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991.
Laure Gouriou Štěpán Vysko?il Pavel Ko?ovský 《Journal of organometallic chemistry》2003,687(2):525-537
The reaction of iso-cinnamyl acetate with NaC(Me)(CO2Me)2, catalysed by Pd-‘MOP’ (MOP=2-methoxy-2′-diphenylphosphino-1,1′-binaphthalene) is known to proceed with a regiochemical memory effect that results in the predominant generation of the branched alkylation product. The analogous reaction employing ‘MAP’ as ligand (MAP=2-N,N-dimethylamino-2′-diphenylphosphino-1,1′-binaphthalene) proceeds with ‘normal’ regioselectivity to generate predominantly the linear isomer of product. A 2H-NMR based analysis, employing quadrupolar coupling in a chiral liquid crystal matrix, has been developed to facilitate the simultaneous study of the regiochemical and stereochemical outcome of the reaction of both enantiomers of iso-cinnamyl ester substrates in 2H-labelled but racemic samples. The analysis allows the comparison of relative rates of two competing isomerisation processes occurring in the π-allyl intermediates in the Pd-catalysed reaction, one of which facilitates asymmetric induction, the other resulting in loss of regiochemical memory. It is demonstrated that the two processes are partially coupled and that this then limits the attainment of high global enantiomeric excess in the branched product to reactions that proceed with low regiochemical retention. A key factor for the observation of high regiochemical memory is found to be the nucleophilicity of the malonate anion and the electrophilicity of the Pd-π-allyl intermediate with reduction in the reactivity of either partner resulting in the onset of substantial loss of memory. 相似文献
992.
Horst Müller 《Analytical and bioanalytical chemistry》1969,247(3-4):145-149
The ions ReBrnCl 6?n 2? (0?n?6) and OsBrnCl 6?n 2? , respectively, ReO4 ? and Br? have been separated on cellulose using the thin-layer chromatographic technique with 3.2 M sulphuric acid as the mobile phase. 相似文献
993.
F U Erko? S Ozsar B Güven G Kalkandelen E U?rar 《Journal of chromatographic science》1989,27(2):86-90
In the present work, a practical, rapid, reliable and isocratic reversed-phase high-performance liquid chromatographic (HPLC) method is described for the qualitative and quantitative analysis of estriol, estradiol-17 beta, estrone, testosterone, and progesterone. Chromatographic separation is complete in 16 min using a mobile phase of 50% acetonitrile (v/v) in water. The order of elution is estriol, testosterone, estradiol-17 beta, estrone, and progesterone; retention times are 2.5, 5.5, 5.6, 6.9, 16.3 min, respectively. Absorbance maxima of individual steroids is the limiting factor in quantitative determination. The recommended wavelengths for UV monitoring are E3 214, E2 280, T 254, E1 214, and P4 254 nm. 相似文献
994.
[reaction: see text] A short synthesis of intermediates possessing the tricyclic core of natural madangamines, bioactive alkaloids found in marine sponges, is described. The key reaction entails the condensation of the sodium salt of diethylacetonedicarboxylate with a dihydropyridinium salt derivative. This new approach is modeled on a biogenetic proposal linking madangamines to ircinals, related alkaloids occurring in sponges of the same order. 相似文献
995.
Storsberg J Yao ML Ocal N de Meijere A Adam AE Kaufmann DE 《Chemical communications (Cambridge, England)》2005,(45):5665-5666
The first example of a pi,sigma domino-Heck reaction under concomitant rearrangement of the tetracyclic allylcyclopropane endo,exo-bishomobarrelene (5) is reported; the stereoselective reaction proceeds via an intramolecular insertion of a primarily-formed carbopalladation intermediate into a strained cyclopropane C-C sigma-bond, giving 9. 相似文献
996.
Montserrat Barquín María J. Gonzlez Garmendia Liher Larrínaga Elena Pinilla María R. Torres 《无机化学与普通化学杂志》2005,631(11):2210-2214
The complexes of copper formato with pyrazine and dimethylpyrazines: Cu(HCOO)2(pyrz) ( 1 ), Cu2(HCOO)4(pyrz) ( 2 ), Cu2(HCOO)4(2,3‐Me2pyrz) ( 3 ), Cu2(HCOO)4(2,5‐Me2pyrz) ( 4 ), and Cu2(HCOO)4(2,6‐Me2pyrz)2 ( 5 ) have been synthesized and characterized by chemical analysis and IR and electronic spectro scopies. The three‐dimensional structure of compound 1 consists of –Cu–pyrz–Cu–pyrz– chains joined by bridging formate groups coordinated, in configuration syn‐anti, to two copper atoms. The coordination around the copper atom is orthorhombic with two Cu–O distances of 2.374(1) Å, two Cu–O of 1.952 Å and two Cu–N of 2.080 Å. Compound 5 is formed by molecular dimers with the [Cu2(μ‐HCOO)4] unit, two copper atoms and four syn‐syn fomate groups, and two ligands coordinated to the copper atoms in the axial positions. In compounds 2 and 3 chains of [Cu2(μ‐HCOO)4] dimers with pyrz or 2,3‐Me2pyrz as bridging ligands are formed. The EPR signal of 1 is orthorhombic (g = 2.23, 2.20 and 2.06). In the EPR spectra of 2 – 5 compounds the triplet (S = 1) signals are observed. The g?, g∥ and D values are been calculated. 相似文献
997.
S. Küppers 《Accreditation and quality assurance》1997,2(1):30-35
Any analytical data is used to provide information about a sample. The "possible error" of the measurement can be of extreme
importance in order to have complete information. The measurement uncertainty concept is a way to achieve quantitative information
about this "possible error" using an estimation procedure. On the basis of the analytical result, the chemist makes a decision
on the next step of the development process. If the uncertainty is unknown, the information is not complete; therefore this
decision might be impossible. The major problem for the in-process control (IPC) procedure is that not only the repeatability
but also the intermediate precision (which expresses the variations within laboratories related to different days, different
analysts, different equipment, etc.) has to be good enough to make a decision. Unfortunately, the statistical information
achieved from one single analytical run only gives information about the repeatability. This paper shows that the estimation
of the measurement uncertainty for IPC is a way to solve the problem and gives the necessary information about the quality
of the procedure. An example demonstrates that an estimate of uncertainty based on the standard deviations of an analytical
method gives a value similar to one based on the standard deviations obtained from a control chart. Therefore, the estimation
is both a very useful and also a very cost-effective tool. Though measurement uncertainty cannot replace validation in general,
it is a viable alternative to validation for all methods that will never be used routinely.
Received: 24 May 1996 Accepted: 10 August 1996 相似文献
998.
Strübing A Wittstock G Szargan R Werner G 《Analytical and bioanalytical chemistry》1996,356(3-4):274-278
Bismuth modified platinum electrodes are used for constant-potential amperometric determination of carbohydrates in flow systems. The monitored response is stable and reproducible over more than two days. An attempt is made to gain more detailed information about the characteristics of the modified layer by electrochemical methods and X-ray photoelectron spectroscopy. The response proved to be linear over the investigated concentration range (1.1–1200 mol/L) and detection limits for glucose and fructose were found to be 1.1 mol/L. 相似文献
999.
C. Sánchez-Pedreño M.Hernández Córdoba P.Viñas López-Pelegrín 《Microchemical Journal》1985,32(2):242-248
A kinetic method for the silver determination based on the catalytic effect of Ag(I) on the oxidation of o-dianisidine by persulfate at pH = 4.5 in the presence of 1,10-phenanthroline is proposed. Ag(I) can be determined by measuring the absorbance of the reaction product at 450 nm, using the fixed time method. Co(II) does not have a catalytic effect in the reaction, but in the simultaneous presence of silver and cobalt the reaction shows an induction period the length of which is related to the Ag/Co molar ratio. As a consequence, two new methods for the determination of cobalt and silver using the induction period method are proposed. The two methods for silver are applied to the determination of silver in lead. 相似文献
1000.
As the first part of our studies on counter-current chromatography, the methodology for selecting suitable solvent systems was established based on detailed investigations of solubility and partition coefficients (log K) of macrolide antibiotic analogues. The solubility of two important macrolides, ascomycin and FK-506, was measured in a series of common solvents, where their polarities were ranked with dielectric constants. The partition coefficients of the two macrolides were compared in various binary, ternary, quaternary solvent systems. Hexane-tert.-butyl methyl ether-methanol-water system was selected based on suitable log K of solutes and hydrogen-bonding properties of solvents. In the further optimisation of composition proportions in the multicomponent solvent system, hexane-tert.-butyl methyl ether-methanol-water (1:3:6:5) showed the best solvent selectivity by giving the most prominent difference of partition coefficient (delta log K) between ascomycin and FK-506. With this solvent system, a baseline preparative separation of these two very closely related 23-membered macrolide antibiotics was successfully achieved by employing the newly introduced Quattro counter-current chromatograph. 相似文献