guest. 相似文献
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Nina I. Giricheva Georgiy V. Girichev Marwan Dakkouri Sergey N. Ivanov Vjacheslav M. Petrov Valentina N. Petrova 《Structural chemistry》2013,24(3):819-826
α-Naphthalenesulfonyl chloride, α-NaphSC, was studied by gas-phase electron diffraction (GED) and quantum chemical calculations (HF/6-311 + G**, HF/aug-cc-pVDZ, B3LYP/cc-pVDZ, B3LYP/cc-pVTZ, B3LYP/aug-cc-pVDZ, B3LYP/aug-cc-pVTZ, MP2/cc-pVDZ, and MP2/cc-pVTZ). The calculations predict the existence of two conformers with C 1 (I) and C s (II) symmetries. The most stable conformer I has an enantiomer. The experimental data of α-NaphSC obtained at 370(5) K could be best fitted by a C 1 symmetry model indicating that only this form exists in the gas-phase. In this model the Cα–S–Cl plane deviates from the perpendicular orientation relative to the plane of the naphthalene skeleton. Under the applied experimental conditions, the mole fraction of a second less stable conformer II of α-NaphSC predicted by calculations is no more than 1 %. The following geometrical parameters of conformer I were obtained from the experiment (Å and °; uncertainties are in parentheses): r h1(C–H) = 1.082(6), r h1(C–C)cp = 1.407(3), r h1(C–S) = 1.764(5), r h1(S–O)av = 1.425(3), r h1(S–Cl) = 2.051(5), ∠C–Cα–C = 122.5(1), ∠Cα–S–Cl = 101.5(10); C9–C1–S–Cl = 71.4(21). The calculated barriers to internal rotation of the sulfonyl chloride group exceed considerably the thermal energy values corresponding to the temperatures of the GED experiments. Natural bond orbitals analysis of the electron density distribution was carried out to explain the peculiarities of the molecular structure of the studied compound and the deviation from the structures of β-NaphSHal molecules and their benzene analogs. 相似文献
50.
Marco Vincenti Daniele Cavanna Enrico Gerace Valentina Pirro Michele Petrarulo Daniele Di Corcia Alberto Salomone 《Analytical and bioanalytical chemistry》2013,405(2-3):863-879
Forensic investigations involving acute or lethal intoxication, drug-facilitated sexual assault, driving or workplace impairment frequently require the analysis of fresh or postmortem blood samples to check out a wide variety of pharmaceutical and illicit drugs, even after single-dose consumption. A sensitive and selective ultrahigh-performance liquid chromatography–tandem mass spectrometry (UHPLC–MS/MS) screening method was developed for fast screening of 88 psychoactive drugs and metabolites in blood samples, including the ones most frequently involved in acute intoxications and forensic investigations in Italy. The new method allows short sample processing and analysis time (the whole procedure can be accomplished in less than 30 min) together with the simultaneous monitoring of a large number of pharmaceutical substances. These features represent crucial factors in the approach of acute intoxications, when the patient requires urgent and appropriate therapy. Blood sample treatment was limited to protein precipitation. Two UHPLC–MS/MS runs in positive and negative electrospray ionization modes were performed. The data were acquired at unit mass resolution in the selected reaction monitoring mode. According to international guidelines, linearity range, precision, trueness, detection and quantification limits, recovery, selectivity, specificity, carryover, and matrix effect phenomena were determined. Despite the limited sample purification and the inherent decreased chance of eliminating any potential interference, the present multiresidue screening method proved extremely effective and sensitive, allowing the detection of all tested drugs, even those belonging to structurally different classes of substances. Moreover, the developed method is easily susceptible to further expansion to encompass more drugs, either new or those becoming important for criminal investigation. This protocol was also applied to the analysis of authentic blood samples collected from victims of various crimes in routine casework, whose relevance in forensic investigations is presented in five cases. 相似文献