全文获取类型
收费全文 | 65551篇 |
免费 | 14900篇 |
国内免费 | 6379篇 |
专业分类
化学 | 62697篇 |
晶体学 | 780篇 |
力学 | 2461篇 |
综合类 | 374篇 |
数学 | 5378篇 |
物理学 | 15140篇 |
出版年
2024年 | 76篇 |
2023年 | 658篇 |
2022年 | 1017篇 |
2021年 | 1326篇 |
2020年 | 2500篇 |
2019年 | 3675篇 |
2018年 | 2136篇 |
2017年 | 1723篇 |
2016年 | 4801篇 |
2015年 | 4944篇 |
2014年 | 5204篇 |
2013年 | 6251篇 |
2012年 | 5817篇 |
2011年 | 5078篇 |
2010年 | 4934篇 |
2009年 | 4801篇 |
2008年 | 4441篇 |
2007年 | 3685篇 |
2006年 | 3293篇 |
2005年 | 3196篇 |
2004年 | 2639篇 |
2003年 | 2259篇 |
2002年 | 3046篇 |
2001年 | 2224篇 |
2000年 | 2021篇 |
1999年 | 1103篇 |
1998年 | 623篇 |
1997年 | 533篇 |
1996年 | 477篇 |
1995年 | 417篇 |
1994年 | 326篇 |
1993年 | 293篇 |
1992年 | 239篇 |
1991年 | 210篇 |
1990年 | 210篇 |
1989年 | 139篇 |
1988年 | 102篇 |
1987年 | 72篇 |
1986年 | 74篇 |
1985年 | 75篇 |
1984年 | 42篇 |
1983年 | 35篇 |
1982年 | 35篇 |
1981年 | 25篇 |
1980年 | 14篇 |
1979年 | 7篇 |
1977年 | 3篇 |
1971年 | 3篇 |
1957年 | 5篇 |
1916年 | 4篇 |
排序方式: 共有10000条查询结果,搜索用时 31 毫秒
931.
记录了常温下二钼酸铵晶体饱和水溶液的Raman光谱,并分别与二钼酸铵晶体、仲钼酸铵晶体、仲钼酸铵晶体饱和水溶液、水溶液状态下单钼酸根离子的Raman光谱进行了比较研究。结果表明:二钼酸铵晶体饱和水溶液Raman光谱相对二钼酸铵晶体Raman光谱,明显地发生了变异现象。二钼酸铵晶体饱和水溶液Raman光谱其主要特征峰最高振动频率937.6 cm-1与仲钼酸铵晶体饱和水溶液Raman光谱主要特征峰最高振动频率937.6 cm-1完全吻合,而其次高振动频率893.9 cm-1,恰好介于水溶液中单钼酸根离子Raman光谱主要特征峰最高振动频率895.1 cm-1与仲钼酸铵晶体饱和水溶液Raman光谱主要特征次高峰振动频率891.0 cm-1之间,而且三者彼此接近。二钼酸铵晶体饱和水溶液Raman光谱主、次特征峰强度之比值为2.1,与仲钼酸铵晶体饱和水溶液Raman光谱主、次特征峰强度之比值4.4相比,一半不足。提出了一种利用Raman光谱主要特征峰振动频率及其主、次特征峰强度之比值对二钼酸铵晶体饱和水溶液组分同时进行定性和半定量分析的新方法。发现了常温下二钼酸铵晶体饱和水溶液中二钼酸根离子Mo2O72-已经不复存在,完全转变成了优势组分仲钼酸根离子Mo7O246-和次要组分单钼酸根离子MoO42-;证明了常温下含钼水溶液酸化过程中溶液Raman光谱离散性变化现象的存在。运用结构化学和物理化学原理同时讨论了二钼酸铵晶体饱和水溶液Raman光谱发生变异现象的机理。 相似文献
932.
Zhuxing Tang Yun Zhou Yikun Zeng Shuliang Zang Pingang He Yuzhi Fang 《Chromatographia》2006,63(11-12):617-622
A method based on capillary electrophoresis with electrochemical detection has been developed for the separation and determination of epicatechin, isovanillic acid, vanillic acid and myricetin in Dioscorea bulbifera L. and its medicinal preparations. The effects of working electrode potential, pH and concentration of running buffer, separation voltage and injection time were investigated. Under optimum conditions, the analytes could be separated in a 40 mmol L?1 borate buffer (pH 8.7) within 15 min. A 300 μm diameter carbon disk electrode has a good response at + 0.95 V (vs. SCE) for all analytes. The response was linear over three orders of magnitude with detection limits (S/N = 3) ranging from 3.0 × 10?8 g mL?1 to 1.0 × 10?7 g mL?1. The method has been successfully applied to the analysis of real samples. 相似文献
933.
Tin dioxide nanoparticles of 5 nm in size were prepared on NaY zeolite external surface by impregnation of SnCl2 solution and subsequent calcination at 623 K. A SnO2-NaY based chemical sensor for detecting H2 was demonstrated. 相似文献
934.
By using molecular dynamics simulation, the dynamic behaviors of particle permeation through a four-helix-bundle model channel are studied. The interior cavity of the four-helix-bundle provides the "routes" for particle permeation. The main structural properties of the model channel are similar to those that appear in natural four-helix-bundle proteins. It is found that the interior structure of the model channel may greatly influence the permeation process. At the narrow necks of the model channel, the particle would be trapped during the permeation. There is a threshold value for the driving force. When the driving force is larger than this threshold value, the mean first permeation time decreases sharply and tends to be saturated. Increasing the temperature of either the model channel or the particle reservoir can also facilitate the permeation. Enhancing the interaction strength between the particle and monomer on the four-helix-bundle model chain will hinder the permeation. Hence, the electrical current which is induced by the particle permeation is a function of the driving force and temperature. It is found that this current increases monotonically as the strength of the driving force or the temperature increases, but decreases as the interaction strength between the particle and monomer increases. It is also found that the larger the friction coefficient, the slower the permeation is. In addition, the multiparticle (or multi-ion) permeation process is also studied. The permeation of multiparticle is usually quicker than that of the single particle. The permeation of particle through a five-helix-bundle shows similar properties as that through a four-helix-bundle. 相似文献
935.
J. Borrs R. Carballo A. Castieiras M. C. Gmez‐Conde M. C. Fernndez‐Vidal J. Nicls 《无机化学与普通化学杂志》2005,631(11):2221-2226
Four new dinuclear copper(II) complexes have been synthesized and have the general formula [Cu2(L)(H2O)2], where L = GLYDTO [N,N′‐bis(carboxymethyl)dithiooxamide], ALADTO [N,N′‐bis(carboxyethyl)dithiooxamide], VALDTO [N,N′‐bis(1‐carboxy‐2‐methylpropyl)dithiooxamide] and LEUDTO [N,N′‐bis(1‐carboxy‐3‐methylbutyl)dithiooxamide]. The complexes were characterized by elemental analysis as well as by IR, electronic and EPR spectroscopy. These techniques provided evidence for the presence of the CuNO2S chromophore. Magnetic susceptibility measurements on all the complexes in the range 4–300 K show the existence of a dominant antiferromagnetic interaction with ?J values greater than 300 cm?1. Thermal decomposition behaviour of the complexes was studied by thermogravimetry. 相似文献
936.
链状[NH3CH2CH2NH3]AgAsS4的溶剂热合成及表征 总被引:2,自引:0,他引:2
利用溶剂热方法合成了链状[NH3CH2CH2NH3]AgAsS4,通过单晶X射线衍射技术对其进行了晶体结构分析,该化合物晶体属单斜晶系,空间群C2/c,晶胞参数a=1.35805(8)nm,b=0.65331(3)nm,c=2.27711(9)nm,β=106.42(3)°,Z=8.化合物具有有趣的梯子状双链结构,该阴离子链由AsS4与AgS3共用顶点交替连接而成,有机阳离子在阴离子链之间存在较强的N—H…S氢键.DSC和Tg分析结果表明化合物在200℃以下是稳定的. 相似文献
937.
A novel 3D polymeric heteropolynuclear sodium(I) lead(II) complex containing different ligands, [NaPb(ClO4)(en)(NO2)2] was synthesized and characterized by elemental analysis and IR, and 1H‐, 13C‐, and 207Pb‐NMR spectroscopy. The single‐crystal X‐ray data of [NaPb(ClO4)(en)(NO2)2]n established that the complex is a three‐dimensional polymer, [(en)Pb(μ3‐ONO)2Na(μ3‐ONO)2Na(μ‐O2ClO2)Na]n. The Pb and Na atoms have four‐ and eight‐coordinate geometry, respectively. The lone pair of electrons at the PbII atom is ‘stereochemically active’. 相似文献
938.
Chitosan samples were irradiated by 60Co γ-rays in the presence of hydrogen peroxide with radiation dose from 10 kGy to 100 kGy. The degradation was monitored by gel permeation chromatography (GPC), revealing the existence of a synergetic effect on the degradation. Structures of the degraded products were characterized with Fourier-transform infrared spectra (FT-IR), ultraviolet-visible spectral (UV-vis) analysis, and X-ray diffraction (XRD). Results showed that the crystallinity of chitosan decreases with degradation, and the crystalline state of water-soluble chitosan is entirely different from that of water-insoluble chitosan. An elemental analysis method was employed to investigate changes in the element content of chitosan after degradation. Mechanism of chitosan radiation degradation with and without hydrogen peroxide was also discussed. 相似文献
939.
用质谱技术对钾、钙同位素体系特征参数测定的初探 总被引:1,自引:0,他引:1
报道了用FinniganMAT 2 62质谱技术和同位素稀释法测定了光谱纯CaO和国际二级标准Tahiti(CaCO3)的同位素40 Ca 42 Ca比值以及后者的40 Ca含量 ,RSD分别为 0 .0 2 %和 0 .1 %。对国家钾标样的测定表明 :39K、40 K和41 K同位素丰度分别为 0 .93 2 60± 0 .0 0 1 2、0 0 0 0 1 1 2 0± 0 .0 0 0 0 1 2 9和 0 .0 672 86± 0 .0 0 0 1 2 5。其中39K含量为 0 .1 2 1 72± 0 .0 0 0 2 9,与标准值在误差范围内一致。实验测定结果为在我国开展40 K 40 Ca同位素体系的定年和环境的示踪研究打下了基础 相似文献
940.
研究了新型Schiff碱双锰配合物在模拟酶催化亚碘酰苯单加氧化环已烷反应及 被亚碘酰苯氧化破坏反应中的温度效应。结果表明,在模拟酶催化反应体系中同时 存在催化环已烷单加氧反应及催化剂的氧化破坏反应;催化反应速率及氧化破坏反 应速率均随反应温度升高有规律地增大,但氧化破坏反应比催化反应对反应温度更 敏感;催化反应总产率一般随反应温度升高而降低;最适宜的反应温度为25 ℃。 相似文献