全文获取类型
收费全文 | 2176篇 |
免费 | 60篇 |
国内免费 | 26篇 |
专业分类
化学 | 1212篇 |
晶体学 | 29篇 |
力学 | 38篇 |
数学 | 456篇 |
物理学 | 361篇 |
综合类 | 166篇 |
出版年
2022年 | 19篇 |
2021年 | 17篇 |
2020年 | 24篇 |
2019年 | 21篇 |
2018年 | 18篇 |
2017年 | 24篇 |
2016年 | 45篇 |
2015年 | 49篇 |
2014年 | 38篇 |
2013年 | 80篇 |
2012年 | 114篇 |
2011年 | 139篇 |
2010年 | 65篇 |
2009年 | 67篇 |
2008年 | 97篇 |
2007年 | 116篇 |
2006年 | 100篇 |
2005年 | 108篇 |
2004年 | 98篇 |
2003年 | 85篇 |
2002年 | 81篇 |
2001年 | 53篇 |
2000年 | 26篇 |
1999年 | 31篇 |
1998年 | 29篇 |
1997年 | 28篇 |
1996年 | 38篇 |
1995年 | 22篇 |
1994年 | 38篇 |
1993年 | 28篇 |
1992年 | 21篇 |
1991年 | 24篇 |
1990年 | 26篇 |
1989年 | 23篇 |
1988年 | 20篇 |
1987年 | 24篇 |
1986年 | 25篇 |
1985年 | 30篇 |
1984年 | 28篇 |
1983年 | 18篇 |
1982年 | 29篇 |
1981年 | 28篇 |
1980年 | 18篇 |
1979年 | 23篇 |
1978年 | 20篇 |
1976年 | 22篇 |
1975年 | 17篇 |
1974年 | 19篇 |
1973年 | 22篇 |
1969年 | 14篇 |
排序方式: 共有2262条查询结果,搜索用时 15 毫秒
71.
Quantum cryptography using any two nonorthogonal states 总被引:6,自引:0,他引:6
Bennett CH 《Physical review letters》1992,68(21):3121-3124
72.
Quantum cryptography without Bell's theorem 总被引:2,自引:0,他引:2
73.
Kenneth P. Ghiggino Louise E. Bennett Robert W. Henderson 《Photochemistry and photobiology》1988,47(1):65-72
Abstract— The absorption and fluorescence properties of porphyrin c (P c ), the porphyrin chromophore present in cytochrome c , have been determined in several solvents and micellar environments. In aqueous buffer solutions at pH 7.5 Pc may exist in both a fluorescent monomeric form with quantum yield of fluorescence, (Φf ,) ∼ 0.03, and fluorescence lifetime, (τf ) ∼ 8 ns, and as a non-fluorescent aggregate. The proportion of monomeric form is higher in organic solvents and micelles but is reduced with increasing porphyrin concentrations in aqueous solutions. Porphyrin c readily complexes with Zn2+ to produce a fluorescent chelate (Zn-P c ) with Φf , ∼ 0.02 and τf , ∼ 2 ns at pH 7.5. The yields of singlet excited oxygen formation from Pc and the Zn-P c complex are higher than observed for hematoporphyrin derivative (HpD). Both P c and Zn-P c are effective agents in tumor phototherapy and do not induce the prolonged cutaneous photosensitivity observed with the use of HpD. 相似文献
74.
Four new supramolecular compounds of Cu(II)-Ni(II) have been synthesized and characterized: [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(ClO(4))(2) (1), [Cu(Me(2)oxpn)Ni(mu-NCS)(H(2)O)(tmen)](2)(PF(6))(2) (2), [Cu(oxpn)Ni(mu-NCS)(NCS) (tmen)](n) (3), and [Cu(Me(2)oxpn)Ni(mu-NCS)(NCS)(tmen)](n) (4), where oxpn = N,N'-bis(3-aminopropyl)oxamidate, Me(2)oxpn = N,N'-bis(3-amino-2,2'-dimethylpropyl)oxamidate, and tmen = N,N,N',N'-tetramethylethylenediamine. Their crystal structures were solved. Complexes 1 and 2 have the same tetranuclear cationic part but a different counteranion. The cationic part consists of two [Cu(Me(2)oxpn)Ni] moieties linked by SCN(-) bridged ligands and intra-tetranuclear hydrogen bonds. In the case of complex 3, a two-dimensional system was built, the thiocyanate ligand linking the dinuclear units gives a chain, and the chains are linked together by hydrogen bonds; intrachain hydrogen bonds are also present. For complex 4, the thiocyanate ligands produce intermolecular linkages between the dinuclear entities, giving a one-dimensional system; intrachain hydrogen bonds are also present. The magnetic properties of the four complexes were studied by susceptibility measurements vs temperature. DFT calculations were made to study the contribution of the SCN(-) and hydrogen bond bridges in the magnetic coupling. 相似文献
75.
Figuerola A Ribas J Llunell M Casanova D Maestro M Alvarez S Diaz C 《Inorganic chemistry》2005,44(20):6939-6948
The reaction of Ln(NO3)3(aq) with K3[Fe(CN)6] or K3[Co(CN)6] and 2,2'-bipyridine in water/ethanol led to eight trinuclear complexes: trans-[M(CN)4(mu-CN)2{Ln(H2O)4(bpy)2}2][M(CN)6].8H2O (M = Fe3+ or Co3+, Ln = La3+, Ce3+, Pr3+, Nd3+, and Sm3+). The structures for the eight complexes [La2Fe] (1), [Ce2Fe] (2), [Pr2Fe] (3), [Nd2Fe] (4), [Ce2Co] (5), [Pr2Co] (6), [Nd2Co] (7), and [Sm2Co] (8) have been solved; they crystallize in the triclinic space group P and are isomorphous. They exhibit a supramolecular 3D architecture through hydrogen bonding and pi-pi stacking interactions. A stereochemical study of the nine-vertex polyhedra of the lanthanide ions, based on continuous shape measures, is presented. No significant magnetic interaction was found between the lanthanide(III) and the iron(III) ions. 相似文献
76.
A rapid and simple fractionation procedure using solid-phase extraction (SPE) cartridges was developed for an accurate determination of aliphatic and polycyclic aromatic hydrocarbons in petroleum residues and further application in chemical fingerprinting of oil spills by gas chromatography-mass spectrometry (GC-MS). Among the adsorbents evaluated, SiO2/C3-CN exhibited the best selectivity, providing, by elution with n-hexane (4 ml) and n-hexane-CH2Cl2 (1:1) (5 ml), two well-resolved aliphatic and aromatic hydrocarbon fractions, with recoveries of 97 +/- 7.2 and 99.7 +/- 13.9%, respectively. The SPE fractionation procedure was compared with the conventional silica-alumina adsorption chromatography showing similar results but practical advantages in terms of reproducibility, analysis time, solvent reduction and cost. Moreover, is particularly suitable for routine analysis with a high sample throughput. The developed methodology was tested in the characterization of fuel-oil samples collected along the Spanish north-west coast, after the Prestige oil spill accident. 相似文献
77.
Porous sol-gel frits are fabricated in a capillary column by filling it with a solution of 3-(trimethoxysilyl)propyl methacrylate, hydrochloric acid, water, toluene (porogen), and a photoinitiator (Irgacure 1800) and exposing it to UV light at 365 nm for 5 min. The separation column (30 cm x 75 microm I.D.) contains between the inlet and outlet frits a 15-cm packed segment filled with 5-microm silica particles modified with the chiral compound (S)-N-3,5-dinitrobenzoyl-1-naphthylglycine. A detection window (1 mm long) is placed immediately after the outlet frit. To demonstrate the performance of this chiral separation column, mixtures of 16 different amino acids (three of which are not naturally occurring) derivatized with the fluorogenic reagent 4-fluoro-7-nitro-2,1,3-benzoxadiazole were separated by capillary chromatography. The enantiomeric separation of the column results in a resolution ranging from 1.21 to 8.29, and a plate height ranging from 8.7 to 39 microm. 相似文献
78.
Summary The new complex double saltscw-[Co(NH3)(en)2(H2O)]2 [M(CN)4]3 (en = ethylenediamine; M = Ni, Pd or Pt),cis-[Co(NH3(en)2(H2O)]2[FeNO(CN)5]3 andcis-[Co(NH3)(en)2(H2O)][Co(CN)6] have been synthesized and by anation in the solid state the corresponding new dinuclear complexes with a cyano bridgecis- ortrans-[(NH3)(en)2Co-NC-M(CN)3]2 [M(CN)4] (M = Ni, Pd or Pt);cis-, trans-[(NH3)(en)2Co-NC-FeNO(CN)4]2[FeNO(CN)5] andcis-[(NH3)(en)2Co-NC-Co(CN)5 have been prepared. The complexes have been characterized by chemical analysis, t.g. measurements, and by i.r. and electronic spectroscopy. With [Ni(CN)4][2– and [Co(CN)in]6
3– only thecis-isomer is produced; with [Pd(CN)4]2–, [Pt(CN)4]2– and [FeNO(CN)5]2– thetrans- isomer is the dominant species. The dinuclear complex derived from [Pt(CN)4]2– shows strong Pt-Pt interactions both in the solid state and in solution. 相似文献
79.
Taoufik Hmidi Joan Mateu Joan Verdera 《Archive for Rational Mechanics and Analysis》2013,209(1):171-208
We show that the boundary of a rotating vortex patch (or V-state, in the terminology of Deem and Zabusky) is C ∞, provided the patch is close to the bifurcation circle in the Lipschitz norm. The rotating patch is also convex if it is close to the bifurcation circle in the C 2 norm. Our proof is based on Burbea’s approach to V-states. 相似文献
80.
Abstract The influence of the composition of the initiator system used in the polymerization of PGE is studied. Structural studies of intermediate species by NMR and IR spectroscopies are made which allow confirmation of some characteristics on the previously proposed mechanism and clarification of the mechanism leading to the chlorinated insoluble polymer fraction. This can be explained by the formation of halogenated oligomers in the first stage of the reaction which interchange with different aluminum alkoxides to give another type of initiator system. 相似文献