全文获取类型
收费全文 | 12688篇 |
免费 | 1323篇 |
国内免费 | 1450篇 |
专业分类
化学 | 4028篇 |
晶体学 | 103篇 |
力学 | 3925篇 |
综合类 | 172篇 |
数学 | 5264篇 |
物理学 | 1969篇 |
出版年
2024年 | 5篇 |
2023年 | 158篇 |
2022年 | 160篇 |
2021年 | 221篇 |
2020年 | 428篇 |
2019年 | 393篇 |
2018年 | 413篇 |
2017年 | 441篇 |
2016年 | 487篇 |
2015年 | 361篇 |
2014年 | 549篇 |
2013年 | 1094篇 |
2012年 | 867篇 |
2011年 | 726篇 |
2010年 | 600篇 |
2009年 | 703篇 |
2008年 | 721篇 |
2007年 | 790篇 |
2006年 | 745篇 |
2005年 | 717篇 |
2004年 | 617篇 |
2003年 | 594篇 |
2002年 | 526篇 |
2001年 | 430篇 |
2000年 | 386篇 |
1999年 | 346篇 |
1998年 | 329篇 |
1997年 | 257篇 |
1996年 | 223篇 |
1995年 | 201篇 |
1994年 | 165篇 |
1993年 | 112篇 |
1992年 | 150篇 |
1991年 | 118篇 |
1990年 | 91篇 |
1989年 | 57篇 |
1988年 | 44篇 |
1987年 | 39篇 |
1986年 | 33篇 |
1985年 | 40篇 |
1984年 | 29篇 |
1983年 | 28篇 |
1982年 | 15篇 |
1981年 | 11篇 |
1980年 | 10篇 |
1979年 | 7篇 |
1978年 | 5篇 |
1977年 | 4篇 |
1973年 | 4篇 |
1957年 | 3篇 |
排序方式: 共有10000条查询结果,搜索用时 140 毫秒
71.
Tania Chowdhury Kaushik Bera Debabrata Samanta Sandip Dolui Suvendu Maity Nakul C. Maiti Prasanta Kumar Ghosh Debasis Das 《应用有机金属化学》2020,34(4):e5556
Four new zinc (II) complexes [Zn (HL1H)Br2] (1), [Zn (HL1H)Cl2] (2), [Zn2(HL2)Br3] (3), and [Zn (HL2)Cl] (4) have been synthesized by adopting template synthetic strategy and utilizing two homologous Schiff base ligands (H2L1 = 4-bromo-2-{[2-(2-hydroxyethylamino)-ethylimino]-methyl}-6-methoxyphenol, H2L2 = 4-bromo-2-{[3-(2-hydroxyethylamino)propylimino]methyl}-6-methoxyphenol), differing in one -CH2- unit in the ligating backbone, by adopting template synthetic strategy. All the complexes have been characterized by single crystal X-ray diffraction analysis as well as by other routine physicochemical techniques. Ligand mediated structural variations have been observed and rationalized by density functional theoretical (DFT) calculations. Interaction of the complexes 1–4 with Bovine Serum Albumin protein (BSA) has been studied by different spectroscopic techniques. A complete thermodynamic profile (ΔHo, ΔSo and ΔGo) was evaluated initially from the change in absorption and fluorescence spectra upon addition of BSA to the complexes. Appreciable binding constant values in the range ~ 0.94–4.51 × 104 M−1 indicate efficient binding tendency of the complexes to BSA with the sequence 1 ≅ 2 > 3 ≅ 4. Circular dichroism (CD), isothermal calorimetric titration experiments, molecular docking and molecular dynamics have been performed to gain deep insight into the binding regions of complex 1 to BSA. Experimental evidences suggest an interaction of zinc complexes at the surface of BSA protein and this particular binding has been exploited to determine unknown concentration of BSA protein. For this purpose complex 1 was explored as a BSA protein quantification tool. 相似文献
72.
A new series of transition-metal complexes of Schiff base ligand containing the amino mercapto triazole moiety ( HL ) was prepared. The Schiff base and its metal complexes were elucidated by different spectroscopic techniques (infrared [IR], 1H nuclear magnetic resonance, UV–Visible, mass, and electron spin resonance [ESR]), and magnetic moment and thermal studies. Quantum chemical calculations have been carried out to study the structure of the ligand and some of its complexes. The IR spectra showed that the ligand is chelated with the metal ion in a neutral, tridentate, and bidentate manner using NOS and NO donors in complexes 1 – 6 , 10–12 , and 7 and 8 , respectively, whereas it behaves in a monobasic tridentate fashion using NOS donor sites in copper(II) nitrate complex ( 9 ). The magnetic moment and electronic spectra data revealed octahedral and square pyramidal geometries for complexes 2 , 11 , 12 , and 5 – 8 and 10 , respectively. However, the other complexes were found to have tetrahedral ( 4 ), trigonal bipyramidal ( 1 and 3 ), and square planar ( 9 ) structures. Thermal studies revealed that the chelates with different crystallized solvents undergo different types of interactions and the decomposition pathway ended with the formation of metal oxygen (MO) and metal sulfur (MS) as final products. The ESR spectrum of copper(II) complex 10 is axial in nature with hyperfine splitting with 2B1g as a ground state. By contrast, complexes 7 and 8 undergo distortion around the Cu(II) center, affording rhombic ESR spectra. The HL ligand and some of its complexes were screened against two bacterial species. Data showed that complex 12 demonstrated a better antibacterial activity than HL ligand and other chelates. 相似文献
73.
In this work, a vanillin complex is immobilized onto MCM-41 and characterized by FT-IR, X-ray diffraction, scanning electron microscopy, energy dispersive spectroscopy, thermogravimetric analysis, and BET techniques. This supported Schiff base complex was found to be an efficient and recoverable catalyst for the chemoselective oxidation of sulfides into sulfoxides and thiols into their corresponding disulfides (using hydrogen peroxide as a green oxidant) and also a suitable catalyst for the preparation of 2,3-dihydroquinazolin-4(1H)-one derivatives in water at 90°C. Using this protocol, we show that a variety of disulfides, sulfoxides, and 2,3-dihydroquinazolin-4(1H)-one derivatives can be synthesized in green conditions. The catalyst can be recovered and recycled for further reactions without appreciable loss of catalytic performance. 相似文献
74.
Ali Pourjavadi Maryam Tavakolizadeh Seyed Hassan Hosseini Navid Rabiee Mojtaba Bagherzadeh 《Journal of polymer science. Part A, Polymer chemistry》2020,58(15):2062-2073
A number of synthetic hydrogels suffer from low mechanical strength. Despite of the recent advances in the fabrication of tough hydrogels, it is still a great challenge to simultaneously construct high stretchability, and self-adhesive and self-healing capability in a hydrogel. Herein, a new type of double network hydrogel was prepared based on irreversible cross-linking of polyacrylamide chains and Schiff-base reversible cross-linking between glycidyl methacrylate-grafted ethylenediamine and oxidized sodium alginate (OSA). The combination of both cross-linkings and their synergistic effect provided a novel hydrogel with high strength, stretchable, rapid self-healing, and self-adhesiveness to different material. Besides, the hydrogels with diverse OSA content could maintain their original shapes after loading–unloading tensile test. The resulting hydrogel has a great potential in various fields for supporting and load-bearing substance. 相似文献
75.
76.
We give a characterization of the cyclic subgroup separability and weak potency of the fundamental group of a graph of polycyclic-by-finite groups and free-by-finite groups amalgamating edge subgroups of the form × D,where h has infinite order and D is finite. 相似文献
77.
Shyam Sundar Mondal Namita Jaiswal Partha Sarathi Bera Ranjay K. Tiwari Jogendra Nath Behera Nripen Chanda Subhas Ghosal Tanmoy Kumar Saha 《应用有机金属化学》2021,35(1)
A series of copper (II) ( 1 and 3 ) and cobalt (II/III) ( 2 , 4 and 5 ) complexes comprising different imino‐phenolate ligands DCH , DTH and DBH 2 (where DCH = 2,4‐dichloro‐6‐((mesitylimino)methyl)phenol, DTH = 2,4‐di‐tert‐butyl‐6‐((mesitylimino)methyl) phenol and DBH 2 = 2,4‐dibromo‐6‐((mesitylimino)methyl)phenol) have been prepared with excellent yield and high purity. By utilizing different spectroscopic tools such as UV–visible, electrospray ionization (ESI)‐mass, Fourier‐transform infrared (FTIR) spectrometry and elemental analysis, the prepared complexes ( 1 – 5 ) were thoroughly characterized. The molecular structure of the synthesized complexes was ascertained by using single‐crystal X‐ray diffraction studies (SCXRDs). The experiment reveals that Complexes 1 – 5 bind to calf thymus DNA (CT‐DNA) through non‐intercalative way with good interacting abilities. However, 1 – 5 are excellent quenchers of the fluorescence intensity of bovine serum albumin (BSA) following the static pathway. Additionally, they had shown remarkable cytotoxic potential against MCF‐7 (mammary gland adenocarcinoma) and A549 (lung adenocarcinoma) cell lines. The IC50 values associated with these complexes were much lower than the conventional drug cisplatin. Apoptosis‐induced cell death was confirmed from the DNA fragmentation studies and Hoechst 33342 staining. The 2′,7′‐dichlorofluorescein diacetate (DCFDA) assay indicates that the complex mediated reactive oxygen species (ROS) generation is accountable for governing the apoptosis mechanism via oxidative cell distress. Apart from these studies, by carrying out density functional theory (DFT) method, highest occupied molecular orbital–lowest unoccupied molecular orbital (HOMO–LUMO) energy gap calculations and optimized structures of the synthesized complexes were accomplished. 相似文献
78.
79.
80.
Siamak Shams Es-haghi Robert A. Weiss 《Journal of polymer science. Part A, Polymer chemistry》2022,60(16):2476-2487
A continuum damage model was developed to describe the finite tensile deformation of tough double-network (DN) hydrogels synthesized by polymerization of a water-soluble monomer inside a highly crosslinked rigid polyelectrolyte network. Damage evolution in DN hydrogels was characterized by performing loading-unloading tensile tests and oscillatory shear rheometry on DN hydrogels synthesized from 3-sulfopropyl acrylate potassium salt (SAPS) and acrylamide (AAm). The model can explain all the mechanical features of finite tensile deformation of DN hydrogels, including idealized Mullins effect and permanent set observed after unloading, qualitatively and quantitatively. The constitutive equation can describe the finite elasto-plastic tensile behavior of DN hydrogels without resorting to a yield function. It was showed that tensile mechanics of DN hydrogels in the model is controlled by two material parameters which are related to the elastic moduli of first and second networks. In effect, the ratio of these two parameters is a dimensionless number that controls the behavior of material. The model can capture the stable branch of material response during neck propagation where engineering stress becomes constant. Consistent with experimental data, by increasing the elastic modulus of the second network the finite tensile behavior of the DN hydrogel changes from necking to strain hardening. 相似文献