全文获取类型
收费全文 | 189722篇 |
免费 | 32068篇 |
国内免费 | 18514篇 |
专业分类
化学 | 141839篇 |
晶体学 | 1914篇 |
力学 | 10339篇 |
综合类 | 962篇 |
数学 | 21746篇 |
物理学 | 63504篇 |
出版年
2024年 | 517篇 |
2023年 | 3102篇 |
2022年 | 5453篇 |
2021年 | 6096篇 |
2020年 | 7037篇 |
2019年 | 7827篇 |
2018年 | 6284篇 |
2017年 | 5614篇 |
2016年 | 10257篇 |
2015年 | 10205篇 |
2014年 | 11836篇 |
2013年 | 14999篇 |
2012年 | 16492篇 |
2011年 | 16214篇 |
2010年 | 12316篇 |
2009年 | 11941篇 |
2008年 | 12087篇 |
2007年 | 10595篇 |
2006年 | 9690篇 |
2005年 | 8393篇 |
2004年 | 6739篇 |
2003年 | 5556篇 |
2002年 | 5904篇 |
2001年 | 4620篇 |
2000年 | 4230篇 |
1999年 | 3661篇 |
1998年 | 2858篇 |
1997年 | 2657篇 |
1996年 | 2678篇 |
1995年 | 2279篇 |
1994年 | 2041篇 |
1993年 | 1672篇 |
1992年 | 1502篇 |
1991年 | 1286篇 |
1990年 | 1085篇 |
1989年 | 846篇 |
1988年 | 676篇 |
1987年 | 569篇 |
1986年 | 542篇 |
1985年 | 438篇 |
1984年 | 322篇 |
1983年 | 246篇 |
1982年 | 198篇 |
1981年 | 142篇 |
1980年 | 118篇 |
1979年 | 61篇 |
1978年 | 53篇 |
1977年 | 57篇 |
1976年 | 52篇 |
1973年 | 46篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
The acid dissociation constants of 1,2-bis(cis-aminophenoxy)ethane-N,N,N′,N′;-tetraacetic acid (H4BAPAT or H4Z), and the stability constants of its chelates with tripositive rare-earth metal ions have been determined by the potentiometric titration and mercury indicator electrode methods at 15°, 25′ and 35°C and an ionic strength of 0.1 (KNO3). The existence of a monohydrogen chelate species, LnHZ, and the normal chelate, LnZ?, is illustrated. Enthalpy and entropy changes characterizing the formation of the normal chelates and the dissociation of the last two protons of chelating acid have been calculated at 25°C. These functions have been compared with corresponding values for related chelating agents. 相似文献
992.
Fu-Ken Liu 《Analytica chimica acta》2005,528(2):249-254
This paper demonstrates that capillary electrophoresis (CE) can be employed for characterizing the sizes of nanometer-scale gold particles. We characterized the gold nanoparticles by effecting CE separation using a buffer of SDS (70 mM) and 3-cyclohexylamino-1-propanesulfonic acid (CAPS; 10 mM) at pH 11.0 and an applied voltage of 18 kV and obtained a linear relationship (R2 > 0.99) between electrophoretic mobilities and size for nanoparticles whose diameters fall in the regime from 5.0 ± 0.5 to 41.2 ± 3.3 nm; the relative standard deviations of these electrophoretic mobilities are <0.8%. We evaluated the feasibility of employing these separation conditions for the size characterization by of gold nanoparticle samples that were synthesized by a rapid microwave heating method. We confirmed that this CE method is a valid one for size characterization by comparing the results obtained by CE with those provided by scanning electron microscopy (SEM); a good correlation exists between these two techniques. Our results demonstrate that CE can be employed to accelerate the analysis of the sizes of nanomaterials. 相似文献
993.
Three new disubstituted benzo-15-crown-5 derivatives (3-5) have been synthesized from 4',5'-bis(bromomethyl)benzo-15-crown-5 (2) and the corresponding alkanols in the presence of Na(2)S(2), and their complexation thermodynamics with light lanthanoid(III) nitrates (La-Gd) have been studied in anhydrous acetonitrile at 25 degrees C. Plots of K(S) against the reciprocal ionic diameter of lanthanoid exhibited monotonically declining pattern for the parent benzo-15-crown-5 (1) and 3 but showed a characteristic peak at Ce(3+) for 4 and 5. It is interesting to note that the simple extension of the alkyl side chains in 4 and 5 can alter the cation selectivity profiles of 1 and 3. Possessing two 2-oxapropyl groups, 3 gave a comparable K(S) for La(3+) but a significantly decreased K(S) for Ce(3+) compared with the corresponding values for 1, thus exhibiting an exceptionally high La(3+)/Ce(3+) selectivity of 11. Thermodynamically, the complexation of lanthanoid perchlorates with 1 is absolutely entropy-driven in acetonitrile, while the complexation of lanthanoid nitrates with 3-5 is primarily driven by exothermic enthalpy changes with accompanying moderate entropic gain or small entropic loss. 相似文献
994.
Top7 is a de novo designed protein with atomic level accuracy and shows a folded structure not found in nature. Previous studies showed that the folding of Top7 is not cooperative and involves various folding intermediate states. In addition, various fragments of Top7 were found to fold on their own in isolation. These features displayed by Top7 are distinct from those of naturally occurring proteins of a similar size and suggest a rough folding energy landscape. However, it remains unknown if and how the intra-polypeptide chain interactions among the neighboring sequences of Top7 affect the folding of these Top7 fragments. Here we used single-molecule optical tweezers to investigate the folding–unfolding pathways of full length Top7 as well as its C-terminal fragment (CFr) in different sequence environments. Our results showed that the mechanical folding of Top7 involves an intermediate state that likely involves non-native interactions/structure. More importantly, we found that the folding of CFr is entirely dependent upon its sequence context in which it is located. When in isolation, CFr indeed folds into a cooperative structure showing near-equilibrium unfolding–folding transitions at ∼6.5 pN in OT experiments. However, CFr loses its autonomous cooperative folding ability and displays a folding pathway that is dependent on its interactions with its neighboring sequence/structure. This context-dependent folding dynamics and pathway of CFr are distinct from those of naturally occurring proteins and highlight the critical importance of intra-chain interactions in shaping the overall energy landscape and the folding pathway of Top7. These new insights may have important implications on the de novo design of proteins.Optical tweezers experiments reveal that the folding of the C-terminal fragment of Top7 (cFr) is context-dependent. Depending on its neighboring sequence, cFr shows very different folding pathways and folding kinetics. 相似文献
995.
De‐Chun Zhang 《Acta Crystallographica. Section C, Structural Chemistry》2002,58(6):o351-o352
In the title compound, N‐(2‐methoxyphenyl)‐4‐nitrobenzylideneamine, C14H12N2O3, the two phenyl rings make a dihedral angle of 48.0 (2)° and the nitro group is at an angle of 6.5 (1)° with respect to its attached phenyl ring. In the crystal structure, molecules are related as centrosymmetric pairs through π–π interactions and are further connected through strong C—H?O hydrogen bonds [C?O 3.4259 (17) Å and C—H?O 167°], forming molecular stacks along [100]. These stacks associate further through longer C—H?O interactions, forming two‐dimensional networks. In the c direction, there are only weak van der Waals interactions. The relationship between the molecular planarity and its centrosymmetry is also briefly described. 相似文献
996.
Julio Belmar Claudio Jimnez C. Ruiz‐Prez F. S. Delgado Ricardo Baggio 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):o599-o601
In the title compound, C15H20N2O, the bond distances and angles are consistent with the presence of the hydroxy tautomer. This tautomer was unambiguously determined by the clear presence of a H atom bonded to oxygen, as well as the total absence of any residual electron density around the N atom in the heterocycle, thus precluding any possibility of desmotropism. 相似文献
997.
Li Gao 《Tetrahedron》2005,61(15):3805-3811
Trihydroxy-2-thiaquinolizidines, a new class of bicyclic dideoxy-iminohexitol glycosidase inhibitor derivatives with nominally the d-gluco, l-ido, d-manno and l-gulo configurations were synthesized. X-ray analyses indicated that the preferred conformation for d-gluco and d-manno derivatives was a flat trans-fused system. Unlike deoxynojirimycin, the compound with d-gluco configuration was selective for α-glucosidases (yeast and rice) and showed no inhibitory activity towards β-glucosidase (almond), α-galactosidase (green coffee beans), α-galactosidase (E. coli) and α-mannosidase (jack bean), while the l-ido derivative was specific for β-glucosidase (almond). 相似文献
998.
Cang Li 《Journal of solid state chemistry》2004,177(12):4569-4575
Reaction of an aqueous slurry of an Mg2Al-NO3 layered double hydroxide with a four-fold excess of Na[Eu(EDTA)] gives a material which analyses for Mg0.68Al0.32(OH)2[Eu(EDTA)]0.10(CO3)0.11·0.66H2O. The interlayer spacing of the material is 13.8 Å, corresponding to a gallery height of 9.0 Å, which accords with the maximal dimensions (9-10 Å) of the anion in metal-EDTA complex salts as determined by single crystal X-ray diffraction. Geometrical considerations show that the charge density on the layered double hydroxide layers is too high to be balanced by intercalation of [Eu(EDTA)]− alone, necessitating the co-intercalation of carbonate ions which have a much higher charge density. 相似文献
999.
Zun‐Ting Zhang Yan‐Chang Wang 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(1):o51-o53
In the lattice of the title compound (systematic name: 5,6,7‐trihydroxy‐4′‐methoxyisoflavone monohydrate), C16H12O6·H2O, the isoflavone molecules are linked into chains through R43(17) motifs composed via O—H⋯O and C—H⋯O hydrogen bonds. Centrosymmetric R42(14) motifs assemble the chains into sheets. Hydrogen‐bonding and aromatic π–π stacking interactions lead to the formation of a three‐dimensional network structure. 相似文献
1000.
Two compounds of a new type, [Mo(2)](CH(3)O)(2)M(CH(3)O)(2)[Mo(2)] where [Mo(2)] is an abbreviation for Mo(2)[(p-MeOC(6)H(4))NCHN(p-MeOC(6)H(4))](3) and M = Zn (1) and Co (2), are reported. Discrete [M(OR)(4)](2-) ions, either as such or in the mu(2),eta(4) role, have not heretofore been described. In these compounds they have distorted tetrahedral structures and bridge two [Mo(2)] groups in much the same way as did SO(4)(2-), MoO(4)(2-), and WO(4)(2-) ions in other recently reported compounds (Cotton, F. A.; Donahue, J. P.; Murillo, C. A. Inorg. Chem. 2001, 40, 2229). The (1)H NMR spectrum of 1 and the visible spectrum and magnetic properties of 2 are consistent with these structures. The M(OCH(3))(4) bridges are moderately effective in coupling the two [Mo(2)] redox centers. Compounds 1 and 2 may also be viewed as having Zn(II) and Co(II) centers tetrahedrally coordinated by the bidentate ligand [Mo(2)[(p-MeOC(6)H(4))NCHN(p-MeOC(6)H(4))](3)(OMe)(2)](-). From that point of view they may be compared with Zn(DPM)(2) and Co(DPM)(2) (3), where DPM is the anion of dipivaloylmethane. For purposes of comparison, 3 has been fully characterized structurally, spectroscopically, and magnetically. Close analogies between 2 and 3 are shown to exist. 相似文献