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991.
Mitja Krnel Primož Koželj Stanislav Vrtnik Andreja Jelen Magdalena Wencka Peter Gille Janez Dolinšek 《无机化学与普通化学杂志》2020,646(14):1099-1104
We present the anisotropic electrical and thermal transport coefficients (electrical resistivity, magnetoresistance, thermoelectric power, thermal conductivity), the magnetic properties, the specific heat and the electronic density of states of a monocrystalline In3Ni2 intermetallic compound, representing a precious-metal-free (and noble-metal-free) intermetallic catalyst for the selective hydrogenation of α,β-unsaturated aldehydes. The investigated physical parameters were determined along three orthogonal crystal-symmetry directions of the trigonal structure, the twofold axis, the 3 axis and within the mirror plane. All the investigated tensorial and vectorial quantities show the same anisotropy, with the quantities being isotropic for the twofold direction and in the mirror plane, whereas there is small, though still significant anisotropy to the 3 direction. The In3Ni2 crystal conducts the electricity and heat somewhat less efficiently along the 3 direction than along the twofold direction and in the mirror plane, but the differences are not large, of about 20 %. In3Ni2 is a diamagnetic intermetallic compound, with a presumably simple Fermi surface and electrons as the majority charge carriers. 相似文献
992.
Gerda Rogl Viktor Soprunyuk Wilfried Schranz Michael J. Zehetbauer Jiri Bursik Herbert Müller Ernst Bauer Peter F. Rogl 《无机化学与普通化学杂志》2020,646(14):1267-1272
Thermoelectric materials with a high figure of merit, ZT, are the essential basis to build thermoelectric generators, which can directly convert heat into electricity. Severe plastic deformation (SPD) via high-pressure torsion (HPT) was successfully applied to enhance ZT of ball-milled and hot-pressed skutterudites as well as to produce bulk nanostructured skutterudites directly from powders. SPD introduces many defects into the sample and in parallel the crystallite size is significantly reduced. During measurement-induced heating these defects anneal partially out, and the grains grow. In this work for the first time systematically the changes of the temperature-dependent electrical resistivity and of thermal expansion were compared. It could be shown that for p- and n-type skutterudites, being hot-pressed and HPT-processed as well as directly HPT-processed from compacted powder, these changes occur more or less simultaneously within the same temperature ranges. This evaluation gives a much deeper insight into the thermoelectric behavior of HPT samples under the influence of changing temperature. 相似文献
993.
Joachim W. Heinicke Nidhi Gupta Peter Mayer Konstantin Karaghiosoff 《无机化学与普通化学杂志》2020,646(13):959-963
NH-Functional 1H-1,3-benzazaphospholes 1a–1c and o-chloranil (tetrachloro-o-benzoquinone - TCBQ) undergo rapid [1+4]-cycloaddition in a 1:2 molar ratio to give 2a – 2c as high-melting zwitterionic σ6λ5-phosphorus compounds. In the case of 2a the yield is high (rel. to TCBQ) even if the reactants were used in a 1:0.5 molar ratio. For the 2-tert-butyl-substituted compounds 2b and 2c the yields were significantly lower, in part by unidentified byproducts. Addition of excess TCBQ to crude 2c containing unconverted 1c did not increase but strongly decrease the amount of 2c . Crystallization and XRD analysis led to detection of a minor side or consecutive product 3c , formally corresponding to P=C bond cleavage and [1+4] cycloaddition of three equivalents TCBQ, two at the phosphinidene and one at the carbene end. NMR spectroscopic data of 2a – 2c including conclusive 13C data for 2a give evidence of the structures of the new compounds. 相似文献
994.
Christian Gentzsch Kerstin Seier Antonios Drakopoulos Dr. Marie-Lise Jobin Dr. Yann Lanoiselée Dr. Zsombor Koszegi Dr. Damien Maurel Dr. Rémy Sounier Dr. Harald Hübner Prof. Dr. Peter Gmeiner Dr. Sébastien Granier Prof. Dr. Davide Calebiro Prof. Dr. Michael Decker 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(15):6014-6020
μ-Opioid receptors (μ-ORs) play a critical role in the modulation of pain and mediate the effects of the most powerful analgesic drugs. Despite extensive efforts, it remains insufficiently understood how μ-ORs produce specific effects in living cells. We developed new fluorescent ligands based on the μ-OR antagonist E-p-nitrocinnamoylamino-dihydrocodeinone (CACO), that display high affinity, long residence time and pronounced selectivity. Using these ligands, we achieved single-molecule imaging of μ-ORs on the surface of living cells at physiological expression levels. Our results reveal a high heterogeneity in the diffusion of μ-ORs, with a relevant immobile fraction. Using a pair of fluorescent ligands of different color, we provide evidence that μ-ORs interact with each other to form short-lived homodimers on the plasma membrane. This approach provides a new strategy to investigate μ-OR pharmacology at single-molecule level. 相似文献
995.
Nathan J. Oldenhuis K. Peter Qin Shu Wang Hong-Zhou Ye Eric A. Alt Adam P. Willard Troy Van Voorhis Stephen L. Craig Prof. Jeremiah A. Johnson 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(7):2806-2814
Photoresponsive materials that change in response to light have been studied for a range of applications. These materials are often metastable during irradiation, returning to their pre-irradiated state after removal of the light source. Herein, we report a polymer gel comprising poly(ethylene glycol) star polymers linked by Cu24L24 metal–organic cages/polyhedra (MOCs) with coumarin ligands. In the presence of UV light, a photosensitizer, and a hydrogen donor, this “polyMOC” material can be reversibly switched between CuII, CuI, and Cu0. The instability of the MOC junctions in the CuI and Cu0 states leads to network disassembly, forming CuI/Cu0 solutions, respectively, that are stable until re-oxidation to CuII and supramolecular gelation. This reversible disassembly of the polyMOC network can occur in the presence of a fixed covalent second network generated in situ by copper-catalyzed azide-alkyne cycloaddition (CuAAC), providing interpenetrating supramolecular and covalent networks. 相似文献
996.
Dr. Matthias Bischoff Dr. Peter Mayer Dr. Christian Meyners Prof. Dr. Felix Hausch 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(21):4677-4681
6-, 7-, and 8-membered rings are assembled from a linear precursor by successive cyclisation reactions to construct a tricyclic diazatricyclo[6.5.1.04, 9]-tetradecanedione scaffold. Advanced building blocks based on d -aspartic acid and l -pyroglutamic acid were combined by a sp3−sp2 Negishi coupling. A carbamate-guided syn-diastereoselective epoxidation followed by an intramolecular epoxide opening allowed the construction of the piperidine ring. An efficient one-pot hydroxyl-group protection twofold deprotection reaction prepared the ground for the cyclisation to the bicycle. A final deprotection of the orthogonal protecting groups and lactamisation led to the novel, sp3-rich tricycle. The final compound is a substrate mimic of peptidyl-prolyl cis-trans isomerases featuring a locked trans-amide bond. Cheminformatic analysis of 179 virtual derivatives indicates favourable physicochemical properties and drug-like characteristics. As proof of concept we, show a low micromolar activity in a fluorescence polarisation assay towards the FK506-binding protein 12. 相似文献
997.
Christina Zovko Dr. Sebastian Bestgen Dr. Christoph Schoo Anne Görner Prof. Jose M. Goicoechea Prof. Peter W. Roesky 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(58):13191-13202
A bis(diphenyl)-phosphine functionalized β-diketimine (PNac-H) was synthesized as a flexible ligand for transition metal complexes. The newly designed ligand features symmetrically placed phosphine moieties around a β-diketimine unit, forming a PNNP-type pocket. Due to the hard and soft donor atoms (N vs. P) the ligand can stabilize various coordination polyhedra. A complete series ranging from coordination numbers 2 to 6 was realized. Linear, trigonal planar, square planar, tetrahedral, square pyramidal, and octahedral coordination arrangements containing the PNac-ligand around the metal center were observed by using suitable metal sources. Hereby, PNac-H or its anion PNac− acts as mono-, bi- and tetradendate ligand. Such a broad flexibility is unusual for a rigid tetradentate system. The structural motifs were realized by treatment of PNac-H with a series of late transition metal precursors, for example, silver, gold, nickel, copper, platinum, and rhodium. The new complexes have been fully characterized by single crystal X-ray diffraction, NMR, IR, UV/Vis spectroscopy, mass spectrometry as well as elemental analysis. Additionally, selected complexes were investigated regarding their photophysical properties. Thus, PNac-H proved to be an ideal ligand platform for the selective coordination and stabilization of various metal ions in diverse polyhedra and oxidation states. 相似文献
998.
Dr. Florian Rauch Peter Endres Dr. Alexandra Friedrich Dr. Daniel Sieh Dr. Martin Hähnel Dr. Ivo Krummenacher Prof. Dr. Holger Braunschweig Prof. Dr. Maik Finze Prof. Dr. Lei Ji Prof. Dr. Todd B. Marder 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(57):12951-12963
Using a new divergent approach, conjugated triarylborane dendrimers were synthesized up to the 2nd generation. The synthetic strategy consists of three steps: 1) functionalization, via iridium catalyzed C−H borylation; 2) activation, via fluorination of the generated boronate ester with K[HF2] or [N(nBu4)][HF2]; and 3) expansion, via reaction of the trifluoroborate salts with aryl Grignard reagents. The concept was also shown to be viable for a convergent approach. All but one of the conjugated borane dendrimers exhibit multiple, distinct and reversible reduction potentials, making them potentially interesting materials for applications in molecular accumulators. Based on their photophysical properties, the 1st generation dendrimers exhibit good conjugation over the whole system. However, the conjugation does not increase further upon expansion to the 2nd generation, but the molar extinction coefficients increase linearly with the number of triarylborane subunits, suggesting a potential application as photonic antennas. 相似文献
999.
Laura Köttner Dr. Monika Schildhauer Dr. Sandra Wiedbrauk Dr. Peter Mayer Prof. Dr. Henry Dube 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(47):10712-10718
The photophysical and photochemical properties of sulfoxide and sulfone derivatives of hemithioindigo photoswitches are scrutinized and compared to the unoxidized parent chromophores. Oxidation results in significantly blue-shifted absorptions and mostly reduction of photochromism while thermal stabilities of individual isomers remain largely unaltered. Effective photoswitching takes place at shorter wavelengths compared to parent hemithioindigos and high isomeric yields can be obtained reversibly in the respective photostationary states. Reversible solid-state photoswitching is observed for a twisted sulfone derivative accompanied by visible color changes. These results establish oxidized hemithioindigo photoswitches as promising and versatile tools for robust light-control of molecular behavior for a wide range of applications. 相似文献
1000.
Peter Roselt Carleen Cullinane Wayne Noonan Hassan Elsaidi Peter Eu Leonard I. Wiebe 《Molecules (Basel, Switzerland)》2020,25(23)
Vitamin E, a natural antioxidant, is of interest to scientists, health care pundits and faddists; its nutritional and biomedical attributes may be validated, anecdotal or fantasy. Vitamin E is a mixture of tocopherols (TPs) and tocotrienols (T-3s), each class having four substitutional isomers (α-, β-, γ-, δ-). Vitamin E analogues attain only low concentrations in most tissues, necessitating exacting invasive techniques for analytical research. Quantitative positron emission tomography (PET) with an F-18-labeled molecular probe would expedite access to Vitamin E’s biodistributions and pharmacokinetics via non-invasive temporal imaging. (R)-6-(3-[18F]Fluoropropoxy)-2,7,8-trimethyl-2-(4,8,12-trimethyltrideca-3,7,11-trien-1-yl)-chromane ([18F]F-γ-T-3) was prepared for this purpose. [18F]F-γ-T-3 was synthesized from γ-T-3 in two steps: (i) 1,3-di-O-tosylpropane was introduced at C6-O to form TsO-γ-T-3, and (ii) reaction of this tosylate with [18F]fluoride in DMF/K222. Non-radioactive F-γ-T-3 was synthesized by reaction of γ-T-3 with 3-fluoropropyl methanesulfonate. [18F]F-γ-T-3 biodistribution in a murine tumor model was imaged using a small-animal PET scanner. F-γ-T-3 was prepared in 61% chemical yield. [18F]F-γ-T-3 was synthesized in acceptable radiochemical yield (RCY 12%) with high radiochemical purity (>99% RCP) in 45 min. Preliminary F-18 PET images in mice showed upper abdominal accumulation with evidence of renal clearance, only low concentrations in the thorax (lung/heart) and head, and rapid clearance from blood. [18F]F-γ-T-3 shows promise as an F-18 PET tracer for detailed in vivo studies of Vitamin E. The labeling procedure provides acceptable RCY, high RCP and pertinence to all eight Vitamin E analogues. 相似文献