全文获取类型
收费全文 | 2649篇 |
免费 | 107篇 |
国内免费 | 21篇 |
专业分类
化学 | 2160篇 |
晶体学 | 21篇 |
力学 | 17篇 |
数学 | 166篇 |
物理学 | 413篇 |
出版年
2023年 | 19篇 |
2022年 | 8篇 |
2021年 | 30篇 |
2020年 | 35篇 |
2019年 | 55篇 |
2018年 | 32篇 |
2017年 | 29篇 |
2016年 | 60篇 |
2015年 | 70篇 |
2014年 | 67篇 |
2013年 | 136篇 |
2012年 | 179篇 |
2011年 | 207篇 |
2010年 | 122篇 |
2009年 | 111篇 |
2008年 | 195篇 |
2007年 | 182篇 |
2006年 | 138篇 |
2005年 | 156篇 |
2004年 | 152篇 |
2003年 | 118篇 |
2002年 | 130篇 |
2001年 | 34篇 |
2000年 | 47篇 |
1999年 | 31篇 |
1998年 | 33篇 |
1997年 | 23篇 |
1996年 | 28篇 |
1995年 | 32篇 |
1994年 | 26篇 |
1993年 | 27篇 |
1992年 | 23篇 |
1991年 | 22篇 |
1990年 | 15篇 |
1989年 | 19篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 24篇 |
1985年 | 26篇 |
1984年 | 25篇 |
1983年 | 6篇 |
1982年 | 13篇 |
1981年 | 8篇 |
1980年 | 7篇 |
1979年 | 6篇 |
1978年 | 6篇 |
1975年 | 6篇 |
1973年 | 6篇 |
1972年 | 5篇 |
1965年 | 4篇 |
排序方式: 共有2777条查询结果,搜索用时 453 毫秒
991.
The effect of transition metal solutes on the lattice parameters of γ-TiAl and α2-Ti3Al were studied by first principles calculations to find suitable elements for controlling the α2/γ interfacial misfit in lamellar Ti–Al alloys. Better agreement was found between the calculated and experimental phase and site preferences of impurity atoms than in a previous first principles study. The calculated lattice parameters suggest that elements in groups 6–11 of the 4th period (Cr, Mn, Fe, Co, Ni and Cu) are effective for increasing the misfit, leading to increasing density of misfit dislocation and, in turn, higher yield strength and ductility. This effect is caused by the change in the lattice parameter of the γ-TiAl phase rather than those of α2-Ti3Al phase. This prediction agrees qualitatively with experimental data from a previous study although the effects of temperature are not taken into account. Further improvements should be possible by considering those effects. Nevertheless, the results highlight the effects of impurity addition on interfacial misfit at a level which cannot be achieved by classical concepts such as atomic size in a hard sphere model. The results will also be valuable in further more quantitative predictions and in understanding the effects of temperature, including off-stoichiometry, thermal expansion and vibration entropy. 相似文献
992.
Matsuoka S Ota Y Washio A Katada A Ichioka K Takagi K Suzuki M 《Organic letters》2011,13(14):3722-3725
Highly selective tail-to-tail dimerization of methyl methacrylate has been realized by an N-heterocyclic carbene catalyst, giving dimethyl 2,5-dimethyl-2-hexenedioate with an E/Z ratio of 95:5 in 86% isolated yield. The umpolung mechanism is proposed on the basis of interception of the intermediates using ESI-MS analyses and deuterium-labeling experiments. 相似文献
993.
Kuroiwa Y Yamashita A Miyati T Furukoji E Takahashi M Azuma T Sugimura H Asanuma T Tamura S Kawai K Asada Y 《Magnetic resonance imaging》2011,29(7):975-984
Venous thrombus is subsequently organized and replaced by fibrous connective tissue. However, the sequential changes in venous thrombi are not reliably detected by current noninvasive diagnostic techniques. The purpose of this study is to reveal whether magnetic resonance (MR) can detect venous thrombus, define thrombus age and predict thrombolytic responses. Thrombus in the rabbit jugular vein was imaged with a 1.5-T MR system at 4 h and at 1, 2 and 4 weeks using three-dimensional (3D) fast asymmetric spin echo T2-weighted (T2W) and 3D-gradient echo T1-weighted (T1W) sequences. The jugular veins were histologically assessed at each time point. Magnetic resonance imaging (MRI) was also performed in vivo before and 30 min after tissue plasminogen activator (t-PA) administration. The thrombi in MRI were comparable in size to histological sections. The signal intensity (SI) of thrombi at 4 h was heterogeneously high or low on T2W or T1W images, respectively. The SI of thrombi on T2W images decreased time-dependently, but increased on T1W images at 1 and 2 weeks. Morphological analysis showed time-dependent decreases in erythrocyte, platelet and fibrin areas and time-dependent increases in smooth muscle cell, macrophage, collagen and iron areas. The t-PA administration significantly decreased thrombus volume at 4 h but not at 1, 2 and 4 weeks. Venous thrombosis can be reliably and noninvasively detected by MRI. Measurement of SI might support assessments of thrombus age and thrombolytic response. 相似文献
994.
Cross-linkedβ-cyclodextrin polymer/Fe3O4 composite nanoparticles with core-shell structures were prepared via cross linking reaction on the surface of carboxymethylβ-cyclodextrin(CM-β-CD) modified Fe3O4 nanoparticles inβ-cyclodextrin alkaline solution by using epichlorohydrin as crosslinking agent.The morphology,structure and magnetic properties of the prepared composite nanoparticles were investigated by transmission electron microscopy(TEM),Fourier transform infrared(FTIR) spectrometry,X-ray diffraction(XRD) measurement,thermogravimetric analysis(TGA) and Vibrating sample magnetometry (VSM),respectively. 相似文献
995.
Reactions of copper(II)-phenol systems with O2: models for TPQ biosynthesis in copper amine oxidases
Tabuchi K Ertem MZ Sugimoto H Kunishita A Tano T Fujieda N Cramer CJ Itoh S 《Inorganic chemistry》2011,50(5):1633-1647
Copper(II) complexes supported by a series of phenol-containing bis(pyridin-2-ylmethyl)amine N(3) ligands (denoted as L(o)H, L(m)H, and L(p)H) have been synthesized, and their O(2) reactivity has been examined in detail to gain mechanistic insights into the biosynthesis of the TPQ cofactor (2,4,5-trihydroxyphenylalaninequinone, TOPA quinone) in copper-containing amine oxidases. The copper(II) complex of L(o)H (ortho-phenol derivative) involves a direct phenolate to copper(II) coordination and exhibits almost no reactivity toward O(2) at 60 °C in CH(3)OH. On the other hand, the copper(II) complex of L(m)H (meta-phenol derivative), which does not involve direct coordinative interaction between the phenol moiety and the copper(II) ion, reacts with O(2) in the presence of triethylamine as a base to give a methoxy-substituted para-quinone derivative under the same conditions. The product structure has been established by detailed nuclear magnetic resonance (NMR), infrared (IR) spectroscopy, and electrospray ionization-mass spectroscopy (ESI-MS) (including (18)O-labeling experiment) analyses. Density functional theory predicts that the reaction involves (i) intramolecular electron transfer from the deprotonated phenol (phenolate) to copper(II) to generate a copper(I)-phenoxyl radical; (ii) the addition of O(2) to this intermediate, resulting in an end-on copper(II) superoxide; (iii) electrophilic substitution of the phenolic radical to give a copper(II)-alkylperoxo intermediate; (iv) O-O bond cleavage concomitant with a proton migration, giving a para-quinone derivative; and (v) Michael addition of methoxide from copper(II) to the para-quinone ring and subsequent O(2) oxidation. This reaction sequence is similar to that proposed for the biosynthetic pathway leading to the TPQ cofactor in the enzymatic system. The generated para-quinone derivative can act as a turnover catalyst for aerobic oxidation of benzylamine to N-benzylidene benzylamine. Another type of copper(II)-phenol complex with an L(p)H ligand (para-phenol derivative) also reacts with O(2) under the same experimental conditions. However, the product of this reaction is a keto-alcohol derivative, the structure of which is qualitatively different from that of the cofactor. These results unambiguously demonstrate that the steric relationship between the phenol moiety and the supported copper(II) ion is decisive in the conversion of active-site tyrosine residues to the TPQ cofactor. 相似文献
996.
Seinberg L Yamamoto T Tassel C Kobayashi Y Hayashi N Kitada A Sumida Y Watanabe T Nishi M Ohoyama K Yoshimura K Takano M Paulus W Kageyama H 《Inorganic chemistry》2011,50(9):3988-3995
We investigated the Fe-site substitution effect on the structural and magnetic properties of the infinite layer iron oxide Sr(Fe(1-x)M(x))O(2) (M = Co, Mn) using synchrotron X-ray diffraction, neutron diffraction, and (57)Fe Mo?ssbauer spectroscopy. Both systems have a similar solubility limit of x ≈ 0.3, retaining the ideal infinite layer structure with a space group of P4/mmm. For the Fe-Co system, both in-plane and out-of-plane axes decrease linearly and only slightly with x, reflecting the ionic radius difference between Fe(2+) and Co(2+). For the Fe-Mn system the lattice evolution also follows Vegard's law but is anisotropic: the in-plane axis increases, while the out-of-plane decreases prominently. The magnetic properties are little influenced by Co substitution. On the contrary, Mn substitution drastically destabilizes the G-type magnetic order, featured by a significant reduction and a large distribution of the hyperfine field in the Mo?ssbauer spectra, which suggests the presence of magnetic frustration induced presumably by a ferromagnetic out-of-plane Mn-Fe interaction. 相似文献
997.
Sakamoto M Fujita K Yagishita F Unosawa A Mino T Fujita T 《Chemical communications (Cambridge, England)》2011,47(14):4267-4269
N-(2-methoxy-1-naphthoyl)pyrrolidine afforded chiral crystals by spontaneous crystallization. The molecular chirality in the crystal was retained after dissolving the crystals in a cooled solvent. Kinetic resolution of racemic amines was performed using the provisional chiral molecular conformation derived from chiral crystals. 相似文献
998.
Nonoguchi Y Nakashima T Tanaka A Miyabayashi K Miyake M Kawai T 《Chemical communications (Cambridge, England)》2011,47(40):11270-11272
Hierarchically-assembled binary cadmium chalcogenide (CdX, X = S, Se, Te) oligomers were engineered. CdTe precursor injections into a solution containing seeded nanocrystals provided longer oligomers possessing alternating and phase-separated CdX and CdTe constituents in the same wire, like an alternating copolymer. 相似文献
999.
Ohtaka A Teratani T Fujii R Ikeshita K Kawashima T Tatsumi K Shimomura O Nomura R 《The Journal of organic chemistry》2011,76(10):4052-4060
Linear polystyrene-stabilized PdO nanoparticles (PS-PdONPs) were prepared in water by thermal decomposition of Pd(OAc)(2) in the presence of polystyrene. The immobilization degree of palladium was dependent on the molecular weight of polystyrene, while the size of the Pd nanoparticles was not. Linear polystyrene-stabilized Pd nanoparticles (PS-PdNPs) were also prepared using NaBH(4) and phenylboronic acid as reductants. The catalytic activity of PS-PdONPs was slightly higher than that of PS-PdNPs for Suzuki coupling reaction in water. PS-PdONPs exhibited high catalytic activity for Suzuki and copper-free Sonogashira coupling reactions in water and recycled without loss of activity. 相似文献
1000.
Glycans exist in nature in various forms of glycoconjugates, i.e., glycoproteins, glycolipids, and glycosaminoglycans, either in soluble or membrane-bound forms. One of their prominent properties distinguished from nucleic acids and proteins is "heterogeneity" largely attributed to their inherent features of biosynthesis. In general, various methods based on the physicochemical principles have been taken for their separation and structural determination although all of them require prior liberation of glycans and appropriate labeling. On the other hand, a series of carbohydrate-binding proteins, or "lectins," have extensively been used in a more direct manner for cell typing, histochemical staining, and glycoprotein fractionation. Although most procedures conventionally used are useful, unfortunately they lack "throughput" comparable to a performance required for current omics studies. Recently, a novel technique called lectin microarray has attracted increasing attention from not only glycoscientists but also researchers in other fields, because it is straightforward and also informative. The method is innovating in that it enables direct approach to glycoconjugates such as glycoproteins and even cells without liberation of glycans from the core substrate, and therefore can be effectively applied for the sake of differential profiling in various fields. Concept, strategy, and technical advancement of lectin microarray are described. Also, as an introduction to glycomics, the authors explain the motivation to challenge this theme. 相似文献