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41.
V. A. Petrov V. K. Kunanets K. N. Makarov L. S. German 《Russian Chemical Bulletin》1989,38(3):572-575
Conclusions When perfluorinated tertiary cyclic amines containing a substituent at the nitrogen atom are heated with antimony pentafluoride, they isomerize to the corresponding azomethines.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 3, pp. 646–649, March, 1989. 相似文献
42.
D. A. Makarov N. A. Kuznetsova O. L. Kaliya 《Russian Journal of Physical Chemistry A, Focus on Chemistry》2006,80(2):268-274
Acridine dyes were found to exhibit a low light fastness in oxygen-containing aqueous solutions because of photooxidation with the participation of molecular oxygen. The values of the quantum yield for the photooxidation of Acridine Yellow, Acridine Orange, and proflavin acetate at their initial concentration 2 × 10?5 mol/l were determined to be 1.8 × 10?3, 1.5 × 10?3, and 0.8 × 10?3, respectively. It was concluded that the photooxidation of these acridine dyes in dilute solutions results in the formation of primary photoproducts of peroxide nature. For proflav in acetate, as an example, it was demonstrated that the increase of the substrate concentration to 6 × 10?4 mol/l results in a fourfold increase in the quantum yield, a behavior indicative of a change in the photodecomposition mechanism. The rate of the interaction between exited and unexcited proflavin molecules, the process responsible for the photodecomposition of this compound, was found to be ~4 × 107 l/(mol s). The quantum yield for the photooxidation of the proflavin base was estimated to exceed that for the photooxidation of the proflavin monocation by more than an order of magnitude. 相似文献
43.
L. I. Makarov 《Journal of Structural Chemistry》2005,46(4):738-743
Some questions emerged from electronic data processing of molecular structures (graphs) and its fragments have been considered in this work. Quantitative estimations of subgraph positions in molecular graphs are presented and some properties of their maximal common subgraphs are described. 相似文献
44.
Morcombe CR Gaponenko V Byrd RA Zilm KW 《Journal of the American Chemical Society》2005,127(1):397-404
(13)C CPMAS NMR has been investigated in application to protein samples with a variety of deuteration patterns. Samples were prepared with protons in either all hydrogen positions, only in the exchangeable sites, or in the exchangeable sites plus select methyl groups. CP dynamics, T(1) relaxation times, and (13)C line widths have been compared. Using ubiquitin as a model system, reasonable (1)H-(13)C CP transfer is observed for the extensively deuterated samples. In the absence of deuterium decoupling, the (13)C line widths observed for the deuterated samples are identical to those observed for the perprotio samples with a MAS rate of 20 kHz. Extensive deuteration has little effect on the T(1) of the exchangeable protons. On the basis of these observations, it is clear that there are no substantive compromises accompanying the use of extensive deuteration in the design of (1)H, (15)N, or (13)C solid-state NMR methods. 相似文献
45.
Four different types of amine-attached MCM-48 silicas were prepared and investigated for CO(2) separation from N(2). Monomeric and polymeric hindered and unhindered amines were attached to the pore surface of the MCM-48 silica and characterized with respect to their CO(2) sorption properties. The pore structures and amino group content in these modified silicas were investigated by XRD, FT-IR, TGA, N(2) adsorption/desorption at 77 K and CHN/Si analysis, which confirmed that in all cases the amino groups were attached to the pore surface of MCM-48 at 1.5-5.2 mmol/g. The N(2) adsorption/desorption analysis showed a considerable decrease of the pore volume and surface area for the MCM-48 silica containing a polymeric amine (e.g., polyethyleneimine). The CO(2) adsorption rates and capacities of the amine-attached MCM-48 samples were studied employing a sorption microbalance. The results obtained indicated that in addition to the concentration of surface-attached amino groups, specific interactions between CO(2) and the surface amino groups, and the resultant pore structure after amine group attachment have a significant impact on CO(2) adsorption properties of these promising adsorbent materials. 相似文献
46.
O. B. Ryabova E. Yu. Khmel’nitskaya V. A. Makarov L. M. Alekseeva N. B. Grigor’ev V. G. Granik 《Russian Chemical Bulletin》2005,54(12):2873-2879
On heating at pH 6.86, 4-(N,N-dialkylthiocarbamoylthio)-5-nitropyrimidines are transformed into dithiolopyrimidines, which are either oxidized to bis(4-dialkylthiocarbamoylpyrimidin-5-yl)
disulfides or converted into 4,6-diamino-5-nitropyrimidine derivatives with carbon disulfide elimination. The direction of
the reaction is determined by the nature of a substituent in position 2 of pyrimidine and the bulk of the thiocarbamate substituent.
Mechanistic schemes for these processes were proposed.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2777–2783, December, 2005. 相似文献
47.
Addition of excess R(2)NCN to an aqueous solution of K(2)[PtCl(4)] led to the precipitation of [PtCl(2)(NCNR(2))(2)] (R(2) = Me(2) 1; Et(2) 2; C(5)H(10) 3; C(4)H(8)O, 4) in a cis/trans isomeric ratio which depends on temperature. Pure isomers cis-1-3 and trans-1-3 were separated by column chromatography on SiO(2), while trans-4 was obtained by recrystallization. Complexes cis-1-3 isomerize to trans-1-3 on heating in the solid phase at 110 degrees C; trans-1 has been characterized by X-ray crystallography. Chlorination of the platinum(II) complexes cis-1-3 and trans-1-4 gives the appropriate platinum(IV) complexes [PtCl(4)(NCNR(2))(2)] (cis-5-7 and trans-5-8). The compound cis-6 was also obtained by treatment of [PtCl(4)(NCMe)(2)] with neat Et(2)NCN. The platinum(IV) complex trans-[PtCl(4)(NCNMe(2))(2)] (trans-5) in a mixture of undried Et(2)O and CH(2)Cl(2) undergoes facile hydrolysis to give trans-[PtCl(4)[(H)=C(NMe(2))OH](2)] (9; X-ray structure has been determined). The hydrolysis went to another direction with the cis-[PtCl(4)(NCNR(2))(2)] (cis-5-7) which were converted to the metallacycles [PtCl(4)[NH=C(NR(2))OC(NR(2))=NH]] (11-13) due to the unprecedented hydrolytic coupling of the two adjacent dialkylcyanamide ligands giving a novel (for both coordination and organic chemistry) diimino linkage. Compounds 11-13 and also 14 (R(2) = C(4)H(8)O) were alternatively obtained by the reaction between cis-[PtCl(4)(MeCN)(2)] and neat undried NCNR(2). The structures of complexes 11, 13, and 14 were determined by X-ray single-crystal diffraction. All the platinum compounds were additionally characterized by elemental analyses, FAB mass-spectrometry, and IR and (1)H and (13)C[(1)H] NMR spectroscopies. 相似文献
48.
Bokach NA Kuznetsova TV Simanova SA Haukka M Pombeiro AJ Kukushkin VY 《Inorganic chemistry》2005,44(14):5152-5160
Treatment of trans-[PtCl4(RCN)2] (R = Me, Et, Ph, NEt2) with 2 equiv of the amidine PhC(=NH)NHPh in a suspension of MeCN (R = Me), CHCl3 (R = Et, Ph), or in CHCl3 solution (R = NEt2) results in the formation of the imidoylamidine complexes trans-[PtCl4{NH=C(R)N=C(Ph)NHPh}2] (1-4) isolated in good yields (66-84%). The reaction of soluble complexes 3 and 4 with 2 equiv of Ph3P=CHCO2Me in CH2Cl2 (40 degrees C, 5 h) leads to dehydrochlorination resulting in a chelate ring closure to furnish the platinum(IV) chelates [PtCl2{NH=C(R)NC(Ph)=NPh}2] (R = Ph, 5; R = NEt2, 6), accordingly, and the phosphonium salt [Ph3PCH2CO2Me]Cl. Treatment of 5 with 3 equiv of Ph3P=CHCO2Me at 50 degrees C for 5 d resulted in only a 30% conversion to the corresponding Pt(II) complex [Pt{NH=C(NEt2)NC(Ph)=NPh}2] (15). The reduction can be achieved within several minutes, when Ph2PCH2CH2PPh2 in CDCl3 is used. When the platinum(II) complex trans-[PtCl2(RCN)2] is reacted with 2 equiv of the amidine, the imidoylamidinato complexes [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) and [PhC(=NH)NHPh] x HCl (7) are formed. The reaction of trans-[PtCl2(RCN)2] with 4 equiv of the amidine under a prolonged reaction time or treatment of [PtCl(RCN){NH=C(R)NC(Ph)=NHPh}] (8-11) with 2 more equiv of the amidine yields the complex bearing two chelate rings [Pt{NH=C(R)NC(Ph)=NHPh}2] (12-15). The treatment of cis-[PtCl2(RCN)2] (R = Me, Et) with the amidine gives ca. 50-60% yield of [PtCl2{NH=C(R)NHC(Ph)=NHPh}] (16 and 17). All of the platinum compounds were characterized by elemental analyses; FAB mass spectrometry; IR spectroscopy; 1H, 13C{1H}, and 195Pt NMR spectroscopies, and four of them (4, 6, 8, and 15) were also characterized by X-ray crystallography. The coupling of the Pt-bound nitriles and the amidine is metal-mediated insofar as RCN and PhC(=NH)NHPh do not react in the absence of the metal centers in conditions more drastic than those of the observed reactions. The nitrile-amidine coupling reported in this work constitutes a route to the synthesis of imidoylamidine complexes, some of them exhibiting luminescent properties. 相似文献
49.
Eugene A. Komissarov Yuri I. Baukov Eugeniya P. Kramarova Sergey Yu. Bylikin Vadim V. Negrebetsky Alexander A. Korlyukov 《Acta Crystallographica. Section C, Structural Chemistry》2007,63(4):m144-m146
In the title compound, [Ge(C8H14NO)2Cl]CF3SO3, which is the first complex containing an eight‐membered lactam (enantholactam) as ligand, the coordination polyhedron of the GeIV atom is intermediate between trigonal–bipyramidal and square‐pyramidal. Quantum chemical calculations of the crystal structure indicate the absence of additional coordination bonding between the GeIV atom and the trifluoromethanesulfonate anion. 相似文献
50.
K. N. Makarov T. N. Abroskina Yu. A. Cheburkov I. L. Knunyants 《Russian Chemical Bulletin》1976,25(4):922-924
1. | The cesium chloride adducts with perfluoroacetone, 1-methyl-2-oxaperfluoroenanthyl fluoride, and perfluoroisobutylene react smoothly with symmetrical dichlorodimethyl ether, replacing both chlorine atoms, with the formation of the corresponding ethers. |
2. | The interaction of,-dihydroperfluoroamyl alcoholate with symmetrical dichlorodimethyl ether leads to the replacement of both chlorine atoms, with the formation of the corresponding ether. |
3. | The reaction of perfluoro-t-butylanion with tris(chloromethyl)amine leads to tris-(1,1-dihydro-perfluoroneopentyl) amine. |
4. | Perfluoro-t-butylanion replaces only one chlorine atom in the molecule of unsymmetrical di-chlorodimethyl ether, forming-chloro- -perfluoro-t-butyldimethyl ether. |