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21.
The thermal decomposition rate of N2O5 in 760 Torr of air as a function of temperature between 314 and 348 K has been investigated using the technique of pulsed laser cavity ring-down spectroscopy (CRDS) detection of NO3 radicals at 662 nm. The Arrhenius expression of the thermal decomposition rates determined by the CRDS experiments, which is incorporated with literature values down to 263 K, is given by 1.36 × 1015 exp{(−11300 ± 200)/T} s−1 over the temperature range 263–348 K. © 2008 Wiley Periodicals, Inc. Int J Chem Kinet 40: 679–684, 2008 相似文献
22.
This Letter reports on the application of the vacuum ultraviolet laser-induced fluorescence detection of Br(2P1/2) atoms at 157.48 nm to the kinetic study of collisional removal of Br(2P1/2) by small molecules at 295 K. Gas mixtures of a small amount of CH3Br and an excess amount of collision partners are exposed to pulsed laser irradiation at 193 nm. Temporal decay profile of the Br* LIF intensity has been monitored to determine the collisional removal rate coefficients. The collision partners are H2, CO2, CF4, CF2H2, H2O, CH3OH, and SF5CF3, and the results are compared to literature data. 相似文献
23.
Solvation properties of aliphatic alcohol–water and fluorinated alcohol–water solutions were probed by amide molecules as
solutes using infrared (IR) and 1H and 13C NMR techniques. These include four alcohols: ethanol (EtOH), 2-propanol (2-PrOH), 2,2,2-trifluoroethanol (TFE), and 1,1,1,3,3,3-hexafluoro-2-propanol
(HFIP) and three amides: N-methylformamide (NMF), N-methylacetamide (NMA) and N-methylpropionamide (NMP). The hydrogen bonds of the amide carbonyl oxygen with water are gradually weakened as the alcohol
content increases. This decreases in the order of HFIP > TFE ≈ 2-PrOH > EtOH. In TFE– and HFIP–water solutions, the hydrogen
bond between the amide amino hydrogen and water is also gradually broken with increasing x
A. This trend is more notable in the order of NMP > NMA > NMF. The hydrophobic moieties of the amide methyl and ethyl groups
are solvated by the fluoroalkyl groups of fluorinated alcohols due to the hydrophobic interaction among them. Thus, the steric
hindrance generated by the solvated alkyl group of amides promotes the breaking of the hydrogen bonds between amide and water. 相似文献
24.
Takamuku T Shimomura T Tachikawa M Kanzaki R 《Physical chemistry chemical physics : PCCP》2011,13(23):11222-11232
We found that addition of N,N-dimethylformamide (DMF) induces phase separation of 1,1,1,3,3,3-hexafluoro-2-propanol (HFIP)-water mixtures. The phase diagram of a DMF-HFIP-water ternary system at 298 K showed that phase separation occurs in a closed-loop area in the water-rich mole fraction range of x(H(2)O) > ~0.4. To clarify the mechanism of DMF-induced phase separation of DMF-HFIP-water mixtures at the molecular level, small-angle neutron scattering (SANS) and (1)H and (13)C NMR measurements were conducted on the mixtures with varying DMF concentrations along a volume ratio of HFIP to water of 1?:?1 (x(S)(HFIP) = 0.147). Additionally, the solvation structure of DMF in water and HFIP-water mixtures was elucidated by molecular dynamics (MD) simulations. The SANS results revealed that the inherent heterogeneity of HFIP-water mixtures is increased with increasing DMF concentration toward the lower phase separation concentration, but decreased when the DMF concentration further increased beyond the upper phase separation one. (1)H and (13)C NMR measurements and MD simulations suggested that preferential solvation of the hydrophobic moiety of DMF by HFIP is the main driver of the phase behaviour of the DMF-HFIP-water system. 相似文献
25.
Ivaylo Dimitrov Shogo Takamuku Katja Jankova Patric Jannasch Sren Hvilsted 《Macromolecular rapid communications》2012,33(16):1368-1374
A multi‐step synthetic strategy to polysulfone (PSU) grafted with phosphonated poly(pentafluorostyrene) (PFS) is developed. It involves controlled radical polymerization resulting in alkyne‐end functional PFS. The next step is the modification of PSU with a number of azide side groups. The grafting of PFS onto PSU backbone is performed via the “click”‐chemistry approach. In a final step, the PFS‐grafts are subjected to the post phosphonation. The copolymers are evaluated as membranes for potential fuel cell applications through thermal analyses, water uptake, and conductivity measurements. The proposed synthetic route opens the possibility to tune copolymers’ hydrophilic–hydrophobic balance to obtain membranes with an optimal balance between proton conductivity and mechanical properties. 相似文献
26.
Takamuku T Wada H Kawatoko C Shimomura T Kanzaki R Takeuchi M 《Physical chemistry chemical physics : PCCP》2012,14(23):8335-8347
Amide-induced phase separation of hexafluoro-2-propanol (HFIP)-water mixtures has been investigated to elucidate solvation properties of the mixtures by means of small-angle neutron scattering (SANS), (1)H and (13)C NMR, and molecular dynamics (MD) simulation. The amides included N-methylformamide (NMF), N-methylacetamide (NMA), and N-methylpropionamide (NMP). The phase diagrams of amide-HFIP-water ternary systems at 298 K showed that phase separation occurs in a closed-loop area of compositions as well as an N,N-dimethylformamide (DMF) system previously reported. The phase separation area becomes wider as the hydrophobicity of amides increases in the order of NMF < NMA < DMF < NMP. Thus, the evolution of HFIP clusters around amides due to the hydrophobic interaction gives rise to phase separation of the mixtures. In contrast, the disruption of HFIP clusters causes the recovery of the homogeneity of the ternary systems. The present results showed that HFIP clusters are evolved with increasing amide content to the lower phase separation concentration in the same mechanism among the four amide systems. However, the disruption of HFIP clusters in the NMP and DMF systems with further increasing amide content to the upper phase separation concentration occurs in a different way from those in the NMF and NMA systems. 相似文献
27.
Theoretical Study on the Relationship between Diradical Character and Second Hyperpolarizabilities of Four‐Membered‐Ring Diradicals Involving Heavy Main‐Group Elements
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Hiroshi Matsui Kotaro Fukuda Shota Takamuku Prof. Dr. Akira Sekiguchi Prof. Dr. Masayoshi Nakano 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(5):2157-2164
By using spin‐unrestricted density functional theory methods, the relationship between the diradical character y and the second hyperpolarizability γ (the third‐order nonlinear optical (NLO) properties at the molecular scale) for four‐membered‐ring diradical compounds, that is, cyclobutane‐1,3‐diyl, Niecke‐type diradicals, and Bertrand‐type diradicals, were investigated by focusing on the substitution effects of heavy main‐group elements as well as of donor/acceptor groups on the y and γ values. It has been found that i) γ is enhanced in the intermediate y region for these four‐membered‐ring diradicals, ii) Niecke‐type diradicals with intermediate y values, which are realized by tuning the combination of the main‐group elements involved, exhibit larger γ values than Bertrand‐type diradicals, and iii) the y value and thus γ value can be controlled by modifying the both‐end donor/acceptor substituents attached to carbon atoms in Nicke‐type C2P2 diradicals. These results demonstrate that four‐membered‐ring diradicals involving heavy main‐group elements exhibit high controllability of the y and γ, which indicates the potential applications of four‐membered‐ring diradicals as a building block of highly efficient open‐shell NLO materials. 相似文献
28.
29.
Mikihiko Saito Tamano Ushijima Kazumi Sasamoto Kenshi Yakata Yosuke Ohkura Keiyu Ueno 《Analytica chimica acta》1995,300(1-3):243-251
The new acid hydrazides, 2-(5-hydrazinocarbonyl-2-thienyl)-5,6-methylenedioxybenzofuran (TMBH) and 2-(5-hydrazin-ocarbonyl-2-furyl)-5, 6-methylenedioxybenzofuran (FMBH), were synthesized as precolumn fluorescence derivatisation reagents for carboxylic acids in liquid chromatography. These compounds readily react with carboxylic acids in the presence of a coupling reagent under mild conditions in aqueous solution to give fluorescent derivatives. The detection limits of lauric acid were both 0.1 pmol per 10 μl injection volume at a signal-to-noise ratio of 3. The methods in which these compounds are used were applied to the assay of a standard mixture of prostaglandins (25 μM) and prostaglandins in a human seminal fluid. 相似文献
30.
Takamuku T Kumai T Yoshida K Otomo T Yamaguchi T 《The journal of physical chemistry. A》2005,109(34):7667-7676
To clarify the structure of solvent clusters formed in halogenoethanol-water mixtures at the molecular level, large-angle X-ray scattering (LAXS) measurements have been made at 298 K on 2,2,2-trifluoroethanol (TFE), 2,2,2-trichloroethanol (TCE), and their aqueous mixtures in the TFE and TCE mole fraction ranges of 0.002 < or = x(TFE) < or = 0.9 and 0.5 < or = x(TCE) < or = 0.9, respectively. The radial distribution functions (RDFs) for TFE-water mixtures have shown that the structural transition from inherent TFE structure to the tetrahedral-like structure of water takes place at x(TFE) approximately 0.2. In the TCE-water mixtures inherent TCE structure remains in the range of 0.5 < or = x(TCE) < or = 1. Small-angle neutron scattering (SANS) experiments have been performed on CF(3)CH(2)OD- (TFE-d(1)-) D(2)O and CF(3)CD(2)OH- (TFE-d(2)-) H(2)O mixtures in the TFE mole fraction range of 0.05 < or = x(TFE) < or = 0.8. The SANS results in terms of the Ornstein-Zernike correlation length have revealed that TFE and water molecules are most heterogeneously mixed with each other in the TFE-water mixture at x(TFE) approximately 0.15, i.e., both TFE clusters and water clusters are most enhanced in the mixture. To evaluate the dynamics of TFE and ethanol (EtOH) molecules in TFE-water and ethanol-water mixtures, respectively, (1)H NMR relaxation rates for the methylene group within alcohol molecules have been measured by using an inversion-recovery method. The alcohol concentration dependence of the relaxation rates for the TFE-water and ethanol-water mixtures has shown a break point at x(TFE) approximately 0.15 and x(EtOH) approximately 0.2, respectively, where the structural transition from alcohol clusters to the tetrahedral-like structure of water takes place. On the basis of the present results, the most likely structure models of solvent clusters predominantly formed in TFE-water and TCE-water mixtures are proposed. In addition, effects of halogenation of the hydrophobic groups on clustering of alcohol molecules are discussed from the present results, together with the previous ones for ethanol-water and 1,1,1,3,3,3-hexafluoro-2-propanol- (HFIP-) water mixtures. 相似文献