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991.
992.
Isabel Iriepa F. Javier Villasante Enrique Gálvez Antonio Herrera Angel Sánchez Felix H. Cano 《Central European Journal of Chemistry》2005,3(4):683-704
This paper synthesizes N-substituted phthalimides derived from nitrogen heterocycles as potential 5-HT4 ligands by using the Mitsunobu reaction. Conformational studies of some of the new compounds have been conducted using 1H and 13C-NMR spectroscopy. Proton and carbon resonances were achieved through the application of one-dimensional selective NOE, two-dimensional
NMR techniques-homonuclear COSY-45, NOESY and heteronuclear 1H-13C HMQC correlated spectroscopy- and double resonance experiments. The crystal structure of compound 1 was determined by X-ray diffraction. 相似文献
993.
Anfonio Domènech Elisa Llopis Enrique Garcia-España Antonio Cervilla 《Transition Metal Chemistry》1990,15(6):425-428
Summary Addition of Na2MoO4 to an excess of aspartic acid (AspH2) can produce any of four different complexes depending on the pH, namely [MoO3(Asp)]2–, [Mo2O5(Asp)2]2–, [Mo2O4(OH)(Asp)2]– and [Mo2O4(Asp)2]. The ranges of formation of these species with pH, the number of equivalents of acid necessary for their formation, and their stoichiometries, condensation degrees and stability constants, have been calculated by potentiometric and spectrophotometric techniques. The aspartic acid acts as a tridentate ligand in all cases. 相似文献
994.
Antonio García Martínez Enrique Teso Vilar Santiago de la Moya Cerero 《Tetrahedron》2005,61(3):599-601
A general and straightforward enantiospecific access to synthetically valuable 10-N-substituted camphors (amines and secondary amides) has been developed. The synthetic method uses camphor as the starting enantiopure material and takes place in five individual steps with a high overall yield. The process involves a stereocontrolled double-Wagner-Meerwein-rearrangement strategy to generate key-intermediate 10-(triflyloxy)camphor, a peculiar and highly-reactive primary triflate, which is able to alkylate soft N-nucleophiles, such as amines and nitriles, easily and without producing Grob-like fragmentation of the β-(triflyloxy)ketone-based norbornane system. 相似文献
995.
Pereira RV Gehlen MH 《Spectrochimica acta. Part A, Molecular and biomolecular spectroscopy》2005,61(13-14):2926-2932
The interaction of the cationic dyes acridine, 9-aminoacridine (9AA), and proflavine, with sodium dodecyl sulfate (SDS) was studied by electronic absorption, steady-state and time-resolved fluorescence spectroscopies. The dyes interact with SDS in the pre-micellar region leading in two cases to dimerization in dye-surfactant aggregates, but with distinct molecular arrangements. For proflavine, the observed red shift of the electronic absorption band indicates the presence of J-aggregate, which are nonfluorescent. In the case of 9AA, the aggregates were characterized as nonspecific (neither J- nor H-type is spectroscopically observed). The time-resolved emission spectra gives evidences of the presence of weakly bound dimers by the recovery of three defined decay times by global analysis: dye monomer (tau1 = 16.4 ns), dimer (tau2 = 7.1 ns), and a faster component (tau3 = 2.1 ns) ascribed to intracluster energy migration between monomer and dimer. Acridine has a weak interaction with SDS forming only an ion pair without further self-aggregation of the dye. 相似文献
996.
Pina J Seixas de Melo J Pina F Lodeiro C Lima JC Parola AJ Soriano C Clares MP Albelda MT Aucejo R García-España E 《Inorganic chemistry》2005,44(21):7449-7458
A new fluorescent macrocyclic structure (L1) bearing two naphthalene units at both ends of a cyclic polyaminic chain containing two phenanthroline units was investigated with potentiometric and fluorescence (steady-state and time-resolved) techniques. The fluorescence emission spectra show the simultaneous presence of three bands: a short wavelength emission band (naphthalene monomer), a middle emission band (phenanthroline emission), and a long-wavelength band. All three bands were found to be dependent on the protonation state of the macrocyclic unit (including the polyaminic and phenanthroline structures). The existence of the long-wavelength emission band is discussed and is shown to imply that a bending movement involving the two phenanthroline units leads to excimer formation. This is determined by comparison with the excimer emission formed by intermolecular association of 1,10-phenanthroline. With ligand L1, excimer formation occurs only at pH values above 4. At very acidic pH values, the protonation of the polyamine bridges is extensive leading to a rigidity of the system that precludes the bending movement. The interaction with metal cations Zn(II) and Cu(II) was also investigated. Excimer formation is, in these situations, increased with Zn(II) and decreased with Cu(II). The long-emission band is shown to present a different wavelength maximum, depending on the metal, which can be considered as a characteristic to validate the use of ligand L1 as a sensor for a given metal. 相似文献
997.
Velasco E Infante M Durán M Esteban-Cardeñosa E Lastra E García-Girón C Miner C 《Electrophoresis》2005,26(13):2539-2552
Mutational analysis of large multiexon genes without prevalent mutations is a laborious undertaking that requires the use of a high-throughput scanning technique. The Human Genome Project has enabled the development of powerful techniques for mutation detection in large multiexon genes. We have transferred heteroduplex analysis (HA) by conformation-sensitive gel electrophoresis of the two major breast cancer (BC) predisposing genes, BRCA1 and BRCA2, to a multicapillary DNA sequencer in order to increase the throughput of this technique. This new method that we have called heteroduplex analysis by capillary array electrophoresis (HA-CAE) is based on the use of multiplex-polymerase chain reaction (PCR), different fluorescent labels and HA in a 16-capillary DNA sequencer. To date, a total of 114 different DNA sequence variants (19 insertions/deletions and 95 single-nucleotide substitutions - SNS) of BRCA1 and BRCA2 from 431 unrelated BC families have been successfully detected by HA-CAE. In addition, we have optimized the multiplex-PCR conditions for the colorectal cancer genes MLH1 and MSH2 in order to analyze them by HA-CAE. Both genes have been amplified in 13 multiplex groups, which contain the 35 exons, and their corresponding flanking intronic sequences. MLH1 and MSH2 have been analyzed in nine hereditary nonpolyposis colorectal cancer patients, and we have found six different DNA changes: one complex deletion/insertion mutation in MLH1 exon 19 and another five SNS. Only the complex mutation and one SNS may be classified as cancer-prone mutations. Our experience has revealed that HA-CAE is a simple, fast, reproducible and sensitive method to scan the sequences of complex genes. 相似文献
998.
Donohue BA Michelotti EL Reader JC Reader V Stirling M Tice CM 《Journal of combinatorial chemistry》2002,4(1):23-32
A library of 422 1-(2-thiazolyl)-5-(trifluoromethyl)pyrazole-4-carboxamides was prepared in five steps using solution-phase chemistry. The first step in the synthesis was the reaction of ethyl 2-ethoxymethylene-3-oxo-4,4,4-trifluorobutanoate with thiosemicarbazide, which is reported in the literature to afford a 1:1 mixture of ethyl 1-thiocarbamoyl-5-(trifluoromethyl)pyrazole-4-carboxylate and ethyl 1-thiocarbamoyl-3-(trifluoromethyl)pyrazole-4-carboxylate. We reassigned the structure of the product to be a single compound, ethyl 5-hydroxy-1-thiocarbamoyl-5-(trifluoromethyl)-4,5-dihydro-1H-pyrazole-4-carboxylate. This common intermediate was diversified by reaction with 17 alpha-bromoketones affording, in two steps, 17 1-(2-thiazolyl)-5-(trifluoromethyl)pyrazole-4-carboxylic acids. Scavenger resins were used to facilitate formation and purification of up to 27 amides from each of these acids in the last step. In addition, the Curtius reaction was applied to 12 of the acids followed by quenching with alcohols to afford a 108-member carbamate library. Certain compounds in the two libraries were toxic to C. elegans. 相似文献
999.
Faria Luis F. Figueiredo Gimenes Maria Antonieta P. Nobrega Ronaldo Pereira Nei 《Applied biochemistry and biotechnology》2002,98(1-9):449-458
Oxygen availability is the most important environmental parameter in the production of xylitol by yeasts, directly affecting
yields and volumetric productivity. This work evaluated the cell behavior in fermentations carried out with different dissolved
oxygen concentrations (0.5–30.0% of saturation), as well as a limited oxygen restriction (0% of saturation), at several oxygen
volumetric transfer coefficients (12 ≤ k
L
a ≤ 70 h−1). These experiments allowed us to establish the specific oxygen uptake rate limits to ensure high yields and volumetric productivity.
When oxygen availability was limited, the specific oxygen uptake rate values were between 12 and 26 mg of O2/of g cell·h, resulting in a yield of 0.71 g of xylitol/xylose consumed, and 0.85 g/[L·h] for the volumetric productivity.
According to the results, the effective control of the specific oxygen uptake rate makes it possible to establish complete
control over this fermentative process, for both cell growth and xylitol production. 相似文献
1000.
Sánchez P Gálvez N Colacio E Miñones E Domínguez-Vera JM 《Dalton transactions (Cambridge, England : 2003)》2005,(4):811-813
It has been traditionally considered that catechols release iron from ferritin by reduction to iron(II), which diffuses through the ferritin channels into the intracellular milieu where it participates in the Fenton reaction, producing highly toxic hydroxyl radicals. However, in the present work we have proved that the mechanism of the release of iron from ferritin by catechol does not take place by iron(II) reduction but by direct iron(III) chelation and therefore without iron(II) production. A possible extension of these findings to other catechols is discussed on the basis of the stability with respect to the internal redox reaction of the iron(III)-catechol complexes. 相似文献