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101.
Pierre Hamel Nicolas Zajac Yves Girard Joseph G. Atkinson 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-4)
Abstract Desulfenylation of indol-3-yl sulfides liberates the most reactive position of the ring for further transformations. The usual procedure, utilizing Raney Nickel (P. G. Gassman, et. al., J. Am. Chem. SOC. 1974,96, 5495) offers a limited scope due to incompatibility of a number of functional groups towards the reducing agent. Based on our recent mechanistic studies of the acid-catalysed rearrangement of indol-3-yl sulfides to indol-2-yl sulfides (P. Hamel, et. al., Chem. Commun. 1989, 63; J. Org. Chem. 1992, 57, 2694), we have developed a novel, non-reductive desulfenylation method which permits easy access to 3-unsubstituted indoles bearing a wide array of substituents. Thus, 3-indolyl sulfides, readily obtained from appropriate phenylhydrazines (via Fischer indolization) or anilines (Gassman method, vide infra) are smoothly desulfenylated in good yields in trifluoroacetic acid in the presence of an appropriate nucleophilic trapping agent. Thiols proved to be very effective trapping agents and thiosalicylic acid (TSA) is a thiol of choice, being non-volatile and easily separable from reaction products. 相似文献
102.
Marcel Corallo Yves Pietrasanta 《Phosphorus, sulfur, and silicon and the related elements》2013,188(3):359-366
Abstract The synthesis of telechelic oligomers with phosphorated end groups was realized by redox catalysis telomerization reaction by addition of phosphorated telogens containing a trichloromethyl group on monomers with two non-conjugated double bonds. Nous effectuons la synthèse d'oligoméres téléchéliques à extrémités phosphorées en additionnant au moyen de la réaction de télomerisation par catalyse Redox des télogènes phosphorés renfernant le groupement trichlorométhyle, sur des monomères à deux doubles liaisons non conjuguées. 相似文献
103.
Yves Gareau André Beauchemin 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1):393-394
Abstract The reaction of diisopropyl xanthogen and thio-diisopropyl xanthogen disulfide with alkynes furnished 1,3-dithiol-2-one and 1,3-dithiol-2-thione. 相似文献
104.
Latifa Latrous Jeanine Tortajada Violette Haldys Emmanuelle Léon Catarina Correia Jean‐Yves Salpin 《Journal of mass spectrometry : JMS》2013,48(7):795-806
Gas‐phase interactions of organotins with glycine have been studied by combining mass spectrometry experiments and quantum calculations. Positive‐ion electrospray spectra show that the interaction of di‐ and tri‐organotins with glycine results in the formation of [(R)2Sn(Gly)‐H]+and [(R)3Sn(Gly)]+ ions, respectively. Di‐organotin complexes appear much more reactive than those involving tri‐organotins. (MS/MS) spectra of the [(R)3Sn(Gly)]+ ions are indeed simple and only show elimination of intact glycine, generating the [(R)3Sn]+ carbocation. On the other hand, MS/MS spectra of [(R)2Sn(Gly)‐H]+complexes are characterized by numerous fragmentation processes. Six of them, associated with elimination of H2O, CO, H2O + CO and formation of [(R)2SnOH]+ (?57 u),[(R)2SnNH2]+( ?58 u) and [(R)2SnH]+ (?73 u), are systematically observed. Use of labeled glycines notably concludes that the hydrogen atoms eliminated in water and H2O + CO are labile hydrogens. A similar conclusion can be made for hydrogens of [(R2)SnOH]+and [(R2)SnNH2]+ions. Interestingly, formation [(R)2SnH]+ ions is characterized by a migration of one the α hydrogen of glycine onto the metallic center. Finally, several dissociation routes are observed and are characteristic of a given organic substituent. Calculations indicated that the interaction between organotins and glycine is mostly electrostatic. For [(R)2Sn(Gly)‐H]+complexes, a preferable bidentate interaction of the type η2‐O,NH2 is observed, similar to that encountered for other metal ions. [(R)3Sn]+ ions strongly stabilize the zwitterionic form of glycine, which is practically degenerate with respect to neutral glycine. In addition, the interconversion between both forms is almost barrierless. Suitable mechanisms are proposed in order to account for the most relevant fragmentation processes. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
105.
Dr. Hui Liu Dr. Yonggang Zhao Zhijuan Zhang Nour Nijem Prof. Dr. Yves J. Chabal Prof. Dr. Xiangfang Peng Prof. Dr. Heping Zeng Prof. Dr. Jing Li 《化学:亚洲杂志》2013,8(4):778-785
We report two new 3D structures, [Zn3(bpdc)3(2,2′‐dmbpy)] (DMF)x(H2O)y ( 1 ) and [Zn3(bpdc)3(3,3′‐dmbpy)]?(DMF)4(H2O)0.5 ( 2 ), by methyl functionalization of the pillar ligand in [Zn3(bpdc)3(bpy)] (DMF)4?(H2O) ( 3 ) (bpdc=biphenyl‐4,4′‐dicarboxylic acid; z,z′‐dmbpy=z,z′‐dimethyl‐4,4′‐bipyridine; bpy=4,4′‐bipyridine). Single‐crystal X‐ray diffraction analysis indicates that 2 is isostructural to 3 , and the power X‐ray diffraction (PXRD) study shows a very similar framework of 1 to 2 and 3 . Both 1 and 2 are 3D porous structures made of Zn3(COO)6 secondary building units (SBUs) and 2,2′‐ or 3,3′‐dmbpy as pillar ligand. Thermogravimetric analysis (TGA) and PXRD studies reveal high thermal and water stability for both compounds. Gas‐adsorption studies show that the reduction of surface area and pore volume by introducing a methyl group to the bpy ligand leads to a decrease in H2 uptake for both compounds. However, CO2 adsorption experiments with 1′ (guest‐free 1 ) indicate significant enhancement in CO2 uptake, whereas for 2′ (guest‐free 2 ) the adsorbed amount is decreased. These results suggest that there are two opposing and competitive effects brought on by methyl functionalization: the enhancement due to increased isosteric heats of CO2 adsorption (Qst), and the detraction due to the reduction of surface area and pore volume. For 1′ , the enhancement effect dominates, which leads to a significantly higher uptake of CO2 than its parent compound 3′ (guest‐free 3 ). For 2′ , the detraction effect predominates, thereby resulting in reduced CO2 uptake relative to its parent structure 3′ . IR and Raman spectroscopic studies also present evidence for strong interaction between CO2 and methyl‐functionalized π moieties. Furthermore, all compounds exhibit high separation capability for CO2 over other small gases including CH4, CO, N2, and O2. 相似文献
106.
The synthesis of novel substituted 3-p-nitro-phenyliminocoumarins and corresponding N-ureaiminocoumarins is described. The condensation of these materials with oxalyl chloride leads to the corresponding N-parabanic iminocoumarins, which have not previously been described, in moderate or good yields and high selectivity. The structures were characterized by Fourier transform infrared, 1H and 13C NMR, and elemental analysis.
107.
Yves Blériotc Arnaud Genre-Grandpierre Anne Imberty Charles Tellier 《Journal of carbohydrate chemistry》2013,32(8):985-1000
ABSTRACT The conformation of two mannose-based amidines, the N-benzylmannoamidine and a pseudo (1→6) dimannoside, has been evaluated using semi-empirical AMI calculations and 1H NMR studies. The most stable conformations of the mannoamidine ring correspond to the half-chair forms 3H4 and 4H3. The conformations (Z) or (E) about the exocyclic C-N bond depend on the substituents and it was shown that, in solution, the N-benzylmannoamidine was (E)-configured whilst the pseudo (1→6) dimannoside was (Z)-configured. Using the grid-search approach, the potential energy maps of both mannoamidines were calculated as a function of the torsion angles which define the orientation of the amidine substituent. Three stable conformers were identified for the N-benzylmannoamidine and seven for the pseudo (1→6) dimannoside. Inter-glycosidic NOE have provided evidence for a preferred conformation of the pseudo (1→6) dimannoside in solution. The transition state structure of the α-phenylmannose hydrolysis was optimized using the AMI method and compared to the N-benzylmannoamidine. The developing oxocarbenium ion is well matched by the mannoamidine ring but the orientation of the phenyl group in the inhibitor differs significantly from the position of the leaving group in the transition state. The use of sugar type amidines as haptens to obtain catalytic antibodies is then discussed. 相似文献
108.
Vincent Sol Alexandre Charmot Pierre Krausz Stéphane Trombotto Yves Queneau 《Journal of carbohydrate chemistry》2013,32(4):345-360
This paper presents the synthesis of two new glucosyl tritolylporphyrins in which the carbohydrate moiety is connected through a carboxymethyl glycosidic α‐D‐linkage. These compounds have been obtained by reaction between porphyrins bearing an amino function with a lactone prepared from the available disaccharide isomaltulose. The photocytotoxicity of these compounds against K562 human chronic myelogenous leukemia cells has been evaluated in comparison to Photofrin II. 相似文献
109.
Dominique Lafont Paul Boullanger Yves Chevalier 《Journal of carbohydrate chemistry》2013,32(4-5):533-550
Abstract Twelve N-acetyl or NH2-free D-glucosaminyl bolaamphiphiles have been synthesized by the intermediate of N-allyloxycarbonyl-d-glucosaminyl precursors. Thus, glycosylation of α,ω-diols with 1,3,4,6-tetra-O-acetyl-2-allyloxycarbonylamino-2-deoxy-β-d-glucopyranose (1) gave the bis(glycosides) 2a-h in good yields and without column chromatography. Alkaline treatment of these derivatives followed by acetylation gave the peracetylated N-acetyl compounds 3a-h which were further deprotected by the Zemplén deacetylation procedure to the N-acetyl-d-glucosaminyl bolaamphiphiles 4a-h. The bis(glycosides) 2c,d,g were also transformed into the O-acetylated amino-free derivatives 5c,d,g by chemospecific deprotection of the N-allyloxycarbonyl groups with palladium (0). Further deprotection of the ester functions led to the completely deprotected bolaamphiphiles 7c,d,g with high yields. Fully deprotected compounds 7a,d,g,h were also obtained from 2a,d,g,h by alkaline treatment and purification by column chromatography. Surface tension measurements were realized for aqueous solutions containing the soluble bolaamphiphiles. 相似文献
110.
Arnaud Chevalier Dr. Cédrik Massif Prof. Pierre‐Yves Renard Dr. Anthony Romieu 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(5):1686-1699
We describe the efficient synthesis and one‐step derivatization of novel, nonfluorescent azo dyes based on the Black Hole Quencher‐3 (BHQ‐3) scaffold. These dyes were equipped with various reactive and/or bioconjugatable groups (azido, α‐iodoacetyl, ketone, terminal alkyne, vicinal diol). The azido derivative was found to be highly reactive in the context of copper‐catalyzed azide–alkyne cycloaddition (CuAAC) reactions and allowed easy synthetic access to the first water‐soluble (sulfonated derivative) and aldehyde‐modified BHQ‐3 dyes, the direct preparation of which failed by means of conventional azo‐coupling reactions. The aldehyde‐ and α‐iodoacetyl‐containing fluorescence quenchers were readily conjugated to aminooxy‐ and cysteine‐containing peptides by the formation of a stable oxime or thioether linkage, respectively. Further fluorescent labeling of the resultant peptide conjugates with red‐ or far‐red‐emitting rhodamine or cyanine dyes through sequential and/or one‐pot bioconjugations, led to novel Förster resonance energy transfer (FRET) based probes suitable for the in vivo detection and imaging of urokinase plasminogen activator, a key protease in cancer invasion and metastasis. 相似文献