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911.
Kaoru Tsuchiya Akihiro Takahashi Naoto Takeda Naoki Asakawa Shigeki Kuroki Isao Ando Akira Shoji Takuo Ozaki 《Journal of Molecular Structure》1995,350(3):233-240
13C cross polarization-magic angle spinning NMR spectra were measured for a series of peptides containing
-valine,
-leucine and
-aspartic acid residues, for which the crystal structures were already determined by X-ray diffraction, in order to investigate the relationship between hydrogen-bond lengths (RN…O) and 13C chemical shifts of amide carbonyl carbons in the peptides. From these experimental results, it was found that the isotropic 13C chemical shifts (δiso) of the amino acid residues move linearly downfield with a decrease in RN…O within the hydrogen-bonded length range considered here and also shown in our previous work on glycine and
-alanine residues as expressed by δiso(ppm) = a − bRN…O(Å) where a and b are 215.4 (ppm) and 14.2 (ppm Å−1) for the
-valine residue, 202.2 (ppm) and 10.0 (ppm Å−1) for the
-leucine residue, and 199.0 (ppm) and 9.6 (ppm Å−1) for the
-aspartic acid residue, respectively. Using these relations, the RN…O values of some polypeptides in the crystalline state were determined through the observation of the amide carbonyl carbon chemical shifts. These values were compared with those determined by the X-ray diffraction method. Furthermore, quantum-chemical calculation of the 13C shielding constant for a model compound was carried out by the finite perturbation theory INDO method in order to ascertain the 13C shielding behavior in the formation of hydrogen bonds. 相似文献
912.
913.
Itoh S Takada N Haranou S Ando T Komatsu M Ohshiro Y Fukuzumi S 《The Journal of organic chemistry》1996,61(25):8967-8974
The reactions of a TTQ model compound [1, 3-methyl-4-(3'-methylindol-2'-yl)indole-6,7-dione] with several amines have been investigated in organic media to obtain mechanistic information on the action of quinoprotein methylamine and aromatic amine dehydrogenases. It has been found that compound 1 acts as an efficient catalyst for the autorecycling oxidation of benzylamine by molecular oxygen in CH(3)OH. In order to evaluate the oxidation mechanism of amines by 1, the product analyses and kinetic studies have been carried out under anaerobic conditions. In the first stage of the reaction of 1 with amines, 1 is converted into an iminoquinone-type adduct (so-called substrateimine), which was isolated and characterized by using cyclopropylamine as a substrate. The observed NOE of the isolated product indicates clearly that the addition position of the amine is C-6 of the quinone. The molecular orbital calculations suggest that the thermodynamic stability of the carbinolamine intermediate is a major factor to determine such regioselectivity; the C-6 carbinolamine is more stable than the C-7 counterpart by 2.9 kcal/mol. The reactivity of several primary amines and the electronic effect of the p-substituents of benzylamine derivatives in the iminoquinone formation suggest that the addition step of the amine to the quinone is rate-determining. When amines having an acidic alpha-proton such as benzylamine derivatives are employed as substrates, formation of the iminoquinone adduct was followed by rearrangement to the productimine. The kinetic analysis has revealed that this rearrangement consists of noncatalyzed and general base-catalyzed processes. Large kinetic isotope effects of 7.8 and 9.2 were observed for both the noncatalyzed and general base-catalyzed processes, respectively, since these steps involve a proton abstraction from the alpha-position of the substrate. In the reaction with benzhydrylamine, the product imine was isolated quantitatively and well characterized by several spectroscopic data. In the case of benzylamine, the product imine is further converted into the aminophenol derivative by the imine exchange reaction with excess benzylamine. These results indicate clearly that the amine oxidation by compound 1 proceeds via a transamination mechanism as suggested for the enzymatic oxidation of amines by TTQ cofactor. 相似文献
914.
Cho HS Rhee H Song JK Min CK Takase M Aratani N Cho S Osuka A Joo T Kim D 《Journal of the American Chemical Society》2003,125(19):5849-5860
Femtosecond fluorescence anisotropy measurements for a variety of cyclic porphyrin arrays such as Zn(II)porphyrin m-trimer and hexamer are reported along with o-dimer and monomer as reference molecules. In the porphyrin arrays, a pair of porphyrin moieties are joined together via triphenyl linkage to ensure cyclic and rigid structures. Anisotropy decay times of the porphyrin arrays can be well described by the F?rster incoherent excitation hopping process between the porphyrin units. Exciton coupling strengths of 74 and 264 cm(-1) for the m-trimer and hexamer estimated from the observed excitation energy hopping rates are close to those of B800 and B850, respectively, in the LH2 bacterial light-harvesting antenna. Thus, these cyclic porphyrin array systems have proven to be useful in understanding energy migration processes in a relatively weak interaction regime in light of the similarity in overall structures and constituent chromophores to natural light-harvesting arrays. 相似文献
915.
The first synthesis of a stereoisomeric mixture of hormone α1, the mating hormone of Phytophthora, was achieved, and the synthetic mixture was confirmed to be hormonally active. 相似文献
916.
The reaction of anilides with phenyliodine(III) bis(trifluoroacetate) (PIFA) in trifluoroacetic acid (TFA), TFA-CHCl3, or hexafluoroisopropyl alcohol (HFIP) is described. When the acyl group of the anilide is highly electronegative, such as trifluoroacetyl, or the phenyl group is substituted with an electron-withdrawing group, the 4-iodophenyl group is transferred from PIFA to the amide nitrogen to afford acetyldiarylamines. On the other hand, when the acyl group contains an electron-donating function, such as 4-methoxyphenyl, or the phenyl group is substituted with an electron-donating group, a trifluoroacetoxy group is transferred to the para position of the anilide aromatic ring. This group is hydrolyzed during workup to produce the corresponding phenol. 相似文献
917.
918.
Chiral N-sulfonylated α-amino acid monomer (5) derived from (S)-tryptophan was copolymerized with styrene and divinylbenzene under radical polymerization conditions to give a polymer-supported N-sulfonyl-(S)-tryptophan (6). Treatment of the polymer-supported chiral ligand with 3,5-bis(trifluoromethyl)phenyl boron dichloride afforded a polymeric Lewis acid catalyst (16) effective for asymmetric Mukaiyama aldol reaction of silyl enol ethers and aldehydes. Various aldehydes were allowed to react with silyl enol ethers in the presence of the polymeric chiral Lewis acid to give the corresponding aldol adducts in high yield with high levels of enantioselectivity. 相似文献
919.
Hisada M Konno K Itagaki Y Naoki H Nakajima T 《Rapid communications in mass spectrometry : RCM》2000,14(19):1828-1834
We have examined the applicability of the 'nested' collision induced dissociation/post-source decay (CID/PSD) method to the sequencing of novel peptides from solitary wasps which have neurotoxic venom for paralyzing other insects. The CID/PSD spectrum of a ladder peptide derived from an exopeptidase digest was compared with that of the intact peptide. The mass peaks observed only in the CID/PSD spectrum of a ladder peptide were extracted as C-terminal fragment ions. Assignment of C-terminal fragment ions enabled calculation of N-terminal fragment masses, leading to differentiation between N-terminal fragment ions and internal fragment ions. This methodology allowed rapid and sensitive identification by removing ambiguity in the assignment of the fragment ions, and proved useful for sequencing unknown peptides, in particular those available as natural products with a limited supply. 相似文献
920.
A bicyclo[2.2.2]octadiene-fused tripyrrane was synthesized as a first versatile reagent for the preparation of π-expanded heteroporphyrins. The reaction of the tripyrrane with 1,3-diformylindene and azulene-1,3-dicarbaldehyde afforded the corresponding heteroporphyrins, which were easily converted into tetrabenzocarbaporphyrin and tribenzoazuliporphyrin by retro Diels-Alder reaction. 相似文献