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61.
62.
Previously, master equation (ME) simulations using semiclassical transition state theory (SCTST) and high-accuracy extrapolated ab initio thermochemistry (HEAT) predicted rate constants in excellent agreement with published experimental data over a wide range of pressure and temperatures ≳250 K, but the agreement was not as good at lower temperatures. Possible reasons for this reduced performance are investigated by (a) critically evaluating the published experimental data and by investigating; (b) three distinct ME treatments of angular momentum, including one that is exact at the zero- and infinite-pressure limits; (c) a hindered-rotor model for HOCO that implicitly includes the cis- and trans-conformers; (d) possible empirical adjustments of the thermochemistry; (e) possible empirical adjustments to an imaginary frequency controlling tunneling; (f) including or neglecting the prereaction complex PRC1; and (g) its possible bimolecular reactions. Improvements include better approximations to factors in SCTST and using the Hill and van Vleck treatment of angular momentum coupling. Evaluation of literature data does not reveal any specific shortcomings, but the stated uncertainties may be underestimated. All ME treatments give excellent fits to experimental data at T ≥ 250 K, but the discrepancy at T < 250 K persists. Note that each ME model requires individual empirical energy transfer parameters. Thermochemical adjustments were unable to match the experimental H/D kinetic isotope effects. Adjusting an imaginary frequency can achieve good fits, but the adjustments are unacceptably large. Whether PRC1 and its possible bimolecular reactions are included had little effect. We conclude that none of the adjustments is an improvement over the unadjusted theory. Note that only one set of experimental data exists in the regime of the discrepancy with theory, and data for DO + CO are scanty. 相似文献
63.
I. Azzouz J. Vial D. Thiébaut R. Haudebourg K. Danaie P. Sassiat J. Breviere 《Analytical and bioanalytical chemistry》2014,406(4):981-994
This review covers the recent development of stationary phases for chip-based gas chromatography (GC). Portable systems for rapid and reliable analysis are urgently needed. One way to achieve this is to miniaturize the entire analysis. Because the column is the central component of the GC system and determines the feasibility and quality of separation, this review focuses on stationary phases reported in the literature and their use in different fields during the last two decades, with emphasis on different methods for introducing the stationary phase into the GC column. 相似文献
64.
Mohanad A. Hussein Dr. Uyen P. N. Tran Dr. Vien T. Huynh Dr. Junming Ho Dr. Mohan Bhadbhade Prof. Dr. Herbert Mayr Dr. Thanh V. Nguyen 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(4):1471-1475
Tropylium bromide undergoes noncatalyzed, regioselective additions to a large variety of Michael acceptors. In this way, acrylic esters are converted into β-bromo-α-cycloheptatrienylpropionic esters. The reactions are interpreted as nucleophilic attack of bromide ions at the electron-deficient olefins and the approach of the tropylium ion to the incipient carbanion. Quantum chemical calculations were performed to elucidate the analogy to the amine- or phosphine-catalyzed Rauhut–Currier reactions. Subsequent synthetic transformations of the bromo-cycloheptatrienylated adducts are reported. 相似文献
65.
Bui Dac Dung Trinh Van Giap Tibor Kovacs Tran Ngoc Toan Le Dinh Cuong Tran Khanh Minh Nguyen Huu Quyet Nguyen Van Khanh 《Journal of Radioanalytical and Nuclear Chemistry》2014,299(3):1943-1948
Mineral sands are mined in several countries to supply to the titanium and zircon producing industries. Coastal black mineral sands usually contain, besides ilmenite (FeTiO3) and rutile (TiO2), radioactive minerals such as zircon (ZrSiO4) and monazite (RePO4). Radon and thoron activity concentration originated from natural radioactive contents of the black mineral sand was monitored at the extraction and processing for black minerals in the coastal areas of Ha Tinh Province, one of the around 40 coastal mineral sand deposits in Vietnam. The survey was carried out with the Raduet chambers made by Radosys Ltd—Hungary. The obtained results for 25 investigated points show that the measured values are not high in the residential houses and in case of the sand extraction site as well. At the titanium processing plant the measured values were higher than outside the facility (Radon: 18–55 Bq/m3 with average of 34 Bq/3 and Thoron 33–118 Bq/m3 with average of 58 Bq/m3) but still comparable to the average concentration of the world published by UNSCEAR. The typical outdoor levels of radon and thoron gas are each of the order of 10 Bq/m3. Although the radon concentrations were low in the zircon and titanium processing plants, the thoron concentrations in the houses for separating rutile and zircon were very high. At zircon processing factory, the thoron concentration could reach 2,931 Bq/m3 and the estimated annual effective dose would be 21.4 mSv/a. Intervention has to be taken in order to reduce the thoron level in this factory since the level of thoron and its progenies corresponding to an annual occupational effective dose is beyond the action level of 6 mSv/a. 相似文献
66.
Thanh Duc Mai Benjamin Bomastyk Hong Anh Duong Hung Viet Pham Peter C. Hauser 《Analytica chimica acta》2012
An extension of a capillary electrophoresis instrument coupled to a sequential injection analysis manifold was developed for automated measurements with on-line solid-phase extraction preconcentration. An in-house built capacitively coupled contactless conductivity detector was employed for sensitive detection with narrow capillaries of 25 μm internal diameter. The system was assembled into standardized 19 in. frames and racks for easy transport and mobile deployment. The system can be left running unattendedly without manual intervention with good operation stability. To demonstrate the application of the system, a method for the determination of four drugs, namely ibuprofen, diclofenac, naproxen and bezafibrate, was developed with enrichment factors of up to several hundreds. Detection of the drug residues down to the nM-scale was found possible and the method was found suitable for the detection of ibuprofen in the waste water of a hospital in Hanoi. 相似文献
67.
68.
Oncogenic MicroRNAs Biogenesis as a Drug Target: Structure–Activity Relationship Studies on New Aminoglycoside Conjugates 下载免费PDF全文
69.
E. Herrmann Nguyen Thi Thu Chau O. Navratil G. Ohms L. Beyer 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract The new 1,1-disubstituted 3-diphenoxy(thio)phosphoryl-(thio)ureas, R1R2NC(X)NHP(0Ph)2, HA, with X,Y = O,S, were synthesized by addition of secondary mines to the corresponding P-iso(thio)cyanates. This reaction is reversible if X,Y = S. (PhO)2P(Y)Cl reacts with H2NC(X)NR2 in the presence of an HCl acceptor only if X,Y a 0. Side reactions are observed. Phosphorylated derivatives of biuret were isolated from such a reaction mixture. 相似文献
70.