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961.
Minoru Isobe Prof. Dr. Masakuni Kurono Dr. Katsunori Tsuboi Dr. Akira Takai Prof. Dr. 《化学:亚洲杂志》2007,2(3):377-385
We have accomplished the synthesis of 13C‐labeled tautomycin at the C18, C19, C21, and C22 positions starting from 100 % [13C]triethylphosphonoacetate for the purpose of elucidating the dynamics and conformation of the C17–C26 moiety. NMR spectroscopy of 13C‐labeled tautomycin revealed strong binding with protein phosphatase type 1 and new features in the 13C NMR spectrum, such as the very small three‐bond coupling constants (2J). 相似文献
962.
Michelle Hernández-Arganis Rubén A. Toscano Mónica Moya-Cabrera Verónica García-Montalvo Raymundo Cea-Olivares Dr. 《无机化学与普通化学杂志》2004,630(11):1627-1631
The alkaline 1-phenyl-1H-1, 2, 3, 4-tetrazole-5-thiolate salts, M[C6H5N4CS] (M = Li ( 1 ), Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 )) were obtained and characterized by means of mass spectrometry (FAB+) and NMR (1H; 13C) spectroscopy. The structures of Na ( 2 ), K ( 3 ), Rb ( 4 ) and Cs ( 5 ) compounds were determined by X-ray diffraction methods. The ligand shows a rich variety of coordination patterns with the alkaline cations. The formation of a four-membered ring MSCN in the compounds with heavier alkali cations (K, Rb and Cs) is shown. In all the cations the coordination number around it increases with the ionic radius. Compounds with Cs+ and Rb+ exhibited the formation of Cs-C and Rb-C interactions with the phenyl group. 相似文献
963.
New complexes {M(CO)4[Ph2P(S)P(S)Ph2]} (M = Cr, Mo and W), (1a)–(3a), [(1a), M = Cr; (2a), M = Mo; (3a), M = W] and {M2(CO)10[-Ph2P(S)P(S)Ph2]} (M = Cr, Mo, W), [(1b)–(3b) [(1b), M = Cr; (2b), M = Mo; (3b), M = W]] have been prepared by the photochemical reaction of M(CO)6 with Ph2P(S)P(S)Ph2 and characterized by elemental analyses, f.t.-i.r. and 31P-(1H)-n.m.r. spectroscopy and by FAB-mass spectrometry. The spectra suggest cis-chelate bidentate coordination of the ligand in {M(CO)4[Ph2P(S)P(S)Ph2]} and cis-bridging bidentate coordination of the ligand between two metals in (M = Cr, Mo and W). 相似文献
964.
C. Glotzmann E. Langer H. Lehner Prof. Dr. K. Schlögl 《Monatshefte für Chemie / Chemical Monthly》1974,105(5):907-916
From racemization studies on optically active [2.2]metacyclophanes substituted in position 4, the parameters of activation for the inversion of the tenmembered ring were found to be: G
423
=31.5 kcal/mole, H
=27.5 kcal/mole and S
=–10 Cl/mole.Racemization does not occurvia bond forming or breaking; the value for the inversion barrier is not affected by substituents in position 4 and therefore corresponds to the value of unsubstituted [2.2]metacyclophane, whereas substituents in the bridge exert a distinct influence. These results can easily be explained on the basis of the isoconformational concept.
Mit 5 Abbildungen
Herrn Prof. Dr.O. Hoffmann-Ostenhof mit besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
Mit 5 Abbildungen
Herrn Prof. Dr.O. Hoffmann-Ostenhof mit besten Wünschen zum 60. Geburtstag gewidmet. 相似文献
965.
The importance of the rheological behaviour of solutions of macromolecules is briefly evaluated. The viscosity of the solutions depends on concentration, shear rate and time of shear, this relation being determined by the structure of the dissolved molecules. In dilute solutions shear dependence of viscosity is very frequently caused by the preferential orientation of anisotropic molecules. In such a case the particle dimensions can be calculated from the true limiting viscosity number, an anisotropy factor, the rotational diffusion constant and the effective particle density. These numbers can be derived from the flow curve, which has been extrapolated to zero concentration. It is necessary to measure the flow curve at shear gradients, which are sufficiently low to allow for an extrapolation to vanishing shear rate. By comparing the experimental flow curve with a choice of theoretical ones, the rotational diffusion constant and the anisotropy factor (axial ratio) can be found. From the limiting viscosity number and the axial ratio, the particle density can be calculated. 相似文献
966.
Compared to the general ionic liquids (ILs), a significant deviation of the binary mixtures of 1-decyl-3-methylimidazolium tri(hexafluoroacetylaceto)-copper(II) ([C10mim][Cu(hfacac)3]) with methanol was found, indicating the way methanol interacts with ILs might be governed by the special structure of the chelating anion. IR results showed that the (C2-H) of 1-decyl-3-methylimidazolium hexafluoroacetylacetonate ([C10mim][hfacac]) blue-shifted more significantly than that of [C10mim][Cu(hfacac)3], meanwhile the (C=O) red-shifted in [C10mim][Cu(hfacac)3], which is contrast with that in [C10mim][hfacac]. Two-dimensional correlation analysis of the FTIR spectra indicated that the chelating cavity has little effect on the sequence of the ILs sites that interact with methanol. Combined with small angle X-ray scattering (SAXS) results, the picture of mixing processes in these two systems were proposed. Methanol interacts directly with the anion followed by the cation in [C10mim][hfacac], while methanol preferentially enters the chelating cavity and enhances the packing effect in the [C10mim][Cu(hfacac)3] system. 相似文献
967.
A simple modification of a previously published ellipticine synthesis is reported, which decreases the reaction time and increases the yield and purity of the product. Benzylic oxidations of 1,4-dimethylcarbazole and ellipticine derivatives were studied and 13-hydroxyellipticine was prepared. 相似文献
968.
Salgado-Petinal C Lamas JP Garcia-Jares C Llompart M Cela R 《Analytical and bioanalytical chemistry》2005,382(6):1351-1359
In this paper a solid-phase microextraction–gas chromatography–mass spectrometry (SPME–GC–MS) method is proposed for a rapid analysis of some frequently prescribed selective serotonin re-uptake inhibitors (SSRI)—venlafaxine, fluvoxamine, mirtazapine, fluoxetine, citalopram, and sertraline—in urine samples. The SPME-based method enables simultaneous determination of the target SSRI after simple in-situ derivatization of some of the target compounds. Calibration curves in water and in urine were validated and statistically compared. This revealed the absence of matrix effect and, in consequence, the possibility of quantifying SSRI in urine samples by external water calibration. Intra-day and inter-day precision was satisfactory for all the target compounds (relative standard deviation, RSD, <14%) and the detection limits achieved were <0.4 ng mL–1 urine. The time required for the SPME step and for GC analysis (30 min each) enables high throughput. The method was applied to real urine samples from different patients being treated with some of these pharmaceuticals. Some SSRI metabolites were also detected and tentatively identified. 相似文献
969.
Rogatsky E Jayatillake H Goswami G Tomuta V Stein D 《Journal of the American Society for Mass Spectrometry》2005,16(11):1805-1811
The development of a sensitive assay for the quantitative analysis of carbohydrates from human plasma using LC/MS/MS is described in this paper. After sample preparation, carbohydrates were cationized by Cs(+) after their separation by normal phase liquid chromatography on an amino based column. Cesium is capable of forming a quasi-molecular ion [M + Cs](+) with neutral carbohydrate molecules in the positive ion mode of electrospray ionization mass spectrometry. The mass spectrometer was operated in multiple reaction monitoring mode, and transitions [M + 133] --> 133 were monitored (M, carbohydrate molecular weight). The new method is robust, highly sensitive, rapid, and does not require postcolumn addition or derivatization. It is useful in clinical research for measurement of carbohydrate molecules by isotope dilution assay. 相似文献
970.
Modeling and simulation of free radical polymerization of styrene under semibatch reactor conditions
The first part of this approach is concerned with the elaboration of a radical polymerization model of styrenne, based on
a kinetic diagram that includes chemical and thermal initiation, propagation, termination by recombination and chain transfer
to the monomer. Furthermore, volume contraction during polymerization is considered, as well as the gel and glass effects.
The mathematical formalism that describes the model in terms of moments is explored in detail. The model was then used to
predict the changes in monomer conversion and molecular weight after intermediate addition of initiator and monomer. The results
of this operation are dependent on the conditions of the reaction mass, quantity, and moment of substance addition. Therefore,
the simulations were performed at different times with respect to the gel effect; before, during and after this phenomenon,
and also with respect to different temperatures and initiators. Increasing the initiator concentration before the gel effect
leads to an earlier appearance of the phenomenon and to a decrease in molecular weight. The ratio
reveals a polydispersity index smaller for the intermediate addition of initiator. No significant changes take place during
or after the gel effect. If along with the initiator, unreacted monomver (used to dissolve the initiator) enters the reactor,
a small dip in conversion is observed. The general conclusion of this paper reveals the intermediate addition of initiator
as a method to control polymer properties and to prevent the “dead-end” polymerization of styrene. 相似文献