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81.
A modified Polonovski reaction has been employed to N-demethylate several opiate alkaloids in moderate to high yield. This method provides an alternative to traditional N-demethylation procedures which utilize toxic reagents such as cyanogen bromide or expensive reagents such as vinyl chloroformate. The current synthesis involves N-oxide formation, isolation of the corresponding N-oxide hydrochloride, and an FeSO(4).7H(2)O mediated Polonovski reaction to afford the desired secondary amine. 相似文献
82.
Lau JK Wong CH Ng PS Siu FM Ma NL Tsang CW 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(14):3383-3396
The potassium cation affinities (PCAs) of 136 ligands (20 classes) in the gas phase were established by hybrid density functional theory calculations (B3-LYP with the 6-311+G(3df,2p) basis set). For these 136 ligands, 70 experimental values are available for comparison. Except for five specific PCA values-those of phenylalanine, cytosine, guanine, adenine (kinetic-method measurement), and Me(2)SO (by high-pressure mass spectrometric equilibrium measurement)-our theoretical estimates and the experimental affinities are in excellent agreement (mean absolute deviation (MAD) of 4.5 kJ mol(-1)). Comparisons with previously reported theoretical PCAs are also made. The effect of substituents on the modes of binding and the PCAs of unsubstituted parent ligands are discussed. Linear relations between Li+/Na+ and K+ affinities suggest that for the wide range of ligands studied here, the nature of binding between the cations and a given ligand is similar, and this allows the estimation of PCAs from known Li+ and/or Na+ affinities. Furthermore, empirical equations relating the PCAs of ligands with their dipole moments, polarizabilities (or molecular weights), and the number of binding sites were established. Such equations offer a simple method for estimating the PCAs of ligands not included in the present study. 相似文献
83.
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85.
Nicewonger R Fowke A Nguyen K Ditto L Caserta J Harris M Baldino CM 《Molecular diversity》2003,7(2-4):247-252
A microwave-assisted method is described for monoacylating 7-amino-5-aryl-6-cyanopyrido[2,3-d]pyrimidines using excess acid chlorides in pyridine. A diacylated intermediate is effectively deacylated to the product amide by a macroporous-Tris resin. A small library of 17 amides was prepared to validate the method. The integration of commercial microwave technology into the ArQule chemistry platform is also discussed. 相似文献
86.
Chandran Karunakaran K.R. Justin Thomas Arunachalam Shunmugasundarama Ramachandran Murugesan 《Journal of chemical crystallography》2000,30(5):351-357
Single crystals of the helical hydrogen-bridged one-dimensional Cu(II) complex, [Cu(stpy)2(CH3COO)2(H2O)2] (1) [Cu(stpy)2(CH3COO)2(H2O)] (2), are prepared and characterized by elemental and thermal analyses, IR, electronic and X-ray crystal structure determination. The crystals are monoclinic, of space group C2/c, with unit cell parameters a = 31.842(7) Å, b = 5.9829(10) Å, c = 30.970(14) Å, = 111.78(3)°, Z = 4. The asymmetric unit contains two different types of Cu(II) polyhedra, namely, octahedron and square pyramid within the same unit cell. 1 has elongated octahedral geometry with two nitrogen atoms from stpy and two oxygen atoms from synmonodentate acetate ligands, transcoordinated to Cu(II) in the basal plane. The oxygen atoms of the two water molecules occupy the axial positions. 2 has Cu(II) coordination polyhedra similar to 1, except that only one of the apical positions is occupied by a water molecule. The structure consists of two independent linear chains, one involving octahedral (1) and the other involving square-pyramidal (2) polyhedra, held by hydrogen bridges. The Cu–Cu intra- and interchain separations in both 1 and 2 are 5.983 and 8.214 Å. The unit cell packing shows weak -stacking between adjacent coordinated stpy ligands in the chain, resulting in ladder-type structure. Further, the extended packing reveals helical arrangement of Cu(II) polyhedra in the lattice. 相似文献
87.
Electronic and atomic structures of different terminations of the (0 0 1) non-polar orientation of BaZrO3 surfaces have been studied using first-principles calculations. We found that surface energies at both possible surface terminations, BaO and ZrO2, were very close. The (0 0 1)-BaO and (0 0 1)-ZrO2 terminated surfaces have bandgap values smaller than that of a bulk BaZrO3 crystal. In addition, the relative surface stability has been analyzed as a function of chemical environment. 相似文献
88.
A low temperature synthesis technique to prepare indium tin oxide (ITO) nanoparticles by the polyol process is proposed. On examining the phase formation of ITO nanoparticles in polyols and alcohols such as ethylene glycol, trimethylene glycol, and 1-heptanol, it was found that ITO nanoparticles could be synthesized directly without any post--annealing treatments at 175 °C in 1-heptanol. The morphology of the particles is influenced by the type of polyol. The composition of Sn in the ITO system could be easily controlled by simply varying the In/Sn precursor ratio in 1-heptanol. The low temperature synthesis method has enabled the formation of highly crystalline ITO nanoparticles with diameters less than 25 nm even at annealing temperatures as high as 700 °C. 相似文献
89.
Justin L. P. Benesch 《Journal of the American Society for Mass Spectrometry》2009,20(3):341-348
Mass spectrometry is fast becoming a vital approach not only for the identification and quantification of proteins, but also
for the study of the noncovalent assemblies they form. Approaches for ionizing, transmitting, and detecting protein complexes
intact in the mass spectrometer are now well established. The challenge has therefore shifted to developing and applying mass
spectrometry approaches to elucidate the structure of such species. A crucial aspect to this goal is inducing their disassembly
in the gas phase to mine information as to their composition and organization. Here the consequences of collisionally activating
protein complexes are illustrated through ion mobility mass spectrometry measurements and discussed in the context of the
current literature. Although a consensus view of the mechanism of dissociation is starting to emerge, it is also clear that
a number of aspects remain unresolved. These outstanding questions and frontier challenges must be addressed if gas-phase
dissociative approaches are to reach their full potential in the study of protein assemblies. 相似文献
90.
Ying Yang Friederike M. Mansfeld Maria Kavallaris Katharina Gaus Richard D. Tilley J. Justin Gooding 《Chemical science》2021,12(7):2558
Impedance spectroscopy is a widely used technique for monitoring cell–surface interactions and morphological changes, typically based on averaged signals from thousands of cells. However, acquiring impedance data at the single cell level, can potentially reveal cell-to-cell heterogeneity for example in response to chemotherapeutic agents such as doxorubicin. Here, we present a generic platform where light is used to define and localize the electroactive area, thus enabling the impedance measurements for selected single cells. We firstly tested the platform to assess phenotypic changes in breast cancer cells, at the single cell level, using the change in the cell impedance. We next show that changes in electrochemical noise reflects instantaneous responses of the cells to drugs, prior to any phenotypical changes. We used doxorubicin and monensin as model drugs and found that both drug influx and efflux events affect the impedance noise signals. Finally, we show how the electrochemical noise signal can be combined with fluorescence microscopy, to show that the noise provides information on cell susceptibility and resistance to drugs at the single cell level. Together the combination of electrochemical impedance and electrochemical noise with fluorescence microscopy provides a unique approach to understanding the heterogeneity in the response of single cells to stimuli where there is not phenotypic change.A light addressable single-cell impedance technique for cell adhesion monitoring and measurement of a cell''s drug response based on electrochemical noise is introduced. 相似文献