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11.
Mojumdar SC Becker DA DiLabio GA Ley JJ Barclay LR Ingold KU 《The Journal of organic chemistry》2004,69(9):2929-2936
The rate constants, k(inh), for reaction of stilbazulenyl-bis-nitrone (STAZN, 1) with peroxyl radicals and the number of radicals trapped, n, are compared with those of phenolic antioxidants 2,2,5,7,8-pentamethyl-6-hydroxychroman (PMHC, 4a), 2,5,7,8-tetramethyl-6-hydroxychroman-2-carboxylic acid (Trolox, 4b), and 2,6-di-tert-butyl-4-methoxyphenol (DBHA, 5). The behavior of STAZN depended markedly on the media and type of initiator used, water-soluble or lipid-soluble. In styrene/chlorobenzene and initiation by azo-bis(isobutyronitrile) (AIBN), k(inh) (STAZN) = 0.64 k(inh) (5) = 0.02k(inh) (4a). On addition of methanol, the k(inh) of STAZN increased 6-fold to be four times that of 5 while that of 4a decreased 6-fold. In aqueous SDS-micelles containing methyl linoleate and initiation with water-soluble azo-bis(amidinopropane)2HCl, ABAP, the relative k(inh) values were 1 >or= 4b > 5. In dilinoleoylphosphatidyl choline (DLPC) bilayers and initiation with lipid-soluble azo-bis-2,4(dimethylvaleronitrile) (DMVN), the k(inh) order was 5 > 4b > 1. During initiation with ABAP in micelles and bilayers, the calculated values of k(inh) for STAZN changed during the induction period. The experimental results are interpreted in terms of the conformation of STAZN, which is transoid in homogeneous solution but cisoid in aqueous dispersions of lipids. In such dispersions, the STAZN lies at the lipid-water interface where it traps water-soluble peroxyl radicals by a single electron-transfer mechanism. The cisoid conformation at lipid-water interfaces is supported by theoretical calculations. 相似文献
12.
In solution, the self-exchange reactions for oxygen-centered pi-radicals, e.g., PhO. + PhOH <==>PhOH + PhO., are known to occur with low activation enthalpies (E(a) approximately equal to 2 kcal/mol). For the PhO./PhOH couple and, we conclude, for other O-centered pi-radicals, exchange occurs by proton-coupled electron transfer (PCET) with the proton transferred between oxygen electron pairs while the electron migrates between oxygen orbitals orthogonal to the -O- - -H- - -O- transition state plane (Mayer et al. J. Am. Chem. Soc. 2002, 123, 11142). Iminoxyls, R(2)C=NO., are sigma-radicals with substantial spin density on the nitrogen. The R(2)C=NO./R(2)C=NOH self-exchange has a significant E(a) (Mendenhall et al. J. Am. Chem. Soc. 1973, 95, 627). For this exchange, DFT calculations have revealed a counterintuitive cisoid transition state in which the seven atoms, >C=NO- - -H- - -ON=C<, lie in a plane (R = H, Me) or, for steric reasons, two planes twisted at 45.2 degrees (R = Me(3)C). The planar transition state has the two N-O dipoles close to each other and pointing in the same direction and an O- - -H- - -O angle of 165.4 degrees . A transoid transition state for R = H lies 3.4 kcal/mol higher in energy than the cisoid despite a more favorable arrangement of the dipoles and a near linear O- - -H- - -O. It is concluded that iminoxyl/oxime self-exchange reactions occur by a five-center, cyclic PCET mechanism with the proton being transferred between electron pairs on the oxygens and the electron migrating between in-plane orbitals on the two nitrogens (R(N-N) = 2.65 A). The calculated E(a) values (8.8-9.9 kcal/mol) are in satisfactory agreement with the limited experimental data. 相似文献
13.
Mulder P Korth HG Pratt DA DiLabio GA Valgimigli L Pedulli GF Ingold KU 《The journal of physical chemistry. A》2005,109(11):2647-2655
The gas-phase O-H bond dissociation enthalpy, BDE, in phenol provides an essential benchmark for calibrating the O-H BDEs of other phenols, data which aids our understanding of the reactivities of phenols, such as their relevant antioxidant activities. In a recent review, the O-H BDE for phenol was presented as 90 +/- 3 kcal mol(-1) (Acc. Chem. Res. 2003, 36, 255-263). Due to the large margin of error, such a parameter cannot be used for dynamic interpretations nor can it be used as an anchor point in the development of more advanced computational models. We have reevaluated the existing experimental gas-phase data (thermolyses and ion chemistry). The large errors and variations in thermodynamic parameters associated with the gas-phase ion chemistry methods produce inconsistent results, but the thermolytic data has afforded a value of 87.0 +/- 0.5 kcal mol(-1). Next, the effect of solvent has been carefully scrutinized in four liquid-phase methods for measuring the O-H BDE in phenol: photoacoustic calorimetry, one-electron potential measurements, an electrochemical cycle, and radical equilibrium electron paramagnetic resonance (REqEPR). The enthalpic effect due to solvation, by, e.g., water, could be rigorously accounted for by means of an empirical model and the difference in hydrogen bond interactions of the solvent with phenol and the phenoxyl radical. For the REqEPR method, a second correction is required since the calibration standard, the O-H BDE in 2,4,6-tri-tert-butylphenol, had to be revised. From the gas-phase thermolysis data and three liquid-phase techniques (excluding the electrochemical cycle method), the present analysis yields a gas-phase BDE of 86.7 +/- 0.7 kcal mol(-1). The O-H BDE was also estimated by state-of-the-art computational approaches (G3, CBS-APNO, and CBS-QB3) providing a range from 86.4 to 87.7 kcal mol(-1). We therefore recommend that in the future, and until further refinement is possible, the gas-phase O-H BDE in phenol should be presented as 86.7 +/- 0.7 kcal mol(-1). 相似文献
14.
15.
铜取代Dawson结构杂多钨磷酸电荷转移配合物的合成与性质研究 总被引:3,自引:1,他引:3
Two new charge-transfer complexes, (DMAH)10[CuP2W17O62]·DMF·2H2O and (DMAH)14[Cu2P2W16O62] have been prepared in aqueous solution from N,N′-dimethylaniline(DMA) and copper substituted polyoxotungstates with Dawson Structure, and characterized by elemental analysis, ICP, TG, IR, diffusion reflectance electronic spectra, polarography, and CV. The results indicate that the structure of anion has little change after the charge-transfer complexes are formed, but the characteristic vibrational bands have some red shift or blue shift. The charge transfer takes place under sunlight. There is a new absorption band at 625 nm in the solid reflectance electronic spectra of the complexes, it is ascribed to the IVCT (W(V)→W(Ⅵ) band of the reduced anion [CuP2W17O62]10-. The conductivities at room temperature of title complexes are 3.6×10-9 S·cm-1 and 5.4×10-9 S·cm-1, respectively. Both of them are weak semiconductors. 相似文献
16.
提供了一种合成噻吩基和呋喃基四硫富有瓦烯(TTF)的方法,并用其合成了3种未见文献报道的噻吩基TTF(Ⅶa,Ⅷb,Ⅶc)和2种呋喃基TTF(Ⅶd1,Ⅶd2)研究这些化合物的循环伏安行为及有关电化学性质,制得了一种Ⅶb与TCNQ反应生成的电荷转移络合物,讨论了噻吩基TTF和呋喃基TTF在产物构型和电化学性质方面的差别。 相似文献
17.
近期在湖北绿松石市场上出现一种带有肉眼可见的灰黑色异形杂质的绿松石,于此种绿松石的研究甚少.故选取来自湖北省十堰的一块该种绿松石原石,蓝色绿松石基底上布满形态各异、大小不一的灰黑色杂质,放大观察可见灰黑色杂质矿物呈金属光泽.对灰黑色杂质采用激光剥蚀电感耦合等离子体质谱仪进行原位微区微量元素测试、背散射电子图像物相观察、... 相似文献
18.
A lactone ring confers unusual stability to a diphenylmethyl-like radical that is virtually unreactive toward oxygen. Thus, the radical derived from HP-136 is about 10,000 times less reactive than typical carbon-centered radicals. A reversible reaction with oxygen is proposed by analogy with triphenylmethyl; however, the association constant is about 1000 times smaller for HP-136 than for triphenylmethyl. While the lactone ring greatly influences the reactivity, the spectroscopy of the HP-136-derived radical is in line with that expected for a substituted diphenylmethyl radical. 相似文献
19.
Bimolecular rate constants for proton transfer from six phenols to the anthracene radical anion have been determined in up to eight solvents using electrochemical techniques. Effects of hydrogen bonding on measured rate constants were explored over as wide a range of phenolic hydrogen-bond donor (HBD) and solvent hydrogen-bond acceptor (HBA) activities as practical. The phenols' values ranged from 0.261 (2-MeO-phenol) to 0.728 (3,5-Cl(2)-phenol), and the solvents' values from 0.44 (MeCN) to 1.00 (HMPA), where and are Abraham's parameters describing relative HBD and HBA activities (J. Chem. Soc., Perkin Trans. 2 1989, 699; 1990, 521). Rate constants for H-atom transfer (HAT) in HBA solvents, k(S), are extremely well correlated via log k(S) = log k(0) - 8.3 , where k(0) is the rate constant in a non-HBA solvent (Snelgrove et al. J. Am. Chem. Soc. 2001, 123, 469). The same equation describes the general features of proton transfers (k(S) decreases as increases, slopes of plots of log k(S) against increase as increases). However, in some solvents, k(S) values deviate systematically from the least-squares log k(S) versus correlation line (e.g., in THF and MeCN, k(S) is always smaller and larger, respectively, than "expected"). These deviations are attributed to variations in the solvents' anion solvating abilities (THF and MeCN are poor and good anion solvators, respectively). Values of log k(S) for proton transfer, but not for HAT, give better correlations with Taft et al.'s (J. Org. Chem. 1983, 48, 2877) beta scale of solvent HBA activities than with . The beta scale, therefore, does not solely reflect solvents' HBA activities but also contains contributions from anion solvation. 相似文献
20.
Thermal decomposition of tetra(piperidinium) octamolybdate tetrahydrate, [C5H10NH2]4[Mo8O26]·4H2O, was investigated in air by means of TG‐DTG/DTA, DSC, TG‐IR and SEM. TG‐DTG/DTA curves showed that the decomposition proceeded through three well‐defined steps with DTA peaks closely corresponding to mass loss obtained. Kinetics analysis of its dehydration step was performed under non‐isothermal conditions. The dehydration activation energy was calculated through Friedman and Flynn‐Wall‐Ozawa (FWO) methods, and the best‐fit dehydration kinetic model function was estimated through the multiple linear regression method. The activation energy for the dehydration step of [C5H10NH2]4[Mo8O26]·4H2O was 139.7 kJ/mol. The solid particles became smaller accompanied by the thermal decomposition of the title compound. 相似文献