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Kozo Arai Atsushi Matsunaga Masaru Yoneyama Shoji Takigami Yoshio Nakamura Haydn E. Edwards Glyn O. Phillips 《Journal of polymer science. Part A, Polymer chemistry》1993,31(1):249-258
The reactions of heparin with 2,4,6-trinitrobenzenesulfonic acid (TNBS) were studied spectrometrically. Seven different commercial heparins were used in this study. The amino groups react with TNBS to form equimolar amounts of trinitrophenylated (TNP) amino groups and bisulfite ions. The TNP-amino groups further react with bisulfite ions to form the monosubstituted anionic sigma complex. The absorption spectrum with two maxima at approximately 350 nm and approximately 420 nm, characteristic of either the TNP-amino groups or the complex, was analyzed for the reaction of TNBS with heparin. It was shown that the reactivities of TNBS with amino groups from α-amino acid and hexosamine residues are greatly different. By combining the results of the reaction kinetics and the reaction of heparin with Sanger's reagent, the number of the α-amino groups and the free amino groups in hexosamine residues were determined. These data have been performed with a range of heparins from different commercial sources, of different activities and physical characteristics. No correlation was found between the free amino contents of these heparins and biological potency. © 1993 John Wiley & Sons, Inc. 相似文献
14.
Rao CN Kulkarni GU Thomas PJ Edwards PP 《Chemistry (Weinheim an der Bergstrasse, Germany)》2002,8(1):28-35
Properties of materials determined by their size are indeed fascinating and form the basis of the emerging area of nanoscience. In this article, we examine the size dependent electronic structure and properties of nanocrystals of semiconductors and metals to illustrate this aspect. We then discuss the chemical reactivity of metal nanocrystals which is strongly dependent on the size not only because of the large surface area but also a result of the significantly different electronic structure of the small nanocrystals. Nanoscale catalysis of gold exemplifies this feature. Size also plays a role in the assembly of nanocrystals into crystalline arrays. While we owe the beginnings of size-dependent chemistry to the early studies of colloids, recent findings have added a new dimension to the subject. 相似文献
15.
Zareen Ahkter Andrew J. Edwards Scott L. Ingham Jack Lewis Ana M. Martin Castro Paul R. Raithby Gregory P. Shields 《Journal of Cluster Science》2000,11(1):217-226
The reaction of the di-gold cation [Au2(dppx)]2+ with the heptanuclear cluster dianion [Os7(CO)20]2– affords the mixed metal cluster [Os7(CO)20{Au2(dppx)}] (x=m (1), e (2), b (3)). On standing, in solution, this complex undergoes decarbonylation to give the cluster [Os7(CO)19{Au2(dppx)}] (x=m (4), e (5), b (6)). The complexes have been characterised spectroscopically, and an X-ray structure determination of the dppm derivative shows that it contains a metal core based on an Os7 edge-bridged bicapped tetrahedron with the two
3-Au atoms capping adjacent triangular Os3 faces of the central tetrahedron. In an analogous reaction, the carbido anion [Os7(H)C(CO)19]– affords the neutral cluster [Os7C(CO)19{Au2(dppm)}] (7) when treated with [Au2(dppm)]2+ in the presence of base. 相似文献
16.
J.G. Edwards 《Progress in Surface Science》1983,13(2):125-196
The proposition is examined that adhesion between cells of animal tissues, and between cells and their extracellular matrix, is brought about by specific molecules present at cell-surfaces. Evidence is surveyed which has begun to emerge from the use of antibodies which inhibit or reverse adhesion. Putative cell-adhesion molecules in cellular slime-moulds and cells of chick and mouse embryos have been identified by their ability to neutralize the adhesion-inhibiting activity of monovalent fragments of polyspecific antibodies. In some instances antibodies have also been used to investigate the role of the cell-adhesion molecules in morphogenetic phenomena. A possible parallel is discussed between the effects of calcium ions on the cell-adhesion molecule uvomorulin from mouse blastomeres, and its effects on certain other cell-adhesion molecules.Although the role of fibronectin in promoting attachment and spreading of cells on artificial substrates and on denatured collagen is firmly established, there is little evidence that this glycoprotein is involved in direct intercellular adhesion. The observation that cells spread on adsorbed fibronectin, whereas binding of individual fibronectin molecules to cells is difficult to demonstrate may merely indicate that fibronectin is a relatively weak ligand for cell-surfaces. It is suggested that rather than being a necessary intermediate in the adhesion of cells to collagen, fibronectin may form matrix in its own right which shares with native collagen the ability to promote cell-attachment and spreading.The long-held view that cell-surface oligosaccharides act as receptors in cell-adhesion appears still to be largely unsubstantiated. However the poorly adhesive properties of cells from many different lines with glycosylation defects strongly suggest N-linked oligosaccharides of glycoproteins are involved in some way as yet not determined. 相似文献
17.
Antonio Doménech María Teresa Doménech‐Carbó Howell G. M. Edwards 《Electroanalysis》2007,19(18):1890-1900
Multivariate chemometric methods are applied for identifying earth pigments from square‐wave voltammetric measurements performed at pigment‐modified paraffin‐impregnated graphite electrodes allowing for a separation between hematite‐based earths, French ochres, Spanish ochres, siennas, umbers and green earths. This methodology is applied to the identification of the pigments in samples from the ceiling frescoes of Antonio Palomino (dated 1707) in the vaulted nave of the Sant Joan del Mercat church in Valencia (Spain). These frescoes suffered considerable damage by fire during the Spanish Civil War in 1936, resulting in severe chemical and chromatic alterations. Electrochemical data, supported by scanning electron microscopy/energy dispersive X‐ray microanalysis and Raman spectroscopy, indicate that thermal stress induced the transformation of goethite‐based yellow ochres into hematite and magnetite. 相似文献
18.
Detection of single molecules, particles, and rapid redox events is a challenge of electrochemical investigations and requires either an amplification strategy or significant averaging for the electrochemical current to exceed the noise level. We consider the minimum number of electrons required to reach the limit of quantification in these electrochemical measurements. A survey of the literature indicates that the state-of-the-art limit in current detection for different types of measurements (e.g. voltammetry, single-molecule redox cycling, ion channel recordings of single molecules, metal nanoparticle collision, and phase nucleation) is independent of the nature of the measurement and increases linearly with reciprocal response time, Δt?1, over ~5 orders of magnitude (from ~10 to ~106 s?1). We demonstrate that the practical limit of quantification requires cumulative measurement of ~2100 electrons during Δt and is determined by statistics of counting electrons, that is, the shot noise in the current. 相似文献
19.
Carmona D Lahoz FJ Atencio R Edwards AJ Oro LA Lamata MP Esteban M Trofimenko S 《Inorganic chemistry》1996,35(9):2549-2557
Treatment of the metallo ligands [ML(pz)(2)(Hpz)] (pz = pyrazolate; L = C(5)Me(5), M = Ir (1); L = mesitylene, M = Ru (3)) with [M'Cl{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (4), Ni (5)) yields heterodinuclear complexes of formula [LM(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (L = C(5)Me(5); M = Ir; M' = Co (6), Ni (7). L = mesitylene; M = Ru; M' = Co (8)). The related complex [Ru(eta(6)-p-cymene)(pz)(2)(Hpz)] (2) reacts with equimolar amounts of 4 or 5 to give mixtures of the corresponding bis(&mgr;-pyrazolato) &mgr;-chloro complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(2)(&mgr;-Cl)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (9), Ni (10)) and the triply pyrazolato-bridged complexes [(eta(6)-p-cymene)Ru(&mgr;-pz)(3)M'{HB(3-i-Pr-4-Br-pz)(3)}] (M' = Co (11), Ni (12)). Complex 1 reacts with 5 in the presence of KOH to give the IrNi complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(3)Ni{HB(3-i-Pr-4-Br-pz)(3)}] (13) whereas its reaction with 4 and KOH rendered the bis(&mgr;-pyrazolato) &mgr;-hydroxo complex [(eta(5)-C(5)Me(5))Ir(&mgr;-pz)(2)(&mgr;-OH)Co{HB(3-i-Pr-4-Br-pz)(3)}] (14). The molecular structure of the heterobridged IrCo complex (6) and those of the homobridged RuNi (12) and IrNi (13) complexes have been determined by X-ray analyses. Compound 6 crystallizes in the monoclinic space group P2(1)/n, with a = 10.146(5) ?, b = 18.435(4) ?, c = 22.187(13) ?, beta = 97.28(4) degrees, and Z = 4. Complex 12 is monoclinic, space group P2(1), with a = 10.1169(7) ?, b = 21.692(2) ?, c = 11.419(1) ?, beta = 112.179(7) degrees, and Z = 2. Compound 13 crystallizes in the monoclinic space group Cc, with a = 13.695(2) ?, b = 27.929(6) ?, c = 13.329(2) ?, beta = 94.11(4) degrees, and Z = 4. All the neutral complexes 6, 12, and 13 consist of linear M.M'.B backbones with two (6) or three (12, 13) pyrazolate ligands bridging the dimetallic M.M' units and three substituted 3-i-Pr-4-Br-pz groups joining M' to the boron atoms. The presence in the proximity of the first-row metal M' of the three space-demanding isopropyl substituents of the pyrazolate groups induces a significant trigonal distortion of the octahedral symmetry, yielding clearly different M'-N bond distances on both sides of the ideal octahedral coordination sphere of these metals. 相似文献
20.
Jerald C. Hinshaw W. Wayne Edwards Clifford George Richard Gilardi 《Journal of heterocyclic chemistry》1992,29(7):1721-1724
Dealkylation of 1-tert-butyl-2,3,4-trinitropyrrole in boiling trifluroacetic acid gave 2,3,4-trinitropyrrole, the structure of which was confirmed by X-ray crystallography. Treatment of this trinitropyrrole with nitric acid/oleum briefly at 60° gave 2,3,4,5-tetranitropyrrole. 相似文献