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71.
The mass spectra of several dibenzo (d.f)-1,3,2,-dioxaphosphorepines of the type where X=0, S, Se and R=2,2′-biphenylylene, have been studied. Dibenzochalcogen ions [RX]+˙ stemming directly from [M]+˙ were observed with high intensities, indicating specific migration of X from phosphorus to carbon with simultaneous destruction of the dioxaphosphorepine ring. Simple cleavage of P? Y as usually observed in similar organophosphorus compounds is not a common process here. 相似文献
72.
Wolfgang A. Herrmann Martina Flöel Cornelia Weber John L. Hubbard Adolf Schäfer 《Journal of organometallic chemistry》1985,286(3):369-397
The eighteen new μ-alkylidene ruthenium complexes 5a–r and 5t are very easily and cleanly obtained along the diazoalkane or the hydrazone routes that involve treatment of the dinuclear, metal-metal doubly bonded precursor compound [(η5-C5H5)Ru(μ-NO)]2 (3) either with the diazoalkanes oxidizing agent (e.g., MnO2), with the respective hydrazones. Similarly, sulfur dioxide adds cleanly to the RuRu double bond of 3, thus giving the complex (μ-SO2)[(η5-C5H5)Ru(NO)]2 (5s). Regardless of the nature of the carbene bridge ligands, the dimetallacyclopropanes exhibit, in contrast to their iron analogues, exclusively terminal nitrosyl ligands. cis/trans-Isomerism with predominating amounts of the trans-isomers is observed for the derivatives that display unsymmetrically substituted carbene bridges.Treatment of the μ-methylene- and μ-ethylidene complexes (μ-CH2)[(η5-C5H5)Ru(NO)]2 (5a) and (μ-CHCH3)[(η5-C tetrafluoroboric acid or trifluoromethanesulfonic acid in diethyl ether yields, at ambient temperature, quantitatively the ionic complexes 6a,b and 7a,b, respectively, which were shown by 1H NMR spectroscopy to contain metal-metal bridging hydrogen functionalities. The reaction of hydrogen bromide with 5a under the same conditions gives the neutral bromo(methyl) complex 6d. This latter compound results from the isolable ionic intermediate of composition [(μ-CH2)(μ-H){(η5C5H5)Ru(NO)}2]+Br? (6c), which reaction stems from the nucleophilicity of the halide ion present in 6c. 相似文献
73.
Wilhelm Prodinger 《Mikrochimica acta》1960,48(5-6):766-770
Zusammenfassung Na-cyklohexyldithiocarbaminat reagiert im pH-Bereich 6,6 bis 7,2 mit Uranylsalzen unter Bildung eines in Wasser mit gelber Farbe lösliehen Komplexes, der bei pH 6,6 ein Absorptionsmaximum bei 392 bis 394 nm besitzt. Die wäßrige Lösung wird durch Zusatz von Alkalilauge bis zum pH 8 bis 9 momentan entfärbt.Es wird ein Kaliumdoppelsalz KUO2(S2HCNC6H11)3 · 3 H2O beschrieben; ferner wird über die Umwandlung des Calciumdoppelsalzes beim Kochen mit NaOH berichtet.
Gewidmet zur 100. Wiederkehr des Geburtstages vonFriedrich Emich. 相似文献
Summary Sodium cyolohexyldithiooarbamate reacts, in the pH range 6.6 to 7.2, with uranium salts to yield a complex which gives a yellow aqueous solution. The absorption maximum is at 392–394 nm at pH 6.6. The aqueous solution loses its color immediately when caustic alkali is added to raise the pH to 8 or 9.A potassium double salt, KUO2(S2HCNC6H11)3 · 3 H2O is described. A report is also given of the transformation of the calcium double salt on boiling with NaOH.
Résumé Le dithiocarbamate de cyclohexylsodium réagit dans le domaine de pH 6,6 à 7,2 sur les sels d'uranyle avec formation d'un complexe coloré en jaune, soluble dans l'eau, qui possède à pH 6,6 un maximum d'absorption pour 392–394 nm. Par addition de lessive alcaline jusqu'à pH 8 à 9 on décolore momentanément la solution aqueuse.On décrit un sel double de potassium KUO2(S2HCNC6H11)3 · 3 H2O; on rend compte, de plus, de la transposition du sel double de calcium par chauffage avec la soude.
Gewidmet zur 100. Wiederkehr des Geburtstages vonFriedrich Emich. 相似文献
74.
Martina Nveke Peter G. Jones Armand Blaschette Dietmar Schomburg Heiko K. Cammenga Matthias Epple 《无机化学与普通化学杂志》1993,619(6):1027-1036
Polysulfonyl Amines. XLI. A Silver(I) Hydrate with an Unusual Composition: Characterization of Tetrakis(dimesylamido)aquatetrasilver(I) [Ag4(N)SO2CH3)2}4(H2O)] by X-Ray Diffraction and Thermal Analysis The title compound is obtained by crystallizing AgN(SO2CH3)2 from water at room temperature. Crystallographic data (at ?95°C): Triclinic space group P1 , a = 864.6(4), b = 1 211.2(5), c = 1 399.1(5) pm, α = 90.97(3), β = 90.90(3), γ = 98.25(4)°, V = 1.4496 nm3, Z = 2, Dx = 2.608 Mg m?3. The four independent silver atoms and the water molecule form zigzag chains Ag(1)-Ag(2)-(μ-H2O)-Ag(3) …? Ag(4) …? Ag(1′) with distances Ag(1)-Ag(2) 309.7, Ag(2)-O(w) 241.8, O(w)-Ag(3) 241.4, Ag(3) …? Ag(4) 342.9, Ag(4) …? Ag(1′) 361.4 pm. The catenated silver atoms are further connected by the dimesylamide anions acting as tridentate bridging (α-O, N, ω-O)-ligands. The resulting strands are interconnected into layers through one O(S)-Ag′ contact (247 pm) and one hydrogen bond O(w)-H(l) …? O′(S) per repeating unit. Between the layers, a weak O(S) …? Ag″ interaction (271 ptn) and a hydrogen bond O(w)-H(2) …? O(S) per repeating unit are observed. The silver atoms Ag(l) to Ag(4) display the coordination numbers 5 [NO,Ag(2), distorted trigonal bipyramid], 5[NO2,O(w)Ag(I), distorted trigonal bipyramid], 5[O4,O(w), trigonal bipyramid], and 2 + 1 (N2, li-near; plus a secondary Ag …? 0 contact). The dehydration of the title compound and a solid-solid phase transformation in anhydrous AgN(SO2CH3)2, were quantitatively investigated by thermoconductometry and time- and temperature-resolved X-ray diffractometry (TXRD). 相似文献
75.
1. Historical remarks concerning magnetic influence on the polarization of resonance fluorescence and its explanation as the Zeeman effect. 2. Rotation of the plane of polarization of the resonance fluorescence of Hg by weak magnetic fields and determination of the lifetime of the excited state. 3. Experiments concerning the excitation of the resonance fluorescence of Hg by light with different kinds and directions of polarization. 相似文献
76.
利用锁定放大器, 恒电势仪, 压控频率正弦波信号发生器等组装成电解池电阻和容抗的快速测定仪。可以快速地自动测是和绘出阻抗谱图和电阻/容抗~时间图。采用微小恒定振幅正弛交流电流(<10 μA)作为微扰, 数据可能较为可靠。给出了线路及所需滤波器元件的数据, 说明仪器各部份之间的干扰可以减少。测定了滴汞电极在1 mol L~(-1)Na_2SO_4溶液中及1 mol L~(-1)Na_2SO_4被正庚醇饱和的溶液中的微分电容~电势数值。证明仪器工作良好。另外, 从实验数据和理论分析, 均表明D.C.Grahame的被广泛引用的有关经典数据有误。本文做了修正。还测定了半导体氧化铁电极在光照下黑暗中的阻抗谱图和氧化银电极充电和停止充电后开路下的电阻~时间图, 显示了仪器在电化学研究中利用的可能性。 相似文献
77.
Wilhelm Geilmann 《Fresenius' Journal of Analytical Chemistry》1962,192(1):14-27
Zusammenfassung Ursprung und Entwicklung der dokimatistischen Analyse sowie die alten Verfahren der Gold-Silber-Trennung werden geschildert. Anschließend werden die klassische Lötrohranalyse sowie die Flammenreaktionen von Bunsen behandelt. Zum Schluß sind die sich auf diese alten Verfahren stützenden Fortentwicklungen der klassischen Probiermethoden erwähnt, die zu den leistungsfähigsten Bestimmungsverfahren der neuzeitlichen Analyse zu rechnen sind, wie die Bestimmung kleiner Hg-Mengen nach Stock, die mikrodokimastischen Verfahren von Haber u. Mitarb. sowie die Verdampfungsanalyse in ihren verschiedenen Anwendungen. 相似文献
78.
Peter Segl'a Martina Palicov Dusan Miklos Marian Koman Milan Melník Maria Korabik Jerzy Mrozinski Tadeusz Glowiak Markku R. Sundberg Peter Lnnecke 《无机化学与普通化学杂志》2004,630(3):470-478
Synthesis and characterization of seven new complexes [Cu(2‐MeSnic)2(CH3OH)]2 (where 2‐MeSnic is 2‐methylthionicotinate), [Cu(2‐MeSnic)2L2]2 (where L is pyridine — py, ethylnicotinate — Etnic and butylnicotinate — Bunic), [Cu(2‐MeSnic)2L2(H2O)2] (where L is py and nicotinamide — nia) and [Cu(2‐MeSnic)2(N‐Menia)2(H2O)2]·2H2O (where N‐Menia is N‐methylnicotinamide) are reported. The characterization were based on elemental analysis, infrared, electronic and EPR spectra, and magnetic susceptibility measurements over a temperature range of 1.8 — 300 K or 70 — 300 K. Three complexes of different type were studied by X‐ray analysis. The molecule of [Cu(2‐MeSnic)2(CH3OH)]2 has dimeric paddle‐wheel cage structure with a tetragonal pyramidal arrangement around CuII. The dimer results from the fact that carboxyl groups of four 2‐MeSnic anions function as bridging in a syn‐syn arrangement. On the other hand [Cu(2‐MeSnic)2(py)2]2 forms dimers with hexacoordinated CuII atoms in highly distorted coordination octahedra, each with two oxygen atoms of bridging carboxyl groups in an anti‐anti arrangement of two 2‐MeSnic anions, with two oxygen atoms of one asymmetrically chelating 2‐MeSnic anion and with two nitrogen atoms of two pyridine ligands. The temperature independent EPR spectrum for this complex exhibits an axial signal which corresponds to almost isolated S = 1/2 magnetic ions. Magnetic data for the dimer show a weak antiferromagnetic interaction between the two metal ions with J = —0.65 cm—1. The CuII atom in complex [Cu(2‐MeSnic)2(py)2(H2O)2] is hexacoordinated in an elongated centrosymmetrical tetragonal‐bipyramidal arrangement (4 + 2). Based on the molecular structure the electronic, infrared, electron paramagnetic resonance spectra and magnetic properties are discussed and stereochemistry as well as the mode of ligand coordination in new solid complexes under study have been determined. 相似文献
79.
James O'Donnell Bruno Rusterholz Barbara Aebersold Denise Rüegg Wilhelm Simon Ernö Pretsch 《Mikrochimica acta》1994,113(1-2):45-52
In an investigation of octamethylene bis(malonic acid diamides) and their selectivities for magnesium, it was found that presence of secondary amides within the particular ionophore played a considerable role in the enhancement of magnesium selectivity. Similar effects in other ionophores, i.e. tris(malonic acid diamides), were thus systematically looked at with the help of selectivity measurements with the hope of optimizing the number of secondary and tertiary amides so as to improve the magnesium selectivity. The syntheses of several investigated tris(malonic acid diamide) isologues are equally reported.Deceased in November 1992 相似文献
80.
Sébastien L.X. Martina 《Tetrahedron letters》2004,45(16):3279-3282
Novel solid-supported phosphonate reagents have been prepared and evaluated for the synthesis of α,β-unsaturated esters with a preference for the Z-alkene. The optimal reagent was a hybrid of both Still-Gennari and Ando reagents, and showed good to high yields and fair to good Z-selectivity for the conversion of both aliphatic and aromatic aldehydes. 相似文献