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161.
Ciampi S James M Michaels P Gooding JJ 《Langmuir : the ACS journal of surfaces and colloids》2011,27(11):6940-6949
We demonstrate a simple method for coupling alkynes to alkynes. The method involves tandem azide-alkyne cycloaddition reactions ("click" chemistry) for the immobilization of 1-alkyne species onto an alkyne modified surface in a one-pot procedure. In the case presented, these reactions take place on a nonoxidized Si(100) surface although the approach is general for linking alkynes to alkynes. The applicability of the method in the preparation of electrically well-behaved functionalized surfaces is demonstrated by coupling an alkyne-tagged ferrocene species onto alkyne-terminated Si(100) surfaces. The utility of the approach in biotechnology is shown by constructing a DNA sensing interface by derivatization of the acetylenyl surface with commercially available alkyne-tagged oligonucleotides. Cyclic voltametry, electrochemical impedance spectroscopy, X-ray photoelectron spectroscopy, and X-ray reflectometry are used to characterize the coupling reactions and performance of the final modified surfaces. These data show that this synthetic protocol gives chemically well-defined, electronically well-behaved, and robust (bio)functionalized monolayers on silicon semiconducting surfaces. 相似文献
162.
Simone Lucarini Francesca Antonietti Andrea TontiniPaola Mestichelli Mauro MagnaniAndrea Duranti 《Tetrahedron letters》2011,52(22):2812-2814
A new synthetic method to obtain the potential anticancer agent 5,6,11,12,17,18,23,24-octahydrocyclododeca[1,2-b:4,5-b′:7,8-b′′:10,11-b′′′]tetraindole (CTet), starting from 1H-indole-3-carboxaldehyde and sulfamide, is described. Although a mixture of CTet and cyclic indole trimer (CTr) is formed, higher CTet/CTr ratio (4:6) and CTet yield (15%) make our protocol more favorable than those reported in the literature. A discussion on the possible reaction mechanism is reported. 相似文献
163.
Gel electrophoresis (GE) is a very common analytical technique for proteome research and protein analysis. Despite being developed decades ago, there is still a considerable need to improve its precision. Using the fluorescence of Colloidal Coomassie Blue -stained proteins in near-infrared (NIR), the major error source caused by the unpredictable background staining is strongly reduced. This result was generalized for various types of detectors. Since GE is a multi-step procedure, standardization of every single step is required. After detailed analysis of all steps, the staining and destaining were identified as the major source of the remaining variation. By employing standardized protocols, pooled percent relative standard deviations of 1.2-3.1% for band intensities were achieved for one-dimensional separations in repetitive experiments. The analysis of variance suggests that the same batch of staining solution should be used for gels of one experimental series to minimize day-to-day variation and to obtain high precision. 相似文献
164.
We present the detailed analysis of the diffusive transport of spatially inhomogeneous fluid mixtures and the interplay between structural and dynamical properties varying on the atomic scale. The present treatment is based on different areas of liquid state theory, namely, kinetic and density functional theory and their implementation as an effective numerical method via the lattice Boltzmann approach. By combining the first two methods, it is possible to obtain a closed set of kinetic equations for the singlet phase space distribution functions of each species. The interactions among particles are considered within a self-consistent approximation and the resulting effective molecular fields are analyzed. We focus on multispecies diffusion in systems with short-range hard-core repulsion between particles of unequal sizes and weak attractive long-range interactions. As a result, the attractive part of the potential does not contribute explicitly to viscosity but to diffusivity and the thermodynamic properties. Finally, we obtain a practical scheme to solve the kinetic equations by employing a discretization procedure derived from the lattice Boltzmann approach. Within this framework, we present numerical data concerning the mutual diffusion properties both in the case of a quiescent bulk fluid and shear flow inducing Taylor dispersion. 相似文献
165.
Sharifi S Capaccioli S Lucchesi M Rolla P Prevosto D 《The Journal of chemical physics》2011,134(4):044510
Dielectric spectroscopy as a function of temperature and pressure was used to study the secondary relaxation in poly [(phenyl glycidyl ether)-co-formaldehyde] at hydrostatic pressure up to 600 MPa and at different temperatures between 315 and 243 K. From the analysis of the isothermal measurements, we observe that the activation volume of the secondary relaxation has nonmonotonic temperature dependence with a maximum at the temperature of the glass transition at ambient pressure. An interpretation in terms of mean hole volume dispersion is proposed based on literature data. Moreover, from isobaric data, we studied the effect of pressure on activation entropy and enthalpy of the secondary relaxation evidencing its local nature but also the presence of a certain complexity of the motion, which supports the idea that this process reflects the motion of a large part of the molecule. 相似文献
166.
The solid sample inhomogeneity is a weak point of traditional MALDI deposition techniques that reflects negatively on quantitative analysis. The recently developed sieve-based device (SBD) sample deposition method, based on the electrospraying of matrix/analyte solutions through a grounded sieve, allows the homogeneous deposition of microcrystals with dimensions smaller than that of the laser spot. In each microcrystal the matrix/analyte molar ratio can be considered constant. Then, by irradiating different portions of the microcrystal distribution an identical response is obtained. This result suggests the employment of SBD in the development of quantitative procedures. For this aim, mixtures of different proteins of known molarity were analyzed, showing a good relationship between molarity and intensity ratios. This behaviour was also observed in the case of proteins with quite different ionic yields. The power of the developed method for quantitative evaluation was also tested by the measurement of the abundance of IGPP[Oxi]GPP[Oxi]GLMGPP (m/z 1219) present in the collagen-α-5(IV) chain precursor, differently expressed in urines from healthy subjects and diabetic-nephropathic patients, confirming its overexpression in the presence of nephropathy. The data obtained indicate that SBD is a particularly effective method for quantitative analysis also in biological fluids of interest. 相似文献
167.
There is an increasing demand for quantitative data on metabolite exposure triggered by regulatory guidances. This contribution describes the accuracy of nanoelectrospray ionization mass spectrometry response of drug compounds and their metabolites from biological matrices compared with radiometric quantification. This is a comprehensive investigation of a set of real-life pharmaceutical compounds in relevant matrices such as urine, bile, feces and plasma. The data suggest that nanoelectrospray mass spectrometry can be used for semi-quantitation of metabolites in the absence of reference standards. Therefore, this approach is suitable to screen out non-relevant metabolites early in development as long as an adequate analytical error margin is applied thus balancing risks and resources. 相似文献
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170.
Badaloni E Barbarino M Cabri W D'Acquarica I Forte M Gasparrini F Giorgi F Pierini M Simone P Ursini O Villani C 《Journal of chromatography. A》2011,1218(25):3862-3875
New monolithic HPLC columns were prepared by γ-radiation-triggered polymerization of hexyl methacrylate and ethylene glycol dimethacrylate monomers in the presence of porogenic solvents. Polymerization was carried out directly within capillary (250-200 μm I.D.) and nano (100-75 μm I.D.) fused-silica tubes yielding highly efficient columns for cap(nano)-LC applications. The columns were applied in the complete separation of core (H2A, H2B, H3, and H4) and linker (H1) histones under gradient elution with UV and/or electrospray ionization (ESI) ion trap mass spectrometry (MS) detections. Large selectivity towards H1, H2A-1, H2A-2, H2B, H3-1, H3-2 and H4 histones and complete separation were obtained within 8 min time windows, using fast gradients and very high linear flow velocities, up to 11 mm/s for high throughput applications. The method developed was the basis of a simple and efficient protocol for the evaluation of post-translational modifications (PTMs) of histones from NCI-H460 human non-small-cell lung cancer (NSCLC) and HCT-116 human colorectal carcinoma cells. The study was extended to monitoring the level of histone acetylation after inhibition of Histone DeACetylase (HDAC) enzymes with suberoylanilide hydroxamic acid (SAHA), the first HDAC inhibitor approved by the FDA for cancer therapy. Attractive features of our cap(nano)-LC/MS approach are the short analysis time, the minute amount of sample required to complete the whole procedure and the stability of the polymethacrylate-based columns. A lab-made software package ClustMass was ad hoc developed and used to elaborate deconvoluted mass spectral data (aligning, averaging, clustering) and calculate the potency of HDAC inhibitors, expressed through a Relative half maximal Inhibitory Concentration parameter, namely R_IC(50) and an averaged acetylation degree. 相似文献