全文获取类型
收费全文 | 1335篇 |
免费 | 9篇 |
国内免费 | 109篇 |
专业分类
化学 | 1309篇 |
晶体学 | 7篇 |
力学 | 1篇 |
综合类 | 1篇 |
数学 | 18篇 |
物理学 | 117篇 |
出版年
2024年 | 2篇 |
2023年 | 68篇 |
2022年 | 6篇 |
2021年 | 5篇 |
2020年 | 5篇 |
2019年 | 13篇 |
2018年 | 9篇 |
2017年 | 19篇 |
2016年 | 8篇 |
2015年 | 8篇 |
2014年 | 15篇 |
2013年 | 106篇 |
2012年 | 170篇 |
2011年 | 47篇 |
2010年 | 31篇 |
2009年 | 57篇 |
2008年 | 77篇 |
2007年 | 67篇 |
2006年 | 47篇 |
2005年 | 63篇 |
2004年 | 43篇 |
2003年 | 30篇 |
2002年 | 31篇 |
2001年 | 23篇 |
2000年 | 25篇 |
1999年 | 50篇 |
1998年 | 60篇 |
1997年 | 33篇 |
1996年 | 38篇 |
1995年 | 48篇 |
1994年 | 46篇 |
1993年 | 29篇 |
1992年 | 32篇 |
1991年 | 30篇 |
1990年 | 21篇 |
1989年 | 20篇 |
1988年 | 15篇 |
1987年 | 13篇 |
1986年 | 3篇 |
1985年 | 6篇 |
1984年 | 11篇 |
1982年 | 4篇 |
1980年 | 8篇 |
1977年 | 1篇 |
1975年 | 1篇 |
1974年 | 1篇 |
1972年 | 2篇 |
1971年 | 1篇 |
1968年 | 1篇 |
1966年 | 1篇 |
排序方式: 共有1453条查询结果,搜索用时 0 毫秒
1.
Yamada Kaoru Matsutani Shigeaki Uchiyama Akira Takahashi Toshio 《Journal of inclusion phenomena and macrocyclic chemistry》1991,11(1):49-54
Analyses of crown ether complexes of alkali metal ions and characterization of the complexes formed inm-nitrobenzyl alcohol have been carried out by fast atom bombardment (FAB) mass spectrometry. By using m-nitrobenzyl alcohol as a matrix for measurements, the stoichiometry of the complexes was assessed on the basis of the observed FAB peaks. In addition, the formation of crown ether-alkali metal complexes at a 2 : 1 molar ratio was enhanced by increasing the ionic radius of the metal ion in agreement with previous observations. On these grounds, FAB mass spectrometry may provide a rapid means for investigation of the complexation behavior of crown ethers and the stoichiometry of the complexes. 相似文献
2.
以1H-NMR谱和13C双自旋回波的APT脉冲序列测定文献中尚未曾发表的化合物HC≡C-CH2-O-CCH3-O-CH2文中计算了峰强度与脉冲间隔时间的关系,讨论了各谱线的相位并区分出-CH3、-CH2、-CH和季碳。 相似文献
3.
Yasuhiro Ishida 《Tetrahedron letters》2004,45(51):9455-9459
A planar-chiral imidazolium salt with a tris(oxoethylene) bridge was synthesized, and its potential application as a room temperature ionic liquid with a molecular-recognition ability was demonstrated. 相似文献
4.
Preparation and Molecular Structures of Oligofunctional Dirhenium Carbonyl Derivatives from Dirhenium Nonacarbonylphosphane Starting with dirheniumdecacarbonyl, one CO-Ligand was eliminated oxidatively and substituted by the labile acetonitrile ligand. As an intermediate eq-Re2(CO)9NCCH3 was received. The reaction of this labilised carbonyl with tris(trimethylsilyl)phosphine and subsequent methanolysis gave ax-Re2(CO)9PH3, which was isolated and characterized for the first time. Photochemical and thermal reaction of ax-Re2(CO)9PH3 led to the new bi- and trinuclear complexes Re2(μ-H)(μ3-PHRe(CO)5)(CO)8, Re2(μ-PH2)2(CO)8 and Re2(μ-H) · (μ-PH2)(CO)8, which were characterized by IR-, 1H- and 31P-NMR spectroscopy. The structures of ax-Re2(CO)9PH3, Re2(μ-H)(μ3-PHRe(CO)5)(CO)8 and Re2(μ-PH2)2(CO)8 were confirmed by single-crystal X-ray analysis. ax-Re2(CO)9PH3 has a very short Re? P bond length of 228(2) pm. 相似文献
5.
Chiral separations by host-guest complexation with cyclodextrin and crown ether in capillary zone electrophoresis 总被引:2,自引:0,他引:2
Summary Capillary zone electrophoresis using cyclodextrins and a chiral crown ether as buffer constituents was studied for the enantiomeric separation of drugs and amino acids. Based on results obtained from separation of racemic -amino acids both chiral selectors are compared with respect to resolution, efficiency and retention time. For (±)-Quinagolide effects of buffer composition and temperature are examined using -cyclodextrin as chiral agent. Optimum conditions were pH 2.5 at 30 mmol L–1 -cyclodextrin. A linear dependence of retention on -cyclodextrin concentration allowed calculation of formation constants of the host-guest complexes. Buffer concentration and temperature also influence resolution. The application of a chiral crown ether to the separation of optical isomers in capillary zone electrophoresis is described for the first time. Chiral recognition of solutes depends on the formation of protonated alkyl amines and separation is attributed to the formation of diastereomeric host-guest complexes with different interactions for each enantiomer. The effects of crown ether concentration on resolution are presented. 相似文献
6.
通过选用不同醚类结构做溶剂加热回流Ti(OBu)_4-AIEt_3催化剂,并采用非溶剂聚合方法进行乙炔聚合发现,所得HPPA膜的强度和电导率都有了较大提高。其中直链醚制得的PA膜强度(抗张强度大于100MPa)和空气稳定性比用环醚得到的PA膜高得多,但用前者时的乙炔聚合速率远低于后者。两体系得到的HPPA膜的碘掺杂电导率值相近(~10~3S/cm),拉伸后可达10~4S/cm量级。SEM、TEM及IR光谱的结果表明,不同醚制得的PA膜的纤维束直径及顺式含量有较大差别。 相似文献
7.
8.
Summary The novel theoretical scheme IMOMM, integrating ab initio and molecular mechanics contributions in a single geometry optimization process, is applied to the structural determination of different [OsO4(NR3)] (NR3 = bulky chiral alkaloid derivative) species closely related to active catalysts for the asymmetric dihydroxylation of olefins. Computed values compare in a satisfactory way with available X-ray data, the relationship between the Os-N distance and the nature of the NR3, ligand being properly reproduced. The computational scheme allows the separate quantification of electronic and steric effects, as well as the identification of the specific steric repulsions responsible for the difference. 相似文献
9.
Junfeng Zhou Xiaochen Dong Tao Chen Qiang Yang Qiaohua Tan Jianjun Wang 《European Polymer Journal》2007,43(5):2088-2095
A series of well-defined two-armed polymers containing a crown ether core, poly(stearyl methacrylate)-crown ether-poly(stearyl methacrylate) (PSMA-crown-PSMA), with different molecular weight were synthesized via atom transfer radical polymerization (ATRP). The resultant polymers were characterized by 1H NMR and GPC. The self-assembly behaviors of this kind of polymer in selective solvents were studied by TEM, and it was found that polymers with different molecular weight can directly self-assemble into hollow spheres, solid spheres and a monolayer film with regular pores by varying molecular weight and water content. The possible molecular packing motels for their self-assembly behaviors were proposed. 相似文献
10.
Simon G. Bott Ulrich Kynast Jerry L. Atwood 《Journal of inclusion phenomena and macrocyclic chemistry》1986,4(3):241-246
18-crown-6 reacts with TiCl3 in CH2Cl2 to form a complex in which the crown ether functions as a tridentate ligand. Addition of moist hexane affords a molecular complex in which the crown ether functions as a bidentate ligand. A water molecule is bonded directly to the titanium atom and is further hydrogen bonded to three of the oxygen atoms of the crown. The deep blue crystals of the CH2Cl2 adduct belong to the monoclinic space groupP21/n witha=13.481(8),b=8.021(5),c=21.425(9) Å, =97.32(5)°, and
calc = 1.51 g cm–3 forZ=4. Refinement led to a conventionalR value of 0.040 based on 873 observed reflections. The Ti–O bond distances for the crown oxygen atoms are 2.123(8) and 2.154(9) Å, while the oxygen atom of the water molecule is bonded at 2.072(8) Å. The octahedral coordination sphere of the titanium atom is completed by the three chlorine atoms at distances of 2.340(5), 2.352(4), and 2.373(4) Å.
Supplementary Data relating to this article are deposited with the British Library as Supplementary Publication No. SUP 82034 (10 pages). 相似文献