全文获取类型
收费全文 | 1748篇 |
免费 | 79篇 |
国内免费 | 23篇 |
专业分类
化学 | 944篇 |
晶体学 | 9篇 |
力学 | 75篇 |
数学 | 548篇 |
物理学 | 274篇 |
出版年
2023年 | 18篇 |
2022年 | 48篇 |
2021年 | 77篇 |
2020年 | 74篇 |
2019年 | 81篇 |
2018年 | 79篇 |
2017年 | 70篇 |
2016年 | 97篇 |
2015年 | 55篇 |
2014年 | 77篇 |
2013年 | 139篇 |
2012年 | 99篇 |
2011年 | 100篇 |
2010年 | 75篇 |
2009年 | 56篇 |
2008年 | 89篇 |
2007年 | 77篇 |
2006年 | 47篇 |
2005年 | 48篇 |
2004年 | 46篇 |
2003年 | 40篇 |
2002年 | 40篇 |
2001年 | 10篇 |
2000年 | 16篇 |
1999年 | 14篇 |
1998年 | 12篇 |
1997年 | 17篇 |
1996年 | 12篇 |
1995年 | 14篇 |
1994年 | 13篇 |
1993年 | 9篇 |
1992年 | 6篇 |
1991年 | 9篇 |
1990年 | 8篇 |
1989年 | 10篇 |
1988年 | 6篇 |
1987年 | 9篇 |
1985年 | 16篇 |
1984年 | 12篇 |
1983年 | 5篇 |
1982年 | 10篇 |
1981年 | 6篇 |
1980年 | 7篇 |
1979年 | 8篇 |
1978年 | 11篇 |
1977年 | 15篇 |
1976年 | 12篇 |
1975年 | 11篇 |
1974年 | 8篇 |
1973年 | 9篇 |
排序方式: 共有1850条查询结果,搜索用时 31 毫秒
21.
The pigments Luteoskyrin (Ls) and Rugulosin (Rg) might adopt a priori two extreme conformations, a planar and an angular one. To determine the predominant conformation in solution, the nature of the lowest energy transition of the chromophores and the presence of intramolecular H-bonding have been investigated. The solvent effects on electronic absorption and CD spectra indicated the π-π* nature of the lowest energy transition. Treatments of the electronic absorption results according to McRae and Kosower relations, IR absorption and PMR spectra suggested the presence of strong intra-molecular H-bonds. From these results it was concluded that Ls and Rg adopted in a variety of solvents the most planar conformation. 相似文献
22.
Anionic polymerization of methyl methacrylate in THF and toluene at ?70° was studied by means of i.r. spectroscopy. The reaction mixtures show characteristic absorption at 1600–1750 cm?1 caused by the stretching vibrations of the propagating centre as well as by the groups obtained in side reactions (metal splitting, addition to a carbonyl group, cyclization). Sec-butyllithium is more effective in THF than n-butyllithium, ethyllithium and fluorenyllithium. When polymerizing in toluene, small amounts of a donor (THF or HMPT) cause formation of active centres similar to those in pure THF. The “living” ends of oligo-MMA form 1:1 complexes with electron acceptors such as trialkylaluminium and triethylboron. 相似文献
23.
The problem of the negative values of the interaction parameter in the equation of Frumkin has been analyzed with respect to the adsorption of nonionic molecules on energetically homogeneous surface. For this purpose, the adsorption states of a homologue series of ethoxylated nonionic surfactants on air/water interface have been determined using four different models and literature data (surface tension isotherms). The results obtained with the Frumkin adsorption isotherm imply repulsion between the adsorbed species (corresponding to negative values of the interaction parameter), while the classical lattice theory for energetically homogeneous surface (e.g., water/air) admits attraction alone. It appears that this serious contradiction can be overcome by assuming heterogeneity in the adsorption layer, that is, effects of partial condensation (formation of aggregates) on the surface. Such a phenomenon is suggested in the Fainerman-Lucassen-Reynders-Miller (FLM) "Aggregation model". Despite the limitations of the latter model (e.g., monodispersity of the aggregates), we have been able to estimate the sign and the order of magnitude of Frumkin's interaction parameter and the range of the aggregation numbers of the surface species. 相似文献
24.
25.
26.
27.
28.
Nguyen Thanh Long Pham Ngoc Dinh Alain 《Mathematical Methods in the Applied Sciences》1993,16(4):281-295
We study the following initial and boundary value problem: In section 1, with u0 in L2(Ω), f continuous such that f(u) + ? non-decreasing for ? positive, we prove the existence of a unique solution on (0,T), for each T > 0. In section 2 it is proved that the unique soluition u belongs to L2(0, T; H ∩ H2) ∩ L∞(0, T; H) if we assume u0 in H and f in C1(?,?). Numerical results are given for these two cases. 相似文献
29.
Pham TN Hinchley SL Rankin DW Liptaj T Uhrín D 《Journal of the American Chemical Society》2004,126(40):13100-13110
We have developed methodology for the determination of solution structures of small molecules from residual dipolar coupling constants measured in dilute liquid crystals. The power of the new technique is demonstrated by the determination of the structure of methyl beta-d-xylopyranoside (I) in solution. An oriented sample of I was prepared using a mixture of C(12)E(5) and hexanol in D(2)O. Thirty residual dipolar coupling constants, ranging from -6.44 to 4.99 Hz, were measured using intensity-based J-modulated NMR techniques. These include 15 D(HH), 4 (1)D(CH), and 11 (n)D(CH) coupling constants. The accuracy of the dipolar coupling constants is estimated to be < +/- 0.02 Hz. New constant-time HMBC NMR experiments were developed for the measurement of (n)D(CH) coupling constants, the use of which was crucial for the successful structure determination of I, as they allowed us to increase the number of fitted parameters. The structure of I was refined using a model in which the directly bonded interatom distances were fixed at their ab initio values, while 16 geometrical and 5 order parameters were optimized. These included 2 CCC and 6 CCH angles, and 2 CCCC and 6 CCCH dihedral angles. Vibrationally averaged dipolar coupling constants were used during the refinement. The refined solution structure of I is very similar to that obtained by ab initio calculations, with 11 bond and dihedral angles differing by 0.8 degrees or less and the remaining 5 parameters differing by up to 3.3 degrees . Comparison with the neutron diffraction structure showed larger differences attributable to crystal packing effects. Reducing the degree of order by using dilute liquid crystalline media in combination with precise measurement of small residual dipolar coupling constants, as shown here, is a way of overcoming the limitation of strongly orienting liquid crystals associated with the complexity of (1)H NMR spectra for molecules with more than 12 protons. 相似文献
30.
Zeta-potentials of self-assembled surface micelles of ionic surfactants adsorbed at hydrophobic graphite surfaces 总被引:1,自引:0,他引:1
Vamsi K. Paruchuri Anh V. Nguyen Jan D. Miller 《Colloids and surfaces. A, Physicochemical and engineering aspects》2004,250(1-3):519-526
The zeta-potentials of the self-assembled surface ionic surfactants (sodium dodecyl sulfate—SDS and hexadecyltrimethyl ammonium bromide—CTAB) on graphite surfaces were determined both from streaming potential and electrophoretic mobility measurements. The adsorption of the surfactants at graphite–liquid interfaces has been studied using atomic force microscopy (AFM) soft-contact imaging which shows the formation of linear, parallel hemicylinders with headgroups oriented towards the solution. The magnitude of the zeta-potential increased with an increase in surfactant concentration, reaching a constant value at a concentration corresponding to the point of surface micelle formation as confirmed from AFM imaging. The streaming potential and electrophoretic mobility measurements showed that the zeta-potentials of SDS and CTAB surface micelles adsorbed at the graphite surface were about −75 and +70 mV, respectively, well in agreement with the values reported for bulk phase micelles in the literature. 相似文献