全文获取类型
收费全文 | 1695篇 |
免费 | 90篇 |
国内免费 | 12篇 |
专业分类
化学 | 1366篇 |
晶体学 | 14篇 |
力学 | 18篇 |
数学 | 86篇 |
物理学 | 313篇 |
出版年
2023年 | 12篇 |
2022年 | 15篇 |
2021年 | 16篇 |
2020年 | 22篇 |
2019年 | 30篇 |
2018年 | 21篇 |
2017年 | 12篇 |
2016年 | 56篇 |
2015年 | 37篇 |
2014年 | 63篇 |
2013年 | 90篇 |
2012年 | 119篇 |
2011年 | 122篇 |
2010年 | 41篇 |
2009年 | 64篇 |
2008年 | 120篇 |
2007年 | 110篇 |
2006年 | 131篇 |
2005年 | 121篇 |
2004年 | 88篇 |
2003年 | 79篇 |
2002年 | 72篇 |
2001年 | 26篇 |
2000年 | 20篇 |
1999年 | 14篇 |
1998年 | 10篇 |
1997年 | 21篇 |
1996年 | 16篇 |
1995年 | 9篇 |
1994年 | 16篇 |
1993年 | 13篇 |
1992年 | 14篇 |
1991年 | 7篇 |
1990年 | 7篇 |
1989年 | 10篇 |
1988年 | 5篇 |
1986年 | 6篇 |
1985年 | 18篇 |
1984年 | 12篇 |
1983年 | 7篇 |
1982年 | 14篇 |
1981年 | 11篇 |
1980年 | 19篇 |
1979年 | 13篇 |
1978年 | 11篇 |
1977年 | 9篇 |
1976年 | 6篇 |
1975年 | 4篇 |
1973年 | 8篇 |
1970年 | 5篇 |
排序方式: 共有1797条查询结果,搜索用时 31 毫秒
51.
Ihori Y Yamashita Y Ishitani H Kobayashi S 《Journal of the American Chemical Society》2005,127(44):15528-15535
Catalytic enantioselective Mannich-type reactions of silicon enolates with aldimines were investigated using chiral zirconium catalysts prepared from Zr(O(t)Bu)(4), N-methylimidazole, and newly designed multidentate BINOL derivatives. These new multidentate BINOL ligands were designed on the basis of an assumed transition state structure of a chiral zirconium catalyst derived from two molecules of (R)-6,6'-Br(2)-BINOL. Not only tetradentate BINOL 4 but also tridentate BINOL derivatives were found to be effective, and high enantioselectivities were attained. In a structural study of the most effective zirconium complex prepared from tridentate ligand 6e, several NMR experiments and DFT calculations were carried out. Consequently, the structure of an active catalyst and plausible mechanism of asymmetric induction were elucidated. 相似文献
52.
John V. Tate William N. Tinnerman Vito Jurevics Harold Jeskey Edward R. Biehl 《Journal of heterocyclic chemistry》1986,23(1):9-11
The acidity of 5-benzylbarbituric acid and a series of 5-substituted benzylbarbituric acids has been determined in 50% ethanol/water and they were found to be more acidic than barbituric acid. The pKas of these derivatives obey Hammett's equation indicating that their acidity is affected by substituents in the same manner as the benzoic acid ionization constants. A synthesis of these acids is described. 相似文献
53.
Anderson MW Ohsuna T Sakamoto Y Liu Z Carlsson A Terasaki O 《Chemical communications (Cambridge, England)》2004,(8):907-916
This article describes a number of important recent microscopy tools and their application in particular to the study of porous inorganic materials. The authors believe that these new techniques are on the threshold of delivering enormous new power in the chemist's arsenal for understanding new and complex behaviour in multi-component, hierarchical or composite materials. In particular we consider the contribution of electron crystallography, three-dimensional electron tomography, ultra-high resolution scanning electron microscopy as well as the combined application of high-resolution electron microscopy and atomic force microscopy to the study of surfaces and crystal growth. Much of this work has taken on a particular significance owing to the ground breaking work of scientists at Mobil and in Japan 10 years ago in the successful synthesis of materials with porosity on many length scales achieved through the cooperative self-assembly between inorganic and organic phases. This resulted in a series of materials known as M41S of which MCM-41 and MCM-48 were two of the first and most important structures to be synthesised. This has led to a wealth of new porous structures with order over many length scales and has presented new problems in characterisation. Microscopy methods properly executed are particularly important in the study of this new class of material. 相似文献
54.
Yoshio Fuchita Katsuma Hiraki Yasuhiro Matsumoto 《Journal of organometallic chemistry》1985,280(2):c51-c54
N,N-Dimethylneopentylamine reacts with Pd(MeCO2)2 to give a novel trinuclear cyclopalladated complex [Me2NCH2CMe2CH2Pd(μ-MeCO2)2Pd(μ-MeCO2)2PdCH2CMe2CH2NMe2]?-0.5C6H6 (I). The reaction of I with PPh3 affords both trans-[Pd(MeCO2)2(PPh3)2] (II) and [Pd(CH2CMe2CH2NMe2)(MeCO2)(PPh3)] (III). The reaction of III with LiCl yields a mononuclear cyclopalladated complex, [Pd(CH2CMe2CH2NMe2)Cl(PPh3)] (IV). 相似文献
55.
Morito Komiya Yuuki Nishikido Yasuhiro Umebayashi Shin-ichi Ishiguro 《Journal of solution chemistry》2002,31(11):931-946
Formation thermodynamics of binary and ternary lanthanide(III) (Ln = La, Ce, Nd, Eu, Gd, Dy, Tm, Lu) complexes with 1,10-phenanthroline (phen) and the chloride ion have been studied by titration calorimetry and spectrophotometry in N,N-dimethyl-formamide (DMF) containing 0.2 mol-dm–3 (C2H5)4NClO4 as a constant ionic medium at 25°C. In the binary system with 1,10-phenanthroline, the Ln(phen)3+ complex is formed for all the lanthanide(III) ions examined. The reaction enthalpy and entropy values for the formation of Ln(phen)3+ decrease in the order La > Ce > Nd, then increase in the order Nd < Eu < Gd < Dy, and again decrease in the order Dy > Tm > Lu. The variation is explained in terms of the coordination structure of Ln(phen)3+ that changes from eight to seven coordination with decreasing ionic radius of the metal ion. In the ternary Ln3+-Cl–-phen system, the formation of LnCl(phen)2+, LnCl2(phen)+, and LnCl3(phen) was established for cerium(III), neodymium(III), and thulium(III), and their formation constants, enthalpies, and entropies were obtained. The enthalpy and entropy values are also discussed from the structural point of view. 相似文献
56.
Ishiguro R Yokoyama Y Maeda H Shimamura A Kameyama K Hiramatsu K 《Journal of colloid and interface science》2005,290(1):91-101
Infrared spectra of hen egg white lysozyme and bovine serum albumin (BSA) adsorbed on a solid poly tris(trimethylsiloxy)silylstyrene (pTSS) surface in D2O solution were measured using attenuated total reflection (ATR) Fourier transform infrared spectroscopy. From the area and shape of the amide I' band of each spectrum, the adsorption amount and the secondary structure were determined simultaneously, as a function of adsorption time. We could show that the average conformation for all the adsorbed lysozyme molecules was solely determined by the adsorption time, and independent of the bulk concentration, while the adsorption amount increased with the bulk concentration as well as the adsorption time. These results suggest that lysozyme molecules form discrete assemblies on the surface, and that the surface assemblies grow over several hours to have a definite architecture independent of the adsorption amount. As for BSA, the extent of the conformational change was solely determined by the adsorption amount, regardless of the bulk concentration and the adsorption time. These differences in the adsorption properties of lysozyme and BSA may reflect differences in their conformational stabilities. 相似文献
57.
Bis-crown ethers in which the benzo-15-crown-5 units were linked to 1,1′-positions of metallocene (M = Fe or Ru) with amide, ester, or ? C? C? bonds were synthesized. Complexing ability of the compounds with alkali, alkali earth, and transition metal cations were measured by the solvent extraction method. The results showed that these crown ethers had high affinity toward alkali metal cations (Li+, Na+, K+, and Rb+) and heavy-metal cations (Ag+ and Tl+). The difference of complexing ability for metal cations between ferrocene and ruthenocene derivatives could not be detected significantly. The extractability of metallocene-bis-crown ethers for metal cations was more larger than that of the corresponding mono-crown ethers, and irregular increments of extractability were explained by assuming the existence of a mixture of 1:1 and 2:1 complexes. 相似文献
58.
Tanase T Doi M Nouchi R Kato M Sato Y Ishida K Kobayashi K Sakurai T Yamamoto Y Yano S 《Inorganic chemistry》1996,35(17):4848-4857
Reactions of [Ni(tren)(H(2)O)(2)]X(2) (tren = tris(2-aminoethyl)amine; X = Cl (1a), Br (1b); X(2) = SO(4) (1c)) with mannose-type aldoses, having a 2,3-cis configuration (D-mannose and L-rhamnose), afforded {bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine}nickel(II) complexes, [Ni(N,N'-(aldosyl)(2)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (2a), Br (2b), X(2) = SO(4) (2c); aldosyl = L-rhamnosyl, X(2) = SO(4) (3c)). The structure of 1c was confirmed by X-ray crystallography to be a mononuclear [Ni(II)N(4)O(2)] complex with the tren acting as a tetradentate ligand (1c.2H(2)O: orthorhombic, Pbca, a = 15.988(2) ?, b = 18.826(4) ?, c = 10.359(4) ?, V = 3118 ?(3), Z = 8, R = 0.047, and R(w) = 0.042). Complexes 2a,c and 3c were characterized by X-ray analyses to have a mononuclear octahedral Ni(II) structure ligated by a hexadentate N-glycoside ligand, bis(N-aldosyl-2-aminoethyl)(2-aminoethyl)amine (2a.CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 16.005(3) ?, b = 20.095(4) ?, c = 8.361(1) ?, V = 2689 ?(3), Z = 4, R = 0.040, and R(w) = 0.027. 2c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.93(2) ?, b = 21.823(8) ?, c = 9.746(2) ?, V = 3176 ?(3), Z = 4, R = 0.075, and R(w) = 0.080. 3c.3CH(3)OH: orthorhombic, P2(1)2(1)2(1), a = 14.560(4) ?, b = 21.694(5) ?, c = 9.786(2) ?, V = 3091 ?(3), Z = 4, R = 0.072, and R(w) = 0.079). The sugar part of the complex involves novel intramolecular sugar-sugar hydrogen bondings around the metal center. The similar reaction with D-glucose, D-glucosamine, and D-galactosamine, having a 2,3-trans configuration, resulted in the formation of a mono(sugar) complex, [Ni(N-(aldosyl)-tren)(H(2)O)(2)]Cl(2) (aldosyl = D-glucosyl (4b), 2-amino-2-deoxy-D-glucosyl (5a), and 2-amino-2-deoxy-D-galactosyl (5b)), instead of a bis(sugar) complex. The hydrogen bondings between the sugar moieties as observed in 2 and 3 should be responsible for the assembly of two sugar molecules on the metal center. Reactions of tris(N-aldosyl-2-aminoethyl)amine with nickel(II) salts gave the tris(sugar) complexes, [Ni(N,N',N"-(aldosyl)(3)-tren)]X(2) (aldosyl = D-mannosyl, X = Cl (6a), Br (6b); L-rhamnosyl, X = Cl (7a), Br (7b); D-glucosyl, X = Cl (9); maltosyl, X = Br (10); and melibiosyl, X = Br (11)), which were assumed to have a shuttle-type C(3) symmetrical structure with Delta helical configuration for D-type aldoses on the basis of circular dichroism and (13)C NMR spectra. When tris(N-rhamnosyl)-tren was reacted with NiSO(4).6H(2)O at low temperature, a labile neutral complex, [Ni(N,N',N"-(L-rhamnosyl)(3)-tren)(SO(4))] (8), was successfully isolated and characterized by X-ray crystallography, in which three sugar moieties are anchored only at the N atom of the C-1 position (8.3CH(3)OH.H(2)O: orthorhombic, P2(1)2(1)2(1), a = 16.035(4) ?, b = 16.670(7) ?, c = 15.38(1) ?, V = 4111 ?(3), Z = 4, R = 0.084, and R(w) = 0.068). Complex 8 could be regarded as an intermediate species toward the C(3) symmetrical tris(sugar) complexes 7, and in fact, it was readily transformed to 7b by an action of BaBr(2). 相似文献
59.
Satoru Hommura Yasuhiro Kunisa Ichiro Terada Masaru Yoshitake 《Journal of fluorine chemistry》2003,120(2):151-155
Characteristics of fibril reinforced membranes developed by Asahi Glass Company are reviewed. PTFE-fibrils <1 μm in diameter are dispersed in ion-exchange membranes uniformly. Mechanical properties, such as tensile strength, tear strength, creep property and compressive property were examined and compared with non-reinforced membranes. Fibril reinforced membranes, even by the addition of a small amount of PTFE-fibrils (2.7 wt.%), show excellent mechanical strength, especially in creep and tear strength. Cell performance is nearly equal to the one using a non-reinforced membrane and cell voltage stays about the same during the cell operation at 80 °C for 3000 h. 相似文献
60.
Tei T Sato Y Hagiya K Tai A Okuyama T Sugimura T 《The Journal of organic chemistry》2002,67(19):6593-6598
The stereocontrol mechanism of the 2,4-pentanediol (PD)-tethered reaction was studied in detail using a reaction system consisting of phenyl and rhodium carbenoid moieties. Different tethers were examined to analyze the effects of the methyl groups on the PD tether. Among the reactions with these tethers, the PD tether achieves an unmeasurably high stereoselectivity in a diastereomeric ratio of >500. Another tether showing a high but measurable stereoselectivity in a ratio of 41 is mostly controlled by the entropy term. To clarify the role of the methyl groups on the chiral tethers, which are the origin of the stereocontrol, the "chiral perturbation factor" is introduced. This parameter is defined as the rate of a chiral reaction relative to that of an achiral reference reaction. By analyzing the temperature dependence of the chiral perturbation factors for different chiral-tethered reactions, high potentials of the PD-tethered reaction in its stereocontrol are concluded to be due to the entropy term. 相似文献