全文获取类型
收费全文 | 4207篇 |
免费 | 202篇 |
国内免费 | 99篇 |
专业分类
化学 | 2682篇 |
晶体学 | 57篇 |
力学 | 199篇 |
综合类 | 6篇 |
数学 | 822篇 |
物理学 | 742篇 |
出版年
2024年 | 8篇 |
2023年 | 60篇 |
2022年 | 114篇 |
2021年 | 139篇 |
2020年 | 159篇 |
2019年 | 130篇 |
2018年 | 125篇 |
2017年 | 94篇 |
2016年 | 170篇 |
2015年 | 130篇 |
2014年 | 164篇 |
2013年 | 344篇 |
2012年 | 273篇 |
2011年 | 312篇 |
2010年 | 197篇 |
2009年 | 181篇 |
2008年 | 268篇 |
2007年 | 231篇 |
2006年 | 219篇 |
2005年 | 200篇 |
2004年 | 159篇 |
2003年 | 141篇 |
2002年 | 131篇 |
2001年 | 70篇 |
2000年 | 41篇 |
1999年 | 51篇 |
1998年 | 35篇 |
1997年 | 38篇 |
1996年 | 31篇 |
1995年 | 31篇 |
1994年 | 23篇 |
1993年 | 23篇 |
1992年 | 15篇 |
1991年 | 12篇 |
1990年 | 9篇 |
1989年 | 10篇 |
1988年 | 9篇 |
1987年 | 7篇 |
1986年 | 13篇 |
1985年 | 11篇 |
1984年 | 14篇 |
1983年 | 20篇 |
1982年 | 16篇 |
1981年 | 12篇 |
1980年 | 9篇 |
1979年 | 12篇 |
1976年 | 9篇 |
1975年 | 8篇 |
1974年 | 4篇 |
1973年 | 5篇 |
排序方式: 共有4508条查询结果,搜索用时 15 毫秒
81.
The near-UV-vis electronic spectroscopy of [Ru(X)(Me)(CO)(2)(iPr-DAB)] (X = Cl or I; iPr-DAB = N,N'-di-isopropyl-1,4-diaza-1,3-butadiene) is investigated through CASSCF/CASPT2 and TD-DFT calculations on the model complexes [Ru(X)(Me)(CO)(2)(Me-DAB)] (X = Cl or I). Convergence of the calculated transition energies for the low-lying metal-to-ligand charge-transfer (MLCT), X-to-ligand charge-transfer (XLCT, X halide ligand), or sigma-bond-to-ligand charge-transfer (SBLCT) to experimental values is analyzed for both methods. On the basis of these accurate calculations, it is shown that whereas the lowest singlet state can be assigned to a nearly pure XLCT state in [Ru(I)(Me)(CO)(2)(Me-DAB)], its character is mainly MLCT in [Ru(Cl)(Me)(CO)(2)(Me-DAB)]. These results are in agreement with time-resolved emission/IR and resonance Raman experimental data. The experimental UV-vis bands are well reproduced by the CASSCF/CASPT2 calculations. The TD-DFT transition energies to the long-range charge transfer states are dramatically affected by the nature of the functional, with lowering leading to meaningless values in the case of nonhybrid functionals. Both methods reproduce well the red shift of the absorption bands on going from the chloride to the iodide complex as well as the shift of the strongly absorbing higher MLCT transition from the visible to the UV domain of energy. 相似文献
82.
A series of spiropyrans with a polyaromatic or heteroaromatic pendant was synthesized conveniently.Their photochromic behaviors were investigated with the aid of absorption spectral measurements.The results indicated that the compounds with the same parent spiropyran but different aromatic pendant show significantly different photochromic properties.This may be due to the π-π orbital interaction between the polyaromatic pendant and the open photomerocyanine form of spiropyran.The results obtained are very useful in the molecule design area. 相似文献
83.
New hybrid organic-inorganic gels have been obtained by reaction of 1,4-butanediol, on tetramethoxysilane Si(OMe)4 dissolved in CCl4. This reaction does not require water and leads to the formation of polymeric transparent materials.Infrared, 29Si and 13C NMR spectroscopy shows that interchange reactions between OMe groups of alkoxide and -O-(CH2)4-O of 1,4-butanediol occurred, leading to the monolithic transparent gels in which both organic (Si-O-(CH2)4-O-Si) and inorganic (Si-O-Si) bridges are formed. 相似文献
84.
Wendt-Pienkowski E Huang Y Zhang J Li B Jiang H Kwon H Hutchinson CR Shen B 《Journal of the American Chemical Society》2005,127(47):16442-16452
Fredericamycin (FDM) A, a pentadecaketide featuring two sets of peri-hydroxy tricyclic aromatic moieties connected through a unique chiral spiro carbon center, exhibits potent cytotoxicity and has been studied as a new type of anticancer drug lead because of its novel molecular architecture. The fdm gene cluster was localized to 33-kb DNA segment of Streptomyces griseus ATCC 49344, and its involvement in FDM A biosynthesis was proven by gene inactivation, complementation, and heterologous expression experiments. The fdm cluster consists of 28 open reading frames (ORFs), encoding a type II polyketide synthase (PKS) and tailoring enzymes as well as several regulatory and resistance proteins. The FDM PKS features a KSalpha subunit with heretofore unseen tandem cysteines at its active site, a KSbeta subunit that is distinct phylogenetically from KSbeta of hexa-, octa-, or decaketide PKSs, and a dedicated phosphopantetheinyl transferase. Further study of the FDM PKS could provide new insight into how a type II PKS controls chain length in aromatic polyketide biosynthesis. The availability of the fdm genes, in vivo characterization of the fdm cluster in S. griseus, and heterologous expression of the fdm cluster in Streptomyces albus set the stage to investigate FDM A biosynthesis and engineer the FDM biosynthetic machinery for the production of novel FDM A analogues. 相似文献
85.
Ben Li Yumeng Ji Chenlong Yi Xufeng Wang Chaoyang Liu Chufan Wang Xiaohu Lu Xiaohan Xu Xiaowei Wang 《Molecules (Basel, Switzerland)》2022,27(13)
Atherosclerosis (AS) is one of the leading causes of death among the elderly, and is primarily caused by foam cell generation and macrophage inflammation. Rutin is an anti-inflammatory, anti-oxidant, anti-allergic, and antiviral flavonoid molecule, known to have anti-atherosclerotic and autophagy-inducing properties, but its biological mechanism remains poorly understood. In this study, we uncovered that rutin could suppress the generation of inflammatory factors and reactive oxygen species (ROS) in ox-LDL-induced M2 macrophages and enhance their polarization. Moreover, rutin could decrease foam cell production, as shown by oil red O staining. In addition, rutin could increase the number of autophagosomes and the LC3II/I ratio, while lowering p62 expression. Furthermore, rutin could significantly inhibit the PI3K/ATK signaling pathway. In summary, rutin inhibits ox-LDL-mediated macrophage inflammation and foam cell formation by inducing autophagy and modulating PI3K/ATK signaling, showing potential in treating atherosclerosis. 相似文献
86.
Secretory group V phospholipase A2 (PLA2-V) is known to be involved in inflammatory processes in cellular studies, nevertheless, the biochemical and the enzymatic characteristics of this important enzyme have been unclear yet. We reported, as a first step towards understanding the biochemical properties, catalytic characteristics, antimicrobial and cytotoxic effects of this PLA2, the production of PLA2-V from dromedary. The obtained DrPLA2-V has an absolute requirement for Ca2+ and NaTDC for enzymatic activity with an optimum pH of 9 and temperature of 45 °C with phosphatidylethanolamine as a substrate. Kinetic parameters showed that Kcat/Kmapp is 2.6 ± 0.02 mM−1 s−1. The enzyme was found to display potent Gram-positive bactericidal activity (with IC50 values of about 5 µg/mL) and antifungal activity (with IC50 values of about 25 µg/mL)in vitro. However, the purified enzyme did not display a cytotoxic effect against cancer cells. 相似文献
87.
研究发现,颗粒物质层被匀速推移挤压过程中,所需推移力先以线性规律增加,在某一确定点后,则会以指数规律增加.而颗粒物质是由众多离散颗粒组成的软凝聚态物质,其宏观上反映的是离散颗粒的个体性质和凝聚态物质的集体效应.颗粒与颗粒之间以及颗粒与边界之间的细观尺度接触力链的构成以及演变规律将会直接影响各种宏观受力情况,其摩擦力与挤压力便是力链的主要构成形式.围绕着定量描述细观力链特征,从而揭示力的变化规律这一目标,采用计算机模拟的方法,依照球形颗粒Hertz法向接触理论和Mindlin-Deresiewicz切向接触理论,对重力作用下不同数目的三维等径球体颗粒层的推移情况进行了离散元仿真模拟,量化分析了推移力变化规律、各摩擦力变化规律以及力链分布规律,发现摩擦力与挤压力在颗粒堆积的不同阶段对力链的构成起到了不同的主次作用,使得力链发生强弱演变,从而发现了推移颗粒物质层时推移力的变化规律及原因.这些结果有利于从力链角度揭示颗粒内部和颗粒与各边界之间的受力情况. 相似文献
88.
Leila Saedi Zahra Javanshir Salah Khanahmadzadeh Maryam Maskanati Milad Nouraliei 《Molecular physics》2020,118(7)
ABSTRACTDensity functional theory calculations were used to investigate the potential application of an AlN nanocluster in the detection of H2S, COS, CS2 and SO2 gases. In overall, the order of strength of interaction of these gases with the nanocluster is as follows: SO2 (Ead?=??17.6?kcal/mol)?>?H2S (Ead?=??14.0?kcal/mol)?>?COS (Ead?=??8.4?kcal/mol)?>?CS2 (Ead?=??4.5?kcal/mol). This indicates that by increasing the electric dipole moment, the adsorption energy becomes more negative. We found that the Al12N12 nanocluster may be a promising work function-type sensor for SO2 gas among the studied gases. Also, it is an electronic sensor for both SO2 and CS2 gases but selectively acts between them because of their different effects on the electrical conductivity. It is neither work function-type nor electronic sensor for H2S and COS gases. The AlN nanocluster benefits from a short recovery time about 7.7?s and 18.0?ms for desorption of SO2 and CS2 gases from its surface at room temperature, respectively. It is also concluded that this cluster can work at a humid environment. 相似文献
89.
Influences of nanoparticles and chain length on thermodynamic and electrical behavior of fluorine liquid crystals 下载免费PDF全文
Ines Ben Amor Lotfi Saadaoui Abdulaziz N. Alharbi Talal M. Althagafi and Taoufik Soltani 《中国物理 B》2022,31(10):104202-104202
Hydrogen-bonded polar nematic liquid crystal series with the general formula nOBAF (n = 7—12) is studied. The mesomorphic characterization is demonstrated through differential scanning calorimetry (DSC) and polarized optical microscopy (POM). The complexes with short alkyl chains (n=7, 8) present a wide nematic range and monotropic smectic F mesophase, whereas the longer alkyl chain (n=10—12) analogues show high melting and low clearing mesomorphic liquid crystals. The thermal range of the mesophase and the birefringence increase with chain length decreasing. Furthermore, the effect of the nanoparticles (LiNbO3) on the thermal and the electrical behavior of 8OBAF are investigated. The presence of LiNbO3 nanoparticles increases the conductivity and reduces the resistivity of the complex. 相似文献
90.