全文获取类型
收费全文 | 45995篇 |
免费 | 8693篇 |
国内免费 | 6940篇 |
专业分类
化学 | 33708篇 |
晶体学 | 733篇 |
力学 | 3029篇 |
综合类 | 497篇 |
数学 | 5234篇 |
物理学 | 18427篇 |
出版年
2024年 | 95篇 |
2023年 | 853篇 |
2022年 | 1487篇 |
2021年 | 1725篇 |
2020年 | 1861篇 |
2019年 | 1937篇 |
2018年 | 1642篇 |
2017年 | 1643篇 |
2016年 | 2265篇 |
2015年 | 2381篇 |
2014年 | 2908篇 |
2013年 | 3633篇 |
2012年 | 4364篇 |
2011年 | 4464篇 |
2010年 | 3355篇 |
2009年 | 3339篇 |
2008年 | 3551篇 |
2007年 | 2989篇 |
2006年 | 2820篇 |
2005年 | 2320篇 |
2004年 | 1693篇 |
2003年 | 1416篇 |
2002年 | 1435篇 |
2001年 | 1147篇 |
2000年 | 951篇 |
1999年 | 820篇 |
1998年 | 613篇 |
1997年 | 585篇 |
1996年 | 524篇 |
1995年 | 441篇 |
1994年 | 422篇 |
1993年 | 316篇 |
1992年 | 262篇 |
1991年 | 222篇 |
1990年 | 211篇 |
1989年 | 156篇 |
1988年 | 133篇 |
1987年 | 89篇 |
1986年 | 112篇 |
1985年 | 79篇 |
1984年 | 42篇 |
1983年 | 43篇 |
1982年 | 28篇 |
1981年 | 21篇 |
1980年 | 18篇 |
1979年 | 21篇 |
1977年 | 13篇 |
1975年 | 12篇 |
1972年 | 11篇 |
1925年 | 10篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
941.
A new method for inductively coupled plasma atomic emission spectrometry (ICP-AES) determination of trace Sc and Y, based on gaseous compound introduction into the plasma as their thenoyltrifluoroacetone (TTA) complexes by electrothermal vaporization was developed. Using the reagent TTA as chemical modifier can not only enhance the analytical signals, but also reduce the vaporization temperature. At a temperature of 1,000 °C the trace Sc and Y can be vaporized completely into ICP. The factors affecting the formation of the chelate and its vaporization behavior, such as drying time, vaporization temperature/time, reaction medium and the amount of TTA, were investigated in detail. Under the optimized conditions (drying temperature/time 100 °C/10 s, vaporization temperature/time 1,000 °C/4 s), the limits of detection for Sc and Y were 19 pg and 34 pg (3), respectively, and the relative standard deviations for Sc and Y were 4.2% (c
Sc=0.2 g mL–1; n=7) and 2.6% (c
Y=0.5 g mL–1; n=7). The linear ranges of the calibration graphs cover three orders of magnitude. The method was applied to the analysis of the biological reference materials (GBW 07602, bush branches and leaves; GBW 07604, poplar leaves), and the results obtained were in good agreement with the certified values. 相似文献
942.
高效液相色谱法检测保健食品中大豆异黄酮含量 总被引:10,自引:1,他引:10
建立了保健食品中大豆异黄酮的高效液相色谱检测方法 ,通过正交试验法得出保健食品中大豆异黄酮的最佳水解条件为 :盐酸浓度2.0mol/L,酸体积40mL ,水解温度80℃ ,水解时间3h;采用HypersilODS2C18 色谱柱 (250mm×4.6mmID ,5μm) ,流动相为甲醇 -水(体积比47∶53) ,流速1.0mL/min ,检测波长260nm ,柱温40℃ ,线性范围在0.5~96mg/L ,相关系数r为0.999 ,相对标准偏差 (RSD)2.09% ,回收率在98.5 %~100.5 %。 相似文献
943.
Reaction of an alkyne‐bridged dicobalt complex, [Co2(CO)6(μ‐Me3SiC=Cpy)] 4 , with bis(diphenylphosphino)methylene (DPPM) or bis(diphenylphosphino)ethylene (DPPE) in THF at 55 °C yielded a DPPM or DPPE doubly bridged dicobalt compound, [{μ‐P,P‐PPh2CH2PPh2}Co2(CO)4(μ‐Me3SiC=Cpy)] 5 or [{μ‐P,P‐PPh2CH2CH2PPh2}Co2(CO)4(μ‐Me3SiC≡Cpy)] 6 . Compound 5 and 6 were characterized by spectroscopic means as well as X‐ray crystal structure determination. 相似文献
944.
在水溶液中培养了镨、钕、钇与甘氨酸形成的三元配合物。元素分析和热分析表明,该配合物可用Pr_xNd_yY_z(Gly)_6(H_2O)_4(ClO_4)_6·5H_2O(X+y+z=2)表示其分子式。X射线衍射方法测定了其单晶结构,结果表明,该晶体属三斜晶系,空间群P1,化学式Pr_(0.775)Nd_(0.700)Y_(0.525)Cl_6O_(45)N_6C_(12)H_(48),M_r=1466.09,晶胞参数如下:a=11.564(1),b=14.118(3),c=15.668(2)A,α=96.99(1),β=102.72(1),γ=105.33(1)°,晶胞体积V=2362(1)A~3,Z=2,D_c=2.060g/cm~3,结构偏离因子R=0.032,R_w=0.048。晶胞中存在两个络合单元,每个单元可用M_1M2(Gly)_6(ClO_4)_6(H_2O)_4.5H_2O表示,M_1=0.4Pr+0.375Nd+0.225Y,M2=0.375Pr+0.325Nd+0.30Y。三种稀土元素按一定比例统计性地占有两个格位。羧基以桥式联结金属离子,形成一维链式聚合物结构。在络合单元中,一个稀土离子是9配位,其配位多面体为畸变? 相似文献
945.
采用不同材料作为有机电致发光器件(OELDs)的电极, 制备了基本结构为[阳极/NPB(40 nm)]/Alq3(50 nm)/阴极]的异质结双层器件, 并通过改变OELDs器件的阴极或阳极来研究电极材料对器件光电性能的影响. 研究结果表明, 各器件电流-电压(I-V)关系的基本特征与陷阱电荷限制电流(TCLC)机制的拟合情况相符. 由于有机材料本身能级的无序性以及载流子迁移率对温度和电场的依赖性, 不同电极的载流子注入能力与其功函数并无直接关系. 双层器件中由于空穴传输层的引入, 使得载流子复合区域位于有机层异质结界面处, 降低了金属阴极对激子的猝灭作用, 从而大大提高了器件性能. 此外, 金属电极OLEDs器件结构具有的微腔效应会导致发射光谱的位移和谱峰宽度变窄, 这表明通过对金属电极的表面改性和优化可使器件性能超过常规结构的器件. 相似文献
947.
948.
Peng Lu Xueli Hu Yujie Li Yazhou Peng Meng Zhang Xue Jiang Youzhou He Min Fu Fan Dong Zhi Zhang 《Journal of Saudi Chemical Society》2019,23(8):1109-1118
A novel CaCO3/graphitic carbon nitride (g-C3N4) photocatalyst was synthesized for the first time via a facile calcination method using CaCO3 and melamine as precursors. The as-prepared samples were characterized using various techniques, such as scanning and transmission electron microscopy, X-ray diffraction, Brunauer-Emmett-Teller analysis, as well as Fourier-transform infrared, X-ray photoelectron, photoluminescence, and UV–vis diffuse reflectance spectroscopy. The results of the experiments confirm the successful coupling of CaCO3 to g-C3N4. The photocatalytic activity of the synthesized CaCO3/g-C3N4 composites was evaluated by assessing their performance in the photocatalytic degradation of crystal violet (CV) in water under visible light irradiation. The analysis shows that CaCO3/g-C3N4 exhibits higher photocatalytic activity towards CV degradation (76.0%) than pristine g-C3N4 (21.6%) and CaCO3 (23.2%). Radical trapping and electron spin resonance experiments show that hydroxyl radicals (OH) and holes (h+) are the key reactive species in the photocatalytic process. The enhanced photocatalytic activity of the composite is mainly attributed to the efficient separation rate of electron-hole pairs achieved through the incorporation of CaCO3. 相似文献
949.
The crystal structure of the title complex with the stoichiometric formula [Cu(PTA)(Phen)2](p-MBA)(H6O) (Phen=1,10-phenanthroline, PTA=terephthalic acid, p-MBA=p-toluic acid) has been determined by single-crystal X-ray diffraction. The crystal (C48H40CuN4O10, Mr=896.38) belongs to the monoclinic space group C2/c, with the following crystallographic parameters: a=1.778 6(3) nm, b=1.912 5(3) nm, c=1.389 9(2) nm, β=114.686(2)°, V=4.295 7(12) nm3, Dc=1.386 g·cm-3, Z=4, μ(Mo Kα)=0.574 mm-1, F(000)=1 860, final GooF=1.019, R=0.054 0, wR=0.148 3 for 2 644 observed reflections (I>2σ(I)). The crystal structure shows that the copper(Ⅱ) ion is coordinated with two oxygen atoms from one terephthalic acid molecule and four nitrogen atoms from two 1,10-phenanthroline molecules, forming a distorted octahedral coordination geometry. The cyclic voltametric behavior of the complex is also reported. CCDC: 298809. 相似文献
950.
水热条件下,合成了三个新的配合物[Ni(en)3] (ndt) ·H2O 1,
[Co(en)3] (ndt) ·H2O 2 和[Mn(en)3] (ndt) ·H2O
3。晶体结构通过X-射线单晶衍射进行了表征。三个配合物均属于单斜晶系,Cc空间群。[M(en)3]2+阳离子、ndt阴离子和结晶水分子通过氢键自组装出相同结构的三维网。通过紫外-可见-近红外漫反射光谱对这三个配合物的光吸收性能和能带进行了测定。 相似文献