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981.
Elisandra Rigo André E. Polloni Daniela Remonatto Francieli Arbter Silvana Menoncin J. Vladimir Oliveira Débora de Oliveira Helen Treichel Susana J. Kalil Jorge L. Ninow Marco Di Luccio 《Applied biochemistry and biotechnology》2010,162(7):1881-1888
The main objective of this work was the isolation and screening of microorganisms with potential for producing lipases for the synthesis of fatty esters as well as evaluating the specificity of the enzymes produced, using different alcohols (methanol, ethanol, n-propanol, and butanol) and fatty acids (oleic and lauric acids) as substrates. Promising biocatalysts for organic synthesis were obtained in this work. The isolated strains 69F and 161Y showed ability to efficiently catalyze the reaction for production of n-propyl oleate. Other strains can also be considered of potential interest, as 74F, 111Y, and 186Y. The future development of production using different substrates could result in cheap crude lipase of high importance to industrial applicability. 相似文献
982.
Binolfi A Rodriguez EE Valensin D D'Amelio N Ippoliti E Obal G Duran R Magistrato A Pritsch O Zweckstetter M Valensin G Carloni P Quintanar L Griesinger C Fernández CO 《Inorganic chemistry》2010,49(22):10668-10679
The aggregation of alpha-synuclein (AS) is a critical step in the etiology of Parkinson's disease (PD). A central, unresolved question in the pathophysiology of PD relates to the role of AS-metal interactions in amyloid fibril formation and neurodegeneration. Our previous works established a hierarchy in alpha-synuclein-metal ion interactions, where Cu(II) binds specifically to the protein and triggers its aggregation under conditions that might be relevant for the development of PD. Two independent, non-interacting copper-binding sites were identified at the N-terminal region of AS, with significant difference in their affinities for the metal ion. In this work we have solved unknown details related to the structural binding specificity and aggregation enhancement mediated by Cu(II). The high-resolution structural characterization of the highest affinity N-terminus AS-Cu(II) complex is reported here. Through the measurement of AS aggregation kinetics we proved conclusively that the copper-enhanced AS amyloid formation is a direct consequence of the formation of the AS-Cu(II) complex at the highest affinity binding site. The kinetic behavior was not influenced by the His residue at position 50, arguing against an active role for this residue in the structural and biological events involved in the mechanism of copper-mediated AS aggregation. These new findings are central to elucidate the mechanism through which the metal ion participates in the fibrillization of AS and represent relevant progress in the understanding of the bioinorganic chemistry of PD. 相似文献
983.
We report on the use of optical Faraday rotation to monitor the nuclear-spin signal in a set of model (19)F- and (1)H-rich fluids. Our approach integrates optical detection with high-field, pulsed NMR so as to record the time-resolved evolution of nuclear-spins after rf excitation. Comparison of chemical-shift-resolved resonances allows us to set order-of-magnitude constrains on the relative amplitudes of hyperfine coupling constants for different bonding geometries. When evaluated against coil induction, the present detection modality suffers from poorer sensitivity, but improvement could be attained via multipass schemes. Because illumination is off-resonant i.e., the medium is optically transparent, this methodology could find extensions in a broad class of fluids and soft condensed matter systems. 相似文献
984.
Valeria Nardelli Daniela dell’Oro Carmen Palermo Diego Centonze 《Journal of chromatography. A》2010,1217(30):4996-5003
A multi-residue method for the determination of organochlorine pesticides in fish feed samples was developed and optimized. The method is based on a cleanup step of the extracted fat, carried out by liquid–liquid extraction on diatomaceous earth cartridge with n-hexane/acetonitrile (80/20, v/v) followed by solid phase extraction (SPE) with silica gel–SCX cartridge, before the identification and quantification of the residues by gas chromatography–triple quadrupole tandem spectrometry (GC–MS/MS). Performance characteristics, such as accuracy, precision, linear range, limits of detection (LOD) and quantification (LOQ), for each pesticide were determined. Instrumental LODs ranged from 0.01 to 0.11 μg L−1, LOQs were in the range of 0.02–0.35 μg L−1, and calibration curves were linear (r2 > 0.999) in the whole range of explored concentrations (5–100 μg L−1). Repeatability values were in the range of 3–15%, evaluated from the relative standard deviation of six samples spiked at 100 μg kg−1 of fat, and in compliance with that derived by the Horwitz's equation. No matrix effects or interfering substances were observed in fish feed analyses. The proposed method allowed high recoveries (92–116%) of spiked extracted fat samples at 100 μg kg−1, and very low LODs (between 0.02 and 0.63 μg kg−1) and LOQs (between 0.05 and 2.09 μg kg−1) determined in fish feed samples. 相似文献
985.
Earlier we reported on the synthesis of α,4-dicarboxy-2-nitrobenyzl caged compounds (Schaper, K. et al. [2002] Eur. J. Org. Chem., 1037–1046). These compounds have the advantage of an increased hydrophilicity compared with the well-established α-carboxy-2-nitrobenzyl caged compounds; however, the release of the active compound becomes slower due to the introduction of the additional carboxy group. Based upon theoretical calculations we predicted that the release would become faster when the additional carboxy group is moved to the 5-position. Here we describe the synthesis and the photochemical and biological characterization of an α,5-dicarboxy-2-nitrobenyzl caged compound. The high hydrophilicity of the new caging group is maintained due to the fact that the additional carboxy moiety is preserved, while the release of the active species from the new derivative is even faster than for the reference, an α-CNB caged compound. 相似文献
986.
Coppola C Paciello A Mangiapia G Licen S Boccalon M De Napoli L Paduano L Tecilla P Montesarchio D 《Chemistry (Weinheim an der Bergstrasse, Germany)》2010,16(46):13757-13772
A novel fluorescently labelled synthetic ionophore, based on a cyclic phosphate-linked disaccharide (CyPLOS) backbone and decorated with four tetraethylene glycol tails carrying dansyl units, has been synthesised in 12 steps in 26% overall yield. The key intermediate in the synthetic strategy is a novel glucoside building block, serving through its 2- and 3-hydroxy groups as the anchor point for flexible tetraethylene glycol tentacles with reactive azido moieties at their ends. To test the versatility of this glucoside scaffold, it was preliminarily functionalised with a set of diverse probes--as fluorescent, redox-active or hydrophobic tags--either by reduction of the azides followed by condensation with activated carboxylic acid derivatives, or by a direct coupling with a terminal alkyne in a Cu(I)-promoted 1,3-dipolar cycloaddition. Tagging of the monomeric building block with dansyl residues allowed us to prepare a fluorescent, amphiphilic macrocycle, which was investigated for its propensity to self-aggregate in CDCl(3)--studied by means of concentration-dependent (31)P NMR spectroscopy experiments--and in aqueous solution, in which combined dynamic light scattering (DLS) and small-angle neutron scattering (SANS) measurements provided a detailed physico-chemical analysis of the self-assembled systems, mainly organised in the form of large vesicles. Its ion-transport properties through phospholipid bilayers, determined by HPTS fluorescence assays, showed this compound to be more active than the previously synthesised CyPLOS congeners. Solvent-dependent fluorescence changes for the labelled ionophore in liposome suspension established that the dansyl moieties are dispersed in environments with polarity intermediate between those of CH(2)Cl(2) and propan-2-ol, suggesting that the CyPLOS tentacles infiltrate the mid-polar region of the membranes. 相似文献
987.
Szychowski J Mahdavi A Hodas JJ Bagert JD Ngo JT Landgraf P Dieterich DC Schuman EM Tirrell DA 《Journal of the American Chemical Society》2010,132(51):18351-18360
The azide-alkyne cycloaddition provides a powerful tool for bio-orthogonal labeling of proteins, nucleic acids, glycans, and lipids. In some labeling experiments, e.g., in proteomic studies involving affinity purification and mass spectrometry, it is convenient to use cleavable probes that allow release of labeled biomolecules under mild conditions. Five cleavable biotin probes are described for use in labeling of proteins and other biomolecules via azide-alkyne cycloaddition. Subsequent to conjugation with metabolically labeled protein, these probes are subject to cleavage with either 50 mM Na(2)S(2)O(4), 2% HOCH(2)CH(2)SH, 10% HCO(2)H, 95% CF(3)CO(2)H, or irradiation at 365 nm. Most strikingly, a probe constructed around a dialkoxydiphenylsilane (DADPS) linker was found to be cleaved efficiently when treated with 10% HCO(2)H for 0.5 h. A model green fluorescent protein was used to demonstrate that the DADPS probe undergoes highly selective conjugation and leaves a small (143 Da) mass tag on the labeled protein after cleavage. These features make the DADPS probe especially attractive for use in biomolecular labeling and proteomic studies. 相似文献
988.
Mihaela Badea Rodica Olar Dana Marinescu Valentina Uivarosi Teodor Octavian Nicolescu Daniela Iacob 《Journal of Thermal Analysis and Calorimetry》2010,99(3):829-834
A series of new complexes with mixed ligands of the type RuL
m
(DMSO)
n
Cl3·xH2O ((1) L: oxolinic acid (oxo), m = 1, n = 0, x = 4; (2) L: pipemidic acid (pip), m = 2, n = 1, x = 2; (3) L: enoxacin (enx), m = 2, n = 1, x = 0; (4) L: levofloxacin (levofx), m = 2, n = 2, x = 8; DMSO: dimethylsulfoxide) were synthesized and characterized by chemical analysis, IR and electronic data. Except oxolinic
acid that behaves as bidentate, the other ligands (quinolone derivatives and DMSO) act as unidentate. Electronic spectra are
in accordance with an octahedral stereochemistry. The thermal analysis (TG, DTA) in synthetic air flow elucidated the composition
and also the number and nature of both water and DMSO molecules. The TG curves show 3–5 well-separated thermal steps. The
first corresponds to the water and/or DMSO loss at lower temperatures followed either by quinolone thermal decomposition or
pyrolisys at higher temperatures. The final product is ruthenium(IV) oxide. 相似文献
989.
Anna Laura Capriotti Giulio Caracciolo Giuseppe Caruso Chiara Cavaliere Daniela Pozzi Roberto Samperi Aldo Laganà 《Analytical and bioanalytical chemistry》2010,398(7-8):2895-2903
Plasma protein adsorption is regarded as a key factor in the in vivo organ distribution of intravenously administered drug carriers, and strongly depends on vector surface characteristics. The present study aimed to characterize the “protein corona” absorbed onto DC-Chol-DOPE cationic liposomes. This system was chosen because it is one of the most efficient and widely used non-viral formulations in vitro and a potential candidate for in vivo transfection of genetic material. After incubation of human plasma with cationic liposomes, nanoparticle–protein complex was separated from plasma by centrifugation. An integrated approach based on protein separation by one-dimensional 12% polyacrylamide gel electrophoresis followed by the automated HPLC-Chip technology coupled to a high-resolution mass spectrometer was employed for protein corona characterization. Thirty gel lanes, approximately 2 mm, were cut, digested and analyzed by HPLC-MS/MS. Fifty-eight human plasma proteins adsorbed onto DC-Chol-DOPE cationic liposomes were identified. The knowledge of the interactions of proteins with liposomes can be exploited for future controlled design of colloidal drug carriers and possibly in the controlled creation of biocompatible surfaces of other devices that come into contact with proteins in body fluids.
Scheme of protein adsorption onto nanoparticle surface 相似文献
990.
Wolf-Walther du Mont Roxana Bîrzoi Delia Bugnariu Constantin G. Daniliuc Christine Goers Rafael Guerrero Gimeno Thorsten Gust Daniela Lungu Antje Riecke Rainer Bartsch Laszlo Nyulászi Zoltan Benkõ Laszlo Könczöl 《Comptes Rendus Chimie》2010,13(8-9):1111-1126
An overview is given on synthesis and structures of new bidentate phosphaalkene ligands [(RMe2Si)2CP]2E (E = O, NR, N?) and (RMe2Si)2CPN(R′)PR′′2. Exceptional properties of these ligands, extending beyond predictable properties of phosphaalkenes are: (i) the NSi bond cleavage of [(iPrMe2Si)2CP]2NSiMe3 with AuI and RhI chloro complexes under mild conditions leading to binuclear complexes of the 6π-delocalised imidobisphosphaalkene anion [(iPrMe2Si)2CP]2N?, and (ii) the chlorotropic formation of molecular 1:2 PdII and PtII metallochloroylid complexes with novel ylid-type ligands [(RMe2Si)2CP(Cl)N(R)PR2]?, and the transformation of a P-platina-P-chloroylid complex into a C-platina phosphaalkene by intramolecular chlorosilane elimination. Properties of the heavier congeners [(RMe2Si)2CP]2E (E = S, Se, Te, PR, P?, As?) and (RMe2Si)2CPEPR′′2 (E = S, Se, Te) are also described. 相似文献