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951.
Protolytic equilibria taking place in aqueous solutions of sodium deoxycholate (DCNa) have been studied at 25°C using 0.5M NaCl as ionic medium. Electromotive force measurements of a galvanic cell were carried out by means of a glass electrode.The reagent necessary to change the acidity of the solutions was produced in situ by supplying a constant small current.Solubility and acid constant of deoxycholic acid (HDC) have been determined for the chosen experimental conditions. Experimental data obtained in less acid solutions have been explained by assuming the presence of the species H(DC)2. The relative stability constant has been determined. At higher deoxycholate concentration the presence of a polymeric micellar species has been assumed.
Protolytische Gleichgewichte in wäßrigen Natriumdesoxycholat-Lösungen
Zusammenfassung Die Protonierung von Natrium-Desoxycholat (DCNa) in wäßrigen Lösungen mit 0.5M NaCl wurde bei 25°C mit Hilfe von E.M.K. Messungen mit einer Glaselektrode untersucht.Das notwendige Reagens für die Umwandlung der Säure in den untersuchten Lösungen wurde in situ durch einen konstanten schwachen Strom erzeugt.Löslichkeit und Dissoziationkonstante von Desoxycholsäure (HDC) wurden unter den gewählten experimentellen Bedingungen bestimmt. Die experimentellen Daten in schwach sauren Lösungen konnten mit der Annahme der Existenz von H(DC)2 erklärt werden. Die entsprechende Konstante wurde bestimmt. Zur Erklärung der Daten in stärker konzentrierten Lösungen von Desoxycholat ist die Annahme einer polynuklearen Spezies nötig.

Symbols H analytical excess of hydrogenions, if negative it corresponds to OH; - h free concentration of hydrogen ions; - A total concentration of deoxycholate; - a free concentration of deoxycholate; - K a acid constant of deoxycholic acid (HDC) defined as follows: [HDC]K a =ha; - q,p stability constant of a speciesH p (DC) q defined as follows: [H p (DC) q ]= q,p h p a q ; - C 0 solubility of HDC; - formation function representing the average number of H+ bonded to deoxycholate.  相似文献   
952.
Reactive oxygen and nitrogen species (ROS and RNS) play important roles in various physiological processes (e.g. phagocytosis) and pathological conditions (e.g. cancer). The primary ROS/RNS, viz., hydrogen peroxide, peroxynitrite ion, nitric oxide, and nitrite ion, can be oxidized at different electrode potentials and therefore detected and quantified by electroanalytical techniques. Nanometer-sized electrochemical probes are especially suitable for measuring ROS/RNS in single cells and cellular organelles. In this article, we survey recent advances in the localized measurements of ROS/RNS inside single cells and discuss several methodological issues, including optimization of nanoelectrode geometry, precise positioning of an electrochemical probe inside a cell, and interpretation of electroanalytical data.  相似文献   
953.
    
Respiratory chain complexes convert energy by coupling electron flow to transmembrane proton translocation. Owing to a lack of atomic structures of cytochrome bc1 complex (Complex III) from thermophilic bacteria, little is known about the adaptations of this macromolecular machine to hyperthermophilic environments. In this study, we purified the cytochrome bc1 complex of Aquifex aeolicus, one of the most extreme thermophilic bacteria known, and determined its structure with and without an inhibitor at 3.3 Å resolution. Several residues unique for thermophilic bacteria were detected that provide additional stabilization for the structure. An extra transmembrane helix at the N‐terminus of cyt. c1 was found to greatly enhance the interaction between cyt. b and cyt. c1, and to bind a phospholipid molecule to stabilize the complex in the membrane. These results provide the structural basis for the hyperstability of the cytochrome bc1 complex in an extreme thermal environment.  相似文献   
954.
    
Fe‐N‐C catalysts containing atomic FeNx sites are promising candidates as precious‐metal‐free catalysts for oxygen reduction reaction (ORR) in proton exchange membrane fuel cells. The durability of Fe‐N‐C catalysts in fuel cells has been extensively studied using accelerated stress tests (AST). Herein we reveal stronger degradation of the Fe‐N‐C structure and four‐times higher ORR activity loss when performing load cycling AST in O2‐ vs. Ar‐saturated pH 1 electrolyte. Raman spectroscopy results show carbon corrosion after AST in O2, even when cycling at low potentials, while no corrosion occurred after any load cycling AST in Ar. The load‐cycling AST in O2 leads to loss of a significant fraction of FeNx sites, as shown by energy dispersive X‐ray spectroscopy analyses, and to the formation of Fe oxides. The results support that the unexpected carbon corrosion occurring at such low potential in the presence of O2 is due to reactive oxygen species produced between H2O2 and Fe sites via Fenton reactions.  相似文献   
955.
    
Hypervalent FeV=O species are implicated in a multitude of oxidative reactions of organic substrates, as well as in catalytic water oxidation, a reaction crucial for artificial photosynthesis. Spectroscopically characterized FeV species are exceedingly rare and, so far, were produced by the oxidation of Fe complexes with peroxy acids or H2O2: reactions that entail breaking of the O?O bond to form a FeV=O fragment. The key FeV=O species proposed to initiate the O?O bond formation in water oxidation reactions remained undetected, presumably due to their high reactivity. Here, we achieved freeze quench trapping of six coordinated [FeV=O,(OH)(Pytacn)]2+ (Pytacn=1‐(2′‐pyridylmethyl)‐4,7‐dimethyl‐1,4,7‐triazacyclononane) ( 2 ) generated during catalytic water oxidation. X‐ray absorption spectroscopy (XAS) confirmed the FeV oxidation state and the presence of a FeV=O bond at ≈1.60 Å. Combined EPR and DFT methods indicate that 2 contains a S=3/2 FeV center. 2 is the first spectroscopically characterized high spin oxo‐FeV complex and constitutes a paradigmatic example of the FeV=O(OH) species proposed to be responsible for catalytic water oxidation reactions.  相似文献   
956.
    
Understanding the biomolecular interactions in a specific organelle has been a long‐standing challenge because it requires super‐resolution imaging to resolve the spatial locations and dynamic interactions of multiple biomacromolecules. Two key difficulties are the scarcity of suitable probes for super‐resolution nanoscopy and the complications that arise from the use of multiple probes. Herein, we report a quinolinium derivative probe that is selectively enriched in mitochondria and switches on in three different fluorescence modes in response to hydrogen peroxide (H2O2), proteins, and nucleic acids, enabling the visualization of mitochondrial nucleoprotein dynamics. STED nanoscopy reveals that the proteins localize at mitochondrial cristae and largely fuse with nucleic acids to form nucleoproteins, whereas increasing H2O2 level leads to disassociation of nucleic acid–protein complexes.  相似文献   
957.
Abstract

The in vitro antifungal activity of extracts obtained from 14 medicinal plants of the mongolian flora were investigated by measuring their minimal inhibitory concentration (MIC) against fungi cause of cutaneous diseases such as Candida species, dermatophytes and Malassezia furfur. Among the species examined, Stellaria dichotoma L., Scutellaria scordifolia L. Aquilegia sibirica Fisch. Et Schrenk. and Hyoscyamus niger L. extracts demonstrated antifungal activity against all studied fungi. In particular, S. scordifolia L. methanol extract, obtained at room temperature, showed the best activity against Candida spp., Malassezia furfur and dermatophytes with GMMIC50 values of 22?µg/mL, 64?µg/mL and 32?µg/mL, respectively. The flavones, luteolin and apigenin, identified in S. scordifolia extracts, and rutin identified in S. dichotoma and Hyoscyamus niger L. extracts, could be responsible of the observed antifungal activity.  相似文献   
958.
959.
    
We used ultraperformance liquid chromatography coupled with a photodiode-array detector and electrospray ionization quadrupole time-of-flight mass spectrometry (UPLC-PDA/ESI-Q-TOF/MS) to rapidly and accurately quantify 17 phenolic compounds. Then, we applied this method to the seed and leaf extracts of two Amaranthus species to identify and quantify phenolic compounds other than the 17 compounds mentioned above. Compounds were eluted within 30 min on a C18 column using a mobile phase (water and acetonitrile) containing 0.1% formic acid, and the specific wavelength and ion information of the compounds obtained by PDA and ESI-Q-TOF/MS were confirmed. The proposed method showed good linearity (r2 > 0.990). Limits of detection and quantification were less than 0.1 and 0.1 μg/mL, respectively. Intra- and interday precision were less than 2.4% and 1.8%, respectively. Analysis of amaranth seed and leaf extracts using the established method showed that the seeds contained high amounts of 2,4-dihydroxybenzoic acid and kaempferol, and leaves contained diverse phenolic compounds. In addition, six tentatively new phenolic compounds were identified. Moreover, seeds potentially contained 2,3-dihydroxybenzaldehyde, a beneficial bioactive compound. Thus, our method was an efficient approach for the qualitative and quantitative analysis of phenolic compounds, and could be used to investigate phenolic compounds in plants.  相似文献   
960.
Experiments were performed in the laboratory on synthetic seawater spiked with different selenium species at trace levels to study the formation of volatile selenium compounds under dark or controlled simulated sunlight conditions. Spiking the reaction media with inorganic and organic selenium compounds demonstrated that several volatile selenium species could be formed under these simulated conditions. Selenoamino acids react to produce significant amounts of volatile selenium species in both light and dark conditions. Products formed include dimethyl selenide (DMSe), dimethyl selenyl sulphide (DMSeS) and dimethyl diselenide (DMDSe). Inorganic selenium oxyanions added to the synthetic reaction media did not form volatile species via abiotic reactions despite the presence of strong methylating agents. These results suggest that the formation of stable volatile species from bio‐organic selenium compounds can occur via abiotic reactions in the marine photic zone. Copyright © 2000 John Wiley & Sons, Ltd.  相似文献   
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