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981.
Leonid Mashlyakovskiy Elena Khomko Natalya Volynkina Claudio Tonelli 《Journal of polymer science. Part A, Polymer chemistry》2002,40(21):3771-3795
The kinetics of the dibutyltin dilaurate (DBTDL)‐catalyzed urethane formation reactions of cyclohexyl isocyanate (CHI) with model monofunctional fluorinated alcohols and fluoropolyether diol Z‐DOL H‐1000 of various molecular weights (100–1084 g mol?1) in different solvents were studied. IR spectroscopy and chemical titration methods were used for measuring the rate of the total NCO disappearance at 30–60 °C. The effects of the reagents and DBTDL catalyst concentrations, the solvent and hydroxyl‐containing compound nature, and the temperature on the reaction rate and mechanism were investigated. Depending on the initial reagent concentration and solvent, the reactions could be well described by zero‐order, first‐order, second‐order, or more complex equations. The reaction mechanism, including the formation of intermediate ternary or binary complexes of reagents with the tin catalyst, could vary with the concentration and solvent and even during the reaction. The results were treated with a rate expression analogous to those used for enzymatic reactions. Under the explored conditions, the rate of the uncatalyzed reaction of fluorinated alcohols with CHI was negligible. Moreover, there was no allophanate formation, nor were there other side reactions, catalysis by urethane in the absence of DBTDL, or a synergetic effect in the presence of the tin catalyst. © 2002 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 40: 3771–3795, 2002 相似文献
982.
Chetiyanukornkul T Toriba A Kizu R Kimura K Hayakawa K 《Biomedical chromatography : BMC》2004,18(9):655-661
A simple liquid chromatography-electrospray ionization mass spectrometry (LC-ESI-MS) method for the determination of nicotine and cotinine in human hair was established. In the procedure, a hair sample (10 mg) was washed with dichloromethane and digested in 2.5 M sodium hydroxide. The digest was extracted with dichloromethane and then 25 mM hydrochloric acid in methanol was added to the extract, to prevent loss of analytes. The solution was evaporated and redissolved in the mobile phase, methanol/10 mM ammonium acetate (30/70, v/v). A 20 microL aliquot of redissolved solution was subjected to analysis. Nicotine and cotinine in human hair were quantified by using deuterated analytes as internal standards. The quantification limits were 8 microg/L for nicotine and 0.9 microg/L for cotinine. The proposed method was applied to measure the concentrations of nicotine and cotinine in hair of smokers and non-smokers to evaluate their self-reported smoking and exposure to environmental tobacco smoke. In both cases, the method provided good selectivity, accuracy and precision. 相似文献
983.
《Chemphyschem》2003,4(1):79-83
We present Monte Carlo simulations of the self‐assembly of bivalent bis‐biotinylated DNA molecules with the tetravalent biotin‐binding protein streptavidin (STV). By fitting the STV binding probabilities for the four possible valencies, the modelling correctly reproduces the dependencies of various network parameters experimentally observed in an earlier study. The combined results from the experimental and theoretical studies suggest that the binding probability for divalent STV formation is about 50 times larger than for the formation of trivalent and about 200 times larger than for tetravalent STV. In accordance with the experimental results, the modelling also indicates that the mixture of an equimolar ratio of DNA and STV leads to a maximum in size of the oligomeric DNA–STV clusters formed. Furthermore, we found a percolation transition in which the DNA cluster size increases rapidly with increasing DNA concentration resulting in the formation of a single supercluster at elevated concentrations. This behaviour coincides with the occurrence of an immobile band previously observed in electrophoretic experiments, indicating the formation of extremely large DNA–STV aggregate networks. 相似文献
984.
Sr3(BS3)2 and Sr3(B3S6)2: Two Novel Non‐oxidic Chalcogenoborates with Boron in a Trigonal‐Planar Coordination The thioborates Sr3(BS3)2 and Sr3(B3S6)2 were prepared from strontium sulfide, amorphous boron and sulfur in solid state reactions at a temperature of 1123 K. In a systematic study on the structural cation influence on this type of ternary compounds, the crystal structures were determined by single crystal X‐ray diffraction. Sr3(BS3)2 crystallizes in the monoclinic spacegroup C2/c (No. 15) with a = 10.187(4) Å, b = 6.610(2) Å, c = 15.411(7) Å, β = 102.24(3)° and Z = 4. The crystal structure of Sr3(B3S6)2 is trigonal, spacegroup R3¯ (Nr. 148), with a = 8.605(1) Å, c = 21.542(4) Å and Z = 3. Sr3(BS3)2 contains isolated [BS3]3— anions with boron in a trigonal‐planar coordination. The strontium cations are found between the layers of orthothioborate anions. Sr3(B3S6)2 consists of cyclic [B3S6]3— anions and strontium cations, respectively. 相似文献
985.
Crystal Structures of KNdTe4, RbPrTe4, and RbNdTe4 — Investigations concerning the Thermal Stability of KNdTe4 as well as some Remarks concerning Additional Representatives of the Composition ALnTe4 (A = K, Rb, Cs and Ln = Rare Earth Metal) Of the compounds ALnQ4 (A = Na, K, Rb, Cs; Ln = Lanthanoid; Q = S, Se and Te) the crystal structures of the three new tellurides KNdTe4, RbPrTe4 and RbNdTe4 were determined by X‐ray single‐crystal structure analysis and of the three additional new ones KCeTe4, KPrTe4 and CsNdTe4 by X‐ray powder diffraction experiments. All six new compounds are isotypic with KCeSe4. Characteristic for the crystal structure of the compounds mentioned above are layers built from (Q2)2— dumbbells in form of 4.32.4.3 nets with embedded cations A+ and Ln3+ between them, which are coordinated eightfold in form of square‐shaped antiprisms by Q ions. The distances Te‐Te within the dumbbells were found to be 277.8(2) pm for all investigated tellurides. By combination of X‐ray diffraction and DTA measurements it was shown that the compound KNdTe4 is metastable at ambient temperature with a limited existence range between the temperatures 260 and 498 °C. 相似文献
986.
Hamelin O Pécaut J Fontecave M 《Chemistry (Weinheim an der Bergstrasse, Germany)》2004,10(10):2548-2554
Recently, we observed that the enantiopure Lambda form of the tributylammonium salt of the chiral anion tris[tetrachlorobenzene-1,2-bis(olato)]phosphate, also named Trisphat, was able to induce an efficient resolution of a Delta,Lambda racemic mixture of cis-[Ru(dmp)2(NCCH3)2](PF6)2 (dmp=2,9-dimethyl-1,10-phenanthroline) due to the spontaneous and selective precipitation of the heterochiral pair [Delta-Ru(dmp)2(CH3CN)2][Lambda-Trisphat]2. We report here that the combination of such a stereoselective precipitation process and irradiation results in the quantitative conversion of the initial [Ru(dmp)2(NCCH3)2]2+ racemate into only one of the two enantiomers. This is the first example in inorganic chemistry of an asymmetric transformation that leads to a chiral complex with no chiral ligand. Finally, three new racemic ruthenium bis(diimine) complexes, namely [Ru(dmp)2(NCCH3)Py](PF6)2 (Py=pyridine), [Ru(dmp)2(1,3-diaminopropane)](PF6)2, and [Ru(dmp)2(ethylenediamine)](PF6)2 were synthesized. For all of them, crystallization-induced asymmetric transformation proved to be an efficient way of obtaining the corresponding optically active chiral-at-metal complexes in high yields and with excellent stereoselectivities. 相似文献
987.
Two new esters, methyl 4‐(prenyloxy)dihydrocinnamate and methyl 4‐(geranyloxy)dihydrocinnamate, together with fourteen known compounds have been isolated from the stem bark of Zanthoxylum pistaciiflorum. The structures of two new compounds were determined through spectral analyses. Among the isolates, four compounds exhibited effective cytotoxicities against P‐388 and HT‐29 cell lines in vitro. 相似文献
988.
A novel hyperbranched polyester acrylate (HPEA) was synthesized based upon ethylenediamine tetraacetic acid as a “core” molecule, 5‐hydroxyisophthalic acid as an AB2 monomer, and 2‐hydroxyethyl acrylate as an endcapping reagent. The obtained oligomer has an unsaturation concentration of 4.10 mmolC?C g?1 measured by nuclear magnetic resonance and a wide molecular weight distribution of 1.64 measured by gel permeation chromatography. The two‐photon absorption (TPA) photopolymerization of HPEA under the exposure of a Ti : sapphire femtosecond laser with a wavelength of 800 nm was investigated through laser exposure dose‐dependant spatial resolutions of its resins. The TPA photopolymerization thresholds at the range 1.6–4.3 × 107 mJ cm?2, and exposure dose windows at the range 3.4–4.3 for three formulations were determined. A spatial resolution of 0.85 μm was obtained through the TPA photopolymerization of the formulation containing 1 wt% photoinitiator and 0.3 wt% photoinhibitor. A diffraction grating and real three‐dimensional coupled gear wheel created by TPA photopolymerization were described to demonstrate the unique capability of HPEA in microfabrications. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
989.
R. Demchyna J. P. F. Jemetio Yu. Prots Th. Doert L. G. Akselrud W. Schnelle Yu. Kuz'ma Yu. Grin 《无机化学与普通化学杂志》2004,630(5):635-641
Single crystals of CeAgAs2 have been obtained by chemical transport reactions starting from a pre‐reacted powder sample. The crystal structure was solved using X‐ray diffraction (space group Pmca, No. 57, a = 5.7586(4) Å, b = 5.7852(4) Å, c = 21.066(3) Å, Z = 8) and refined to a residual of R(F) = 0.029 for 46 refined parameters and 1020 reflections. The structure of CeAgAs2 represents a new distorted and ordered variant of the HfCuSi2 type. The characteristic feature of this structure are infinite cis‐trans chains of As atoms with As—As distances of 2.563(1) Å and 2.601(1) Å. CeAgAs2 is paramagnetic (μeff = 2.37 μB, θ = —10.5(2) K), with antiferromagnetic ordering at 5.5(2) K and exhibits a metamagnetic transition starting at 4.6 kOe and T = 1.8 K. 相似文献
990.
Polymer colloids based on 3‐O‐methacryloyl‐1,2:5,6‐di‐O‐isopropylidene‐α‐D ‐glucofuranose (3‐MDG) and butyl acrylate (BA) were prepared via free radical mini‐emulsion polymerization. The kinetic and colloidal features of the copolymerization were investigated. The final particle size (D) of the sugar latexes is inversely proportional to the concentration of the anionic emulsifier (sodium dodecyl sulphate, SDS) and the non‐ionic one (alkyl polyglucoside, APG). It was also found that D is independent of the concentration of either the water‐soluble initiator (potassium persulfate, KPS), or the oil‐soluble initiator (2,2′‐azobisisobutyronitrile, AIBN). The rate of mini‐emulsion polymerization is lower in comparison with the conventional emulsion polymerization under the same conditions. The polymerization rate (Rp) and the total number of particles (Np) are proportional to the 0.72th and 0.93th power of the SDS, and to the 1.40th and 2.22th of the APG concentration. Following reaction orders, 0.79/0.06 were obtained for Rp/Np versus the concentration of KPS, and 0.22/?0.01 for AIBN, respectively. Copyright © 2004 John Wiley & Sons, Ltd. 相似文献