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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.
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
3.
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
4.
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
5.
6.
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
7.
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
8.
Preparation, Crystal Structure, and Normal Coordinate Analysis of Linkage Isomeric Pentachloroiodoselenocyanatoosmates(IV). Crystal Structure of trans‐(PPh4)2[OsCl4I(NCSe)] By treatment of the solution of (n‐Bu4N)2[OsCl5I] in dichloromethane with suspended Pb(SeCN)2 the linkage isomers trans‐(n‐Bu4N)2[OsCl4I(NCSe)] ( 1 ) and trans‐(n‐Bu4N)2[OsCl4I(SeCN)] ( 2 ) are formed, which have been separated by ion exchange chromatography on diethylaminoethyl cellulose. The X‐Ray structure determination on a single crystal of trans‐(PPh4)2[OsCl4I(NCSe)] (triclinic, space group P1¯, a = 10.8950(13), b = 11.076(2), c = 20.980(2)Å, α = 96.940(10), β = 98.747(9), γ = 104.419(11)°, Z = 2) reveals, that the nearly linear selenocyanate group in trans position to the iodine atom is coordinated with the Os‐N‐C angle of 171.1°. Based on the molecular parameters of the X‐ray determination ( 1 ) and estimated data ( 2 ) the IR and Raman spectra of both linkage isomers are assigned by normal coordinate analysis. The valence force constants are fd(OsN) = 1.70 und fd(OsSe) = 1.15 mdyn/Å. 相似文献
9.
A. Ono 《Chromatographia》1980,13(12):752-754
Summary Xylenol isomers can be resolved on most polyols (sugars or sugar alcohols) and polyethers (polyethylene glycol or polypropylene glycol) with hydrogen-bonding interaction. They are separated on vinical polyols which have more hydroxy hydrogen than tetrol, and even on vicinal triol when its hydroxy hydrogen is acidic (stronger proton donor). The stronger is the hydrogen bonding interaction between xylenols and the liquid phase, the better is the separation of 2,4- and 2,5-xylenol, and the poorer the separation of 2,4-and 2,3-xylenol. 相似文献
10.
Using the Picker flow microcalorimeter, excess heat capacities have been obtained at 25°C throughout the concentration range for 2,2-dimethylbutane,n-hexane, and cyclohexane each mixed with a series of hexadecane isomers of increasing degrees of orientational order, as determined by depolarized Rayleigh scattering. The isomers are 2,2,4,4,6,8,8-heptamethylnonane, 6-, 4-, and 2-methylpentadecane, andn-hexadecane. Thec
p
E
values are negative, increasing rapidly in magnitude with increase of orientational order, and are not predicted by the Prigogine—Flory theory which neglects order. Values ofc
p
E
are obtained at 10, 25, and 55°C for cyclohexane +6-, 4-, and 2-methylpentadecane which with other literature data lead to the temperature dependence of the thermodynamic excess functions for cyclohexane solutions of the five C16 isomers. The excess enthalpy and entropy vary with the C16 isomer and with temperature, but the corresponding variation of the excess free energy is small, indicating a high degree of enthalpy-entropy compensation. This is consistent with a rapid decrease with temperature of orientational order in the C16 isomers. 相似文献