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1.
Switching kinetics of uniaxial ferroelastic ferroelectrics (FFs) in external electric and stress fields is studied using classical theory of nucleation and growth. The stage in which the polarization and deformation reversal involves the main body of the FF and the final stage (Ostwald ripening) of the FF switching are studied with allowance for the change in the repolarization and redeformation during the phase transition. The time dependences of the repolarization and redeformation are found, and equations are derived from which the polarization current and the deformation flux, as well as their time dependence, can be calculated. The calculated main characteristics of the FF switching are compared with the experimental data for switching of Rochelle salt single crystals. 相似文献
2.
The interaction of the clathrate Pt6Cl12 · 0.1 EtCl · 5.7H2O with RCN nitriles results in cis-[Pt(PhCH2CN)2Cl2] and in [Pt(RCN)2Cl2] (R = CH2CO2Et, Ph) complexes as a mixture of cis- and trans-isomers which separated and characterized. Cis-[Pt(MeCN)2Cl2] has been synthesized using a well known technique of K2[PtCl4] interaction with acetonitrile in water. Heating cis-[Pt(RCN)2Cl2] (R = Me, CH2Ph, CH2CO2Et) in the solid phase leads to cis-trans isomerization. In case of cis-[Pt(PhCN)2Cl2] thermal conversion results in trans-[Pt(PhCN)2Cl2] but the process of geometrical isomerizations accompained by a considerable decomposition of starting material and/or final products. Boiling of cis-[Pt(PhCH2CN2)Cl2] in mixture of EtNO2? PhCH2CN or cis-[Pt(EtCO2CH2CN)2Cl2] in MeNO2 or EtNO2 solutions results in complete cis-trans conversion. Similarily heating of cis-[Pt(RCN)2Cl2] (R = Me, Ph) in solution produces an equilibrium mixture of cis- and transisomers. 相似文献
3.
4.
S. Yu. Kukushkin P. Yu. Ivanov L. M. Alekseeva V. I. Levina K. I. Kobrakov N. B. Grigor'ev V. G. Granik 《Russian Chemical Bulletin》2005,54(8):1887-1891
The half-wave potentials of polarographic reduction of the carbonyl group in unsubstituted and N-methyl- and N-phenylsulfonyl-substituted 1- and 4-oxotetrahydrocarbazoles and their reactivities in reactions with nucleophilic (NaBH4, malonodinitrile, and cyanoacetamide) and electrophilic (DMF dimethyl acetal) reagents were compared. 4-Oxotetrahydrocarbazoles
are much less reactive than 1-oxotetrahydrocarbazoles.
__________
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 8, pp. 1832–1836, August, 2005. 相似文献
5.
6.
By the end of the XX century, much progress was achieved in examination of photosynthesis. The chemical composition and spatial organization of the photosynthetic apparatus components were elucidated. The sequence of photophysical processes and biochemical reactions, from quantum absorption to carbohydrate formation, was described. The physical mechanisms of energy migration, charge separation, and electron transfer in the photosynthesizing systems were qualitatively identified. 相似文献
7.
8.
Ferreira CM Guedes da Silva MF Fraústo da Silva JJ Pombeiro AJ Kukushkin VY Michelin RA 《Inorganic chemistry》2001,40(6):1134-1142
The dialkylcyanamide complexes cis-[PtCl(NCNR(2))(PPh(3))(2)][BF(4)] 1 and cis-[Pt(NCNR(2))(2)(PPh(3))(2)][BF(4)](2) 2 (R = Me or Et) have been prepared by treatment of a CH(2)Cl(2) solution of cis-[PtCl(2)(PPh(3))(2)] with the appropriate dialkylcyanamide and one or two equivalents of Ag[BF(4)], respectively. Compounds 2 can also be obtained from 1 by a similar procedure. Their reaction with oximes, HON=CR'R' ' (R'R' ' = Me(2) or C(4)H(8)), in CH(2)Cl(2) and in the presence of Ag[BF(4)] or Cu(CH(3)COO)(2), leads to the novel type of azametallacycles cis-[Pt(NH=C(ON=CR'R")-NR2)(PPh3)2][BF4]2 4 upon an unprecedented coupling of the organocyanamides with oximes, in a process that proceeds via the mixed oxime-organocyanamide species cis-[Pt(NCNR(2))(HON=CR'R' ')(PPh(3))(2)][BF(4)](2) 3, and is catalyzed by either Ag(+) or Cu(2+) which activate the ligating organocyanamide by Lewis acid addition to the amide group. In contrast, in the organonitrile complexes cis-[Pt(NCR)(2)(PPh(3))(2)][BF(4)](2) 5 (R = C(6)H(4)OMe-4 or Et), obtained in a similar way as 2 (but by using NCR instead of the cyanamide), the ligating NCR is not activated by the Lewis acid and does not couple with the oximes. The spectroscopic properties of those complexes are reported along with the molecular structures of 2b (R = Et), 4a1 (R = Me, R'R' ' = Me(2)), and 4b1 (R = Et, R'R' ' = Me(2)), as established by X-ray crystallography which indicates that in the former complex the amide-N-atoms are trigonal planar, whereas in the latter (4a1 and 4b1) the five-membered rings are planar with a localized N=C double bond (imine group derived from the cyanamide) and the exocyclic amide and alkylidene groups (in 4b1) are involved in two intramolecular H-bonds to the oxygen atom of the ring. 相似文献
9.
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
10.
A. V. Makarycheva-Mikhailova S. I. Selivanov N. A. Bokach V. Yu. Kukushkin P. F. Kelly A. J. L Pombeiro 《Russian Chemical Bulletin》2004,53(8):1681-1685
Reactions of the platinum(IV) nitrile complexes [PtCl4(RCN)2] (R = Me, CH2Ph, Ph) with 1,2- and 1,4-PhS(=NH)C6H4SPh in CH2Cl2 afforded addition products of sulfimides and coordinated nitriles, viz., the [PtCl4{NH=C(R)N=S(Ph)(C6H4SPh)}2] complexes. The latter were isolated in 75—90% yields and characterized by elemental analysis, positive-ion FAB mass spectrometry, IR spectroscopy, and 1H and 13C1H NMR spectroscopy. The temperature dependence of the 1H NMR spectra of the model [PtCl4{NH=C(R)N=SPh2}2] complexes (R = Me, Et) in CD2Cl2 studied in a temperature range from +40 to -70 °C demonstrated that E—Z isomerization of the ligands is a dynamic process in a range from +40 to -10 °C. The activation free energy of this process was calculated.Published in Russian in Izvestiya Akademii Nauk.
Seriya Khimicheskaya, No. 8, pp. 1618–1622, August, 2004. 相似文献