全文获取类型
收费全文 | 332篇 |
免费 | 7篇 |
专业分类
化学 | 188篇 |
力学 | 1篇 |
数学 | 19篇 |
物理学 | 131篇 |
出版年
2020年 | 3篇 |
2019年 | 5篇 |
2017年 | 3篇 |
2015年 | 4篇 |
2014年 | 4篇 |
2013年 | 12篇 |
2012年 | 10篇 |
2011年 | 11篇 |
2010年 | 6篇 |
2009年 | 2篇 |
2008年 | 9篇 |
2007年 | 13篇 |
2006年 | 16篇 |
2005年 | 10篇 |
2004年 | 17篇 |
2003年 | 8篇 |
2002年 | 7篇 |
2001年 | 12篇 |
2000年 | 14篇 |
1999年 | 11篇 |
1998年 | 7篇 |
1997年 | 2篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 14篇 |
1993年 | 6篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 6篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 7篇 |
1986年 | 2篇 |
1985年 | 8篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1981年 | 5篇 |
1980年 | 3篇 |
1979年 | 6篇 |
1978年 | 3篇 |
1977年 | 8篇 |
1976年 | 2篇 |
1975年 | 2篇 |
1974年 | 4篇 |
1973年 | 2篇 |
1970年 | 3篇 |
1959年 | 2篇 |
1929年 | 2篇 |
1927年 | 4篇 |
1919年 | 2篇 |
排序方式: 共有339条查询结果,搜索用时 46 毫秒
91.
[structure: see text]. A one-pot, diastereoselective synthesis of a cis,cis-tris[60]fullerene adduct of 6,8,15,17-tetraphenylheptacene has been demonstrated starting from [60]fullerene and 5,7,9,14,16,18-hexahydro-6,8,15,17-tetraphenylheptacene. 相似文献
92.
Polubarinova-Kochina's analytical differential equation methodis used to determine the pseudo-steady-state solution to problemsinvolving the freezing (solidification) of wedges of liquidwhich are initially at their fusion temperature. In particular,we consider four distinct problems for wedges which are: freezingwith the same constant boundary temperature, freezing with thesame constant boundary heat fluxes, freezing with distinct constantboundary temperatures and freezing with distinct constant fluxesat the boundaries. For the last two problems, a Heun's differentialequation with an unknown singularity is derived, which in bothcases admits a particularly elegant simple solution for thespecial case when the wedge angle is . The moving boundariesobtained are shown pictorially. 相似文献
93.
Alves GA Amato S Anjos JC Appel JA Astorga J Bernard T Bracker SB Cremaldi LM Darling CL Dixon RL Errede D Gay C Green DR Jedicke R Karchin PE Kwan S Lueking LJ de Mello Neto JR Metheny J Milburn RH de Miranda JM da Motta Filho H Napier A Passmore D Rafatian A dos Reis AC Ross WR Santoro AF Sheaff M Souza MH Spalding WJ Stoughton C Streetman ME Summers DJ Takach SF Wallace A Wu Z 《Physical review letters》1994,72(6):812-815
94.
95.
96.
97.
Previously published differential pulse methods for the determination of certain progestogens (laevonorgestrel and norethisterone) are not applicable to combined low-dosage oral contraceptives because interference from excipients in the tablets completely eliminates the polarographic response. An ultrafiltration device allows rapid prior extraction of the interfering substances before the polarographic determination in 50% () methanol—phosphate buffer (pH 6.0). Recoveries of 100 ± 1% were obtained by the recommended method, and data for a range of formulations are in excellent agreement with expected values. Electrode characteristics of the progestogens and interfering substances are reported, based on studies employing cyclic voltammetry at a hanging mercury drop electrode, a.c. polarography and normal pulse polarography. Competitive adsorption processes seem to occur when the progestogen and excipients are simultaneously present. 相似文献
98.
Caroline R.S. Briggs David O’Hagan Judith A.K. Howard 《Journal of fluorine chemistry》2003,119(1):9-13
The conformation of 2-fluoro-N-(2-fluoroethyl)-propionamide 4 in the solid state indicates the influence of both a β-fluorine-amide gauche effect and an α-fluoroamide effect. The structure reveals the influence of two recently observed stereoelectronic effects associated with the CF bond, which has resulted in the successful prediction of the solid state conformation of amide 4. A gauche relationship (−69.9°) was observed for atoms N(1)C(4)C(5)F and a syn planar (2.0°) relationship was observed for N(1)C(3)C(2)F. The paper demonstrates the predictive power of using the CF bond as a tool in influencing the conformation of amides and peptides. 相似文献
99.
Single crystal X-ray diffraction studies and a theoretical analysis indicate a preferred conformation for O-β-fluoroethyl esters, where the CF and CO(CO) bonds are gauche rather than anti to each other. The OCCF dihedral angles for three compounds and five independent structures indicate a range of only 63.4-69.6°. Evaluation of a rotational energy profile around this bond in a model system (β-fluoroethyl acetate) predicted a similar dihedral angle and the gauche conformation to be the minimum on the rotational energy profile. High level ab initio calculations measured the gauche conformer to be 0.95 kcal mol−1 lower in energy than the anti conformer and application of a solvation model further increased this differential to 1.6 kcal mol−1, consistent with a previous solution state (NMR) evaluation of this system. 相似文献
100.
John R. Briggs Christopher Crocker Walter S. McDonald Bernard L. Shaw 《Journal of organometallic chemistry》1979,181(1):213-221
Five complexes of type cis-[PtCl2(PR3)Q] (PR3 =PMe3, PMe2Ph, PEt3; Q = CH2 CHOCOCH3 or CH2=CHCH2OCOCH3) have been prepared. The crystal structure of cis-[PtCl2[PME2Ph)(CH2=CHOCOCH3)] is described. Crystals of cis-[PtCl2(PME2Ph)(CH2-CHOCOCH3)] are triclinic, with a 8.441(4), b 13.660(5), c 7.697(3) Å, a 101.61(3)°, β 111.85(3)° γ 95.22(3)°, pP1, Z = 2. The structure was determined from 2011 reflections I σ 3σ (I) and refined to R = 0.037. The CH3COO grouping is syn to the cis-PMe2Ph ligand, with bond lengths of PtCl (trans to P) 2.367(3), PtCl (trans to olefin) 2.314(3), PtP 2.264(2), and PtC of 2.147(12) and 2.168(11) Å. The complexes cis-[PtCl2- (PR3)Q] were studied by variable temperature 1H and 31P NMR spectroscopy. Spectra of the vinyl acetate complexes were temperature dependent as a result of rotation about the platinum—olefin bond. The rotation was “frozen out” at ca. 240 K; for cis-[PtCl2(PME2Ph)(CH2=CHOCOCH3] ΔG≠ (rotation) 15.0 ± 0.2 kcal mol-1. NMR parameters for the rotamers are reported. NMR studies of the interaction between chloro-bridged complexes of type [Pt2Cl2(PR3)2] (PR3 = P-N-Pr3 or PMe2Ph) and vinyl acetate shows that even at low temperatures (213 K) equilibrium favours the bridged complex and the proportion of trans-[PtCl2(PR3)CH2=CHOCOCH3)] is very small e.g. 2%. The allyl acetate complexes cis-[PtCl2(PR3)(CH2=CHCH2OCOCH3)] showed only one rotamer over the range 333–213 K. Reversible dissociation of cis-[PtCl2(PMe2Ph)- (CH2=CHCH2OCOCH3)] to [Pt2Cl4(PMe2Ph)2] + allyl acetate was studied at ambient temperature. At low temperatures e.g. 213–190 K addition of allyl acetate to a CDCl3 solution of [Pt2Cl2(P-n-Pr3)2] reversibly gave some olefin complex trans-[PtCl2(P-n-Pr3)(CH2=CHCH2OCOCH3)] and some O-bonded complex trans-[PtCl2(P-n-Pr3)(CH2=CHCH2OCOCH3)]. 相似文献