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891.
892.
893.
Using two-colour visible (Vis)–ultraviolet (UV) photoionisation and pulsed field ionisation–photoelectron (PFI–PE) methods, we have obtained cleanly rotationally resolved photoelectron spectra for ZrO+(X 2Δ3/2,5/2; v+ = 0, 1, and 2). The rotation assignment of these state-to-state Vis–UV–PFI–PE spectra has allowed the unambiguous determination of the ground state term symmetry for ZrO+(X) to be 2Δ3/2, and the adiabatic ionisation energy of 90Zr16O, IE(90Zr16O) = 54,948.3(8) cm?1 [6.81272(10) eV]. The symmetry of the ionic ZrO+(X 2Δ3/2) ground state determined here disagrees with that reported in previous experiments. The rotational and vibrational constants determined in this experiment for the ionic 90Zr16O+(X 2Δ3/2) ground state are: Be+ = 0.4343(8) cm?1 and αe+ = 0.0019(5) cm?1, and ωe+ = 991.2(8) cm?1 and ωe+xe+ = 3.5(8) cm?1; and those for the ionic 90Zr16O+(X 2Δ5/2) excited spin-orbit state are: Be+ = 0.4357(6) cm?1 and αe+ = 0.0022(4) cm?1, and ωe+ = 991.9(8) cm?1 and ωe+xe+ = 3.6(8) cm?1, respectively. Based on the latter Be+ value, the equilibrium bond distances are determined to be re+ = 1.691(2) Å for 90Zr16O+(X 2Δ3/2) and re+ = 1.688(1) Å for 90Zr16O+(X 2Δ5/2). The IE(ZrO) along with the spectroscopic constants obtained here are valuable for benchmarking the ab initio quantum chemical calculations for energetic and structural predictions of ZrO/ZrO+. 相似文献
894.
Ping Yin Yucai Hu Chunhua Wang Yuan Tian Qinghua Tang Chongrong Bao 《Phosphorus, sulfur, and silicon and the related elements》2013,188(2):514-522
Theoretical studies on the thermodynamic and kinetic properties of the reactions of Ti+ with sulfur transfer reagent SCO via the C═S bond activation pathway have been carried on using DFT/B3LYP method, general statistical thermodynamics, and Eyring transition state theory with Wigner correction. The relevant reactions include reaction 1 4 Ti++1SCO → 4 IM 1 → 4 TS 1 → 4 IM 2 → 4 TiS++ 1 CO, and reaction 2 4Ti++1SCO →4IM1→ CP →2IM2→2TiS++1CO in which the spin multiplicity changes from the quartet state to the doublet state in the crossing region. It is concluded that the increase of the temperature is favored to the reaction 1 process, since the equilibrium constants (K) rises from 0.566 × 10[P]-9 at 200 K to 0.109 × 100 at 1200 K, and the reaction rate constant (k) from 0.222 × 100 s[P]-1 at 200 K to 0.540 × 10 11 s[P]-1 at 1200 K. Moreover, reaction 1 is endothermic, and non-spontaneous in the way the entropy increases, while reaction 2 is exothermic and spontaneous in the way their entropy decreases. The reaction path 2 is the energetically favorable channel, and its thermodynamic data change not largely with the rise of temperature. 相似文献
895.
Jin Luo Shu Li Qiongwen Kang Yi Sun 《Phosphorus, sulfur, and silicon and the related elements》2013,188(12):1180-1186
AbstractSixteen novel 3-methylthio-5-substituted benzamido-6-arylamino-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H)-one derivatives (4a–p) were successfully synthesized from iminophosphoranes, aryl isocyanate, and substituted benzoylhydrazine. The structures of the title compounds were elucidated by FT-IR, 1H NMR, 13C NMR, and HRMS. Herbicidal activity of the compounds 4a–p against Brassica napus (rape), Echinochloa crusgalli (barnyard grass), Cucumis sativus (cucumber), and Triticum aestivum (wheat) were determined. The results showed that 5-(2-chlorobenzamido)-6-phenylamino-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H)-one (4c) displayed remarkable inhibition activity against the stalk and root of rape with 100% inhibition rate at the dosages of 10?mg/L and 100?mg/L, and 5-(4-nitrobenzamido)-6-phenylamino-3-methylthio-1-phenyl-1H-pyrazolo[3,4-d]pyrimidin-4 (5H) -one (4d) exhibited excellent activity against the stalk and root of barnyard grass with 100% inhibition rate at the same dosages. 相似文献
896.
Jiang-Sheng Han Yin-Lin Shao Xiao-Hong Zhang Ping Zhong 《Phosphorus, sulfur, and silicon and the related elements》2013,188(11):1599-1610
Abstract An efficient and green aqueous protocol to access 3-chalcogen benzo[b]furan derivatives has been developed. The reaction can proceed via I2-mediated intramolecular annulation reaction of 2-alkynylanisoles with diaryl disulfides (diselenides) in water or under solvent-free conditions at room temperature. With the participation of I2, a variety of 3-chalcogen benzo[b]furan derivatives were obtained in good to excellent yields. This reaction was considered to work via an iodocyclization cascade mechanism and the intermediate 3-iodo-2-phenylbenzofuran was detected by GC-MS. 相似文献
897.
The analysis on the recovery performance and characteristics in shape memory effects is helpful for the optimal design and engineering applications of shape memory polymers and their composites. To investigate the relationships among recovery performance, material parameters, and loading conditions, by taking aliphatic polyether urethane as an example, the researchers simulate the shape memory behaviors numerically using a three‐dimensional viscoelastic model. The material parameters for this model are taken from stress relaxation tests, rather than dynamic mechanical analysis tests. Both the unconstrained and the constrained recovery behaviors during strain‐controlled shape memory processes are analyzed. The results reveal that the unconstrained recovery occurs at the same temperature regardless of the applied strain values. Another interesting result is that the shape recovery temperature in unconstrained recovery situations increases and the maximum recovery stress under constrained recovery conditions decreases with the increase of heating rates. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
898.
Yunzhi Ling Yuqiong Luo Jiwen Luo Xiaoying Wang Runcang Sun 《高分子科学杂志,A辑:纯化学与应用化学》2013,50(12):1194-1200
The optimal conditions for synthesizing quaternized chitosan (QCS) via microwave irradiation were explored. The microwave temperature, time, power, mole ratio between chitosan and 2,3-epoxypropyltrimethyl ammonium chloride (ETA), volume ratio between isopropanol and water, and pH value of the reaction system were studied to evaluate the effect on the degree of substitution (DS). The structure of QCS was characterized by means of FT-IR, NMR, XPS and XRD. TGA and DTG were used to measure its thermal stability. At last, QCS acted as a reducing and stabilizing agent to greenly synthesize gold nanoparticles without adding any other chemical reagent. 相似文献
899.
Poly(L‐lactic acid‐co‐glycolic acid) (PLGA) was prepared from hydroxy‐acids with melt polymerization. In this way, the copoly(L‐LA/GA) (PLGA) was synthesized directly using a binary catalyst (tin chloride dihydrate/p‐toluenesulfonic acid). The thermal properties of PLGA were studied by differential scanning calorimetry (DSC) and nuclear magnetic resonance (NMR). The results show that the melting point of PLGA decreases with increasing mole fraction of GA units in the copolymer. In addition, the melting point of polymer also decreases with increasing degree of racemization of the polymer. 相似文献
900.
For the first time, N-(2-hydroxyl) propyl-3-trimethyl ammonium chitosan chloride (HTCC) was prepared through a fast, easy and efficient method with the assistance of microwave irradiation, and the quaternized chitosan was also degraded via the microwave irradiation. A comparative study was performed by using the conventional heating method to prepare HTCC. The structure and property of the quaternized chitosan obtained by these two methods were characterized by GPC, XRD, FTIR, NMR, TG and elemental analysis. It was shown that quaternized chitosan was successfully prepared within 50 min via microwave irradiation method, while a much longer time of 6–7 h was needed with the conventional heating method. The substitutions both occurred on the C2 position of chitosan with the two different methods, and their HTCC products had weight average similar molecular weight (Mw), structure and thermal stability. The HTCC prepared by the microwave irradiation method had a little lower degree of substitution (DS) than those prepared via conventional heating with the same mole ratio (6:1) of the intermediate to chitosan. The degradation study showed that the Mw of HTCC decreased rapidly from 4.6 × 105 to 1.1 × 105 in 1 h under microwave irradiation, while it only decreased from 4.6 × 105 to 2.1 × 105in 1 h through conventional heating degradation. These results revealed that microwave irradiation is a more efficient and environment-friendly way to obtain the water-soluble chitosan derivatives and their degraded products. 相似文献