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31.
Liquid and solid cyclic peroxides derived from aliphatic ketones are explosive materials so their enthalpies of vaporization
and other thermodynamic or condensed-phase properties cannot be measured directly. In this work the enthalpies of vaporization
of peroxides at 298.15 K were estimated simply from gas chromatographic retention times measured at different temperatures.
The technique correlates changes in the retention times of compounds whose enthalpies of vaporization are known (called the
reference series), with those of the compounds of interest. If t
R′ is the adjusted retention time (retention time of each compound minus the retention time of unretained diethyl ether, used
as solvent) a plot of ln t
R′ against 1/T for each compound (reference compounds and cyclic peroxides) results in a straight line (r
2 > 0.99 for all compounds). The enthalpy of transfer from solution to the vapor state (Δsolg
H
m) can be obtained by multiplying the slope by the gas constant (R). A second plot correlates the enthalpies of transfer from
solution to the vapor state (Δsolg
H
m), as measured by gas–liquid chromatography (GLC), with enthalpies of vaporization of reference materials (Δvap
H
m at 298.15 K) available in the literature. C9–C15 fatty acid methyl esters and hydrocarbons were used as reference compounds. The enthalpies of vaporization of the cyclic
organic peroxides were calculated from the equation of the line obtained in this second correlation, the slope of which was
Δvap
H
m (at 298.15 K)/Δg
sol
H
m. The experiments were performed under isothermal conditions with a DB-5 capillary column, flame-ionization detection (FID),
and nitrogen as carrier gas. The column temperature was varied over a range of at least 30–70 K between 403 and 473 K, with
chromatograms being acquired at 10 K intervals. Enthalpies of vaporization of cyclic organic peroxides are not available in
the literature, and the values given in this paper, obtained by gas chromatography, are the first to be reported. 相似文献
32.
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A general, practical and efficient one-pot synthesis of cyclic enecarbamates is described. The protocol proceeds via reduction of lactam carbamate with Super-Hydride®, followed by in situ dehydration with trifluoroacetic anhydride (TFAA) and diisopropylethylamine (DIPEA). 相似文献
34.
Raul Aguayo Felipe Arias Alvaro Cañete Carolina Zuñiga Enrique A. Castro Paulina Pavez José G. Santos 《国际化学动力学杂志》2013,45(3):202-211
The reactions of the title compounds with phenoxides, secondary alicyclic (SA) amines, and pyridines, in 44 wt% ethanol–water, at 25°C and an ionic strength of 0.2 M, were subjected to kinetic and product studies. From analytical techniques (HPLC and NMR), two pathways were detected (nucleophilic attack at the phosphoryl center and at the C‐1 aromatic carbon) for the reactions of all the nucleophiles with the phosphate ( 2 ) and for the pyridinolysis of the thionophosphate ( 1 ). Only aromatic nucleophilic substitution was found for the reactions of 1 with phenoxides and SA amines. For the dual reactions, the nucleophilic rate constants (kN) were separated in two terms: $k_{\rm N}^{\rm P}$ and $k_{\rm N}^{{\rm Ar}}$, which are the rate constants for the corresponding electrophilic centers. The absence of a break in the Brønsted‐type plots for the attack at P is consistent with concerted mechanisms. The Brønsted slopes, βAr 0.32–0.71, for the attack at the aromatic C‐1, are in agreement with stepwise mechanisms where formation of a Meisenheimer complex is the rate‐determining step. © 2013 Wiley Periodicals, Inc. Int J Chem Kinet 45: 202–211, 2013 相似文献
35.
36.
Matilda Vojnović Ana J. Šetrajčić-Tomić Siniša M. Vučenović Jovan P. Šetrajčić 《Optical and Quantum Electronics》2018,50(4):198
Recent research in nano-optical engineering and in nanomedicine as well, seeks for methods of construction of various types of nano-markers, nano-carriers, and ways to deliver drugs to the exactly determined regions of body. In this process it is important to find methods of recognition of certain types of molecules. It is obvious that optical recognition would be the easiest and the most effective way to do it. Our research presents a model of a molecular ultrathin crystalline film and generated exciton system inside it and corresponding methodology of analysis of their optical characteristics. Properties of these spatially very restricted structures are very sensitive to their surrounding surfaces. Using the two-time Green’s functions adapted for crystalline structures with symmetry breaking, and graphical-numerical software, we have calculated the energy spectra and possible exciton states. We have shown that the appearance and the presence of localized states on the surfaces and in the boundary layers of the film depend on the thickness of the film and the film surroundings, presented through the perturbation of parameters on surfaces. Optical properties in these structures demonstrate discrete and very selective resonant absorption spectra, depending on the perturbation on their surfaces. 相似文献
37.
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39.
Andreea L. Turcu Antoine Versini Nadjib Khene Christine Gaillet Dr. Tatiana Cañeque Dr. Sebastian Müller Dr. Raphaël Rodriguez 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(33):7369-7373
Cancer stem cells (CSC) constitute a cell subpopulation in solid tumors that is responsible for resistance to conventional chemotherapy, metastasis and cancer relapse. The natural product Salinomycin can selectively target this cell niche by directly interacting with lysosomal iron, taking advantage of upregulated iron homeostasis in CSC. Here, inhibitors of the divalent metal transporter 1 (DMT1) have been identified that selectively target CSC by blocking lysosomal iron translocation. This leads to lysosomal iron accumulation, production of reactive oxygen species and cell death with features of ferroptosis. DMT1 inhibitors selectively target CSC in primary cancer cells and circulating tumor cells, demonstrating the physiological relevance of this strategy. Taken together, this opens up opportunities to tackle unmet needs in anti-cancer therapy. 相似文献
40.
Truemper configurations (thetas, pyramids, prisms, and wheels) have played an important role in the study of complex hereditary graph classes (eg, the class of perfect graphs and the class of even-hole-free graphs), appearing both as excluded configurations, and as configurations around which graphs can be decomposed. In this paper, we study the structure of graphs that contain (as induced subgraphs) no Truemper configurations other than (possibly) universal wheels and twin wheels. We also study several subclasses of this class. We use our structural results to analyze the complexity of the recognition, maximum weight clique, maximum weight stable set, and optimal vertex coloring problems for these classes. Furthermore, we obtain polynomial -bounding functions for these classes. 相似文献