全文获取类型
收费全文 | 6208篇 |
免费 | 356篇 |
国内免费 | 1602篇 |
专业分类
化学 | 6646篇 |
晶体学 | 122篇 |
力学 | 91篇 |
综合类 | 42篇 |
数学 | 255篇 |
物理学 | 1010篇 |
出版年
2024年 | 8篇 |
2023年 | 114篇 |
2022年 | 66篇 |
2021年 | 111篇 |
2020年 | 112篇 |
2019年 | 171篇 |
2018年 | 141篇 |
2017年 | 183篇 |
2016年 | 190篇 |
2015年 | 185篇 |
2014年 | 270篇 |
2013年 | 487篇 |
2012年 | 355篇 |
2011年 | 381篇 |
2010年 | 320篇 |
2009年 | 385篇 |
2008年 | 407篇 |
2007年 | 499篇 |
2006年 | 466篇 |
2005年 | 448篇 |
2004年 | 420篇 |
2003年 | 268篇 |
2002年 | 222篇 |
2001年 | 197篇 |
2000年 | 214篇 |
1999年 | 196篇 |
1998年 | 157篇 |
1997年 | 153篇 |
1996年 | 142篇 |
1995年 | 132篇 |
1994年 | 114篇 |
1993年 | 88篇 |
1992年 | 106篇 |
1991年 | 79篇 |
1990年 | 74篇 |
1989年 | 71篇 |
1988年 | 53篇 |
1987年 | 35篇 |
1986年 | 30篇 |
1985年 | 29篇 |
1984年 | 23篇 |
1983年 | 23篇 |
1982年 | 15篇 |
1981年 | 5篇 |
1980年 | 7篇 |
1979年 | 7篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1968年 | 1篇 |
排序方式: 共有8166条查询结果,搜索用时 265 毫秒
71.
具有C2对称轴的手性配体及其不对称催化反应 总被引:2,自引:0,他引:2
按配位原子的数目进行分类,综述了近年来研究较多的具有C2对称轴的手性配体及其相关的不对称催化反应,并对该类手性配体的设计做了分析和总结。参考文献79篇。 相似文献
72.
73.
含铜三元类水滑石化合物的合成及其性质 总被引:11,自引:0,他引:11
以Cu(NO3)2,Zn(NO3)2和Al(NO3)3为原料,以NaOH为沉淀剂,利用共沉淀法合成了含铜三元类水滑石化合物CuZnAl-HTLcs.从不同Cu/Zn/Al比的混合原料溶液的滴定曲线入手,详细探讨了溶液pH值、原料加入方式、组分配比及水热处理条件对类水滑石合成的影响,利用XRD,ICP及比表面积测定对合成物进行了表征,并以苯酚羟基化为探针反应评价了催化剂的催化性能.结果表明,在体系pH=5.0~6.2,(Cu+Zn)/Al摩尔比=2.0,Cu/Zn摩尔比≤1.0及室温条件下共沉淀后,于100℃水热处理3h,即可得到晶相单一和结晶度高的CuZnAl-HTLcs.变化pH法合成的样品的相对结晶度为100%,低过饱和法为76.5%,高过饱和法为75.9%.合成的CuZnAl-HTLcs中Cu2+的含量均比原料液中Cu2+的含量有所增加,这可能是由于在pH=5.8时Cu2+对Al(OH)3的同晶取代能力比Zn2+强.随着CuZnAl-HTLcs中Cu含量的增加,催化剂对苯酚羟化反应的催化活性逐渐增大. 相似文献
74.
The carbobenzyloxy (cbz) protecting group is evaluated for it's potential to enhance the resolution of chiral amine enantiomers using high-performance liquid chromatography (HPLC) and supercritical fluid chromatography (SFC). A series of cbz derivatives of commercially available racemates was prepared and analyzed by enantioselective chromatography using a variety of mobile phases and polysaccharide and Pirkle-type chiral stationary phases (CSPs). The cbz-derivatized product consistently demonstrated enhanced chiral resolution under HPLC and SFC conditions. Improved selectivity and resolution combined with an automated preparative HPLC or SFC system can lead to the rapid generation of highly purified enantiomers of desirable starting materials, intermediates or final products. 相似文献
75.
76.
Duringthelastdecade,1,3-dioltypechiralbuildingbIocksofvariousconfigurationshavebeensynthesizedandappliedwidelyinthetotalsynthesisofnaturalpolyenemacrolideantibiotics1'2andla,25-dihydroxyvitaminD3analogues'.RecentlyWeigandandBrucker4synthesizedachiralbuildingblock(4R,6R)-2,2-dimethyl-5-tert-butyldip4-hydroxymethyl-l,3-dioxane1inlOsteps.Herein,wereportasyntheticrouteofnewbuildingblock(4S,6S)-2,2-dimethyl-5-tert-butyldip2,anenantiomerofl,startingfromreadilyavailableandinexpensiveD( )-xylose3i… 相似文献
77.
Summary Chiral stationary phases (CSPs) for liquid chromatography were prepared by the way of an activated carbamate intermediate.
The amino group of aminopropylsilyl silica gel was first activated by carbamylation with disuccinimido carbonate (DSC). The
obtained activated carbamate silica gel (ACsil) proved useful as an intermediate for the preparation of urea-type CSPs. The
reaction of ACsil with (S)- of (R)-1-(α-naphthyl)-ethylamine gave naphthylethylurea type CSPs. These CSPs were also obtained
directly from aminopropylsilyl silica gel by its reaction with optically active (S)- or (R)-succinimido 1-(α-naphthyl)ethyl
carbamate (SINEC). Several phenylthiohydantoin amino acid enantiomers and p-bromophenylcarbamyl amino acid enantiomers were
resolved on the CSPs by elution with aqueous mobile phase. 相似文献
78.
Summary Three -Cyclodextrin derivatives (-CDs) were synthesized by substituting the 2,6-OH groups of -CD with allyl groups and the 3-OH groups with three different acyl groups (valeryl, heptanonyl, octanoyl). The chromatographic properties of these -CDs as stationary phases for capillary gas chromatography (CGC) were studied. The test results showed that the three -CDs possessed good coating properties and that the capillary columns coated with them exhibited high column efficiency. These -CDs can separate not only the disubstituted benzene isomers but also some racemic compounds. 相似文献
79.
Summary Electronic structure of hydrogen nitryl HNO2, a yet not identified entity, and the path of its possible isomerization totrans-HONO have been investigated byab initio SCF and MRD-CI computations using the 6-31G** basis set. HNO2 isC
2v
-symmetric and its ground state (1
A
1) is less stable thantrans-HONO by 66 kJ/mol (with the SCF vibrational zero-point energy correction). The lowest two excited singlet states (1
A
2 and1
B
1) are nearly degenerate, their vertical excitation energies being predicted to be 4.8 eV. The isomerization path is traced by the CASSCF procedure and the activation barrier height is evaluated by the CI treatment. HNO2 in its ground state isomerizes totrans-HONO by maintaining the planar (C
s-symmetric) structure. The activation energy is calculated to be 171 kJ/mol, which is clearly lower than the calculated H-N bond energy (253 kJ/mol). The transition state seems to be more adequately described as an interacting system of proton and the nitrite anion rather than as a pair of two fragment radicals. 相似文献
80.
Diastereoselective allylation of imine derived from N‐glyoxyloyl camphorpyrazolidinone and amines was treated with allyltributylstannane in the presence of triflic acid. The corresponding optically enriched homoallylic amines were obtained in reasonable to high material yields and with practical levels of stereoselectivity in 10 min at ambient temperature. 相似文献