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941.
Uwe Hamann Jan Kmpen Peter Bubenitschek Henning Hopf Peter G. Jones 《Acta Crystallographica. Section C, Structural Chemistry》2006,62(4):o178-o181
The title 1,2‐diol derivative, C10H12O2, crystallizes with two independent but closely similar molecules in the asymmetric unit. Only two of the four OH groups are involved in classical hydrogen bonding; the molecules thereby associate to form chains parallel to the short c axis. The other two OH groups are involved in O—H⋯(C[triple‐bond]C) systems. Additionally, three of the four C[triple‐bond]C—H groups act as donors in C—H⋯O interactions. The 1,4‐diol derivative crystallizes with two independent half‐molecules of the diol (each associated with an inversion centre) and one water molecule in the asymmetric unit, C12H16O2·H2O. Both OH groups and one water H atom act as classical hydrogen‐bond donors, leading to layers parallel to the ac plane. The second water H atom is involved in a three‐centre contact to two C[triple‐bond]C bonds. One acetylenic H atom makes a very short `weak' hydrogen bond to a hydroxy O atom, and the other is part of a three‐centre system in which the acceptors are a hydroxy O atom and a C[triple‐bond]C bond. 相似文献
942.
Rudolf Schmid Joseph Foricher Marco Cereghetti Peter Schnholzer 《Helvetica chimica acta》1991,74(2):370-389
The new axially dissymmetric diphosphines (R)- and (S)-(6,6′-dimethoxybiphenyl-2,2′-diyl)bis(diphenyl phosphine) ((R)- and (S)- 5a ; ‘MeO-BIPHEP’) and the analogues (R)- and (S)- 5b and 5c have been synthesized in enantiomerically pure form. These ligands have become readily available by a synthetic scheme which employs, as key steps, an ortho-lithiation/iodination reaction of the (m-methoxyphenyl)diprienylphosphine oxides 8 and a subsequent Ullmann reaction of the resulting iodides 9 to provide the racemic bis(phosphine oxides) 10 . The bis(phosphine oxides) 10 subsequently are resolved with (?)-(2R,3R)- and (+)-(2S,3S)-O-2,3-dibenzoyltartaric acid and reduced to diphosphines 5 . The Ullmann reaction constitutes a new and efficient route to 2,2′-bis(phosphinoyl)-substituted biphenyl systems. Absolute configurations were established for (R)- 5a by X-ray analysis of the derived Pd complex (R,R)- 17a , and for 5b and 5c by means of 1H-NMR comparisons of the derived Pd complexes 16 or 17 , respectively, and by means of CD comparisons. The MeO-BIPHEP diphosphine 5a proved to be as efficient as the previously described BIPHEMP diphosphine ((6,6′-dimethylbiphenyl-2,2′-diyl)bis(diphenylphosphine)) in enantioselective isomerizations and hydrogenations. 相似文献
943.
Jan Blomberg Peter J. Schoenmakers Jan Beens Robert Tijssen 《Journal of separation science》1997,20(10):539-544
In general, petrochemical products contain only a limited number of chemical classes of compounds (sample dimensionality). The enormous number of individual components within these classes, however, soon puts limitations upon a single chromatographic technique when it comes to adequate characterization of these products. Comprehensive two-dimensional gas chromatography (GC×GC) clearly opens the possibility of estimating the composition of hydrocarbon mixtures in a far more detailed fashion than hitherto possible. Although the emphasis of papers of GCxGC thus far almost exclusively applies to the unsurpassed peak-capacity, in the oil industry there is a need for characterization, rather than for analyzing all the individual compounds. In principle a GCxGC system can provide an almost perfect match between its intrinsic properties and the dimensionality of oil samples. To establish the applicability of GCxGC towards petrochemical analytical challenges, a commercially aavailable prototype instrument was subjected to an exhaustive characterization of a typical hydrocarbon precess stream and a fast characterization of a light gas oil. Although there are no fundamental limitations towards the quantitative aspects of a GCxGC system, this paper confines itself to qualitative results only. Quantitative aspects of GCxGC will be published in a forthcoming paper. 相似文献
944.
Phillip T. Mead John C. Traeger John R. Christie Peter. J. Derrick 《Journal of mass spectrometry : JMS》1978,13(7):386-388
The internal energies of [C3H7]+ ions contributing to the metastable peak [C3H7]+ → [C3H5]+ + H2 are higher (by perhaps > 100 kJ mol?1) than those of the ion contributing to the threshold current in appearance energy measurements on [C3H5]+. The measured appearance energy may lead to an underestimation of the activation energy, i.e. negative ‘kinetic shift’, due to quantum, mechanical tunnelling. The distribution of energy released in the decomposition can be explained on the basis that much of the reverse activation energy and a statistical proportion of the excess energy is released as translation. 相似文献
945.
Grald Lelais Peter Micuch Delphine Josien‐Lefebvre Francesco Rossi Dieter Seebach 《Helvetica chimica acta》2004,87(12):3131-3159
The Ser, Cys, and His side chains play decisive roles in the syntheses, structures, and functions of proteins and enzymes. For our structural and biomedical investigations of β‐peptides consisting of amino acids with proteinogenic side chains, we needed to have reliable preparative access to the title compounds. The two β3‐homoamino acid derivatives were obtained by Arndt–Eistert methodology from Boc‐His(Ts)‐OH and Fmoc‐Cys(PMB)‐OH (Schemes 2–4), with the side‐chain functional groups' reactivities requiring special precautions. The β2‐homoamino acids were prepared with the help of the chiral oxazolidinone auxiliary DIOZ by diastereoselective aldol additions of suitable Ti‐enolates to formaldehyde (generated in situ from trioxane) and subsequent functional‐group manipulations. These include OH→OtBu etherification (for β2hSer; Schemes 5 and 6), OH→STrt replacement (for β2hCys; Scheme 7), and CH2OH→CH2N3→CH2NH2 transformations (for β2hHis; Schemes 9–11). Including protection/deprotection/re‐protection reactions, it takes up to ten steps to obtain the enantiomerically pure target compounds from commercial precursors. Unsuccessful approaches, pitfalls, and optimization procedures are also discussed. The final products and the intermediate compounds are fully characterized by retention times (tR), melting points, optical rotations, HPLC on chiral columns, IR, 1H‐ and 13C‐NMR spectroscopy, mass spectrometry, elemental analyses, and (in some cases) by X‐ray crystal‐structure analysis. 相似文献
946.
Ellen Herlihy Peter H. Gies Colin R. Roy Michael Jones 《Photochemistry and photobiology》1994,60(3):288-294
Abstract Quantifying individual exposure to ultraviolet radiation (UVR) is critical to understanding the etiology of a number of diseases including nonmelanotic and melanotic skin cancers. Measurements of personal exposure to solar UVR were made in Hobart, Tasmania in February (summer) 1991 for six different outdoor activities using UVR-sensitive polysulfone (PS) film attached at seven anatomical sites. Concurrent behavioral and environmental observations were also made. To date many studies have relied on subject recall to quantify past solar UVR exposures. To gain insight into the accuracy of subject recall the measured UVR exposures received by different subjects using the PS film were compared to those calculated from personal diaries and ambient solar UVB levels from a monitoring station. In general, when UVR exposure activities took place under close supervision, good correlations were obtained between the PS badges and the ambient measurements/diaries approach. Ultraviolet radiation exposures for the field study involving 94 subjects engaged in a number of outdoor activities are presented. 相似文献
947.
Murat Acemoglu Peter Uebelhart Max Rey Conrad Hans Eugster 《Helvetica chimica acta》1988,71(5):931-956
Syntheses of Enantiomerically Pure Violaxanthins and Related Compounds The epoxides 16 and ent- 16 , prepared by Sharpless-Katsuki oxidation of 15 in excellent yield and very high enantiomeric purity, were used as synthons for the preparation of (+)-(S)-didehydrovomifoliol (45) , (+)-(6S, 7E, 9E)-abscisic ester 46 , (+)-(6S, 7E, 9Z)-abscsic ester 47 , (?)-(3S, 7E, 9E)-xanthoxin (49) , (?)-(3R, 7E, 9E)-xanthoxin (50) , (3S, 5R, 6S, 3′S,5′R, 6′S, all-E)-violaxanthin (1) (3R, 5R,6S,3′R,5′R,6′S, all-E)-violaxanthin (55) and their (9Z) (see 53 , 57 ), (13Z) (see 54 , 58 ), and (15Z) (see 60 ) isomers. The novel violadione ( 61 ) was prepared from 1 by oxidation with DMSO/Ac2O. By base treatment, 61 was converted into violadienedione (62) , a potential precursor of carotenoids with phenolic end groups. 相似文献
948.
Incorporation of 14C-labelled acetate and amino acids as well as of [1-13C]-, [2-13C]-, and [1,2-13C2] acetate, L -[methyl13C] methionine, [2,3-13C2] succinate, and L -[2,3-13C2] aspartate into spirostaphylotrichin A ( 1 ) by Staphylotrichum coccosporum demonstrates that the building blocks of 1 are 5 units of acetate/malonate, 1 unit of methionine, and a C4-dicarboxylic acid. The latter is most likely aspartate and derived from the citric-acid cycle. Using [2-13C, 2-2H3] acetate as a precursor, the starter unit of the polyketide chain was identified. 相似文献
949.
Peter C Fishburn 《Journal of Combinatorial Theory, Series B》1983,35(3):309-318
The sphericity of a graph G is the smallest n such that the vertices in G can be mapped into unit-diameter spheres in n-space in such a way that two vertices are adjacent in G if and only if their assigned spheres intersect. The cubicity of G is defined similarly with unit cubes (edges parallel to the axes) used instead of unitdiameter spheres. In his study of molecular conformation, Havel (Ph.D. dissertation, Univ. of Calif., Berkeley, 1982) showed that there are finite graphs of sphericity 2 that have arbitrarily large cubicity, but he left open the question of whether there are graphs with sphericity greater than cubicity. It is shown here that such graphs exist for cubicity 2 or 3. The construction used to prove this generalizes to larger values for cubicity, but the proof technique does not. Hence it remains open whether there are graphs with large cubicities whose sphericities exceed their cubicities. 相似文献
950.
Seturam Bandacharaya Katti Peter Rüedi Conrad Hans Eugster 《Helvetica chimica acta》1982,65(7):2189-2197
Diterpenoids from Leaf Glands of Plectranthus purpuratus: p-Quinomethanes, Extended Quinones, p-Acylcatechols and a Novel Phyllocladanon Derivative From the complex mixture of terpenoids from the title plant, the following novel diterpenoids have been isolated: 11-hydroxy-19-(3-methyl-2-butenoyloxy)- and 11-hydroxy-19-(3-methylbutanoyloxy)-5,7,9 (11), 13-abietatetraen-12-one ( 1a / 1b ), 11-hydroxy-19-(3-methyl-2-butenoyloxy)- and 11-hydroxy-19-(3-methylbutanoyl-oxy)-7,9(11), 13-abietatrien-6,12-dione ( 2a / 2b ), 6α, 11-dihydroxy-19-(3-methyl-2-butenoyloxy)- and 6α, 11 -dihydroxy-19-(3-methylbutanoyloxy)-7,9 (11), 13-abieta-trien-12-one ( 3a / 3b ), 11,12-dihydroxy-19-(3-methyl-2-butenoyloxy)- and 11,12-di-hydroxy-19-(3-methylbutanoyloxy)-8,11,13-abietatrien-7-one ( 4a / 4b ), and (16R)-17,19-diacetoxy-16-hydroxy-13β-kauran-3-one (=(16R)-17,19-diacetoxy-16-hydro-xyphyllocladan-3-one; 10 ). Compounds 2 and 3 are derivates of taxodione and taxodone, respectively, 4 is a derivative of cryptojaponol. The structure of 10 is Wised on a single-crystal- X -ray analysis and CD . data. 相似文献