全文获取类型
收费全文 | 196篇 |
免费 | 6篇 |
国内免费 | 3篇 |
专业分类
化学 | 140篇 |
晶体学 | 1篇 |
力学 | 3篇 |
数学 | 22篇 |
物理学 | 39篇 |
出版年
2023年 | 2篇 |
2021年 | 2篇 |
2020年 | 4篇 |
2019年 | 2篇 |
2018年 | 6篇 |
2016年 | 5篇 |
2015年 | 2篇 |
2014年 | 2篇 |
2013年 | 7篇 |
2012年 | 8篇 |
2011年 | 5篇 |
2010年 | 6篇 |
2009年 | 3篇 |
2008年 | 10篇 |
2007年 | 7篇 |
2006年 | 7篇 |
2005年 | 13篇 |
2004年 | 15篇 |
2003年 | 14篇 |
2002年 | 13篇 |
2001年 | 2篇 |
2000年 | 4篇 |
1999年 | 2篇 |
1997年 | 1篇 |
1996年 | 2篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1992年 | 1篇 |
1985年 | 3篇 |
1984年 | 5篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 5篇 |
1979年 | 1篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 4篇 |
1975年 | 3篇 |
1974年 | 3篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1971年 | 2篇 |
1970年 | 2篇 |
1969年 | 3篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1935年 | 1篇 |
排序方式: 共有205条查询结果,搜索用时 15 毫秒
91.
A series of optically active silatrane derivatives, [Si{N(CHRCH(2)O)(CH(2)CH(2)O)(2)}X] (R = Me, i-Pr; X = Ph, OMe) has been synthesized by the reaction of optically active triethanolamine derivatives with XSi(OMe)(3), and characterized by (1)H NMR, (13)C NMR, (29)Si NMR, and mass spectroscopy, and the structures of six compounds have been determined by X-ray analysis. Molecular mechanics methods have also been employed to obtain the energy-minimized structures. The (29)Si NMR chemical shifts and the lengths of Si-N determined by X-ray analysis are sensitive to the bulkiness of the substituent (R). The Si-X bond lengths (X: trans position to nitrogen) do not appreciably differ from one another. The MM2 calculations indicated that the substituent exists in the equatorial position, and the results are in agreement with those of X-ray analysis and (1)H NMR spectroscopy. Crystallographic data: [R = H; X = OMe], C(7)H(15)NO(4)Si, orthorhombic, Pna2(1), a = 13.407(1) ?, b = 8.761(2) ?, c = 8.191(1) ?, Z = 4; [R = Me; X = OMe], C(8)H(17)NO(4)Si, orthorhombic, P2(1)2(1)2(1), a = 10.110(3) ?, b = 11.083(2) ?, c = 9.474(2) ?, Z = 4; [R = i-Pr; X = OMe], C(10)H(21)NO(4)Si, monoclinic, P2(1), a = 8.481(1) ?, b = 7.805(1) ?, c = 10.218(2) ?, beta = 111.31(1) degrees, Z = 2; [R = Me; X = Ph], C(13)H(19)NO(3)Si, orthorhombic, P2(1)2(1)2(1), a = 8.813(1) ?, b = 11.137(2) ?, c = 13.757(1) ?, Z = 4; [R = i-Pr; X = Ph], C(15)H(23)NO(3)Si, orthorhombic, P2(1)2(1)2(1), a = 8.365(1) ?, b = 13.538(2) ?, c = 13.841(2) ?, Z = 4. 相似文献
92.
Koshi Okazaki Shunji Nagase Hajime Baba Kazuo Kodaira 《Journal of fluorine chemistry》1974,4(4):387-397
The electrochemical fluorination of chlorine-containing ethers has been studied. In general, it was found that a chlorine bonded to an a-carbon atom in the ethers was readily removed during electrochemical reaction in anhydrous hydrogen fluoride, whilst a chlorine bonded to the β-carbon atom was retained to yield β-chlorinated polyfluoroethers.Through the use of this method, several new chloropolyfluoroethers, e.g. 2-chloro-1,1,2,2-tetrafluoroethyl difluoromethyl ether, 2,2-dichloro-1,1,2-trifluoroethyl trifluoromethyl ether 2,2-dichloro-1,1,2-trifluoroethyl difluoromethyl ether, 2,2-dichloro-1,1,2-trifluoroethyl chlorodifluoromethyl ether, 2-chloro-1,1,2,2-tetrafluoroethyl chlorodifluoromethyl ether and 2,2-trichloro-1,1-difluoroethyl trifluoromethyl ether, have isolated and characterized. 相似文献
93.
Yotaro Morishima Toru Kitani Takaomi Kobayashi Yasuhiro Saeki Shun-ichi Nozakura Takeshi Ohno Shunji Kato 《Photochemistry and photobiology》1985,42(5):457-464
Abstract— Anionic polyelectrolytes functionalized with the 5-deazaflavin group (dFl) were synthesized. The lifetime of the triplet excited dFl in the polyelectrolytes with a 2-mol% dFl content (AdFl-2) was about 10 times longer than that of a low molecular weight analog (AdFl-M). 2-Mercaptoethanol (RSH) reduced the triplet dFl with the rate constant of k red = 2.01 × 108 M −1 s−1 for AdFl-M and k red = 4.4 × 107 M −1 s−1 for AdFl-2. A zwitterionic viologen (SPV) oxidized the triplet dFl with the rate constant of k red = 3.69 × 109 M −1 s−1 for AdFl-M and k ox = 7.4 × 108 M−1 s−1 for AdFl-2. The smaller rate constants for the polymer system were discussed in terms of the hindering effect of the macromolecular microenvironment. The back electron transfer was shown to be drastically slowed in the AdFl-2-SPV system as a result of the intensive electrostatic effect of the polyelectrolytes. The buildup of the viologen radicals was studied under the steady-state illumination of the three component systems including viologen and RSH. The dFl group was demonstrated to serve as a very efficient photosensitizer in the oxidative cycle in case back electron transfer was retarded. This is the case of the AdFl-2-SPV system which gave the quantum yield of about 0.4 for the SPV− buildup. By comparison, the AdFl-2-MV2 + system resulted in a much slower buildup of MV +radicals. 相似文献
94.
Kota Omori Shunji Nagase Hajime Baba Kazuo Kodaira Takashi Abe 《Journal of fluorine chemistry》1977,9(4):279-291
The electrochemical fluorination of chlorine-containing alkylamines has been studied. It was found that, in general, the carbon-chlorine bond in the alkylamines is retained during electrochemical fluorination is anhydrous hydrogen fluoride, yielding chlorine-containing polyfluoroalkylamines. Perfluoroalkylamines and fluorocarbons were also produced.By the use of this method, several new chloropolyfluoroamines such as (CF3)2NCF2CClF2, (C2F5)2NCF2CClF2, (CF3)(C2F5)NCF2CClF2, (CClF2CF2)2NCF3, (CClF2CF2)2NC2F5, (C2F5)(CClF2CF2)NF, (CClF2CF2)2NF, (CF3)2NCF2CF2CClF2, CF2CClF2, and CF2CClF2 have been isolated and characterized. 相似文献
95.
Ito S Inabe H Morita N Ohta K Kitamura T Imafuku K 《Journal of the American Chemical Society》2003,125(6):1669-1680
A series of poly(6-azulenylethynyl)benzenes substituted with n-hexyloxycarbonyl chains at 1,3-positions in azulene rings, i.e., hexakis-, 1,2,4,5-tetrakis-, 1,3,5-tris-, and 1,4-bis(6-azulenylethynyl)benzene derivatives 1, 2, 3, and 4b, have been prepared by a simple one-pot reaction involving repeated Pd-catalyzed alkynylation of halogenated arenes with substituted 6-ethynylazulene and/or ethynylated arenes with substituted 6-bromoazulene under Sonogashira-Hagihara conditions. The redox behavior of these novel poly(6-azulenylethynyl)benzene derivatives was examined by cyclic voltammetry (CV), which revealed the presumed multielectron redox properties. Compound 4b exhibited a one-step, two-electron reduction wave upon CV, which revealed the formation of the dianion stabilized by two 6-azulenylethynyl substituents under electrochemical reduction conditions. Four 6-azulenylethynyl substituents on a benzene ring in a 1,2,4,5 relationship increased the electron-accepting properties because of the formation of a stabilized closed-shell dianionic structure, whereas 3 was reduced at more negative reduction potentials. In contrast to the multistep redox behavior of 2, compound 1 was reduced in one step at -1.28 V upon CV. Compound 1 showed a wide temperature range of columnar mesophases (Col(ho) and Col(ro)) from 77.3 degrees C to the decomposition temperature at ca. 270 degrees C. Compounds 2, 3, and 4b exhibited columnar mesomorphism (Col(ro)) with crystalline polymorphs for 2, unusual triple-melting behavior for 3, and both double-melting behavior and columnar mesomorphism (Col(ho)) for 4b. Therefore, the investigated systems exemplify a new principle for multielectron redox behavior with liquid crystalline properties. 相似文献
96.
Takashi Shibahara Noriko Kurimoto Shunji Kiyoda Yoshimasa Kobayashi Genta Sakane 《Journal of Cluster Science》2000,11(2):333-341
Oxygen/sulfur-bridged incomplete cubane-type molybdenum aqua clusters [Mo3(
3-S)(-X)(-S)2(H2O)9]4+ (X=O, S) in hydrochloric acid react with dien (diethylenetriamine) to give [Mo3(
3-S)(-X)(-S)2(dien–)(dien)2]Cl3·nH2O [1, X=O, n=3; 2, X=S, n=4; dien–=NH2(CH2)2NH(CH2)2NH–], respectively, where each cluster has a deprotonated dien. The X-ray structural analysis of 1 revealed proton dissociation from an amino group of one of the three dien ligands: one Mo–N distance [1.987(4) Å] is clearly shorter than the other eight Mo–N distances [2.229(3)–2.276(3) Å]. The 1H NMR spectra of the Mo–dien clusters 1 and 2 in D2O show two well-resolved methylene proton signals in the 2.8- to 3.0-ppm region, which indicates that both deprotonated amines in 1 and 2 receive D+ ions from solvent D2O. The factors for the proton dissociation are discussed. 相似文献
97.
A solid-phase extraction (SPE) method was optimized for accurate determination of polychlorinated dibenzo-p-dioxins (PCDDs), polychlorinated dibenzofurans (PCDFs), and coplanar polychlorinated biphenyls (CoPCBs) in humic acid containing surface water. Recovery experiments using humic materials revealed that humic acids permit dioxins to pass through an octadecylsilica (C18) extraction disk by associating with them under weakly alkaline conditions. Acidification of the sample before percolation improved this otherwise insufficient recovery. The analysis of surface water acidified to pH 2 gave better recovery with surrogate standards and lower quantitative values for higher-chlorinated homologues than the sample at pH 9. In all samples, the native octachlorodibenzo-p-dioxin (OCDD) peak abundance showed no difference between at pH 2 and at pH 9, indicating overestimation of the quantitative value of the homologue at pH 9. Acidification of a humic acid containing water sample can avoid overestimation of higher-chlorinated congeners caused by insufficient recovery of their corresponding surrogates. 相似文献
98.
It is assumed that a unit is either in operation or is in repair. When the main unit is under repair, spare units which cannot be repaired are used. In this system the following quantities are of interest: (i) The time distribution and the mean time to first-system failure, given that the n spare units are provided at time 0. (ii) The probability that the number of the failed spare units are equal to exactly n during the interval (0, t], and its expected number during the interval (0, t]. These quantities are derived by solving the renewal-type equations.Two optimization problems are discussed using the results obtained, viz.: (i) The expected cost of two systems, one with both a main unit and spare units and the other with only spare units is considered. (ii) A preventive maintenance policy of the main unit is considered in order to minimize the expected cost rate. Some policies of the two problems are discussed under suitable conditions. Numerical examples are also presented. 相似文献
99.
Microfabrication of FeMnPt films involving magnetic phase change due to structural transformation caused by ion irradiation 下载免费PDF全文
Correlations between crystal structures and magnetic properties of Fe1–xMnx Pt films were studied. The disordered films with x ≥ 0.44 had paramagnetic properties and the ordered films with x ≥ 0.46 had antiferromagnetic properties, viz. a difference of 0.02 in the x ‐value (i.e., 1.0 at%) was found. At x = 0.44 with the ordered structure, the uniaxial magnetocrystalline anisotropy was about 2.1 × 107 erg cm–3. A microfabrication process involving the slight composition difference of 0.02, which results in ferromagnetic–paramagnetic phase change due to the structural transformation caused by ion irradiation, was investigated. Only the area irradiated by Mn ions changed from ferromagnetic to paramagnetic phase. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim) 相似文献
100.
Rie Haruki Masanori Koshimizu Fumihiko Nishikido Ryo Masuda Yasuhiro Kobayashi Makoto Seto Yoshitaka Yoda Shunji Kishimoto 《Hyperfine Interactions》2016,237(1):71
The dynamics of iodine ions in potassium iodide (KI) and lithium iodide (LiI) aqueous solutions have been studied through 127I nuclear resonant quasi-elastic scattering (NRQES). A newly developed Si (12 2 2) double crystal monochromator for 127I 57.6 keV excitation is used. Broadening due to a diffusive motion is measured in the energy spectra of the NRQES from the solutions. 相似文献