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101.
Cabaleiro-Lago EM Rodríguez-Otero J García-López RM Peña-Gallego A Hermida-Ramón JM 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(20):5966-5974
A comprehensive B3LYP/6-31+G* study on the electrocyclization of 1,2,4,6-heptatetraene analogues was conducted. Starting from the cyclization of (2Z)-2,4,5-hexatrienal, a pericyclic disrotatory process favored by the assistance of a electron lone pair, we incorporated small modifications in its molecular structure to obtain a truly pseudopericyclic process. To this purpose electronegative atoms (fluorine and nitrogen) were added to give a more electrophilic character on the carbon atom which is attacked by the electron lone pair of the oxygen atom. The complete pathway for each reaction was determined, and changes in magnetic properties were monitored with a view to estimating the aromatization associated with each process. This information, together with the energetic and structural results, allowed us to classify the reactions as pseudopericyclic or pericyclic. Among all studied reactions only one was a truly pseudopericyclic process and another was a borderline case. The features of this unequivocally pseudopericyclic case were analyzed in depth. 相似文献
102.
The preparation of ethyl 4-(2-bromoethyl)thieno[2,3-b]pyrrole-5-carboxylate and ethyl 6-(2-bromoethyl)thieno[3,2-b]pyrrole-5-carboxylate by reaction of t-butyl 2-(2-thienyl)carbazate and t-butyl 2-(3-thienyl)carbazate with ethyl-5-bromo-2-oxopentanoate are described. 相似文献
103.
Villar-Rodil S. Paredes J. I. Martínez-Alonso A. Tascón J.M.D. 《Journal of Thermal Analysis and Calorimetry》2002,70(1):37-43
The pyrolysis behaviour of Nomex, poly(m-phenylene isophthalamide) fibres under argon has been investigated up to a temperature of 1173 K with different methods to
get direct information on the progressive changes taking place in the solid material and its carbon fibre residues. The main
stages of the pyrolytic degradation of the fibres were determined by thermal analysis (TG and DTA) and their chemical and
morphological evolution through the different steps was subsequently followed by Fourier transform infrared spectroscopy (FTIR)
and atomic force microscopy (AFM) measurements, respectively, on samples treated to various temperatures.
This revised version was published online in July 2006 with corrections to the Cover Date. 相似文献
104.
M. N. Moreno-Carretero J. M. Salas-Peregrín 《Journal of Thermal Analysis and Calorimetry》1984,29(5):1053-1059
The following cadmium(II) complexes of deprotonated 6-amino-5-nitroso-uracil (AH), deprotonated 6-amino-3-methyl-5-nitroso-uracil (BH) and neutral 6-amino-1-methyl-5--nitroso-uracil (CH) have been prepared and their thermal behaviour studied by TG and DSC techniques: CdA2 · 3 H2O, CdB2 · 2 H2O, CdB2 and CdCl2(CH)2 · 2 H2O.Dehydration processes of these complexes take place in only one step and the enthalpy values associated with them are comprised in the 42.7–80.5 kJ · mole–1 H2O range. The pyrolytic reactions finish in the 630–900 C temperature range, remaining as final residue in the case of CdA2 · 3 H2O, CdB2 · 2 H2O and CdB2 complexes, cadmium oxide. The pyrolytic decomposition of CdCl2(CH)2 · 2 H2O complex does not yield any residue, due to the elimination of cadmium chloride.
Zusammenfassung Folgende Cadmium(II)-Komplexe von deprotoniertem 6-Amino-5-nitrosouracil (AH), deprotoniertem 6-Amino-3-methyl-5-nitroso-uracil (BH) und neutralem 6-Amino-1-methyl-5-nitroso-uracil (CH) wurden hergestellt: CdA2 · 3 H2O, CdB2· 2 H2O, CdB2 und CdCl2(CH)2 · 2 H2O. Das thermische Verhalten dieser Komplexe wurde mittels TG und DSC untersucht. Die Dehydratisierung der Komplexe verlÄuft in nur einem Schritt. Die Enthalpiewerte für diese Prozesse liegen im Bereich von 42.7–80.5 kJ · mol–1 H2O. Die pyrolytischen Reaktionen verlaufen im Temperaturbereich von 630–900C zu Ende, wobei im Falle der Komplexe CdA2 · 3 H2O, CdB2 · 2 H2O und CdB2 Cadmiumoxid als Rückstand zurückbleibt. Die pyroytische Zersetzung von CdCl2(CH)2 · 2 H2O verlÄuft wegen der Flüchtigkeit von CdCl2 rückstandslos.
CdA2 · 3 H2O, CdB2 · 2 H2O, CdB2 CdCl2(CH)2 · 2 H2O, A — 6--5-, B — 6--3--5- CH — 6--1--5- . . 42.7–80.5 · –1. 630–900, . CdCl2(CH)2 · 2 H2O - , .相似文献
105.
An analytical potential energy surface (PES) representation of the O(+)((4)S)+H(2)(X (1)Sigma(g) (+)) system was developed by fitting around 600 CCSD(T)/cc-pVQZ ab initio points. Rate constant calculations for this reaction and its isotopic variants (D(2) and HD) were performed using the quasiclassical trajectory (QCT) method, obtaining a good agreement with experimental data. Calculations conducted to determine the cross section of the title reaction, considering collision energies (E(T)) below 0.3 eV, also led to good accord with experiments. This PES appears to be suitable for kinetics and dynamics studies. Moreover, the QCT results show that, although the hypotheses of a widely used capture model are not satisfied, the resulting expression for the cross section can be applied within a suitable E(T) interval, due to errors cancellation. This could be a general situation regarding the application of this simple model to ion-molecule processes. 相似文献
106.
A universal temperature controlled membrane interface (TCMI) has been constructed for hollow-fibre membranes. The membrane temperature is controllable in the range -70 to 250 degrees C using an electric heater and a flow of cooled nitrogen or helium gas. Volatile and semi-volatile organic compounds may be detected either by continuous diffusion across the membrane or by in-membrane pre-concentration followed by thermal desorption into the detector. The TCMI interface is demonstrated in combination with mass spectrometry and GC-MS, for the determination of VOCs and SVOCs in aqueous and air samples and for the on-line monitoring of a bioreactor. 相似文献
107.
Manuel A. Fernandes Marcus Layh Bernard Omondi 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(7):o384-o385
The title compound, C10H11N, displays a crystallographic mirror plane that incorporates all the non‐H atoms, as well as the H atoms attached to the aromatic ring. The isocyano group is almost linear and shows an N[triple‐bond]C bond distance of 1.158 (3) Å. 相似文献
108.
The global optimization basin-hopping (BH) method has been used to locate the global minima (GM) of Mg(n)F(2n) (n=1-30) clusters using a Born-Mayer-type potential. Some of the GM were particularly difficult to find, requiring more than 1.5 x 10(4) BH steps. We have found that both the binding energy per MgF2 unit and the effective volume of the GM isomers increase almost linearly with n, and that cluster symmetry decreases with cluster size. The data derived from the BH runs reveal a growing density of local minima just above the GM as n increases. Despite this, the attraction basin around each GM is relatively large, since after all their atomic coordinates are randomly displaced by values as high as 2.0 bohrs, the perturbed structures, upon reoptimization, relax back to the GM in more than 50% of the cases (except for n=10 and 11). The relative stabilities derived from energy second differences suggest that n=8,10,13,15, and 20 are probably the magic numbers for these systems. Mass spectrum experiments would be very useful to clarify this issue. 相似文献
109.
Fernández-Varela R Suárez-Rodríguez D Gómez-Carracedo MP Andrade JM Fernández E Muniategui S Prada D 《Talanta》2005,68(1):116-125
The combination of attenuated total reflectance-fourier transform mid-infrared spectrometry (ATR-FTMIR) and multivariate pattern recognition is presented as a fast and convenient methodology to ascertain the source product an oil slick comes from and to evaluate the extent of its weathering. Different types of hydrocarbons (including crude oils, several heavy distillates and the Prestige's heavy fuel oil) were spilled on metallic containers designed ad hoc and their fate monitored by ATR-FTMIR. Not only environmental conditions were considered for weathering but artificial IR- and UV-irradiation. Pattern-recognition studies revealed that the different hydrocarbons clustered at different locations on the score plots and that the samples corresponding to each oil became ordered according to the extent of their weathering. Among them, fuel oil samples coming from the recent disaster of the Prestige tanker off the Galician shoreline showed a distinctive behaviour. Comparison of natural-, IR- and UV-weathering of a crude oil showed that IR solar radiation can be important in oil-weathering, in addition to broadly-reported UV degradation. 相似文献
110.
The principle of tandem on-line continuous separation techniques as an alternative means of introducing samples into plasmas was applied to the development of a sensitive, selective and convenient method for the determination of arsenic by inductively coupled plasma atomic emission spectrometry (ICP-AES). Arsenic is continuously extracted as AsI3 into xylene from the sample dissolved in 0.1 M potassium iodide solution in 7.2 M hydrochloric acid. The xylene phase (containing the analyte) is continuously mixed on-line with NaBH4 in dimethylformamide and acetic acid solutions. Arsine is thus continuously generated directly from the organic phase and is separated in a gas—liquid separation device which prevents most of the xylene phase vapour from reaching the ICP. The system was optimized for the continuous extraction of AsI3, the direct generation of arsine from xylene and the final ICP determination of arsenic. Finally, the tandem on-line continuous separation ICP detection system was applied to the determination of arsenic in real samples (white metal, cast iron, cupro-nickel and orchard leaves standard materials). Very good agreement between the experimental results and the certified values was obtained. 相似文献