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41.
Dhungana S Miller MJ Dong L Ratledge C Crumbliss AL 《Journal of the American Chemical Society》2003,125(25):7654-7663
The coordination chemistry of an extracellular siderophore produced by Mycobacterium neoaurum, exochelin MN (ExoMN), is reported along with its pK(a) values, Fe(III) and Fe(II) chelation constants, and aqueous solution speciation as determined by spectrophotometric and potentiometric titration techniques. Exochelin MN is of particular interest as it can efficiently transport iron into pathogenic M. leprae, which is responsible for leprosy, in addition to its own parent cells. The Fe(III) coordination properties of ExoMN are important with respect to understanding the Fe(III) acquisition and uptake mechanism in pathogenic M. leprae, as the siderophores from this organism are very difficult to isolate. Exochelin MN has two hydroxamic acid groups and an unusual threo-beta-hydroxy-l-histidine available for Fe(III) chelation. The presence of threo-beta-hydroxy-l-histidine gives rise to a unique mode of Fe(III) coordination. The pK(a) values for the two hydroxamic acid moieties, the histidine imidazole ring and the alkylammonium groups on ExoMN, correspond well with the literature values for these moieties. Proton-dependent Fe(III)- and Fe(II)-ExoMN equilibrium constants were determined using a model involving sequential protonation of the Fe(III)- and Fe(II)-ExoMN complexes. These data were used to develop a model whereby deprotonation reactions on the surface of the complex in the second coordination shell result in first coordination shell isomerization. The overall formation constants were calculated: log beta(110) = 39.12 for Fe(III)-ExoMN and 16.7 for Fe(II)-ExoMN. The calculated pFe value of 31.1 is one of the highest among all siderophores and their synthetic analogues and indicates that ExoMN is thermodynamically capable of removing Fe(III) from transferrin. The E(1/2) for the Fe(III)ExoMN/Fe(II)ExoMN(-) couple was determined to be -595 mV from quasi-reversible cyclic voltammograms at pH = 10.8, and the pH-dependent E(1/2) profile was used to determine the Fe(II)-ExoMN protonation constants. 相似文献
42.
Colin Thomson 《Theoretical chemistry accounts》1973,32(2):93-100
Non-empirical LCAO-MO-SCF calculations on SiF2 using two Gaussian basis sets are reported. The larger basis set gives a calculated geometry in good agreement with experiment. The effect on the energy and population analysis of optimization of the Si 3d exponent was investigated. 3d orbitals are found to be much less important in the bonding than in the isoelectronic molecule SO2. 相似文献
43.
Relative rates of solvolysis of some N-triorganosilylanilines in mixtures of ethanol and aqueous potassium hydroxide have been determined, with results as follows. (i) For XC6H4NHSiEt3 compounds in MeOH (5 vol) + aq. alkali (2 vol) at 50°: (X =) H, 1.0;p-Me, 0.80;p-OMe, 0.83;m-Me, 0.90; o-Me, 0.87; p-SMe, 1.90; p-F, 1.7; p-Cl, 2.8; o-Cl, 14; m-Cl, 4.2; m-NO2, 18; p-CN, ca. 43; p-NO2, ca. 120. (ii) For PhNHSi(C6H4Y)3 compounds in MeOH (10 vol) + aq. alkali (1 vol) at 50°: (Y =) H, 1.0; p-OMe, 0.12; p-Cl, ca. 32; m-Cl, ca. 84. (iii) For PhNHSiR3 compounds in MeOH (5 vol) + aq. alkali (2 vol) : (R3 =) Et3, 1.0; Et2Me, 18 (at 30°); Me2-i-Pr, 8 (at 30°);Me2-t-Bu, 0.012 (at 50°);i-Pr3, 0.006 (at 50°). In series (i) the relative rates correlate with σ, or where appropriate σ?-constants, with a ? value of 1.6. It is suggested that in the transition state of the rate-determining step the OSi bond is fully formed, or almost so, the SiN bond approximately 20—50% broken, and the bond between the nitrogen atom and a proton from the solvent ca. 10—30% formed. 相似文献
44.
The photochemical aquation of K2 TcBr6 in 2M HRr, 1M HClO4 and 1M H2SO4 has been studied. The absorption spectra of the various Tc(IV) species were measured after the electrophoretic separation. The spectrophotometric changes and the yield of each species as a function of the UV irradiation time were determined. After 25 hours of irradiation of HBr and HClO4 solutions the main species were the cationic ones (80%) but in H2SO4 solution the neutral species reached a yield of 90%. The oxidation of Tc(IV) species to TcO
4
–
proceeded more rapidly and extensively in HClO4 than in HBr and H2SO4. 相似文献
45.
46.
Single p-toluic acid pendant groups were attached to 1,4,7,10,13-pentaazacyclopentadecane (15aneN5) and 1,4,8,11-tetraazacyclotetradecane (cyclam) to prepare bifunctional reagents for radiolabeling monoclonal antibodies with (64,67)Cu. The ligands are 1,4,7,10,13-pentaazacyclopentadecane-1-(alpha-1,4-toluic acid) (PCBA) and 1,4,8,11-tetraazacyclotetradecane-1-(alpha-1,4-toluic acid) (CPTA). For the parent macrocycles and their pendant arm derivatives, the 1:1 Cu(2+) complexes dissociate only below pH 2. At pH 0.0 and 25 degrees C the CPTA-Cu complex has a half-life toward complete dissociation of 24 days. A new approach was developed for the estimation of the Cu(2+) stability constant for the kinetically robust CPTA. All other formation constants were determined at 25.0 degrees C with batch spectrophotometric techniques. Potentiometric titrations were used to determine the protonation constants of the macrocyclic ligands as well as of the metal chelates. The protonation constants, stability constants, and pM's are discussed in terms of both molecular mechanics calculations and the ligands' potential applicability as copper(II) radiopharmaceuticals. 相似文献
47.
Simon S. Jones Colin B. Reese Samson Sibanda Aiko Ubasawa 《Tetrahedron letters》1981,22(47):4755-4758
The protection of uracil and 2--acyl guanine residues with 4--phenyl [or 4--(2,4-dimethylphenyl)] and 6--(2-nitrophenyl) groups as in [or ] and , respectively, is described. These -aryl protecting groups, which appear to withstand the usual conditions of oligonucleotide synthesis, may readily be removed by treatment with 2-nitrobenzaldoximate ions. 相似文献
48.
Tetra-n-butylammonium hexachloroplatinate (IV) reacts with lithium methyl/lithium iodide in ether to give a solution containing lithium hexamethylplatinate (IV). With lithium methyl/lithium bromide in ether however, tetrabutylammonium hexamethylplatinate (IV) is precipitated together with lithium halides. Solid [Bu4N)2[Pt(Ch3)6] is stable under nitrogen at room temperature, but ether solutions of [Pt(Ch3)6]2- decompose in a few minutes at room temperature in the absence of excess lithium methyl. 相似文献
49.
The linking of pyrimidines to polystyrene supports via either a 2- or 4-thioether provides access to pteridines through solid-phase synthesis. Oxidative cleavage (dimethyldioxirane) followed by nucleophilic substitution by amines, azide, or water completes a traceless synthesis of pteridines. 相似文献
50.
Jensen BP Smith CJ Bailey CJ Rodgers C Wilson ID Nicholson JK 《Rapid communications in mass spectrometry : RCM》2005,19(4):519-524
Inductively coupled plasma mass spectrometry (ICPMS) has been used to determine the rate and routes of excretion of bromine following the intraperitoneal administration (50 mg kg(-1)) of 2-, 3- and 4-bromobenzoic acids to male bile-duct-cannulated rats. Analysis of urine and bile for (79/81)Br using ICPMS showed that all three bromobenzoic acids were rapidly excreted (82-98%) within 48 h of dosing, primarily via the urine. High-performance liquid chromatography/inductively coupled plasma mass spectrometry (HPLC/ICPMS) was then used to obtain metabolite profiles for bile and urine. These profiles revealed that extensive metabolism had taken place, with the unchanged bromobenzoic acids forming a minor part of the total of compound-related material detected. Concomitant MS studies, supplemented by alkaline hydrolysis, enabled the identification of the major metabolite of all three of the bromobenzoic acids as a glycine conjugate. Ester glucuronide conjugates were also identified, but formed only a small proportion of total. 相似文献