全文获取类型
收费全文 | 5571篇 |
免费 | 546篇 |
国内免费 | 882篇 |
专业分类
化学 | 4050篇 |
晶体学 | 103篇 |
力学 | 32篇 |
综合类 | 32篇 |
数学 | 248篇 |
物理学 | 1381篇 |
综合类 | 1153篇 |
出版年
2024年 | 16篇 |
2023年 | 108篇 |
2022年 | 119篇 |
2021年 | 137篇 |
2020年 | 282篇 |
2019年 | 234篇 |
2018年 | 215篇 |
2017年 | 237篇 |
2016年 | 246篇 |
2015年 | 195篇 |
2014年 | 303篇 |
2013年 | 702篇 |
2012年 | 423篇 |
2011年 | 374篇 |
2010年 | 267篇 |
2009年 | 342篇 |
2008年 | 335篇 |
2007年 | 374篇 |
2006年 | 289篇 |
2005年 | 224篇 |
2004年 | 247篇 |
2003年 | 204篇 |
2002年 | 174篇 |
2001年 | 153篇 |
2000年 | 123篇 |
1999年 | 99篇 |
1998年 | 94篇 |
1997年 | 98篇 |
1996年 | 72篇 |
1995年 | 82篇 |
1994年 | 40篇 |
1993年 | 30篇 |
1992年 | 29篇 |
1991年 | 28篇 |
1990年 | 26篇 |
1989年 | 15篇 |
1988年 | 20篇 |
1987年 | 4篇 |
1986年 | 5篇 |
1984年 | 3篇 |
1983年 | 3篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 2篇 |
1978年 | 5篇 |
1977年 | 2篇 |
1976年 | 3篇 |
1974年 | 3篇 |
1973年 | 3篇 |
排序方式: 共有6999条查询结果,搜索用时 15 毫秒
71.
72.
The reaction of various α-silyl-α-keto esters with thiosemicarbazide at 50 °C in ethyl acetate was found to give α-silyl-substituted thiosemicarbazone-acetic acid esters in good yield. These may then be converted to their corresponding silyl-substituted 1,2,4-triazin-5-ones by cyclization under basic conditions. 相似文献
73.
A simple, sensitive and rapid derivative spectrophotometric method using 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP) has been developed for simultaneous determination of Co(II), Ni(II) and Fe(II) which have very similar chemical behavior and appear together in many real samples. The complexes of all these metal ions with 5-Br-PADAP were formed immediately at pH 7.0 ammonium acetate buffered solution and were stable for at least 24 h. Second derivative spectra were selected for evaluation, because working wavelength determination was more precise and spectral overlap was less than in the ordinary and first derivative spectra. Three wavelengths at which the complexes exhibit extremum 2D values for Co(II), Ni(II) and Fe(II) were selected as analytical wavelengths, i.e., 640, 600 and 740 nm, respectively. Calibration curves drawn with zero-to-peak values at mentioned wavelengths were linear between 80 and 2000 ng ml−1 for each metal ion. Concentrations of Co(II) and Ni(II) were calculated from the total 2D values and the sum of the linear equations for these three cations at 640 and 600 nm, after Fe(II) assay by making use of the 2D value at 740 nm. Limits of detection (LOD) for Co(II), Ni(II) and Fe(II) were 2.7, 13.9 and 3.0 ng ml−1, respectively. The method has been applied to tool steel and heater resistance wire samples successfully. 相似文献
74.
在 1× 1 0 - 3 Pa~ 4 GPa的压力和 5 80~ 930 K温度范围内 ,利用高压技术并结合机械球磨 ,研究了压力、温度和晶粒尺寸对α-Fe与非晶 BN的固态反应的影响 .发现高压和晶粒细化可以极大地促进α-Fe和非晶 BN的固态反应过程 ,α-Fe与非晶 BN发生固态反应的临界晶粒尺寸约 8nm.压力和温度对反应产物及其晶体结构有明显影响 .2 GPa和 80 0 K时 ,反应产物为具有正交结构的 Fe-N新相 ;在 3~ 4 GPa和 690~80 0 K时 ,可形成单一ε-Fex N合金相 ;而在 4 GPa和 930 K以上 ,反应产物由 Fe-N合金相转变为 Fe3B相 相似文献
75.
76.
Toshiaki Sunazuka Masaki Handa Tatsuya Shirahata Kazuhiko Otoguro Satoshi ōmura 《Tetrahedron》2004,60(36):7845-7859
In the current studies, we used the Kakisawa-Kashman modification of the Mosher NMR method to determine the complete absolute stereochemistry of arisugacins. We also report the convergent total synthesis of (+)-arisugacins A and B by a sequence including (i) ruthenium complex-catalyzed asymmetric reduction of the cyclohexenone derivative; (ii) stereoselective construction of the arisugacin skeleton by a Knoevenagel-type reaction of an α,β-unsaturated aldehyde derivative with production of a 4-hydroxy-2-pyrone derivative as a key reaction; and (iii) stereoselective dihydroxylation to give the diol derivative, followed by deoxygenation. Accordingly, we defined the absolute structures of arisugacins A and B as 4a-(R),6a-(R),12a-(R), and 12b-(S). Finally, we characterized the bioactivities of the synthetic intermediates to understand the structure-activity relationships of the arisugacins. 相似文献
77.
稀土高氯酸盐-谷氨酸配合物[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O的低温热容和热化学研究 总被引:1,自引:0,他引:1
合成了一种稀土高氯酸盐-谷氨酸配合物. 经TG/DTG、化学和元素分析、FTIR及与相关文献对比, 确定其组成为[Pr2(L-α-Glu)2(ClO4)(H2O)7](ClO4)3•4H2O, 纯度为99.0%以上. 利用显微熔点仪分析发现其没有熔点. 在78~370 K温区, 用精密绝热量热仪测量其低温热容, 在285~306 K温区发现一明显吸热峰, 归结为固-固相变过程. 通过相变温区三次重复热容测量, 得到相变温度Ttr、相变焓ΔtrHm和相变熵ΔtrSm分别为(297.158±0.280) K, (12.338±0.016) kJ•mol-1和(41.520±0.156) J•K-1•mol-1. 用最小二乘法将非相变温区的热容对温度进行拟合, 得到了热容随温度变化的两个多项式方程. 用此方程进行数值积分, 得到每隔5 K的舒平热容值和相对于273.15 K的热力学函数值. 根据TG/DTG结果, 推测了该配合物的热分解机理. 依据Hess定律, 选择1 mol•dm-3盐酸为量热溶剂, 利用等温环境溶解-反应量热计, 测定了该配合物的标准摩尔生成焓为: ΔfHm0=-(7223.1±2.4) kJ•mol-1. 相似文献
78.
金负载量对低温水煤气变换Au/α-Fe2O3催化剂结构和性能的影响 总被引:5,自引:3,他引:5
采用共沉淀法制备了低温水煤气变换Au/α-Fe2O3催化剂。通过正交实验优化催化剂的还原活化条件,考察了金负载量对催化剂性能的影响。采用BET、XRD、UV-VIS、XRF、H2-TPR和O2-TPO等表征手段对催化剂的结构进行分析,并与其催化性能进行关联。结果表明,(1)采用10%-H2/N2还原气将催化剂在150 ℃原位还原9 h,其催化活性最高;(2)金的最佳负载量为8.00%,此时在催化剂制备过程中金的流失量较少,金粒子较小,也有利于抑制催化剂在反应过程中烧结;(3)TPR-TPO结果表明,金的负载量为8.00%时,Au/α-Fe2O3催化剂具有较易被还原、不易被氧化的性质,从而显示出最高催化活性。(4)Au/α-Fe2O3催化剂中的金以单质金(Au0)形式存在;其高活性与Au0-Fe3O4间的协同作用有关。 相似文献
79.
80.
Takashi Kagayama 《Tetrahedron letters》2005,46(21):3687-3689
A new route to α-hydroxy-γ-butyrolactones through three-component radical coupling of 1,3-dioxoranes, acrylates, and molecular oxygen using N-hydroxyphthalimide (NHPI) as a key catalyst has been developed. For example, the addition of 1,3-dioxarane to methyl acrylate under dioxygen by NHPI followed by catalytic hydrogenation of the resulting adduct on Pd/C afforded α-hydroxy-γ-butyrolactone in good yield. This method provides a facile approach to α-hydroxy-γ-butyrolactones, which are difficult to synthesize by conventional methods. 相似文献