全文获取类型
收费全文 | 3079篇 |
免费 | 561篇 |
国内免费 | 545篇 |
专业分类
化学 | 2556篇 |
晶体学 | 46篇 |
力学 | 148篇 |
综合类 | 21篇 |
数学 | 351篇 |
物理学 | 1063篇 |
出版年
2024年 | 6篇 |
2023年 | 55篇 |
2022年 | 90篇 |
2021年 | 115篇 |
2020年 | 145篇 |
2019年 | 138篇 |
2018年 | 116篇 |
2017年 | 126篇 |
2016年 | 177篇 |
2015年 | 161篇 |
2014年 | 191篇 |
2013年 | 279篇 |
2012年 | 264篇 |
2011年 | 248篇 |
2010年 | 230篇 |
2009年 | 177篇 |
2008年 | 219篇 |
2007年 | 177篇 |
2006年 | 167篇 |
2005年 | 181篇 |
2004年 | 158篇 |
2003年 | 108篇 |
2002年 | 115篇 |
2001年 | 122篇 |
2000年 | 76篇 |
1999年 | 73篇 |
1998年 | 42篇 |
1997年 | 30篇 |
1996年 | 27篇 |
1995年 | 24篇 |
1994年 | 25篇 |
1993年 | 18篇 |
1992年 | 16篇 |
1991年 | 14篇 |
1990年 | 20篇 |
1989年 | 8篇 |
1988年 | 5篇 |
1987年 | 8篇 |
1986年 | 13篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1981年 | 2篇 |
1980年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有4185条查询结果,搜索用时 15 毫秒
71.
Pei Yuan Wu 《Integral Equations and Operator Theory》1984,7(6):899-904
If T is a contraction on the Hilbert space H and there is an invariant subspace K for T such that T/K is similar to a backward shift, then T is reflexive. If similarity is replaced by quasi-similarity, then the same conclusion holds under the additional condition that the defect index of T be finite.This research was partially supported by National Science Council (Republic of China). 相似文献
72.
Zi-Zhong Li Qing-Xiang Guo Tan Ren Xiao-Qing Zhu You-Cheng Liu 《Journal of inclusion phenomena and macrocyclic chemistry》1993,15(1):37-42
Tetramethylsilane (TMS) can be included by -cyclodextrin (-CD), and sodium 2,2-dimethylsilapentane-5-sulphonate (DSS) can form inclusion complexes with - and -CD. The NMR chemical shifts are changed considerably as a result of the strong interaction between CD and the guest compound in the inclusion complexes. A downfield shift of as much as 0.63 ppm shift downfield has been observed for the protons of external TMS in CD aqueous solution. In view of this, the question arises of whether TMS and DSS can be used as internal references. DSS in D2O is suggested as an external reference for aqueous cyclodextrin solution in NMR measurements. 相似文献
73.
74.
Projection-reconstruction (PR) NMR enables rapid collection of multidimensional NMR data. NOESY represents a particularly difficult challenge for currently existing reconstruction algorithms, as it requires the quantitative reconstruction of an unknown number of peaks, at full sensitivity. We have demonstrated the successful application of PR-NMR to NOESY by determining the 4D methyl/amide NOESY spectrum of a 29 kDa protein, human carbonic anhydrase II, from 2D projections, using filtered backprojection for reconstruction. Compared with a 3D control spectrum, all expected peaks were faithfully reconstructed, with correct volumes and with no artifacts. Filtered backprojection thus provides a way to obtain high-resolution 4D NOESY data in the time required for conventional 3D data collection. 相似文献
75.
High-level computations at G3, CBS-Q, and G3B3 levels were conducted, and good-quality C-H and N-H bond dissociation energies (BDEs) were obtained for a variety of saturated and unsaturated strained hydrocarbons and amines for the first time. From detailed NBO analyses, we found that the C-H BDEs of hydrocarbons are determined mainly by the hybridization of the parent compound, the hybridization of the radical, and the extent of spin delocalization of the radical. The ring strain has a significant effect on the C-H BDE because it forces the parent compound and radical to adopt certain undesirable hybridization. A structure-activity relationship equation (i.e., BDE (C-H) = 61.1-227.8 (p(parent)% - 0.75)(2) + 152.9 (p(radical)% - 1.00)(2) + 40.4 spin) was established, and it can predict the C-H BDEs of a variety of saturated and unsaturated strained hydrocarbons fairly well. For the C-H BDEs associated with the bridgehead carbons of the highly rigid strained compounds, we found that the strength of the C-H bond can also be predicted from the H-C-C bond angles of the bridgehead carbon. Finally, we found that N-H BDEs show less dependence on the ring strain than C-H BDEs. 相似文献
76.
以皮胶原纤维为基质,通过交联剂分别将黑荆树单宁和杨梅单宁固化在胶原纤维上制备吸附材料。实验表明,这两种吸附材料对稀土金属离子La^3+有很好的吸附作用。在pH为4.5的条件下,当吸附剂用量为0.1 g,La^3+初始浓度为9.952 mmol·L^-1,固化杨梅单宁的平衡吸附量为0.388 mmol·g^-1,比固化黑荆树单宁略大,其吸附平衡均符合Freundlich方程。进一步研究了固化杨梅单宁的吸附动力学、温度、pH值等对吸附平衡的影响。结果表明,温度对吸附平衡的影响不明显;pH值对吸附平衡有较大影响,在适当范围内提高pH值会增加平衡吸附量;吸附动力学可用拟二级速度方程来描述。当吸附温度为293 K时,由拟二级速率方程计算所得的平衡吸附量与实测的平衡吸附量误差在3%以内。同时固化杨梅单宁也具有良好的柱动力学特性。 相似文献
77.
This study examines the reagent gas pressure and ion source temperature dependence for dimethyl ether chemical ionization (DME CI) mass spectra recorded with an external source ion trap mass spectrometer (ITMS). Information for better controls of the reagent gas pressure in order to obtain fair CI spectra is provided. The origin of M+? ions observed in DME CIMS is discussed in detail. Furthermore, the ion source temperature effect on the DME CI is also investigated. 相似文献
78.
ZuPeiLIANG YaQingFENG ShuXianMENG ZhiYanLIANG 《中国化学快报》2005,16(1):135-138
Urease was immobilized onto the glutaraldehyde cross-linked chitosan beads that were prepared under microwave irradiation. The activity and the yield of activity of immobilized urease was 10.83 U/g B and 47.7%, respectively. The conditions of urease immobilization were optimized. The properties of the immobilized urease were investigated and compared with that of the free enzyme. 相似文献
79.
Systematic studies were performed on SnCl2-mediated carbonyl allylation reaction between aldehydes and allyl halides in fully aqueous media. Totally three valuable reaction systems were discovered, which were SnCl2/CuCl2, SnCl2/TiCl3, and SnCl2/PdCl2. They all provided good to excellent yields in the allylation of aliphatic and aromatic aldehydes under very mild and convenient conditions. SnCl2, by itself, was also found to be effective for the allylation reaction when allyl bromide was employed. However, the SnCl2-only reaction could only tolerate very small amount of water as the solvent. The SnCl2/CuCl2, SnCl2/TiCl3, and SnCl2/PdCl2-mediated reactions exhibited good regioselectivity favoring the γ-adduct when cinnamyl halides were employed as the allylation reagent. The same reactions with cinnamyl halides also showed good diastereoselectivity favoring the anti-product. Mechanistic studies using proton NMR techniques suggested that the additive (i.e., CuCl2, TiCl3, PdCl2) could accelerate the formation of allyltin intermediate, but this step was shown not to be the most important for the allylation. Thus we proposed that the Lewis acid catalysis effect exerted by the additive was the main reason for the observed reactivity enhancement. 相似文献
80.
Rong Chen Yu-Hui Cheng Lei Liu Xiao-Song Li Qing-Xiang Guo 《Research on Chemical Intermediates》2002,28(1):41-48
MP2/6-31+G* calculations were performed on the cation- complexes of ethylene, cyclobutadiene and benzene with a number of atomic cations. It was found that except B+ all the atomic cations form -type cation- complexes with ethylene. On the other hand, with cyclobutadiene Li+, N+, Na+, P+ and K+ form -type complexes, whereas H+, F+, and Cl+ form covalent -type complexes. With benzene Li+, B+, Na+, Al+, and K+ form -type complexes whereas H+, F+, and Cl+ form -type complexes. It was concluded that the driving force to form the -type complex is chemical bonding, and that for metal cations to form -type complexes is non-covalent interaction. 相似文献