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81.
The reaction of [(mu3,mu3-EDBP)Li2]2[(mu3-nBu)Li(0.5Et2O)]2 (1) [EDBP-H2 = 2,2'-ethylidenebis(4,6-di-tert-butylphenol)] with 1 equiv of ROH in toluene gave [(mu3,mu3-EDBP)Li2]2[(mu3-OR)Li]2 [R = Bn (2), CH2CH2OEt (3), and nBu (4)]. In the presence of 3 equiv of tetrahydrofuran (THF), the hexanuclear compound 1 slowly decomposed to an unusual pentanuclear Li complex, [(mu2,mu3-EDBP)2Li4(THF)2][(mu3-nBu)Li] (5). Further reaction of 5 with ROH gave [(mu2,mu3-EDBP)2Li4(THF)3][(mu4-OR)Li] [R = Bn (6), nBu (7), and CH2CH2OEt (8)] without a major change in its skeleton. Treatment of 2 with an excess of hexamethylphosphoramide (HMPA) yields [(mu2,mu2-EDBP)Li2(HMPA)2][(mu3-OBn)Li(HMPA)] (9). Compounds [(mu2,mu3-EDBP)2Li4(THF)][(mu4-OCH2CH2OEt)Li]2 (10) and [(mu2,mu2-EDBP)2Li4(mu4-OCH2CH2OEt)(HMPA)]-[Li(HMPA)4]+ (11) can be obtained by the reaction of 3 with an "oxygen-donor solvent" such as THF and HMPA, respectively. Among the compounds described above, 8 has shown great reactivity toward ring-opening polymerization of L-lactide, yielding polymers with very low polydispersity indexes in a wide range of monomer-to-initiator ratios. 相似文献
82.
Two mononuclear Co(II) complexes based upon 2-(1H-benzimidazol-2-yl)phenol, abbreviation Hsalbim ligand, have been prepared and studied. The structure of Hsalbim and [Co(salbim)2] have been confirmed by X-ray structure analysis. The second cobalt(II) complex matches the formula [Co(salbim)2]·(Hsalbim)·MeOH assuming a co-crystallization of one neutral ligand. The electronic spectra are consistent with the tetrahedral pattern. Magnetic susceptibility measurements down to T = 2 K along with the magnetization data until B = 7 T show that the Co(II) complexes are high-spin with a considerable zero-field splitting of the 4B1(D2d) term: D/hc = 67 and 55 cm−1, respectively. 相似文献
83.
Baki B. Sadi Chunsheng Li Gary H. Kramer Cassandra L. Johnson Queenie Ko Edward P. C. Lai 《Journal of Radioanalytical and Nuclear Chemistry》2011,290(2):415-425
A new radioanalytical method was developed for rapid determination of 226Ra in drinking water samples. The method is based on extraction and preconcentration of 226Ra from a water sample to an organic solvent using a dispersive liquid-liquid microextraction (DLLME) technique followed by
radiometric measurement using liquid scintillation counting. In DLLME for 226Ra, a mixture of an organic extractant (toluene doped with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone) and a disperser
solvent (acetonitrile) is rapidly injected into the water sample resulting in the formation of an emulsion. Within the emulsion,
226Ra reacts with dibenzo-21-crown-7 and 2-theonyltrifluoroacetone and partitions into the fine droplets of toluene. The water/toluene
phases were separated by addition of acetonitrile as a de-emulsifier solvent. The toluene phase containing 226Ra was then measured by liquid scintillation counting. Several parameters were studied to optimize the extraction efficiency
of 226Ra, including water immiscible organic solvent, disperser and de-emulsifier solvent type and their volume, chelating ligands
for 226Ra and their concentrations, inorganic salt additive and its concentration, and equilibrium pH. With the optimized DLLME conditions,
the accuracy (expressed as relative bias, B
r
) and method repeatability (expressed as relative precision, S
B
) were determined by spiking 226Ra at the maximum acceptable concentration level (0.5 Bq L−1) according to the Guidelines for Canadian Drinking Water Quality. Accuracy and repeatability were found to be less than −5%
(B
r
) and less than 6% (S
B
), respectively, for both tap water and bottled natural spring water samples. The minimum detectable activity and sample turnaround
time for determination of 226Ra was 33 mBq L−1 and less than 3 h, respectively. The DLLME technique is selective for extraction of 226Ra from its decay progenies. 相似文献
84.
In continual study on the heartwood of Rhamnus nakaharai, a new alaternin-8-O-glucoside, namely 1,2,6,8-tetrahydroxy-3-methylanthraquinone-8-O-β-glucopyranoside (1), together with some known compounds were further isolated and characterised by 1-D, 2-D NMR and other spectral evidences. The free radical scavenging and antityrosinase activities of the isolates, including alaternin (1a), emodin (2a), emodin-8-O-β-glucopyranoside (2), 6-methoxysorigenin-8-O-β-glucopyranoside (3) and 6-methoxysorigenin (3a) were tested. Alaternin (1a) exhibited to be mild DPPH radical scavenger with half as potent as vitamin C, while both alaternin (1a) and emodin-8-O-β-glucopyranoside (2) exhibited stronger SOD-like activity than that of BHA. 6-Methoxysorigenin (3a), a reported potential antioxidant, and its 8-O-glucoside (3) both performed significant inhibitory effect on mushroom tyrosinase with about twice as potent as kojic acid, the positive control. 相似文献
85.
Kozmon S Matuška R Spiwok V Koča J 《Physical chemistry chemical physics : PCCP》2011,13(31):14215-14222
In this article we present the first systematic study of the additive properties (i.e. degree of additivity) of the carbohydrate-aromatic moiety CH-π dispersion interaction. The additive properties were studied on the β-D-glucopyranose, β-D-mannopyranose and α-L-fucopyranose complexes with the naphthalene molecule by comparing the monodentate (single CH-π) and bidentate (two CH-π) complexes. All model complexes were optimized using the DFT-D approach, at the BP/def2-TZVPP level of theory. The interaction energies were refined using single point calculations at highly correlated ab initio methods at the CCSD(T)/CBS level, calculated as E + (E(CCSD(T))-E(MP2))(Small Basis). Bidentate complexes show very strong interactions in the range from -10.79 up to -7.15 and -8.20 up to -6.14 kcal mol(-1) for the DFT-D and CCSD(T)/CBS level, respectively. These values were compared with the sum of interaction energies of the appropriate monodentate carbohydrate-naphthalene complexes. The comparison reveals that the bidentate complex interaction energy is higher (interaction is weaker) than the sum of monodentate complex interaction energies. Bidentate complex interaction energy corresponds to 2/3 of the sum of the appropriate monodentate complex interaction energies (averaging over all modeled carbohydrate complexes). The observed interaction energies were also compared with the sum of interaction energies of the corresponding previously published carbohydrate-benzene complexes. Also in this case the interaction energy of the bidentate complex was higher (i.e. weaker interaction) than the sum of interaction energies of the corresponding benzene complexes. However, the obtained difference is lower than before, while the bidentate complex interaction energy corresponds to 4/5 of the sum of interaction energy of the benzene complexes, averaged over all structures. The mentioned comparison might aid protein engineering efforts where amino acid residues phenylalanine or tyrosine are to be replaced by a tryptophan and can help to predict the changes in the interactions. The observed results also show that DFT-D correctly describes the CH-π interaction energy and their additive properties in comparison to CCSD(T)/CBS calculated interaction energies. Thus, the DFT-D approach might be used for calculation of larger complexes of biological interest, where dispersion interaction plays an important role. 相似文献
86.
A series of calixcrown ethers for which the cavity size of the crown ring is varied from crown-6 to crown-7 to crown-8 were examined for the transport abilities toward alkali metal ions. These ligands were incorporated into supported liquid membranes (SLMs) and into polymer inclusion membranes (PIMs) composed of cellulose triacetate (CTA) as a support and 2-nitrophenyl octyl ether (NPOE) and tris(2-butoxyethyl) phosphate (TBEP) as a plasticizer. In both membrane systems, calixcrown-6 showed the best selectivity toward a cesium ion over other alkali metal ions. The polymeric CTA membrane showed more rapid transport rate as well as higher durability than did the SLMs. 相似文献
87.
Anna A. Kończyk Joanna Szawkało Jan K. Maurin Zbigniew Czarnocki 《Helvetica chimica acta》2013,96(7):1348-1354
The highly functionalized tetrahydropyridine 4 was obtained in an indium(III) chloride catalyzed multi‐component reaction from benzaldehyde, 4‐methoxyaniline, and ethyl acetoacetate (=ethyl 3‐oxobutanoate) in the presence of [1,1′‐binaphthalene]‐2,2′‐diol (binol). It was found that binol played a beneficial role in this reaction, allowing a substantial decrease of the amount of indium salt. Also, simple organic Brønsted acids may serve as effective organocatalysts in this process. 相似文献
88.
89.
A polyacrylonitrile (PAN) fiber was adopted for the backbone of a chelate polymer and poly(acrylo‐amidino ethylene amine) (PAEA) was prepared through a one‐step reaction between the PAN fiber and ethylenediamine (EDA). The maximum removal capacity and degree of substitution were 7.8 meq per gram of dried PAEA and 98%, respectively. The PAEA was tested as an adsorbent in single and two‐component metal aqueous solutions under changing pH. The Cu2+ ion accomplished maximum adsorption amount at pH 3 and the order of maximum adsorbed amounts on PAEA is Cu2+ > Ag+ > Zn2+ > Ni2+ > Pb2+ in molar basis. FT‐IR spectroscopy was employed to characterize the chemical bonding in metal aqueous solutions and surface morphology was examined using atomic force microscopy (AFM) and scanning electron microscopy (SEM). Copyright © 2004 John Wiley & Sons, Ltd. 相似文献
90.
Ceborska M Zimnicka M Pietrzak M Troć A Koźbiał M Lipkowski J 《Organic & biomolecular chemistry》2012,10(27):5186-5188
The formation of different complexes of folic acid depending on the size of the host cyclodextrin resulting in either an exclusion compound (with the smallest α-cyclodextrin) or 2-rotaxane, where cyclodextrin is threaded over folic acid (with β- and γ-cyclodextrins), is presented. The formation is carried out in water which allows both possible application in pharmaceutical sciences and usage of environmentally friendly "green chemistry". The obtained compounds are thoroughly characterized using one and two dimensional NMR, mass spectrometry, differential scanning calorimetry and thermogravimetric analysis. 相似文献