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81.
Pascal Moucheront François BertrandGeorg Koval Laurent Tocquer Stéphane RodtsJean-Noël Roux Alain CorfdirFrançois Chevoir 《Magnetic resonance imaging》2010
The rheology of granular materials near an interface is investigated through proton magnetic resonance imaging. A new cylinder shear apparatus has been inserted in the magnetic resonance imaging device, which allows the control of the radial confining pressure exerted by the outer wall on the grains and the measurement of the torque on the inner shearing cylinder. A multi-layer velocimetry sequence has been developed for the simultaneous measurement of velocity profiles in different sample zones, while the measurement of the solid fraction profile is based on static imaging of the sample. This study describes the influence of the roughness of the shearing interface and of the transverse confining walls on the granular interface rheology. 相似文献
82.
Monika Karpierz Jan Suchanicz Krzysztof Konieczny Dorota Sitko Pascal Marchet Urszula Lewczuk 《Phase Transitions》2015,88(7):662-667
The 0.5K0.5Bi0.5TiO3–0.5PbTiO3 ceramics were prepared by following a standard solid-state method. The Raman, thermal and dielectric properties of these ceramics were investigated. The X-ray measurements showed that samples have single perovskite-type structure with tetragonal symmetry. Dielectric study revealed that the dielectric behaviour of the investigated ceramics is rather of normal ferroelectrics with large thermal hysteresis. The transition temperature observed by means of differential scanning calorimetry measurements is in good agreement with that obtained from dielectric study. 相似文献
83.
Pascal Gosselin Serge Masson Monique Saquet André Thuillier 《Phosphorus, sulfur, and silicon and the related elements》2013,188(1-2):103-104
Abstract A new synthesis of dithioesters, starting from phenylisothiocyanate is described (scheme I) and this method is convenient for the preparation of β-olefinic dithioesters (e. g. 1, scheme II). 相似文献
84.
Devrishi Goswami Srikripa Devarakonda Michael J. Chalmers Bruce D. Pascal Bruce M. Spiegelman Patrick R. Griffin 《Journal of the American Society for Mass Spectrometry》2013,24(10):1584-1592
Application of typical HDX methods to examine intrinsically disordered proteins (IDP), proteins that are natively unstructured and highly dynamic at physiological pH, is limited because of the rapid exchange of unprotected amide hydrogens with solvent. The exchange rates of these fast exchanging amides are usually faster than the shortest time scale (10 s) employed in typical automated HDX-MS experiments. Considering the functional importance of IDPs and their association with many diseases, it is valuable to develop methods that allow the study of solution dynamics of these proteins as well as the ability to probe the interaction of IDPs with their wide range of binding partners. Here, we report the application of time window expansion to the millisecond range by altering the on-exchange pH of the HDX experiment to study a well-characterized IDP; the activation domain of the nuclear receptor coactivator, peroxisome proliferator-activated receptor gamma coactivator-1 alpha (PGC-1α). This method enabled mapping the regions of PGC-1α that are stabilized upon binding the ligand binding domain (LBD) of the nuclear receptor peroxisome proliferator-activated receptor gamma (PPARγ). We further demonstrate the method’s applicability to other binding partners of the IDP PGC-1α and pave the way for characterizing many other biologically important ID proteins. Figure
? 相似文献
85.
Jean Guillon Jean-Michel Leger Cecilia Dapremont Lou Apollonia Denis Pascal Sonnet Stéphane Massip 《Supramolecular chemistry》2013,25(5):319-329
The synthesis of new 25,27-dialkyloxy-5,17-diarylcalix[4]arenes-crown-6 1a–f in 1,3-alternate conformation by Suzuki cross-coupling reaction is reported. Their conformation was determined using 1H, 13C, 2D NMR and ROESY analysis, and X-ray crystallography. Extraction experiments using a two-phase solvent method involving sodium, potassium or cesium picrate showed good extraction of the cesium cation. The X-ray crystal structures of 1,3-alternate 25,27-dipropoxy-5,17-diphenylcalix[4]arene-crown-6 ether 1a and its cesium picrate complex were established. Solid-state data were used to determine the complexation behavior of these new ligands. The efficiency of calixarenes 1a–f for cesium ion extraction could be ascribed to the rigidity and flatness linkages caused by the aryl groups at the lower rim of the aromatic moieties in the calixarene skeleton. In addition, the introduction of these aromatic moieties in positions 5 and 17 enhanced the solubility of the metal complexes in organic media. 相似文献
86.
Monique?SabatyEmail author Sandrine?Grosse Geraldine?Adryanczyk Séverine?Boiry Frédéric?Biaso Pascal?Arnoux David?Pignol 《BMC biochemistry》2013,14(1):28
Background
YedY, a molybdoenzyme belonging to the sulfite oxidase family, is found in most Gram-negative bacteria. It contains a twin-arginine signal sequence that is cleaved after its translocation into the periplasm. Despite a weak reductase activity with substrates such as dimethyl sulfoxide or trimethylamine N-oxide, its natural substrate and its role in the cell remain unknown. Although sequence conservation of the YedY family displays a strictly conserved hydrophobic C-terminal residue, all known studies on Escherichia coli YedY have been performed with an enzyme containing a 6 histidine-tag at the C-terminus which could hamper enzyme activity.Results
In this study, we demonstrate that the tag fused to the C-terminus of Rhodobacter sphaeroides YedY is detrimental to the enzyme’s reductase activity and results in an eight-fold decrease in catalytic efficiency. Nonetheless this C-terminal tag does not influence the properties of the molybdenum active site, as assayed by EPR spectroscopy. When a cleavable His-tag was fused to the N-terminus of the mature enzyme in the absence of the signal sequence, YedY was expressed and folded with its cofactor. However, when the signal sequence was added upstream of the N-ter tag, the amount of enzyme produced was approximately ten-fold higher.Conclusion
Our study thus underscores the risk of using a C-terminus tagged enzyme while studying YedY, and presents an alternative strategy to express signal sequence-containing enzymes with an N-terminal tag. It brings new insights into molybdoenzyme maturation in R. sphaeroides showing that for some enzymes, maturation can occur in the absence of the signal sequence but that its presence is required for high expression of active enzyme.87.
Arbia Khemiri Bertrand Naudin Xavier Franck Philippe Chan Tchi Song Thierry Jouenne Pascal Cosette 《Analytical and bioanalytical chemistry》2013,405(30):9835-9842
In prokaryote organisms, N-glycosylation of proteins is often correlated to cell–cell recognition and extracellular events. Those glycoproteins are potential targets for infection control. To date, many surface-glycosylated proteins from bacterial pathogens have been described. However, N-linked Pseudomonas surface-associated glycoproteins remain underexplored. We report a combined enrichment and labeling strategy to identify major glycoproteins on the outside of microorganisms. More precisely, bacteria were exposed to a mix of biotinylated lectins able to bind with glycoproteins. The latter were then recovered by avidin beads, digested with trypsin, and submitted to mass spectrometry. The targeted mixture of glycoproteins was additionally deglycosylated in the presence of H2 18O to incorporate 18O during PNGase F treatment and were also analyzed using mass spectrometry. This approach allowed us to identify a few tens of potential N-glycoproteins, among which flagellin FliC was the most abundant. To detect the possible sites of FliC modifications, a de novo sequencing step was also performed to discriminate between spontaneous deamidation and N-glycan loss. This approach led to the proposal of three potential N-glycosylated sites on the primary sequence of FliC: N26, N69, and N439, with two of these three asparagines belonging to an N-X-(S/T) consensus sequence. These observations suggest that flagellin FliC is a heterogeneous protein mixture containing both O- and N-glycoforms. Figure
Analytical scenario developed for bacterial glycoprotein enrichment. This strategy includes three main steps: (1) exposure of Pseudomonas aeruginosa cells to a mixture of biotinylated lectins [wheat germ agglutinin (WGA) and concanavalin A (ConA)]; (2) enrichment of N-glycoproteins by elution with avidin beads; and (3) mass spectrometry (MS) identification and characterization of intact and deglycosylated peptides before and after H2 18O PNGase F enzymatic treatment, respectively 相似文献
88.
A series of cyclophanes composed of two triarylelement caps linked by two-atom bridges has been synthesized. The bridgehead functional groups include phosphines in combination with amines, hydrosilanes, methylsilanes, and ethoxysilanes. Computational studies accurately predicted that when the bridgehead substituents are small (lone pairs or protons), an in,in bridgehead stereochemistry is strongly favored, but larger bridgehead substituents favor the formations of in,out stereoisomers. The X-ray structures, spectra, and reactivity of these compounds are discussed, as well as the resolution of one of the cyclophanes into pure enantiomers. 相似文献
89.
Pascal Munier Marie-Béatrice Giudicelli Dominique Picq et Daniel Anker 《Journal of carbohydrate chemistry》2013,32(8):1225-1230
Abstract L'hydrolyse acide des acétals et en particulier des osides fait intervenir un carbocation intermédiaire stabilisé par l'oxygène voisin; un substituant électroattracteur en α de l'atome d'oxygène ou de carbone d'un tel cation déstabilise cedernier et rend l'hydrolyse des acétals plus difficile. C'est ainsi que pour un 2-méthoxy-tétrahydropyrane, le remplacement en C-6 d'un groupement CH2OH par CO2Et1 provoque une diminution de la vitesse d'hydrolyse d'un facteur de 200. Il est également bien connu que les 2-désoxy glycosides sont hydrolysés bien plus rapidement que leurs analogues 2-hydroxylés. Le même résultat est obtenu avec un atome d'halogène; c'est ainsi que Horton et coll.2 en introduisant un atome d'iode en position 2′ d'analogues de la daunorubicine et de l'adriamycine ont pu augmenter leur efficacité in vivo. Compte tenu de la taille réduite de l'atome de fluor qui modifie peu l'encombrement de la molécule, plusieurs travaux ont été consacrés à l'introduction d'un fluor en position 2 d'osides pour ralentir leur vitesse d'hydrolyse in vivo. 3-5 Cette même démarche a conduit d'autres auteurs à synthétiser des 2,2-difluorosucres.6 On pouvait donc envisager de remplacer l'hydrogène en C-1 de certains sucres par un groupement trifluorométhyle pour obtenir ainsi une nouvelle classe d'osides, dont la liaison osidique serait très stabilisée, ce qui devrait accroître leur durée de vie in vivo; on sait en effet 7 que les acétals de trifluorométhylcétones sont très difficiles à hydrolyser. Nous avons récemment décrit8 l'obtention des composés 1 et 9 et, on pouvait envisager de substituer l'hydroxyle anomérique de tels 2-uloses par divers nucléophiles. Les substitution nucléophiles en α d'un groupe CF3 sont difficiles9,10 et font en général intervenir un carbocation du type CF3-C+R1-XR2 stabilisé par un hétéroatome X(O, S)11-15 ou par un phényle.9 Ce carbocation est formé dans quelques cas par voie électrochimique,14-15 mais, dans la plupart des travaux, il résulte soit de la rupture d'une liaison CR1-Y assistée par un acide de Lewis soit de la solvolyse de cette liaison.9 Pour éviter l'emploi d'un acide de Lewis incompatible avec des groupes protecteurs acido-sensibles, nous avons mésylé l'hydroxyle anomérique pour obtenir un meilleur groupe partant. Nous décrivons dans cette note les résultats préliminaires obtenus principalement par action de divers nucléophiles sur ces mésylates. 相似文献
90.
Prof. Dr. A. Stephen K. Hashmi Tobias Lauterbach Dipl.‐Chem. Pascal Nösel Dr. Mie Højer Vilhelmsen Dr. Matthias Rudolph Dr. Frank Rominger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):1058-1065
A series of dinuclear gold σ,π‐propyne acetylide complexes were prepared and tested for their catalytic ability in dual gold catalysis that was based on the reaction of an electrophilic π‐complex of gold with a gold acetylide. The air‐stable and storable catalysts can be isolated as silver‐free catalysts in their activated form. These dual catalysts allow a fast initiation phase for the dual catalytic cycles without the need for additional additives for acetylide formation. Because propyne serves as a throw‐away ligand, no traces of the precatalyst are generated. Based on the fast initiation process, side products are minimized and reaction rates are higher for these catalysts. A series of test reactions were used to demonstrate the general applicability of these catalysts. Lower catalyst loadings, faster reaction rates, and better selectivity, combined with the practicability of these catalysts, make them ideal catalysts for dual gold catalysis. 相似文献