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61.
Novel Inorganic Ring Systems. 34. Derivatives of the Cyclo-1-thiaIV- and of the Cyclo-1-thia VI-3,4-disila-2,5-diazane Variations of fivemembered “hetero” cyclosilazanes of the type Si2N2El could be enlarged to the systems with El = SO and SO2. They are obtained by the formation principles 4 + 1 and 2 + 3 respectively, according to the equation (1), (4) and (5). The prepared compound are described in their properties and confirmed in their structure (Tables 1–2). 相似文献
62.
The synthetically interesting processes available for indolization reactions are discussed and illustrated in tabular form and particular emphasis is placed on the more recent methods. 相似文献
63.
Ti7Cl16 and Ti7Br16 and Further Investigations with Titanium Halides. Al2X6 as a Complex Forming Agent TiCl3,s can be transported with Al2Cl6 via TiAlCl6,g in a temperature gradient. The equilibrium of this reaction was studied by mass spectroscopy. There is no indication of the existence of a TiAl2Cl9 molecule as assumed in the literature. β-TiBr3 was prepared from the elements in the presence of the transporting agent Al2Br6,g. The transport of TiCl2 with Al2Cl6,g involves, as an important step, the disproportionation which is favoured by the reaction of Ti with the glass wall. If the disproportionation is made impossible by addition of Ti the novel compound Ti7Cl16 is obtained. Independent of Ti7Cl16, a phase TiCl(2 + x) with a broad range of homogeneity exists. The compound Ti7Br16, being isostructural with Ti7Cl16, was also prepared. Results of magnetic measurements and observations on the thermal decomposition of the compounds are reported. 相似文献
64.
65.
Frank C Sottmann T Stubenrauch C Allgaier J Strey R 《Langmuir : the ACS journal of surfaces and colloids》2005,21(20):9058-9067
In ternary water-oil-nonionic alkyl polyglycol ether (C(i)E(j)) microemulsions, an increase in efficiency is always accompanied by the formation of a lamellar (L(alpha)) phase. The addition of an amphiphilic block copolymer to the ternary base system increases the efficiency of the microemulsion drastically while suppressing--at least partly--the formation of the L(alpha) phase. However, amphiphilic block copolymers can be used not only to suppress the formation of lyotropic liquid crystals but also for the opposite effect, namely, to induce their formation. To understand to what extent the increase in efficiency is accompanied by the formation of lyotropic liquid crystals, we studied phase diagrams of water-n-alkane-n-alkyl polyglycol ethers (C(i)E(j))-PEPX-PEOY at a constant volume fraction of oil in the water/oil mixture. Using polymers of the poly(ethylene propylene)-copoly(ethylene oxide) type, with M(PEP) = X kg mol(-1) and M(PEO) = Y kg mol(-1), we determined phase diagrams as a function of the polymer concentration, size, and symmetry. Moreover, the influence of a particular polymer mixture was studied, which turned out to be the best system if both a high efficiency and a low tendency to form an L(alpha) phase are needed. 相似文献
66.
1,3-Dimethylated hydrocarbon segments occur frequently as structural elements in polyketide natural products. The (13)C NMR chemical shifts of a series of model compounds containing such segments can be well reproduced by a combination of molecular mechanics and SOS-DFPT/IGLO calculations. (13)C NMR chemical shifts are calculated on MM3 geometries and are Boltzmann weighted according to the MM3 energies. On the basis of the resulting thermally averaged chemical shifts, all diastereomers of the model compounds can be unequivocally distinguished. Significant differences in chemical shifts occur at methyl groups and methylene groups that are adjacent to a single stereogenic center. The method is applied to predict the relative configuration of two stereocenters in the side chains of two natural products, sambutoxin and the bradykinin inhibitor L-755,897. 相似文献
67.
Ion Neda Carsten Melnicky Alexander Vollbrecht Axel Fischer Peter G. Jones Reinhard Schmutzler 《无机化学与普通化学杂志》1996,622(6):1047-1059
The reaction of methylisatoic acid anhydride 1 with benzylamines led to the N-benzyl-N′-methylanthranilamide derivatives 2 – 4 . Their reaction with phosphorus trichloride furnished the 2-chloro-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 5 – 7 which, upon reaction with bis-(2-chloroethyl)ammonium chloride/triethylamine, were converted into the P-bis-(2-chloroethyl)amino-1-halobenzyl/benzyl-3-methyl-4(1 H)-1,3,2-benzodiazaphosphorin-4-ones 8 – 10 and 12 . With 2-chloroethylammonium chloride/triethyl-amine the P? NHCH2CH2Cl-substituted compound 11 was obtained from the PIIICl-species 6 . The reaction of 8 – 10 and 12 with hexafluoroacetone (HFA) took an unusual course: apart from the oxidative addition of HFA and formation of the perfluoropinacolyl ring system, one of the two CH2CH2Cl groups was found to alkylate the CH3N atom with formation of a five-membered (diazaphospholane) ring in the tricyclic phosphoranes 13 – 16 . The reaction of 11 with HFA also produced a spirophosphorane 17 which involved a λ5-oxazaphosphetidine ring system. In the reaction of 8, 10 and 12 with tetrachloro-o-benzoquinone, an oxidative addition reaction with concomitant N-alkylation and formation of the tricyclic phosphoranes 18 – 20 was found to take place. Single crystal X-ray structure determinations are described for the phosphoranes 13, 14 and 16 , and for the precursor compound 9 . The following features are common to the isostructural compounds 13 and 16 and the diethyl ether hemisolvate of 14 : the (λ5)-spiro phosphorus atom lies out of the plane of the other atoms of the rings to which it is common, and the dioxaphospholane rings display a twist conformation. In the λ3P-compound 9 the phosphorus atom also lies out of the plane of the other ring atoms. 相似文献
68.
Molecular dynamics computer simulations on regular, tightly meshed model networks exhibit variations of the network density with system size. We show that these variations are due mainly to network elasticity. A theoretical expression derived on the basis of the self-consistent-field approach yields finite size scaling behavior in good accord with the simulation for a wide range of thermodynamic conditions. 相似文献
69.
The effect of surfactants on surface instabilities of thin liquid film flow on a rotating disk was studied at different flow rates Q (0.5相似文献
70.
Efforts are described to design simple, fully flexible but conformationally preorganised omega-hydroxy-nonanoic acids that could serve as the conformation controlling unit in analogues of the potent protein-kinase C activator aplysiatoxin. Such analogues are macrodilactones incorporating the designed omega-hydroxy-nonanoic acid and 3,4-dihydroxy-pentanoic acid, which contains the pharmacophoric groups. The design process (replacement of CH(2) groups by an oxygen atom, annelation of a six-membered ring and placement of alkyl substituents) of the omega-hydroxy-nonanoic acids was monitored by force-field calculations. In the end of this process simple analogues of aplysiatoxin are proposed in which the proper disposition of the pharmacophoric groups is secured by a conformationally flexible but preorganised template structure as part of the macrodilactone ring. 相似文献