全文获取类型
收费全文 | 69919篇 |
免费 | 10238篇 |
国内免费 | 6641篇 |
专业分类
化学 | 46912篇 |
晶体学 | 659篇 |
力学 | 4661篇 |
综合类 | 515篇 |
数学 | 8449篇 |
物理学 | 25602篇 |
出版年
2024年 | 228篇 |
2023年 | 1399篇 |
2022年 | 2280篇 |
2021年 | 2389篇 |
2020年 | 2521篇 |
2019年 | 2422篇 |
2018年 | 2188篇 |
2017年 | 1939篇 |
2016年 | 2964篇 |
2015年 | 3078篇 |
2014年 | 3650篇 |
2013年 | 4843篇 |
2012年 | 5889篇 |
2011年 | 6015篇 |
2010年 | 4079篇 |
2009年 | 4018篇 |
2008年 | 4187篇 |
2007年 | 3788篇 |
2006年 | 3567篇 |
2005年 | 3092篇 |
2004年 | 2478篇 |
2003年 | 1895篇 |
2002年 | 1682篇 |
2001年 | 1520篇 |
2000年 | 1418篇 |
1999年 | 1563篇 |
1998年 | 1330篇 |
1997年 | 1169篇 |
1996年 | 1227篇 |
1995年 | 1071篇 |
1994年 | 1007篇 |
1993年 | 865篇 |
1992年 | 768篇 |
1991年 | 664篇 |
1990年 | 555篇 |
1989年 | 481篇 |
1988年 | 366篇 |
1987年 | 349篇 |
1986年 | 297篇 |
1985年 | 300篇 |
1984年 | 202篇 |
1983年 | 176篇 |
1982年 | 145篇 |
1981年 | 112篇 |
1980年 | 82篇 |
1978年 | 56篇 |
1977年 | 52篇 |
1976年 | 50篇 |
1975年 | 57篇 |
1973年 | 57篇 |
排序方式: 共有10000条查询结果,搜索用时 0 毫秒
751.
研究了高效液相色谱-火焰原子吸收光谱联用系统分析信号处理方法,比较了各种处理方法的优缺点,用积分与适应平滑法综合处理色谱峰分析信号,不仅能有效地消除噪声,而且能使分析信号得到加强,以测定镍为例,经积分与适应平滑法综合处理后,检出限改善了2.7倍。 相似文献
752.
Adsorption of CF4 on the internal and external surfaces of opened single-walled carbon nanotubes: a vibrational spectroscopy study 总被引:1,自引:0,他引:1
Byl O Kondratyuk P Forth ST FitzGerald SA Chen L Johnson JK Yates JT 《Journal of the American Chemical Society》2003,125(19):5889-5896
Infrared spectroscopy has been used to make the first experimental discrimination between molecules bound by physisorption on the exterior surface of carbon single-walled nanotubes (SWNTs) and molecules bound in the interior. In addition, the selective displacement of the internally bound molecules has been observed as a second adsorbate is added. SWNTs were opened by oxidative treatment with O(3) at room temperature, followed by heating in a vacuum to 873 K. It was found that, at 133 K and 0.033 Torr, CF(4) adsorbs on closed SWNTs, exhibiting its nu(3) asymmetric stretching mode at 1267 cm(-1) (red shift relative to the gas phase, 15 cm(-1)). Adsorption on the nanotube exterior is accompanied by adsorption in the interior in the case of opened SWNTs. Internally bound CF(4) exhibits its nu(3) mode at 1247 cm(-1) (red shift relative to the gas phase, 35 cm(-1)). It was shown that, at 133 K, Xe preferentially displaces internally bound CF(4) species, and this counterintuitive observation was confirmed by molecular simulations. The confinement of CF(4) inside (10,10) single-walled carbon nanotubes does not result in the production of lattice modes that are observed in large 3D ensembles of CF(4). 相似文献
753.
Chun‐Xiang Wang Chen‐Xia Du Zhi‐Feng Li 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(10):m488-m490
In the title compound, [Zn(C17H10N5O)2(H2O)2]·4H2O, cyclic water hexamers forming one‐dimensional metal–water chains are observed. The water clusters are trapped by the co‐operative association of coordination interactions and hydrogen bonds. The ZnII ion resides on a centre of symmetry and is in an octahedral coordination environment comprising two O atoms and two N atoms from two 2′‐(4,5‐diazafluoren‐9‐ylidene)picolinohydrazidate ligands and two water molecules. 相似文献
754.
A solution-phase synthesis of bicyclic prolines containing four points of diversity has been developed by a two-step synthesis involving 1,3-dipolar cycloaddition of perfluoroalkylsulfonyl-protected hydroxybenzaldehydes followed by Pd-catalyzed Suzuki coupling reaction of fluorous sulfonates with boronic acids. Both reactions are conducted under microwave irradiation and reaction mixtures are purified by solid-phase extractions without performing chromatography. 相似文献
755.
Three new alkaloids, longistylumphyllines A–C (1–3), together with the six known alkaloids deoxycalyciphylline B, deoxyisocalyciphylline B, methyl homosecodaphniphyllate, daphnicyclidin A, daphnicyclidin B, and daphnicyclidin F, were isolated from the stems and leaves of Daphniphyllum longistylum. Their structures and relative configuration were elucidated on the basis of spectroscopic data, especially 1D and 2D NMR techniques. 相似文献
756.
大庆渣油族组分非等温热反应的研究 总被引:2,自引:0,他引:2
采用动态热重分析法在升温速率为6.2K·min ̄(-1)及惰性气流量100cm ̄3·min ̄(-1)的条件下,对大庆渣油族组分的热转化行为进行了考察,获得了族组分的热转化速率峰值、速率峰值处的反应温度、转化率和剧裂分解温度区间等动力学基本数据以及各族组分的生焦性能。数据分析表明,族组分的热反应活性顺序为:饱和分>胶质>芳香分>沥青质。在大庆渣油族组分热转化的两个温区内,采用分段一级动力学模型较好地拟合了实验数据,确定了各族组分在两个温区内的热反应动力学参数。 相似文献
757.
微分倒数示波计时电位法的研究—定量测试及滴定分析 总被引:3,自引:0,他引:3
首次利用微分倒数示波图定量测试微量金属离子并滴定分析药物,结果满意。 相似文献
758.
Chen Luo Chenggang Zhou Jinping Wu T. J. Dhilip Kumar Naduvalath Balakrishnan Robert C. Forrey Hansong Cheng 《International journal of quantum chemistry》2007,107(7):1632-1641
Structures and physical properties of small palladium clusters Pdn up to n = 15 and several selected larger clusters were studied using density functional theory under the generalized gradient approximation. It was found that small Pdn clusters begin to grow 3‐dimensionally at n = 4 and evolve into symmetric geometric configurations, such as icosahedral and fcc‐like, near n = 15. Several isomers with nearly degenerate average binding energies were found to coexist and the physical properties of these clusters were calculated. For several selected isomers, relatively moderate energy barriers for structural interchange for a given cluster size were found, implying that isomerization could readily occur under ambient conditions. © 2007 Wiley Periodicals, Inc. Int J Quantum Chem, 2007 相似文献
759.
It is proposed that in molecular mechanics calculation points belonging to various stable or meta-sta-ble conformtrs are mixed up and form fractal structures in conformation space.The calculation results show the following two phenomena:(i)Two levels of structure with fractal feature were observed.Around the conformer without mirror symmetry points belonging to the conformer and its enantiomer are mixed up and form the first level of fractal structure; on the boundary of the attractive basin o{ each atlractor,points belonging to different attractors form the second level of fractal structure.(ii) The variation of molecular mechanics parameters will influence the structure and area of each attractive basin significantly The above phenomena may become the basis of a new method for solving the troublesome multi-minimum-point problem in molecular mechanics calculation. 相似文献
760.
动力学体系二维数据的秩分析及其应用 总被引:2,自引:0,他引:2
详细论证了动力学体系中存在的多种共线性情况,以及在此情况下二维数据阵的秩与独立反应数及组分数的关系.分析了通过增秩这一方式来判断体系组分数的条件.讨论了反应间存在物质交换对数据阵秩的影响.建立起一套通过秩分析判断未知动力学体系中存在的反应组分数、独立反应数以及可能反应机理的方法.将秩分析技术应用到聚苯胺与质子酸反应,初步分析了该体系存在的多种吸光性结构及结构变化.确定了[H+]=0.01~0.1 mol•L-1范围内,聚苯胺与质子酸反应存在一个三结构两步互变过程. 相似文献