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101.
The synthesis of 16a'-homo-leurosidine was achieved through enantioselective generation of a ring D'-seco-precursor 33 (without requirement of a chiral auxiliary). Its cyclization provided the N(b')-quaternary salt 35 with a configuration corresponding to the atropisomeric form 8a rather than 8b of the target product. On debenzylation, the amine 8a was obtained and found not to isomerize thermally to the anticipated atropisomer 8b (in contrast to its lower homologue, with its formation of natural leurosidine). However, on protonation, a 1:1 mixture of atropisomers of 16a'-homo-leurosidine was obtained. A synthesis of 16a'-homo-vinblastine provided two atropisomers 5a and 5b for the free base at equilibrium (1:2.3 at room temperature in CDCl(3)), with a shift to the major conformer 5b with increasing solvent acidity or decreasing temperature. The synthesis was achieved through a stereoselective inversion of the tertiary hydroxyl function in the enantioselectively generated C-20' progenitor 39. 相似文献
102.
Zou Q Bennion BJ Daggett V Murphy KP 《Journal of the American Chemical Society》2002,124(7):1192-1202
Trimethylamine n-oxide (TMAO) is a naturally occurring osmolyte that stabilizes proteins and offsets the destabilizing effects of urea. To investigate the molecular mechanism of these effects, we have studied the thermodynamics of interaction between TMAO and protein functional groups. The solubilities of a homologous series of cyclic dipeptides were measured by differential refractive index and the dissolution heats were determined calorimetrically as a function of TMAO concentration at 25 degrees C. The transfer free energy of the amide unit (-CONH-) from water to 1 M TMAO is large and positive, indicating an unfavorable interaction between the TMAO solution and the amide unit. This unfavorable interaction is enthalpic in origin. The interaction between TMAO and apolar groups is slightly favorable. The transfer free energy of apolar groups from water to TMAO consists of favorable enthalpic and unfavorable entropic contributions. This is in contrast to the contributions for the interaction between urea and apolar groups. Molecular dynamics simulations were performed to provide a structural framework for the interpretation of these results. The simulations show enhancement of water structure by TMAO in the form of a slight increase in the number of hydrogen bonds per water molecule, stronger water hydrogen bonds, and long-range spatial ordering of the solvent. These findings suggest that TMAO stabilizes proteins via enhancement of water structure, such that interactions with the amide unit are discouraged. 相似文献
103.
104.
105.
A novel chemiluminescence (CL) flow system has been developed for the sequential determination of Fe(II) and Fe(III) in water.
Fe(II) was detected by its catalytic effect on the CL reaction between luminol immobilized on an anion exchange resin column
and dissolved oxygen; Fe(III) was determined by difference measurement after on-line conversion to Fe(II) in a reducing mini-column
packed with Cu plated Zn granules. For both ions, the calibration graph was linear in the range 1 × 10–9 to 1 × 10–6 g/mL, and the detection limit was 4 × 10–10 g/mL. A complete analysis could be performed in 1.5 min with a relative standard deviation of less than 5%. The system could
be reused for over 200 times and has been applied successfully to the determination of Fe(II) and Fe(III) in natural water
samples.
Received: 13 March 1997 / Revised: 3 June 1997 / Accepted: 6 June 1997 相似文献
106.
Qin B Lin J Lin Z Ren H Xue Y 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(4):717-720
The vibration spectrum and FAB mass spectrum of (+/-)-1-[3-(2-methoxyphenoxy)-2-hydroxypropyl]-4-[(2,6-dimethylphenyl)aminocarbonylmethyl]piperazine dihydrochloride salt was studied. By comparing with the spectra of free base, different bands of IR were found in the NH+ stretching, the NH+ deformation motion, the CH2 of NCH2 group symmetric stretching, the CH2 of N-CH2 group twisting and the CN stretching. FAB shows the basic peak is M + H. Other m/e peaks are consistent with the structure. 相似文献
107.
108.
Qin C Wang XL Li YG Wang EB Su ZM Xu L Clérac R 《Dalton transactions (Cambridge, England : 2003)》2005,(15):2609-2614
Two new three-dimensional nickel coordination polymers, [Ni3(BTC)2(4,4'-bpy)2(H2O)5].1.5H2O (1) and [Ni(PDB)(4,4'-bpy)].0.5H2O (2)(4,4'-bpy = bipyridine, BTC = 1,2,4-benzenetricarboxylate, PDB = pyridine-3,4-dicarboxylate), have been synthesized under hydrothermal conditions and characterized by elemental analysis, IR, TGA, and single crystal X-ray diffraction. Both compounds contain 2D scaffolding motifs, and most interestingly adjacent scaffolds are connected by infinite helical chains into unique three-dimensional mesomeric networks. Moreover, temperature-dependent magnetic susceptibilities for the two compounds were studied, and ferromagnetic interactions through syn-anti carboxylate bridges between Ni sites have been observed. 相似文献
109.
The influence of Stokes shift in optosensing was discussed. Then, the current status of large Stokes shift-based optosensing was reviewed here. 相似文献
110.
The geometric and electronic structures of FeS(2) (100) surface have been studied by a quantum-mechanical calculation using a total-energy pseudopotential code, CASTEP. The (100) surface is very stable and does not give any significant geometric relaxation. The electronic structure of FeS(2) (100) surface is characterized by the appearance of new native surface states in the bulk band gap, which correspond to antibonding mixed Fea-Ssp(3) states. These surface states play an important role as mediators of electron transfer on both anodic and cathodic sites in the incipient oxidation of pyrite. Moreover, the (100) surface has small band gaps and shows some metallic character. It is predicted that the rate of cathodic reductive reaction of O(2) in the incipient oxidation of pyrite is much faster than previously considered. The transport of electrons from the anodic sites to the cathodic sites on the (100) surface is faster and hole injection of anodic sites is not the rate-determining step. So we can deduce that the rate-determining step of incipient oxidation for pyrite consists of both electron transfer of pyrite/aqueous O(2) interface and the splitting of H(2)O. 相似文献