全文获取类型
收费全文 | 13098篇 |
免费 | 998篇 |
国内免费 | 847篇 |
专业分类
化学 | 13420篇 |
晶体学 | 162篇 |
力学 | 91篇 |
综合类 | 35篇 |
数学 | 156篇 |
物理学 | 1079篇 |
出版年
2024年 | 6篇 |
2023年 | 94篇 |
2022年 | 155篇 |
2021年 | 319篇 |
2020年 | 445篇 |
2019年 | 354篇 |
2018年 | 308篇 |
2017年 | 322篇 |
2016年 | 388篇 |
2015年 | 292篇 |
2014年 | 369篇 |
2013年 | 838篇 |
2012年 | 1357篇 |
2011年 | 557篇 |
2010年 | 488篇 |
2009年 | 665篇 |
2008年 | 747篇 |
2007年 | 886篇 |
2006年 | 697篇 |
2005年 | 636篇 |
2004年 | 625篇 |
2003年 | 523篇 |
2002年 | 430篇 |
2001年 | 378篇 |
2000年 | 369篇 |
1999年 | 353篇 |
1998年 | 302篇 |
1997年 | 293篇 |
1996年 | 322篇 |
1995年 | 321篇 |
1994年 | 214篇 |
1993年 | 187篇 |
1992年 | 163篇 |
1991年 | 106篇 |
1990年 | 66篇 |
1989年 | 49篇 |
1988年 | 53篇 |
1987年 | 42篇 |
1986年 | 39篇 |
1985年 | 32篇 |
1984年 | 33篇 |
1983年 | 13篇 |
1982年 | 26篇 |
1981年 | 15篇 |
1980年 | 17篇 |
1979年 | 12篇 |
1978年 | 7篇 |
1977年 | 7篇 |
1975年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 734 毫秒
991.
The traditional method for opening the electron shells of noble gas atoms involves a strong electronegative atom or group. However, this approach is limited to only heavy noble‐gas atoms, such as Kr and Xe. In this paper, we performed accurate calculations of He@C8H8 and He@C10H16 and showed the possibility of opening the electron shell of a light noble‐gas atom. © 2012 Wiley Periodicals, Inc. 相似文献
992.
This work demonstrates an efficient way to prepare chiral propargylic alcohols by asymmetric addition of terminal Zn-acetylide to aldehydes catalyzed by bifunctional zinc-based complexes. The corresponding products with moderate to good yields and enantioselectivities were obtained in the absence of moisture-sensitive Ti(O i Pr)4. 相似文献
993.
Ying Liu Ying‐Hui Yu Yi‐Fu Liu Guang‐Feng Hou Xiao‐Dan Wang Bo Wen Jin‐Sheng Gao 《无机化学与普通化学杂志》2013,639(1):193-196
The cage‐like complex, Ag4L4(NO3)4 ( 1 ) [L = 1, 4‐bis(pyridine‐2‐ylmethoxy)benzene] was synthesized by the reaction of the flexible bidentate ligand and silver nitrate. It was characterized by elemental analysis, IR spectroscopy, TG, and single‐crystal X‐ray analysis. Complex 1 is reported as the first cage‐like cluster constructed by four nitrate anions bridging two [2+2] macrocycles. A blue luminescent emission and luminescent enhancement effect are observed in complex 1 . 相似文献
994.
Two dinuclear succinato‐bridged nickel(II) complexes [Ni(RR‐L)]2(μ‐SA)(ClO4)2 ( 1 ) and [Ni(SS‐L)]2(μ‐SA)(ClO4)2 ( 2 ) (L = 5, 5, 7, 12, 12, 14‐hexamethyl‐1, 4, 8, 11‐tetraazacyclotetradecane, SA = succinic acid) were synthesized and characterized by EA, Circular dichroism (CD), as well as IR and UV/Vis spectroscopy. Single crystal X‐ray diffraction analyses revealed that the NiII atoms display a distorted octahedral coordination arrangement, and the succinato ligand bridges two central NiII atoms in a bis bidentate fashion to form dimers in 1 and 2 . The monomers of {[Ni(RR‐L)]2(μ‐SA)}2+ and {[Ni(SS‐L)]2(μ‐SA)}2+ are connected by O–H ··· O and N–H ··· O hydrogen bonds into a 1D right‐handed and left‐handed helical chain along the b axis, respectively. The homochiral natures of 1 and 2 are confirmed by the results of CD spectroscopy. 相似文献
995.
Xiao‐Ying Cheng Ming‐Fang Wang Zheng‐Yin Yang Yong Li Zeng‐Chen Liu Qiao‐Xia Zhou 《无机化学与普通化学杂志》2013,639(5):832-841
The Schiff base ligand, 1‐phenyl‐3‐methyl‐5‐hydroxypyrazole‐4‐methylene‐8′‐quinolineimine, and its CuII, ZnII, and NiII complexes were synthesized and characterized. The crystal structure of the ZnII complex was determined by single‐crystal X‐ray diffraction, indicating that the metal ions and Schiff base ligand can form mononuclear six‐coordination complexes with 1:1 metal‐to‐ligand stoichiometry at the metal ions as centers. The binding mechanism and affinity of the ligand and its metal complexes to calf thymus DNA (CT DNA) were investigated by UV/Vis spectroscopy, fluorescence titration spectroscopy, EB displacement experiments, and viscosity measurements, indicating that the free ligand and its metal complexes can bind to DNA via an intercalation mode with the binding constants at the order of magnitude of 105–106 M –1, and the metal complexes can bind to DNA more strongly than the free ligand alone. In addition, antioxidant activities of the ligand and its metal complexes were investigated through scavenging effects for hydroxyl radical in vitro, indicating that the compounds show stronger antioxidant activities than some standard antioxidants, such as mannitol. The ligand and its metal complexes were subjected to cytotoxic tests, and experimental results indicated that the metal complexes show significant cytotoxic activity against lung cancer A 549 cells. 相似文献
996.
Formation, crystal structure, polymorphism, and transition between polymorphs are reported for M(thd)3, (M = Al, Cr, Mn, Fe, Co, Ga, and In) [(thd)– = anion of H(thd) = C11H20O2 = 2, 2, 6, 6‐tetramethylheptane‐3, 5‐dione]. Fresh crystal‐structure data are provided for monoclinic polymorphs of Al(thd)3, Ga(thd)3, and In(thd)3. Apart from adjustment of the M–Ok bond length, the structural characteristics of M(thd)3 complexes remain essentially unaffected by change of M. Analysis of the M–Ok, Ok–Ck, and Ck–Ck distances support the notion that the M–Ok–Ck–Ck–Ck–Ok– ring forms a heterocyclic unit with σ and π contributions to the bonds. Tentative assessments according to the bond‐valence or bond‐order scheme suggest that the strengths of the σ bonds are approximately equal for the M–Ok, Ok–Ck, and Ck–Ck bonds, whereas the π component of the M–Ok bonds is small compared with those for the Ok–Ck, and Ck–Ck bonds. The contours of a pattern for the occurrence of M(thd)3 polymorphs suggest that polymorphs with structures of orthorhombic or higher symmetry are favored on crystallization from the vapor phase (viz. sublimation). Monoclinic polymorphs prefer crystallization from solution at temperatures closer to ambient. Each of the M(thd)3 complexes subject to this study exhibits three or more polymorphs (further variants are likely to emerge consequent on systematic exploration of the crystallization conditions). High‐temperature powder X‐ray diffraction shows that the monoclinic polymorphs convert irreversibly to the corresponding rotational disordered orthorhombic variant above some 100–150 °C (depending on M). The orthorhombic variant is in turn transformed into polymorphs of tetragonal and cubic symmetry before entering the molten state. These findings are discussed in light of the current conceptions of rotational disorder in molecular crystals. 相似文献
997.
Yoshio Kobayashi Tsukasa Shirochi Takafumi Maeda Yusuke Yasuda Toshiaki Morita 《Surface and interface analysis : SIA》2013,45(9):1424-1428
This paper describes a metal–metal bonding technique using metallic Cu nanoparticles prepared in aqueous solution. A colloid solution of metallic Cu particles with a size of 54 ± 15 nm was prepared by reducing Cu2+ (0.01 M (CH3COO)2Cu) with hydrazine (0.6 M) in the presence of stabilizers (5 × 10?4 M citric acid and 5 × 10?3 M cetyltrimethylammonium bromide) in water at room temperature in air. Discs made of metallic materials (Cu, Ni/Cu, or Ag/Ni/Cu) were successfully bonded under annealing at 400 °C and pressurizing at 1.2 MPa for 5 min in H2 gas with help of the metallic Cu particle powder. Shear strength required for separating the bonded discs was 27.9 ± 3.9 for Cu discs, 28.1 ± 4.1 for Ni/Cu discs, and 13.8 ± 2.6 MPa for Ag/Ni/Cu discs. Epitaxial crystal growth promotes on the discs with a good matching for the lattice constants between metallic nanoparticles and metallic disc surfaces, which leads to strong bonding. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
998.
999.
Angelika Baranowska‐Łączkowska Berta Fernández Robert Zaleśny 《Journal of computational chemistry》2013,34(4):275-283
Interaction‐induced static electric properties, that is, dipole moment, polarizability, and first hyperpolarizability, of the CO? (HF)n and N2? (HF)n, n = 1–9 hydrogen‐bonded complexes are evaluated within the finite field approach using the Hartree–Fock, density functional theory, Møller–Plesset second‐order perturbation theory, and coupled cluster methods, and the LPol‐n (n = ds, dl, fs, fl) basis sets. To compare the performance of the different methods with respect to the increase of the complex size, we consider as model systems linear chains of the complexes. We analyze the results in terms of the many‐body and cooperative effects. © 2012 Wiley Periodicals, Inc. 相似文献
1000.
Redox-active polyelectrolyte-surfactant complexes (PSC) were prepared via the ionic self-assembly of sodium polyacrylate (PAAS) and ferrocenyl surfactant, n-alkyl (ferrocenylmethyl)ammonium bromide (Fcn, n = 8, 12, 16, where n is the carbon number of the alkyl chain), in solution. The obtained PAAS-Fcn complex exhibited crystalline and lamellar mesomorphous structure. Moreover, the ferrocenyl moieties formed H-aggregation in the solid complex as known from the blue shift in the ultraviolet-visible spectrum. Cyclic voltammogram (CV) measurements indicated that the reversibility of the electrode process became worse when the surfactant tail length increases because of the more ordered packing in the complex film formed by longer surfactant tails. The present results demonstrate that the electrochemical activity of the redox-active polyacrylate-ferrocenyl surfactant complex can be easily tuned by changing the surfactant tail length. Our work provides a simple and facile approach to the preparation of redox-active polymers with ordered mesomorphous structure by the ionic self-assembly. 相似文献