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1.
《Journal of separation science》2018,41(10):2288-2295
New psychoactive substances represent serious social and health problem as tens of new compounds are detected in Europe annually. They often show structural proximity or even isomerism, which complicates their analysis. Two methods based on ultra high performance supercritical fluid chromatography and ultra high performance liquid chromatography with mass spectrometric detection were validated and compared. A simple dilute‐filter‐and‐shoot protocol utilizing propan‐2‐ol or methanol for supercritical fluid or liquid chromatography, respectively, was proposed to detect and quantify 15 cathinones and phenethylamines in human urine. Both methods offered fast separation (<3 min) and short total analysis time. Precision was well <15% with a few exceptions in liquid chromatography. Limits of detection in urine ranged from 0.01 to 2.3 ng/mL, except for cathinone (5 ng/mL) in supercritical fluid chromatography. Nevertheless, this technique distinguished all analytes including four pairs of isomers, while liquid chromatography was unable to resolve fluoromethcathinone regioisomers. Concerning matrix effects and recoveries, supercritical fluid chromatography produced more uniform results for different compounds and at different concentration levels. This work demonstrates the performance and reliability of supercritical fluid chromatography and corroborates its applicability as an alternative tool for analysis of new psychoactive substances in biological matrixes. 相似文献
2.
As borders between different entities, lines are an important element of natural images. Indeed, the neurons of the mammalian
visual cortex are tuned to respond best to lines of a given orientation. This preferred orientation varies continuously across
most of the cortex, but also has vortex-like singularities known as pinwheels. In attempting to describe such patterns of
orientation preference, we are led to consider underlying rotation symmetries: Oriented segments in natural images tend to
be collinear; neurons are more likely to be connected if their preferred orientations are aligned to their topographic separation.
These are indications of a reduced symmetry requiring joint rotations of both orientation preference and the underlying topography.
This is verified by direct statistical tests in both natural images and in cortical maps. Using the statistics of natural
scenes we construct filters that are best suited to extracting information from such images, and find qualitative similarities
to mammalian vision.
PACS84.35+i 89.70.+c 87.57.Nk 相似文献
3.
Ab initio calculations showed that the tetrachlorodibenzo-para-dioxin radical cations (TCDD RCs) with a planar structure have two steady states with asymmetric dioxin cycles. The activation barriers between these states are up to 2 kcal/mole, so that the RCs may be regarded as being structurally nonrigid within the dioxin cycle. The 2,3,7,8-TCDD RC is more stable than the 1,4,6,9-TCDD RC, the energy difference being 5.2 kcal/mole. The adiabatic ionization potential of 2,3,7,8-TCDD (7.54 eV) is 0.1 eV smaller than the corresponding potential of 1,4,6,9-TCDD. These factors account for the increased hemoproteide affinity and hence increased biological activity of 2,3,7,8-TCDD. 相似文献
4.
The rotational spectra of three low-energy conformers of thiodiglycol (TDG) (HOCH2CH2SCH2CH2OH) have been measured in a molecular beam using a pulsed-nozzle Fourier-transform microwave spectrometer. To determine the likely conformational structures with ab initio approach, conformational structures of 2-(ethylthio)ethanol (HOEES) (CH3CH2SCH2CH2OH) were used as starting points together with the consideration of possible intramolecular hydrogen bonding in TDG. Three lower-energy conformers have been found for TDG at the MP2=Full/6311G** level and ab initio results agree nicely with experimentally determined rotational constants. In addition, Stark measurements were performed for two of the three conformers for dipole moment determinations, adding to our confidence of the conformational structure matches between experimental observations and ab initio calculations. Of the three lower-energy conformers, one displays a compact folded-like structure with strong hydrogen bonding between the two hydroxyl groups and the central sulfide atom. Two other conformers have relatively open chain-like structures with hydrogen bonding between each of the hydroxyl groups to the central sulfur atom, of which one has pure b-type dipole moment according to the ab initio results. 相似文献
5.
An FT-IR study of pyrrole self-association in CCl4 solutions was carried out. According to the IR measurements, pyrrole forms self-associated dimeric species via N-H?π hydrogen bonding. This was also confirmed by quantum chemical calculations for pyrrole monomer and dimer at B3LYP/6-31++G(d,p) level of theory. A T-shaped minimum was located on B3LYP/6-31++G(d,p) PES of pyrrole dimer characterized with a hydrogen bond of an N-H?π type, with centers-of-mass separation of monomeric units of 4.520 Å, H?π distance of 2.475 Å, the interplanar angle between the two monomeric units being 72.9°. The anharmonic vibrational frequency shift upon dimer formation calculated on the basis of 1D DFT vibrational potentials is in excellent agreement with the experimental data (84 vs. 87 cm−1). Harmonic vibrational analysis predicts somewhat smaller shift (68 cm−1). On the basis of NIR spectroscopic data, anharmonicity constants for the 2ν(N-H) and 2ν(N-H?π) vibrational transitions were calculated. The orientational dynamics of monomeric and self-associated pyrrole species was studied within the framework of the transition dipole moment time correlation function formalism. The period of essentially free rotation in the condensed phase reduces from 0.05 ps for the monomeric pyrrole to 0.02 ps for the proton-donor molecule within the dimer. 相似文献
6.
Yu. Gangrsky 《Hyperfine Interactions》2006,171(1-3):203-208
This review summarizes the experimental data on charge radii differences among ground state and high spin isomeric states
determined by high-resolution laser spectroscopic methods. A comparison is presented between radii changes obtained from the
isomeric shifts in the atomic spectra and from the quadrupole moments of both ground and isomeric states under the assumption
that the radii changes are determined by the difference of the quadrupole deformations. Special attention is paid to isomers
arising from the break-up of nucleon pairs and isomers of odd–odd nuclei. The characteristic features of the radii changes
for isomeric states of different origin are discussed. 相似文献
7.
介绍了核磁共振(NMR)波谱,尤其是核磁共振二维谱(2D NMR)在最近几年内的进展。内容包括怎样用NMR测定高聚物的序列分布、共聚物结构、聚合物的混溶性、聚合物液晶的取向度、分子量、短链度和长链支化度、凝聚态高聚物的多相结构等。 相似文献
8.
9.
O. G. Stradella S. A. Maluendes E. A. Castro A. H. Jubert 《Theoretical chemistry accounts》1987,72(1):57-62
By means of Bader's approach on topological properties of the electronic density, the major stability of the O-bonded adduct over the C-bonded one between MgF2 and CO is reinforced. 相似文献
10.
Host-guest complexes of cucubit[8]uril with phenanthrolines and some methyl derivatives 总被引:1,自引:0,他引:1
DAY Anthony I 《中国科学B辑(英文版)》2005,48(4):305-314
Cucurbituril a molecular container (or host) has a rigid hollow interior cavity which is large enough to accommodate, one or more, smaller molecules (or guests). The cavity is accessible through two carbonyl portal openings. Molecules or guests enter the … 相似文献