全文获取类型
收费全文 | 9280篇 |
免费 | 246篇 |
国内免费 | 899篇 |
专业分类
化学 | 5679篇 |
晶体学 | 65篇 |
力学 | 372篇 |
综合类 | 2篇 |
数学 | 641篇 |
物理学 | 3666篇 |
出版年
2024年 | 10篇 |
2023年 | 156篇 |
2022年 | 66篇 |
2021年 | 89篇 |
2020年 | 140篇 |
2019年 | 182篇 |
2018年 | 161篇 |
2017年 | 205篇 |
2016年 | 252篇 |
2015年 | 246篇 |
2014年 | 390篇 |
2013年 | 805篇 |
2012年 | 416篇 |
2011年 | 710篇 |
2010年 | 553篇 |
2009年 | 653篇 |
2008年 | 603篇 |
2007年 | 648篇 |
2006年 | 586篇 |
2005年 | 506篇 |
2004年 | 493篇 |
2003年 | 309篇 |
2002年 | 245篇 |
2001年 | 247篇 |
2000年 | 247篇 |
1999年 | 188篇 |
1998年 | 188篇 |
1997年 | 145篇 |
1996年 | 124篇 |
1995年 | 136篇 |
1994年 | 110篇 |
1993年 | 95篇 |
1992年 | 94篇 |
1991年 | 76篇 |
1990年 | 54篇 |
1989年 | 45篇 |
1988年 | 47篇 |
1987年 | 38篇 |
1986年 | 29篇 |
1985年 | 22篇 |
1984年 | 27篇 |
1983年 | 12篇 |
1982年 | 17篇 |
1981年 | 7篇 |
1980年 | 12篇 |
1979年 | 13篇 |
1978年 | 6篇 |
1977年 | 6篇 |
1976年 | 4篇 |
1973年 | 6篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
121.
Masaaki Omote 《Tetrahedron letters》2005,46(2):319-322
A new axially dissymmetric ligand with large perfluoroalkyl groups, 2,2′-bis(1-hydroxy-1H-perfluorooctyl)biphenyl (1c), which could not be obtained by the coupling reaction of the aryl bromide using copper powder, was synthesized successfully by the coupling reaction using Ni(COD)2. This ligand showed much higher asymmetric induction in the reaction of diethylzinc with benzaldehyde than the trifluoromethyl (1a) or pentafluoroethyl (1b) analogues. 相似文献
122.
手性液晶聚硅氧烷毛细管柱的制备及应用 总被引:3,自引:0,他引:3
合成了一种手性液晶侧链的聚硅氧烷固定液,并涂制成毛细管柱,此柱适合于分离各种取代基的酚类异构体。对柱效和选择性进行了评价。 相似文献
123.
Summary Polymerisation of bicontinuous microemulsions yields porous monolithic structures with well defined pore sizes that are potentially
suitable for use as stationary phases for capillary electrochromatography (CEC). A variety of pore sizes can be achieved by
altering the composition of the microemulsion, which typically consists of butyl methacrylate (BMA) and ethylene glycol dimethacrylate
(EGDMA) as the polymerisable oil phase. The aqueous phase consists of water, a surfactant (sodium dodecyl sulphate, SDS) and
a co-surfactant (1-propanol). 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) is also added to provide charges along
the polymer backbone to allow electroosmotic flow (EOF) to occur. SEM analysis shows that in-situ polymerisation yields a
monolithic structure with a porous topography. Investigations have shown that these monoliths are easy to prepare, robust
and suitable for the separation of phthalates. They generate higher linear velocities than are achieved using the silica based
HPLC packings normally used for CEC. 相似文献
124.
125.
126.
低共熔混合锂盐相图的绘制及应用 总被引:3,自引:0,他引:3
采用热分析法对不同组成的混合锂盐二元体系进行研究, 绘制了混合锂盐体系的步冷曲线和T-x相图, 结果表明体系均为具有最低共熔点的二元体系. LiOH-LiNO3、LiOH-LiCl、LiOH-Li2CO3及LiNO3-LiCl体系的最低共熔点分别为175.7、294.5、418.2及221.6 ℃. 利用低共熔混合物LiNO3-LiOH为锂盐与不同前驱体反应, 制备出了层状结构良好的锂离子电池正极材料LiNiO2、LiNi0.8Co0.2O2及LiNi1/3Co1/3Mn1/3O2. X射线衍射分析表明, 合成的材料具有规整的层状NaFeO2结构, 且XRD衍射峰强度之比I(003)/I(104)>2.0, 电性能测试表明, 在2.7-4.3 V(vs Li/Li+)的电压范围内进行0.1C倍率充放电, LiNiO2、LiNi0.8Co0.2O2、LiNi1/3Co1/3Mn1/3O2首次充电比容量分别达168.0、225.4、194.0 mAh·g-1, 放电比容量分别为138.4、165.8、157.7 mAh·g-1. 相似文献
127.
合成了新型手性Salen配体(H3L)及新型手性Salen双核锌配合物(主体).通过研究主体对咪唑类客体及氨基酸酯类客体的分子识别行为,测定了这些配位反应的缔合常数.主体对咪唑类客体分子识别的缔合常数顺序为:K(Im) >K(2-MeIm) >K(2-Et-4-MeIm).主体对氨基酸酯类客体分子识别的缔合常数顺序为:K(LeuOCH3) >K(ValOCH3) >K(AlaOCH3) >K(SerOCH3),配位数均为2.主体与D、 L型氨基酸酯分子识别反应在不同温度下的缔合常数结果表明,随着温度的升高,对映选择性下降.实验发现反应体系中存在焓熵补偿关系. CD光谱的研究结果也反映了主体对不同客体识别能力的差异. 相似文献
128.
The binary phase diagram of KNO3-KClO3 is studied by means of differential scanning calorimetry (DSC) and high-temperature X-ray diffraction. The limited solid solutions, K(NO3)1−x(ClO3)x (0<x<0.20) and K(NO3)1−x(ClO3)x (0.90<x<1.0), were formed in the KNO3-based solid solutions and KClO3-based solid solutions phase, respectively. For KNO3-based solid solutions, KNO3 ferroelectric phase can be stable from 423 to 223 K as a result of substituting of NO3 by ClO3-radicals. The temperatures for solidus and liquidus have been determined based on limited solid solutions. Two models, Henrian solution and regular solution theory for KNO3-based (α) phase and KClO3-based (β) phase, respectively, are employed to reproduce solidus and liquidus of the phase diagram. The results are in good agreement with the DSC data. The thermodynamic properties for α and β solid solutions have been derived from an optimization procedure using the experimental data. The calculated phase diagram and optimized thermodynamic parameters are thermodynamically self-consistent. 相似文献
129.
The high pressure behaviour of InI is studied by DFT‐calculations and compared with experimental data. The existence of a 5s2 electron pair in In+ represents an unfavourable bonding situation for high symmetry structures because of effective closed shell repulsion. Since cations with a ns2 electron pair are highly polarizable and the electronic situation is more favourable in the low symmetry structure InI prefers a TlI‐type structure at ambient pressure. A pressure induced transition to the more densely packed high symmetry CsCl‐type structure takes place at about 19 GPa according to our calculations. At ambient pressure the interactions are predominantly ionic. However with increasing pressure the distances between In+ cations in the TlI‐type structure diminish drastically, mainly due to the changing space requirement of the lone electron pair. Apart from ionic interactions further bonding interactions between the In+ cations occur. At elevated pressure the electron localization function (ELF) as well as the band structure diagrams suggest metallic bonding between the In+ within the zigzag chain, i. e. increasing bonding interactions between the In+ cations due to the electron pair and its s‐p‐mixing. At ambient pressure In‐In interactions are rather weak and the space requirement of the lone electron pair mainly determines the characteristic arrangement of the ions. At elevated pressure the In‐In interactions become stronger and stabilise themselves additionally the specific structural arrangement. 相似文献
130.
Magnetic field-induced orientation of a chiral side chain liquid crystalline polyacrylate(P-11) was studied by using IR dichroism. For the investigated P-11, it has been shown thatthe magnetic alignment takes place over the entire temperature range between its meltingpoint and clearing point and the orientation level is strongly temperature-dependent, thedevelopment with time of the magnetic orieatation follows an exponeotial-type relation,and the smectic phase state influences the thermal relaxation process in the absence of themagnetic field. 相似文献