全文获取类型
收费全文 | 30470篇 |
免费 | 5374篇 |
国内免费 | 4130篇 |
专业分类
化学 | 22208篇 |
晶体学 | 354篇 |
力学 | 2008篇 |
综合类 | 293篇 |
数学 | 3609篇 |
物理学 | 11502篇 |
出版年
2024年 | 26篇 |
2023年 | 650篇 |
2022年 | 678篇 |
2021年 | 909篇 |
2020年 | 1290篇 |
2019年 | 1184篇 |
2018年 | 996篇 |
2017年 | 848篇 |
2016年 | 1424篇 |
2015年 | 1391篇 |
2014年 | 1731篇 |
2013年 | 2177篇 |
2012年 | 2771篇 |
2011年 | 2846篇 |
2010年 | 1990篇 |
2009年 | 1780篇 |
2008年 | 2034篇 |
2007年 | 1858篇 |
2006年 | 1809篇 |
2005年 | 1557篇 |
2004年 | 1180篇 |
2003年 | 1009篇 |
2002年 | 1001篇 |
2001年 | 848篇 |
2000年 | 653篇 |
1999年 | 711篇 |
1998年 | 562篇 |
1997年 | 497篇 |
1996年 | 566篇 |
1995年 | 477篇 |
1994年 | 459篇 |
1993年 | 359篇 |
1992年 | 317篇 |
1991年 | 280篇 |
1990年 | 219篇 |
1989年 | 204篇 |
1988年 | 169篇 |
1987年 | 108篇 |
1986年 | 88篇 |
1985年 | 87篇 |
1984年 | 72篇 |
1983年 | 48篇 |
1982年 | 33篇 |
1981年 | 31篇 |
1980年 | 20篇 |
1979年 | 4篇 |
1978年 | 3篇 |
1977年 | 3篇 |
1957年 | 9篇 |
1936年 | 2篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
Hou Conghui Zhang Hongfang Zheng Jianbin 《Journal of Solid State Electrochemistry》2017,21(10):3029-3035
Journal of Solid State Electrochemistry - This contribution described the electrochemical study of organosoluble gold nanoclusters (AuNCs).The AuNCs were characterized with UV-vis absorption... 相似文献
992.
Evolution of concentration fluctuation during phase separation of polystyrene/poly(vinyl methyl ether) blend in the presence of nanosilica 下载免费PDF全文
Qi Chen Min Zuo Ruiquan Yang Jifei Zhang Xiong Lv Wenjing Zhang Yihu Song Qiang Zheng 《Journal of Polymer Science.Polymer Physics》2017,55(17):1337-1349
The influence of nanosilica on the concentration fluctuation of polystyrene/poly (vinyl methyl ether) (PS/PVME) mixtures was investigated during phase separation. The amplitude of concentration fluctuation was quantified by dielectric spectrums based on the idea of Lodge–Mcleish model and the linearized Cahn–Hilliard theory could describe the amplitude evolution of concentration fluctuation at the early stage of phase separation. Hydrophilic nanosilica A200 dispersed in PVME‐rich phase behaved an obvious inhibition effect on the concentration fluctuation of blend matrix, while hydrophobic nanosilica R974 dispersed in PS‐rich phase had little effect on the concentration fluctuation. The kinetics and amplitude evolution of concentration fluctuation during phase separation for PS/PVME/A200 nanocomposites were remarkably restrained due to the surface adsorption of PVME on A200. As the segmental dynamics of PVME and PS in homogeneous matrix was hardly influenced by A200 and R974, the enhanced miscibility and the significantly constrained flow relaxation of PVME chains might contribute to the retarded concentration fluctuation of PS/PVME/A200 nanocomposites. While the weak interaction between R974 and components of blend matrix and little effect of R974 on the molecular dynamics of PS chains may result in the weak retardation of concentration fluctuation for blend matrix. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part B: Polym. Phys. 2017 , 55, 1337–1349 相似文献
993.
994.
Lin-Feng You Tao Wei Qian-Wang Zheng Jun-Fang Lin Li-Qiong Guo Bing-Hua Jiang Jia-Jun Huang 《Applied biochemistry and biotechnology》2018,186(4):949-959
Taxoid 10β-O-acetyl transferase (DBAT) is a key enzyme in the biosynthesis of the famous anticancer drug paclitaxel, which catalyses the formation of baccatin III from 10-deacetylbaccatin III (10-DAB). However, the activity essential residues of the enzyme are still unknown, and the acylation mechanism from its natural substrate 10-deacetylbaccatin III and acetyl CoA to baccatin III remains unclear. In this study, the homology modelling, molecular docking, site-directed mutagenesis, and kinetic parameter determination of the enzyme were carried out. The results showed that the enzyme mutant DBATH162A resulted in complete loss of enzymatic activity, suggesting that the residue histidine at 162 was essential to DBAT activity. Residues D166 and R363 which were located in the pocket of the enzyme by homology modelling and molecular docking were also important for DBAT activity through the site-directed mutations. Furthermore, four amino acid residues including S31 and D34 from motif SXXD, D372 and G376 from motif DFGWG also played important roles on acylation. This was the first report of the elucidation of the activity essential residues of DBAT, making it possible for the further structural-based re-design of the enzyme for efficient biotransformation of baccatin III and paclitaxel. 相似文献
995.
A mild, efficient, and environmentally benign one-pot synthesis of functionalized chromeno[4,3-b]pyrrol-4(1H)-ones by a three-component domino reaction of 4-aminocoumarins, arylglyoxal monohydrates, and 1,3-dicarbonyl compounds in refluxing ethanol without the use of catalyst is reported. The present protocol features operational simplicity, short reaction time, good yields, and the absence of aqueous workup procedure and chromatographic separation. 相似文献
996.
Weiping Gan Xiaosong Cao Yi Shi Lei Zou Haifeng Gao 《Journal of polymer science. Part A, Polymer chemistry》2018,56(19):2238-2244
Copper-catalyzed azide-alkyne cycloaddition polymerization (CuAACP) of AB2 monomers demonstrated a chain-growth mechanism without any external ligand because of the complexation of in situ formed triazole groups with Cu catalysts. In this study, we explored the use of various ligands that affected the polymerization kinetics to tune the polymers’ molecular weights and the degree of branching (DB). Eight ligands were studied, including polyethylene glycol monomethyl ether (PEG350, Mn = 350), tris(benzyltriazolylmethyl)amine (TBTA), 2,6-bis(1-undecyl-1H-benzo[d]imidazol-2-yl)pyridine (Py(DBim)2), 2,2′-bipyridyl (bpy), 4,4′-di-n-nonyl-2,2′-bipyridine (dNbpy), N,N,N′,N″,N″-pentamethyldiethylenetriamine (PMDETA), N,N,N′,N″,N″-penta(n-butyl)diethylenetriamine (PBuDETA), and N,N,N′,N″,N″-pentabenzyldiethylenetriamine (PBnDETA). All ligands except PEG350 exhibited stronger coordination with Cu(I) than the polytriazole polymer, which freed the Cu catalyst from polymers and resulted in dominant step-growth polymerization with simultaneous chain-growth feature. Meanwhile, the use of PEG350 ligand retained the confined Cu in the polymer, demonstrating a chain-growth mechanism, but lower polymer molecular weights as compared with the no-external-ligand polymerization. Results indicated that aliphatic substituent groups on ligands had little effect on the molecular weights and DB of the polymers, but rigid aromatic substituent groups decreased both values. By varying the ligand species and amounts, hyperbranched polymers with DB value ranging from 0.53 ([TBTA]0/[Cu]0 = 5) to 0.98 ([PMDETA]0/[Cu]0 = 2) have been achieved. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 2238–2244 相似文献
997.
Two water‐soluble 6‐(pyrazin‐2‐yl)‐1,3,5‐triazine‐2,4‐diamino (pzta)‐based Cu(II) complexes, namely [Cu(l ‐Val)(pzta)(H2O)]ClO4 ( 1 ) and [Cu(l ‐Thr)(pzta)(H2O)]ClO4 ( 2 ) (l ‐Val: l ‐valinate; l ‐Thr: l ‐threoninate), were synthesized and characterized using elemental analyses, molar conductance measurements, spectroscopic methods and single‐crystal X‐ray diffraction. The results indicated that the molecular structures of the complexes are five‐coordinated and show a distorted square‐pyramidal geometry, in which the central copper ions are coordinated to N,N atoms of pzta and N,O atoms of amino acids. The interactions of the complexes with DNA were investigated using electronic absorption, competitive fluorescence titration, circular dichroism and viscosity measurements. These studies confirmed that the complexes bind to DNA through a groove binding mode with certain affinities (Kb = 4.71 × 103 and 1.98 × 103 M?1 for 1 and 2 , respectively). The human serum albumin (HSA) binding properties of the complexes were also evaluated using fluorescence and synchronous fluorescence spectroscopies, indicating that the complexes could quench the intrinsic fluorescence of HSA in a static quenching process. The relevant thermodynamic parameters revealed the involvement of van der Waals forces and hydrogen bonds in the formation of complex–HSA systems. Finally, molecular docking technology was also used to further verify the interactions of the complexes with DNA/HSA. 相似文献
998.
Using the phase field crystal approach, the crystallization process within the liquid–solid coexistence region is investigated for a square lattice on an atomic scale. Two competing growth modes, i.e., the diffusion-controlled growth through long-range atomic migration in liquid and the diffusionless growth through local atom rearrangement, which give rise to two completely different crystallization behaviors, are compared. In the diffusion-controlled regime, the interface migrates in a layerwise manner, leading to a gradual change of crystal morphology from truncated square to four-fold symmetric dendrite with the increase of driving force. For the diffusionless growth mode, a single crystal with no significant density change occupies the whole system at a faster rate while exhibiting a small growth anisotropy. The competition between these two modes is also discussed from the key input of the phase field crystal model: the correlation function. 相似文献
999.
One‐dimensional (1D) quantitative NMR (qNMR) is a useful tool for concentration determination due to its experimental simplicity and the direct proportionality of the integrated signal area to the number of nuclei spin. For complex mixtures, however, signal overlapping often in one‐dimensional quantitative 1H NMR (1D 1H qNMR) spectrum limits the accurate quantification of individual compound. Here, we introduced employing joint 1D qNMR methods of different nuclei, such as 1H and 31P (or/and 19F), to quantify multiple compounds in a complex mixture using a single universal concentration reference. When the concentration ratio of several compounds containing different elements in a complex mixture is of interest, the result calculated from measured intensities from 1D qNMR of different nuclei is independent of the gravimetric error from the reference. In this case, the common reference also serves as a ‘quantitative bridge’ among these 1D qNMR of different nuclei. Quantitative analysis of choline, phosphocholine, and glycerophosphocholine mixture is given as an example using trimethylphosphine oxide ((CH3)3P(O)) as concentration reference. Compounds containing multiple elements, such as tetramethylammonium hexafluorophosphate (N+(CH3)4PF6?), are proposed as the common concentration reference for 1H, 13C, 15N, 31P, and 19F qNMR for the quantitative analysis of complex mixture containing these different elements. We anticipate that the proposed joint 1D qNMR approach using a universal concentration reference will be a valuable alternative for simultaneous quantification of multiple compounds in a complex mixture due to its accuracy and single and simple sample preparation. Copyright © 2014 John Wiley & Sons, Ltd. 相似文献
1000.
Extraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN filmExtraordinary terahertz transmission through subwavelength spindle-like apertures in NbN film 下载免费PDF全文
We studied numerically the temperature dependent extraordinary terahertz transmission through niobium nitride (NbN) film perforated with subwavelength spindle-like apertures. Both the resonant frequency and intensity of extraor- dinary terahertz transmission peaks can be greatly modified by the transition of NbN film from the normal state to the superconducting state. An enhancement of the (~1,0) NbN/magnesium oxide (MgO) peak intensity as high as 200% is demonstrated due to the combined contribution of both the superconducting transition and the excitation of localized surface plasmons (LSPs) around the apertures. The extraordinary terahertz transmission through spindle-fike hole arrays patterned on the NbN film can pave the way for us to explore novel active tuning devices. 相似文献