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101.
102.
Jean-Pierre Fayet Marie-Claire Vertut Alain Fruchier El Mostafa Tjiou Jos Elguero 《Magnetic resonance in chemistry : MRC》1978,11(5):234-238
The carbon-13 chemical shifts and the 1J(CH) coupling constants for 18 azolium salts (di-N-methyl-pyrazolium, -indazolium, -benzimidazolium and -benzotriazolium iodides) have been determined and assigned. The chemical shifts are discussed as a function of substituent effects, positive charge introduction and total electronic density (calculated by the CNDO/2 method). The general problem of correlations between chemical shifts and total charge densities in azoles is discussed. A statistical approach shows that these correlations are of poor quality. 相似文献
103.
Sebastian Juli Pilar Sala Jos Del Mazo Manuel Sancho Carmen Ochoa Jos Elguero Jean-Pierre Fayet Marie-Claire Vertut 《Journal of heterocyclic chemistry》1982,19(5):1141-1145
Thirteen N,N-diazolylmethanes, including derivatives of pyrazole, imidazole, 1,2,4-triazole, benzimidazole and indazole were prepared by reaction of azoles with methylene chloride under phase transfer catalysis conditions. The relative amounts of isomeric mixtures obtained with ‘asymmetric’ azoles or with equimolar mixtures of azoles are compared with literature results on monoalkylation of azoles. Proton and carbon-13 nmr spectra of the N,N'-diazolylmethanes are discussed. 相似文献
104.
Takahara S Sumiyama N Kittaka S Yamaguchi T Bellissent-Funel MC 《The journal of physical chemistry. B》2005,109(22):11231-11239
Quasielastic neutron scattering (QENS) spectra of water-filled MCM-41 samples (pore diameters: 21.4 and 28.4 Angstrom) were measured over the temperature range 238-298 K and the momentum transfer range 0.31-0.99 A(-1) to investigate the dynamics of confined water molecules. The spectra, which consist mainly of contributions from the translational diffusion of water molecules, were analyzed by using the Lorentzian and the stretched exponential functions. Comparison of the fits indicated that the latter analysis is more reliable than the former one. The fraction of immobile water molecules located in the vicinity of the pore walls, which give an elastic component, was found to be 0.044-0.061 in both pores. The stretch exponent beta was determined as 0.66-0.80. It was shown that the translational diffusion of water molecules in the pores is decelerated by confinement and that the deceleration becomes marked with a decrease in pore size. The ratios of the translational diffusion coefficient D(T) of confined water to that of bulk water at room temperature were within a range of 0.47-0.63. 相似文献
105.
Vendeuvre C Ruiz-Guerrero R Bertoncini F Duval L Thiébaut D Hennion MC 《Journal of chromatography. A》2005,1086(1-2):21-28
The detailed characterisation of middle distillates is essential for a better understanding of reactions involved in refining process. Owing to higher resolution power and enhanced sensitivity, comprehensive two-dimensional gas chromatography (GC x GC) is a powerful tool for improving characterisation of petroleum samples. The aim of this paper is to compare GC x GC and various ASTM methods -- gas chromatography (GC), liquid chromatography (LC) and mass spectrometry (MS) -- for group type separation and detailed hydrocarbon analysis. Best features of GC x GC are demonstrated and compared to these techniques in terms of cost, time consumption and accuracy. In particular, a new approach of simulated distillation (SimDis-GC x GC) is proposed: compared to the standard method ASTM D2887 it gives unequal information for better understanding of conversion process. 相似文献
106.
This paper describes the palladium-catalyzed arylation of 1-substituted 3-aminopyrrolidines or piperidines. Palladium(0) (1-2 mol %) in conjunction with "Buchwald's ligand" [2-(dimethylamino)-2'-(dicyclohexylphosphine)biphenyl] was shown to be the catalyst of choice for the coupling with aryl bromides or chlorides. When bromobenzene was used, a strong temperature effect was noticed. Whereas no reaction occurred at 100 degrees C, yields higher than 85% were obtained at 130 degrees C for each substrate. Such an effect was not observed when diphosphines were used. Whereas Xantphos and, to a lesser extent BINAP, were moderately efficient in the coupling of all diamines, the palladium-mediated arylation in the presence of monophosphines was strongly dependent on the substrate. The results suggest the participation of both nitrogens of the aminoheterocycle in the reactive intermediate. This participation could also account for the highly selective arylation of the endocyclic nitrogen of unsubstituted 3-aminopyrrolidine or piperidine. Optimal conditions were found for the arylation using 2- or 4-substituted electron-poor or enriched aryl halides. 相似文献
107.
Sekkal Majda Declerck Christine Huvenne Jean-Pierre Legrand Pierre Sombret Bernard Verdus Marie-Claire 《Mikrochimica acta》1993,112(1-4):11-18
The use of the infrared microspectrometry analytical technique as a new tool for the identification of the polysaccharides contained in the red algaeGracilaria verrucosa has demonstrated that in addition to agar spectra, features of the other coexisting constituents can also be obtained. Indeed, the infrared spectra recorded previously, all exhibit two important bands at about 1645 and 1530cm–1. These two bands were not present in the infrared spectra of the extracted agars and they are expected to be due to the amide I and amide II protein vibrations. In order to confirm this supposition, we have applied some enzymatic treatments, firstly on the whole algae and secondly on the ground algae (the algae has been previously depigmented and then dehydrated). Agarase, xylanase and cellulase were successively carried out on the algae. The last resulting spectrum, i.e. the spectrum obtained from the fraction which has undergone the three treatments, has been identified to be characteristic of proteins. This spectrum contained, both the amide I and II vibrations and in addition, weak absorption at 1230 cm–1 due probably to the amide III, was observed. Additional weak bands in the 1400–1300 cm–1 due to the different skeletal modes of the proteins were also present in this spectrum.The infrared spectra also revealed that the use of the enzymatic treatments on the ground algae is more efficient than when it is carried out on the whole algae. 相似文献
108.
Paté F Duguet N Oulyadi H Harrison-Marchand A Fressigné C Valnot JY Lasne MC Maddaluno J 《The Journal of organic chemistry》2007,72(18):6982-6991
The effect of lithium halides on the enantioselectivity of the addition of methyllithium on o-tolualdehyde, in the presence of chiral lithium amides derived from chiral 3-aminopyrrolidines (3APLi), has been investigated. The enantiomeric excess of the resulting 1-o-tolylethanol was found to drop upon addition of significant amounts of LiCl, introduced before the aldehyde. The competitive affinity between the lithium amide, the methyllithium, and the lithium halides in THF was examined by multinuclear NMR spectroscopy and DFT calculations. The results showed that the original mixed aggregate of the chiral lithium amide and methyllithium is rapidly, totally, and irreversibly replaced by a similar 1:1 complex involving one lithium chloride or bromide and one lithium amide. While the MeLi/LiX substitution occurs with some degree of epimerization at the nitrogen for the endo-MeLi:3APLi complex, it is mostly stereospecific for the exo-type arrangements of the aggregate. The thermodynamic preference for mixed aggregates between 3APLi and LiX was confirmed by static DFT calculations: the data show that the LiCl and LiBr aggregates are more stable than their MeLi counterparts by more than 10 kcal.mol(-1) provided THF is explicitly taken into account. These results suggest that a sequestration of the source of chirality by the lithium halides is at the origin of the detrimental effect of these additives on the ee of the model reaction. 相似文献
109.
Gev Dovrat Marie-Claire Illy Dr. Claude Berthon Ana Lerner Prof. Dr. Moshe H. Mintz Dr. Eric Maimon Dr. Radion Vainer Dr. Yeshayahu Ben-Eliyahu Yulia Moiseev Prof. Dr. Philippe Moisy Prof. Dr. Armand Bettelheim Prof. Dr. Israel Zilbermann 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(15):3390-3403
The 1,4,7,10-tetrazacyclodecane-1,4,7,10-tetraacetic acid (DOTA) aqueous complex of UIV with H2O, OH−, and F− as axial ligands was studied by using UV/Vis spectrophotometry, ESI-MS, NMR spectroscopy, X-ray crystallography, and electrochemistry. The UIV–DOTA complex with either water or fluoride as axial ligands was found to be inert to oxidation by molecular oxygen, whereas the complex with hydroxide as an axial ligand slowly hydrolyzed and was oxidized by dioxygen to a diuranate precipitate. The combined data set acquired shows that, although axial substitution of fluoride and hydroxide ligands instead of water does not seem to significantly change the aqueous DOTA complex structure, it has an important effect on the electronic configuration of the complex. The UIV/UIII redox couple was found to be quasi-reversible for the complex with both axially bonded H2O and hydroxide, but irreversible for the complex with axially bonded fluoride. Intriguingly, binding of the axial fluoride renders the irreversible one-electron UV/UIV oxidation of the [UIV(DOTA)(H2O)] complex quasi-reversible, which suggests the formation of the short-lived pentavalent form of the complex, an aqueous non-uranyl chelated UV cation. 相似文献
110.
Pardo E Dul MC Lescouëzec R Chamoreau LM Journaux Y Pasán J Ruiz-Pérez C Julve M Lloret F Ruiz-García R Cano J 《Dalton transactions (Cambridge, England : 2003)》2010,39(20):4786-4801
Homo- and heterometallic octanuclear complexes of formula Na?{[Cu?(mpba)?][Cu(Me?dien)]?}-(ClO?)?·12H?O (1), Na?{[Cu?(Mempba)?][Cu(Me?dien)]?}(ClO?)?·12H?O (2), Na?{[Ni?(mpba)?]-[Cu(Me?dien)]?}(ClO?)?·12H?O (3), Na?{[Ni?(Mempba)?][Cu(Me?dien)]?}(ClO?)?·9H?O (4), {[Ni?(mpba)?][Ni(dipn)(H?O)]?}(ClO?)?·12.5H?O (5), and {[Ni?(Mempba)?][Ni(dipn)-(H?O)]?}(ClO?)?·12H?O (6) [mpba = 1,3-phenylenebis(oxamate), Mempba = 4-methyl-1,3-phenylenebis(oxamate), Me?dien = N,N,N',N',N'-pentamethyldiethylenetriamine, and dipn = dipropylenetriamine] have been synthesized through the "complex-as-ligand/complex-as-metal" strategy. Single-crystal X-ray diffraction analyses of 1, 3, and 5 show cationic M(II)?M'(II)? entities (M, M' = Cu and Ni) with an overall double-star architecture, which is made up of two oxamato-bridged M(II)M'(II)? star units connected through three meta-phenylenediamidate bridges between the two central metal atoms leading to a binuclear metallacryptand core of the meso-helicate-type. Dc magnetic susceptibility data for 1-6 in the temperature range 2-300 K have been analyzed through a "dimer-of-tetramers" model [H = - J(S(1A)·S(3A) + S(1A)·S(4A) + S(1A)·S(5A) + S(2B)·S(6B) + S(2B)·S(7B) + S(2B)·S(8B)) - J'S(1A)·S(2B), with S(1A) = S(2B) = S(M) and S(3A) = S(4A) = S(5A) = S(6B) = S(7B) = S(8B) = S(M')]. The moderate to strong antiferromagnetic coupling between the M(II) and M'(II) ions through the oxamate bridge in 1-6 (-J(Cu-Cu) = 52.0-57.0 cm?1, -J(Ni-Cu) = 39.1-44.7 cm?1, and -J(Ni-Ni) = 26.3-26.6 cm?1) leads to a non-compensation of the ground spin state for the tetranuclear M(II)M'(II)? star units [S(A) = S(B) = 3S(M') - S(M) = 1 (1 and 2), 1/2 (3 and 4), and 2 (5 and 6)]. Within the binuclear M(II)? meso-helicate cores of 1-4, a moderate to weak antiferromagnetic coupling between the M(II) ions (-J'(Cu-Cu) = 28.0-48.0 cm?1 and -J'(Ni-Ni) = 0.16-0.97 cm?1) is mediated by the triple m-phenylenediamidate bridge to give a ground spin singlet (S = S(A) - S(B) = 0) state for the octanuclear M(II)?Cu(II)? molecule. Instead, a weak ferromagnetic coupling between the Ni(II) ions (J'(Ni-Ni) = 2.07-3.06 cm?1) operates in the binuclear Ni(II)? meso-helicate core of 5 and 6 leading thus to a ground spin nonet (S = S(A) + S(B) = 4) state for the octanuclear Ni(II)? molecule. Dc magnetization data for 5 reveal a small but non-negligible axial magnetic anisotropy (D = -0.23 cm?1) of the S = 4 Ni(II)? ground state with an estimated value of the energy barrier for magnetization reversal of 3.7 cm?1 (U = -DS2). Ac magnetic susceptibility data for 5 show an unusual slow magnetic relaxation behaviour at low temperatures which is typical of "cluster glasses". The temperature dependence of the relaxation time for 5 has been interpreted on the basis of the Vogel-Fulcher law for weakly interacting clusters, with values of 2.5 K, 1.4 × 10?? s, and 4.0 cm?1 for the intermolecular interaction parameter (T?), the pre-exponential factor (τ?), and the effective energy barrier (U(eff)), respectively. 相似文献