全文获取类型
收费全文 | 310篇 |
免费 | 5篇 |
专业分类
化学 | 273篇 |
晶体学 | 1篇 |
数学 | 9篇 |
物理学 | 32篇 |
出版年
2021年 | 2篇 |
2020年 | 3篇 |
2019年 | 3篇 |
2018年 | 2篇 |
2016年 | 8篇 |
2015年 | 7篇 |
2013年 | 10篇 |
2012年 | 6篇 |
2011年 | 16篇 |
2010年 | 10篇 |
2008年 | 7篇 |
2007年 | 11篇 |
2006年 | 10篇 |
2005年 | 10篇 |
2004年 | 11篇 |
2003年 | 9篇 |
2002年 | 8篇 |
2000年 | 2篇 |
1999年 | 4篇 |
1997年 | 4篇 |
1996年 | 5篇 |
1994年 | 5篇 |
1993年 | 10篇 |
1992年 | 5篇 |
1991年 | 5篇 |
1990年 | 9篇 |
1989年 | 4篇 |
1988年 | 12篇 |
1987年 | 6篇 |
1986年 | 10篇 |
1985年 | 6篇 |
1984年 | 10篇 |
1983年 | 3篇 |
1982年 | 4篇 |
1981年 | 7篇 |
1980年 | 11篇 |
1979年 | 8篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1976年 | 8篇 |
1975年 | 5篇 |
1974年 | 4篇 |
1973年 | 4篇 |
1971年 | 2篇 |
1970年 | 3篇 |
1969年 | 2篇 |
1967年 | 2篇 |
1923年 | 1篇 |
1922年 | 1篇 |
1920年 | 1篇 |
排序方式: 共有315条查询结果,搜索用时 15 毫秒
1.
2.
Structures of New SeII and TeII Complexes Containing 2,2-Dicyanethylene-1,1-dithiolate, 2,2-Dicyanethylene-1,1-thioselenolate, and 2,2-Dicyanethylene-1,1-diselenolate (NBu4)2{Se[S2C?C(CN)2]2} ( I ), (AsPh4)2 · {Te[SSeC?C(CN)2]2} ( II ), and (NBu4)2{Te[Se2C?C(CN)2]2} ( III ) containing the bidentate chelate ligands 2,2-dicyanethylene-1,1-dithiolate i-mnt , 2,2-dicyanethylene-1,1-thioselenolate i-mnts , and 2,2-dicyanethylene-1,1-diselenolate i-mns have been prepared and characterized by X-ray structure analysis. The central units consist of [M(X? X)2E2]2? (M = Se, Te; X? X = ligand; E = lone-pair) with fourfold coordinated SeII and TeII, respectively. The complex anions [Se(i-mnt)2E2]2? as well as [Te(i-mnts)2E2]2? show a trapezoide distortion with d(Se? S) = 2.276(5); 2.287(5); 2.803(5); 2.789(5) Å and d(Te? Se) = 2.611(2); 2.617(3); d(Te? S) = 2.889(5); 2.935(4) Å. In III there are centrosymmetric complex anions [Te(i-mns)2E2]2? with nearly identical Te? Se-bond-lengths: 2.674(3) and 2.692(2) Å. These Te? Se bonds are elongated compared to usual Te? Se bonds. 相似文献
3.
The characterization of the compounds CF3SeX (X = H, Cl, Br, CN, CF3, SeCF3) is completed by the report of melting points, boiling points, enthalpies of vaporization and entropies of vaporization. Ultraviolet and mass spectra are presented and discussed. An improved synthesis for CF3SeH is reported. 相似文献
4.
Eberhard Bothe Helmut Gorner Joachim Opitz Dietrich Schulte-Frohlinde Aslam Siddiqi Malgorzata Wala 《Photochemistry and photobiology》1990,52(5):949-959
Double-stranded (ds) calf thymus DNA (0.4 mM), excited by 20 ns laser pulses at 248 nm, was studied in deoxygenated aqueous solution at room temperature and pH 6.7 in the presence of a sodium salt (10 mM). The quantum yields for the formation of hydrated electrons (phi c-), single-strand breaks (phi ssb) and double-strand breaks (phi dsb) were determined for various laser pulse intensities (IL). phi c- and phi ssb increase linearly with increasing IL; however, phi ssb has a tendency to reach saturation at high IL (greater than 5 X 10(6) Wcm-2). The ratio phi ssb/phi c-, representing the number of ssb per radical cation, is about 0.08 at IL less than or equal to 5 X 10(6) Wcm-2. For comparison, the number of ssb per OH radical reacting with dsDNA is 0.22. On going from argon to N2O saturation, phi ssb and phi dsb become larger by factors of approximately 5 and 10-15, respectively. This enhancement is produced by attack on DNA bases by OH radicals generated by N2O-scavenging of the photoelectrons. While phi ssb is essentially independent of the dose (Etot), phi dsb depends linearly on Etot in both argon- and N2O-saturated solutions. The linear dependence of phi dsb implies a square dependence of the number of dsb on Etot. This portion of dsb formation is explained by the occurrence of two random ssb, generated within a critical distance (h) in opposite strands. For both argon- and N2O-saturated solutions h was found to be of the order of 40-70 phosphoric acid diester bonds. On addition of electron scavengers such as 2-chloroethanol (or N2O plus t-butanol), phi dsb is similar to that in neat, argon-saturated solutions. Thus, hydrated electrons are not involved in the chemical pathway leading to laser-pulse-induced dsb of DNA. 相似文献
5.
Chelates of 8-Quinolinol Derivatives. V. Coordination and Extraction of Nickel with Alkylsubstituted 8-Quinolinols . The nickel chelates of 2-, 5-, and 7-methyl-8-quinolinols and of a series of 7-alkyl-8-quinolinols were synthesized in the water-free state. Spectroscopic and magnetochemical differences between the compounds with 2-, 5-, and 7-methyl-8-quinolinols were explained by structural peculiarities. For the nickel chelates with 7-alkyl-8-quinolinols a somewhat distorted square-planar structure is supposed. To characterize the influence of substituents the adduct formation with pyridine was studied. For the extraction of nickel with 8-quinolinols the kind of the alkyl or alkenyl substituent in 7-position has no distinct influence on the state of the extraction equilibrium but it impairs the quickness of the extraction with increasing hydrophobicity. 相似文献
6.
Contributions to the Chemistry of Transition Metal Alkyl Compounds. XIV. Investigations on Benzyl Tungsten Compounds. – On the Formation and Characterization of Tetrabenzyl Tungsten Unstable benzyl tungsten pentachloride is formed from tribenzyl boron and tungsten hexachloride. Other benzylating agents yield only less defined reduction products. – Reacting WCl4 · 2 THF with dibenzyl magnesium W(CH2C6H5)4 can be obtained. The new compound is stable at room temperature and is thoroughly characterized. 相似文献
7.
Werner Bihlmaier Rolf Huisgen Hans-Ulrich Reissig Sabine Vass 《Tetrahedron letters》1979,20(28):2621-2624
Whereas diazomethane cycloadditions are only accelerated by electron-attracting substituents in the olefinic or acetylenic dipolarophile, the cycloadditions of diazoacetic, diazomalonic and diazo(phenylsulfonyl)acetic ester show in accordance with the PMO treatment U-shaped activity functions when log k2 is plotted versus the lowest IP of the dipolarophiles. 相似文献
8.
9.
Complexes of FeI2 and FeI3 with Tetramethylurea [FeI2(OC(NMe2)2)2] ( 1 , [Fe2I4(OC(NMe2)2)2] ( 2 ), and [FeI3(OC(NMe2)2] ( 3 ) were prepared by the reaction of FeI2 and FeI2/iodine, respectively, with tetramethylurea. The structures of 1 and 3 were determined from single crystal X-ray diffraction data. 1 crystallizes in the triclinic space group P1 , with a = 809.9(1), b = 923.2(1), c = 1 374.6(1) pm, α = 106.80(1), β = 90.47(1), γ = 101.55(1)°; Z = 2; R = 0.045., 3 : monoclinic, P21/c, a = 1 311.4(1), b = 783.3(1), c = 1 409.1(1) pm, β = 97.36(1)°; Z = 4; R = 0.047. 1 and 3 are isolated neutral complexes with distorted tetrahedral coordination of iron. 3 is the first FeI3-complex with an O-donor ligand. The IR-spectra exhibit strong shifts of n?C = O and n?asC—N of tetramethylurea especially on coordinating to FeI3. 相似文献
10.
Flögel O Dash J Brüdgam I Hartl H Reissig HU 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(17):4283-4290
Addition of lithiated methoxyallene to pivalonitrile afforded after aqueous workup the expected iminoallene 1 in excellent yield. Treatment of this intermediate with silver nitrate accomplished the desired cyclization to the electron-rich pyrrole derivative 2 in moderate yield. Surprisingly, trifluoroacetic acid converted iminoallene 1 to a mixture of enamide 3 and trifluoromethyl-substituted pyridinol 4 (together with its tautomer 5). A plausible mechanism proposed for this intriguing transformation involves addition of trifluoroacetate to the central allene carbon atom of an allenyl iminium intermediate as crucial step. Enamide 3 is converted to pyridinol 4 by an intramolecular aldol-type process. A practical direct synthesis of trifluoromethyl-substituted pyridinols 4, 10, 11, and 12 starting from typical nitriles and methoxyallene was established. Pyridinol 10 shows an interesting crystal packing with three molecules in the elementary cell and a remarkable helical supramolecular arrangement. Trifluoromethyl-substituted pyridinol 4 was converted to the corresponding pyridyl nonaflate 13, which is an excellent precursor for palladium-catalyzed reactions leading to pyridine derivatives 14-16 in good to excellent yields. The new synthesis of trifluoromethyl-substituted pyridines disclosed here demonstrates a novel reactivity pattern of lithiated methoxyallene which is incorporated into the products as the unusual tripolar synthon B. 相似文献