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131.
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133.
Sonnenschein H Kreher T Gründemann E Krüger RP Kunath A Zabel V 《The Journal of organic chemistry》1996,61(2):710-714
The first compounds of a new series of redox-active cyclophanes were prepared by dehydrocyclization of bridged indolizines of type 1. The bridged dipyridino-compounds 2a and 2b obtained by reaction of 2 mol of lithiated alpha-picolines with dihalides were used as starting materials. Subsequent treatment of 2a,b with 2 mol of alpha-bromo ketones gave quaternary pyridinium halides. Ring closure in an alkaline medium (Chichibabin reaction) yielded the starting material for the synthesis of the macrocycles. Oxidative C-C coupling gave the diastereomeric cyclophanes of type 3. In all cases one pair of the enantiomers was obtained in excess. CV-investigations have shown that the main products are reversible redox systems. To clarify their conformations, compounds 3c, 3d/1, and3d/2 were subjected to X-ray analysis. 相似文献
134.
Prässler F Hoffmann V Schumann J Wetzig K 《Analytical and bioanalytical chemistry》1996,355(7-8):840-846
An algorithm is presented as a concept for the quantification in direct current and radiofrequency glow discharge (GD) modes for GD optical emission spectroscopy. The algorithm is divided into excitation and sputtering part and thus it is possible to distinguish between the different excitation processes and to consider equivalent sputtering crater formations in both modes. Intensity-time profiles are affected corresponding to the method by several effects. One important effect is that sputtering occurs at a single time in different depths because of curved crater bottoms, this is usually called crater effect. The main purpose is to introduce an iterative deconvolution technique which for the quantification numerically takes into account the curved sputtering crater bottom. Input data for the deconvolution technique are the calibrated mass-time profile, the partial densities of the sample constituents and the measured final shape of the sputtering crater. Using a relatively simple model for ion sputtering the deconvolution technique improves iteratively the calculated layer structure by means of information on crater formation. The mathematical handling is illustrated for the quantification of a depth profile of a multilayer sample of ten 100 nm layers. The resulting concentration-depth profile reflects excellently the real elemental distribution of the multilayer system. 相似文献
135.
Rik R. Tykwinski Franois Diederich Paul Seiler Volker Gramlich 《Helvetica chimica acta》1996,79(3):634-645
The synthesis of functionalized 1,1,2,2-tetraethynylethanes (= 3,4-diethynylhexa-1,5-diynes) as synthons for tetraethynylethenes (3,4-diethynylhex-3-ene-1,5-diynes) and as building blocks for three-dimensional acetylenic molecular scaffolding targeting the synthesis of the molecular carbon belts 3 and 4 is reported (Scheme 1). Reaction of diethyl oxalate and (trialkylsilyl)ethynyl Grignard reagents afforded the silyl-protected 3,4-diethynylhexa-1,5-diyne-3,4- diols 7 and 8 which were transformed in high yields into the cyclic carbonate 9 and the cyclic orthoesters 10–13 , respectively (Scheme 2). The solid-state structures of 9 and 10 were elucidated by X-ray crystallography. The alkyne protecting groups in 9, 10 , and 12 were smoothly removed to give the free tetraynes 14–16 as relatively stable oils in nearly quantitative yields (Scheme 3). Orthoesters 15 and 16 underwent Pd-catalyzed cross-coupling with iodobenzene to give the tetraphenyl derivatives 17 and 18 (Scheme 4). Thermal acid-catalyzed elimination of the orthoester moieties in 12 and 13 produced the silyl-protected tetraethynylethenes 19 and 20 and concluded a novel, simple three-step synthesis of these fully two-dimensionally conjugated π-chromophores (Scheme 5). 相似文献
136.
Mandy Mende Volker Steinert Stefan Zschoche 《Journal of polymer science. Part A, Polymer chemistry》1999,37(13):1949-1955
Potentiometric and conductometric titrations were used to study the dissociation behaviour of poly(propene-co-maleic acid) and poly(propene-co-maleic acid) modified with various contents of taurine (2-aminoethanesulfonic acid) in salt-free solution. Copolymers of propene and maleic acid with different molecular weights were titrated with LiOH, NaOH, and KOH. The influence of molecular weight on pKa is ascertainable in both the first and second dissociation step. Of the various alkali metal cations studied, lithium had the most significant effect on the dissociation behaviour. The acidic strength decreased in the order lithium > sodium ≥ potassium. After insertion of sulfonic acid groups into poly(propene-co-maleic acid), the influence of strong acidic groups on the dissociation behaviour of carboxylic groups was studied. The contents of taurine were 10, 25, and 50 mol%. The second dissociation step was analyzed in this case. The pKa values increased with increasing content of taurine for titrations with LiOH and KOH, but not NaOH. When NaOH was used, the pKa decreases if the polymer was modified with 10% taurine. Higher taurine contents had no influence on the magnitude of pKa. The results demonstrate the strong influence of short-range electrostatic interactions on the dissociation behaviour of weak polyacids. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1949–1955, 1999 相似文献
137.
Dr. Jens Atzrodt Dr. Volker Derdau Prof. Dr. William J. Kerr Dr. Marc Reid 《Angewandte Chemie (International ed. in English)》2018,57(12):3022-3047
The various applications of hydrogen isotopes (deuterium, D, and tritium, T) in the physical and life sciences demand a range of methods for their installation in an array of molecular architectures. In this Review, we describe recent advances in synthetic C?H functionalisation for hydrogen isotope exchange. 相似文献
138.
Detlef Günther Albrecht v. Quadt Ronny Wirz Herve Cousin Volker J. Dietrich 《Mikrochimica acta》2001,136(3-4):101-107
Laser ablation-inductively coupled plasma-mass spectrometry (LA-ICP-MS) was used as a complementary technique to X-ray fluorescence
(XRF), for multi-element analysis of geological samples fused with lithium-tetraborate Li2B4O7). Different calibration strategies using external non-matrix matched reference materials were investigated. Various internal
standards were tested, including the use of Li from the flux, and the use of the naturally occurring internal standards, Si
or Ca. The use of a naturally occurring standard is not as efficient as this required a prior analysis of the samples using
XRF. The obtained values for the analysis of geological reference materials were compared with consensus literature values,
and satisfactory agreement was found. Laser pits, which were formed, had a diameter of 80 μm and 3–5 replicates on each fused
disc were measured. The reproducibility of the method was better than 10% for concentrations above 1 μg/g and better than
15% for lower concentrations. The use of Li as the internal standard offers the possibility of multi-element determinations
in geological samples, which have an unknown composition when the laser ablation analysis is carried out. However, using the
calculated stoichiometric composition of the lithium-tetraborate for the calculation of the Li concentration leads to a constant
deviation from the recommended values. Therefore, it was necessary to determine the Li concentration within each sample batch
using at least one lithium tetraborate fused geological reference material. This resulting Li concentration in the beads was
then used for all subsequent samples in a run. Limits of detection, reproducibility, deviation from reference values indicate
the potential of LA-ICP-MS for such bulk analysis without matrix matched calibration standards. 相似文献
139.
Franziska Lauer Sabrina Diehn Stephan Seifert Janina Kneipp Volker Sauerland Cesar Barahona Steffen Weidner 《Journal of the American Society for Mass Spectrometry》2018,29(11):2237-2247
Mixtures of pollen grains of three different species (Corylus avellana, Alnus cordata, and Pinus sylvestris) were investigated by matrix-assisted laser desorption/ionization time-of-flight imaging mass spectrometry (MALDI-TOF imaging MS). The amount of pollen grains was reduced stepwise from >?10 to single pollen grains. For sample pretreatment, we modified a previously applied approach, where any additional extraction steps were omitted. Our results show that characteristic pollen MALDI mass spectra can be obtained from a single pollen grain, which is the prerequisite for a reliable pollen classification in practical applications. MALDI imaging of laterally resolved pollen grains provides additional information by reducing the complexity of the MS spectra of mixtures, where frequently peak discrimination is observed. Combined with multivariate statistical analyses, such as principal component analysis (PCA), our approach offers the chance for a fast and reliable identification of individual pollen grains by mass spectrometry. 相似文献
140.