全文获取类型
收费全文 | 33185篇 |
免费 | 2063篇 |
国内免费 | 1784篇 |
专业分类
化学 | 19060篇 |
晶体学 | 139篇 |
力学 | 1337篇 |
综合类 | 625篇 |
数学 | 6972篇 |
物理学 | 8899篇 |
出版年
2023年 | 213篇 |
2022年 | 368篇 |
2021年 | 1196篇 |
2020年 | 653篇 |
2019年 | 759篇 |
2018年 | 532篇 |
2017年 | 550篇 |
2016年 | 726篇 |
2015年 | 814篇 |
2014年 | 1058篇 |
2013年 | 1966篇 |
2012年 | 1273篇 |
2011年 | 1472篇 |
2010年 | 1360篇 |
2009年 | 1856篇 |
2008年 | 1902篇 |
2007年 | 2082篇 |
2006年 | 1562篇 |
2005年 | 962篇 |
2004年 | 923篇 |
2003年 | 1011篇 |
2002年 | 3476篇 |
2001年 | 927篇 |
2000年 | 647篇 |
1999年 | 533篇 |
1998年 | 518篇 |
1997年 | 387篇 |
1996年 | 465篇 |
1995年 | 408篇 |
1994年 | 433篇 |
1993年 | 466篇 |
1992年 | 465篇 |
1991年 | 327篇 |
1990年 | 248篇 |
1989年 | 205篇 |
1988年 | 235篇 |
1987年 | 190篇 |
1986年 | 206篇 |
1985年 | 318篇 |
1984年 | 236篇 |
1983年 | 145篇 |
1982年 | 293篇 |
1981年 | 469篇 |
1980年 | 427篇 |
1979年 | 466篇 |
1978年 | 374篇 |
1977年 | 281篇 |
1976年 | 237篇 |
1974年 | 74篇 |
1973年 | 149篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
71.
The electronic (energy gap and work function) as well as electrical properties (dipole moment, polarizability, and first hyperpolarizabilities) of the first-row transition metals decorated C24N24 cavernous nitride fullerene were explored using DFT calculations. The transition metals are decorated at N4 cavity of C24N24 fullerene. According to our spin polarized computations, the most stable spin state monotonically increases to sextet for Mn@C24N24 and thereafter dropped off gradually to singlet state for Zn@C24N24 system. The findings demonstrate that transition metals can remarkably decrease the HOMO-LUMO energy gap and work function values up to 63% and 21% of bare C24N24, respectively. As can be seen, when the Sc and Ti metals are located above the N4 cavity of fullerene, systems of enhanced static hyperpolarizabilities (β0) are delivered. These findings might provide an effective strategy to design high performance eletcro-optical materials based on carbon- nitride fullerene. 相似文献
72.
73.
74.
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
75.
A greener and efficient method for the synthesis of ynones and 1,3-diynes using copper oxide nanoparticles (CuONPs) doped reduced graphene oxide (CuO@rGO) catalyst under palladium, ligand and solvent free conditions have been developed. The catalyst was subsequently utilized for the synthesis of biologically active 1,5-benzodiazepines in one pot via sequential addition of acyl chlorides, terminal alkynes and o-phenylenediamines. The methodology initially involves in situ formation of ynones which react with o-phenylenediamines in presence of ethanol to afford a wide variety of benzodiazepines. Mild reaction conditions, good to an excellent yield of the products, cheap and recyclable catalyst make this methodology environmentally benign and sustainable. 相似文献
76.
Suresh P S Ravi Kumar Trivedi Nuggehally R. Srinivas Ramesh Mullangi 《Biomedical chromatography : BMC》2020,34(1):e4742
Quantitation of drugs used for the treatment of chronic lymphocytic leukemia in various biological matrices during both pre-clinical and clinical developments is very important, often in routine therapeutic drug monitoring. The first developed methods for quantitation were traditionally done on LC in combination with either UV or fluorescence detection. However, the emergence of LC with mass spectrometry in tandem in early 1990s has revolutionized the quantitation as it has provided better sensitivity and selectivity within a shorter run time; therefore it has become the choice of method for the analysis of various drugs. In this article, an overview of various bioanalytical methods (HPLC or LC–MS/MS) for the quantification of drugs for the treatment of chronic lymphocytic leukemia, along with applicability of these methods, is given. 相似文献
77.
Séan J. Cassady Rishav Choudhary Vivek Boddapati Nicolas H. Pinkowski David F. Davidson Ronald K. Hanson 《国际化学动力学杂志》2020,52(11):725-738
The pyrolysis of propane plays an important role in determining the combustion properties of natural gas mixtures and offers insight into the cracking patterns of larger fuels. This work investigates propane pyrolysis behind reflected shock waves with a multiwavelength laser-absorption speciation technique. Nine laser wavelengths, sensitive to key pyrolysis species, were used to measure absorbance time histories during the decomposition of 2% propane in argon between 1022 and 1467 K, 3.7-4.3 atm. Absorbance models were developed at each diagnostic wavelength to interrogate common initial conditions, and time histories of all major species are reported at 1250, 1290, 1330, 1370, and 1410 K. Nearly complete carbon recovery observed at lower temperatures enabled the inference of hydrogen formation from atomic conservation, while decaying carbon recovery at high temperatures suggests the formation of allene and 1-butene. The results show systematically faster pyrolysis than predicted by kinetic modeling and motivate further study into the kinetics of propane pyrolysis. 相似文献
78.
Yuto Kurasaki Yasuhito Suzuki Akikazu Matsumoto 《Journal of polymer science. Part A, Polymer chemistry》2020,58(7):923-931
We carried out the thermal curing of the copolymers of N-allylmaleimide (AMI) and 2-ethylhexyl acrylate (2EHA) using 1,3,4,6-tetra(2-mercaproethyl)glycoluril ( G1 ), 1,3,4,6-tetra(3-mercaptopropyl)glycoluril ( G2 ), 1,3,4,6-tetraallylglycoluril ( G3 ), triallylisocyanurate (TAIC), and pentaerythritol tetrakis(3-mercaptobutyrate) (PEMB) as the crosslinkers. Based on the results for the analysis of thiol–ene reactions monitored by IR spectroscopy, it was confirmed that the curing rate significantly depended on the combination of the used crosslinkers. The insoluble fraction after curing was more than 90% for the systems using the glycoluril crosslinkers, while the conversion of the allyl groups was suppressed due to the rigid structure of these crosslinkers. The heat resistance and the mechanical properties of the crosslinked polymers were investigated by thermogravimetric analysis, differential scanning calorimetry, dynamic mechanical analysis, and mechanical tensile tests. For the products cured using the glycoluril crosslinkers, the glass transition temperature (Tg) and the maximum temperature of thermal decomposition (Tmax) were 54–59 °C and 395–409 °C, respectively, being higher than those for the cured product prepared with PEMB and TAIC as the conventional crosslinkers. The elasticity (75–139 MPa), the maximum strength (3.0–4.1 MPa), and the adhesion strength (6.7–10.7 MPa) for the polymers cured with the glycoluril crosslinkers, determined by the mechanical tensile and single lap-shear adhesion tests, were higher than those for cured materials produced with PEMB. Thus, the thermal and mechanical properties of the maleimide copolymers were efficiently enhanced by crosslinking using the rigid glycoluril compounds. © 2020 Wiley Periodicals, Inc. J. Polym. Sci. 2020 , 58, 923–931 相似文献
79.
Yu-Yi Zhang De-Shan Zhang Tian Li Dr. Mohamedally Kurmoo Prof. Dr. Ming-Hua Zeng 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(3):721-728
Dehydration of (S,S)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethane-1,2-diol (H4L) to (Z)-1,2-bis(1H-benzo[d]imidazol-2-yl)ethenol) (H3L′) was found to be metal-assisted, occurs under solvothermal conditions (H2O/CH3OH), and leads to [MnII4(H3L)4Cl2]Cl2 ⋅ 5 H2O ⋅ 5 CH3OH ( Mn4L4 ) and [MnII4(H2L′)6(μ3-OH)]Cl ⋅ 4 CH3OH ⋅ H2O ( Mn4L′6 ), respectively. Their structures were determined by single-crystal XRD. Extensive ESI-MS studies on solutions and solids of the reaction led to the proposal consisting of an initial stepwise assembly of Mn4L4 from the reactants via [MnL] and [Mn2L2] below 80 °C, and then disassembly to [MnL] and [MnL2] followed by ligand modification before reassembly to Mn4L′6 via [MnL′], [MnL′2], and [Mn2L′3] with increasing solvothermal temperature up to 140 °C. Identification of intermediates [Mn4LxL′6−x] (x=5, 4, 3, 2, 1) in the process further suggested an assembly/disassembly/in situ reaction/reassembly transformation mechanism. These results not only reveal that multiple phase transformations are possible even though they were not realized in the crystalline state, but also help to better understand the complex transformation process between coordination clusters during “black-box” reactions. 相似文献
80.
We propose a conjecture on the relative twist formula of l-adic sheaves, which can be viewed as a generalization of Kato—Saito's conjecture. We verify this conjecture under some transversal assumptions. We also define a relative cohomological characteristic class and prove that its formation is compatible with proper push-forward. A conjectural relation is also given between the relative twist formula and the relative cohomological characteristic class. 相似文献