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121.
K. L. Ngai S. Capaccioli M. Shahin Thayyil N. Shinyashiki 《Journal of Thermal Analysis and Calorimetry》2010,99(1):123-138
In several current important problems in different areas of soft matter physics, controversy persists in interpreting the
molecular dynamics observed by various spectroscopies including dielectric relaxation, light scattering, nuclear magnetic
resonance, and neutron scattering. Outstanding examples include: (1) relaxation of water in aqueous mixtures, in molecular
sieves and silica-gel nanopores, and in hydration shell of proteins; and (2) dynamics of each component in binary miscible
polymer blends, in mixtures of an amorphous polymer with a small molecular glassformer, and in binary mixtures of two small
molecular glassformers. We show the applications of calorimetry to these problems have enhanced our understanding of the dynamics
and eliminated the controversies. 相似文献
122.
A microwave-assisted, one-pot, iridium-catalyzed aromatic C-H borylation/rhodium-catalyzed 1,4-conjugate addition sequence provides a highly robust protocol suitable for high-throughput array synthesis. Selective formation of either β-aryl-substituted ketones or the corresponding alcohols can be achieved in good overall yields by simple variation of the reaction conditions. 相似文献
123.
Mohammad-Reza Zamani-Meymian Lena Jentjens Niels L. Raeth Konrad Peithmann Karl Maier 《Applied Physics A: Materials Science & Processing》2010,98(4):909-912
Irradiation of congruently melting, nominally undoped lithium niobate crystals (LiNbO3) with high-energy, low-mass 3He ions, which are transmitted through the crystal, causes large and stable changes of the refractive index. In the irradiated
regions, the extraordinary index is increased whereas the ordinary index is diminished. The decay of these changes upon annealing
treatments up to 400°C is investigated, exhibiting a strongly non-monoexponential decay behaviour. Long-term measurements
of the refractive index changes yield no pattern erasure on a timescale of four years. 相似文献
124.
Lena G Lallemand E Gruner AC Boeglin J Roussel S Schaffner AP Aubry A Franetich JF Mazier D Landau I Briand JP Didierjean C Rénia L Guichard G 《Chemistry (Weinheim an der Bergstrasse, Germany)》2006,12(33):8498-8512
The development of the 1,3,5-triazepane-2,6-dione system as a novel, conformationally restricted, and readily accessible class of dipeptidomimetics is reported. The synthesis of the densely functionalized 1,3,5-triazepane-2,6-dione skeleton was achieved in only four steps from a variety of simple linear dipeptide precursors. To extend the practical value of 1,3,5-triazepane-2,6-diones, a general polymer-assisted solution-phase synthesis approach amenable to library production in a multiparallel format was developed. The conformational preferences of the 1,3,5-triazepane-2,6-dione skeleton were investigated in detail by NMR spectroscopy and X-ray diffraction. The ring exhibits a characteristic folded conformation which was compared to that of related dipeptide-derived scaffolds including the more planar 2,5-diketopiperazine (DKP). Molecular and structural diversity was increased further through post-cyclization appending operations at urea nitrogens. Preliminary biological screens of a small collection of 1,3,5-triazepane-2,6-diones revealed inhibitors of the underexplored malaria liver stage and suggest strong potential for this dipeptide-derived scaffold to interfere with and to modulate biological pathways. 相似文献
125.
Ngai KL 《The journal of physical chemistry. B》2006,110(51):26211-26214
From their experimental studies of the supercooled molecular ionic liquid 1-butyl-3-methylimidazolium hexafluorophosphate (BMIM-HFP), Ito and Richert [J. Phys. Chem. B 2006, in press.] found that the Stokes-Einstein and the Debye-Stokes-Einstein laws do not hold. Instead, enhanced translational diffusion or fractional Stokes-Einstein and fractional Debye-Stokes-Einstein relations are observed, just like in nonionic glass-forming liquids, including 1,3-bis(1-naphthyl)-5-(2-naphthyl)benzene, o-terphenyl, and sucrose benzoate. The comprehensive measurements made by Ito and Richert have determined the critical parameters that the coupling model needs to explain the observed fractional Stokes-Einstein and fractional Debye-Stokes-Einstein relations in the supercooled molecular ionic liquid. 相似文献
126.
Kaminski K Kaminska E Paluch M Ziolo J Ngai KL 《The journal of physical chemistry. B》2006,110(49):25045-25049
Broadband isothermal dielectric relaxation measurements of anhydrous fructose, glucose, galactose, sorbose, and ribose were made at ambient pressure in their liquidus and glassy states. We found a new secondary relaxation in fructose and glucose that is slower than those seen before by others. This new secondary relaxation also appears in the dielectric spectra of galactose, sorbose, and ribose, and hence it is a general feature of the relaxation dynamics of the monosaccharides. Dielectric measurements at elevated pressure of fructose and ribose show that the new secondary relaxation shifts to lower frequencies with applied pressures, mimicking the behavior of the alpha-relaxation. In contrast, the faster secondary relaxation remains stationary on applying pressure. These results together with other inferences indicate that the slower secondary relaxation bears relations to the alpha-relaxation, and hence, it is the true Johari-Goldstein secondary relaxation of the monosaccharides. 相似文献
127.
Terence C. W. Poon Irene L. Ang Man‐Ki Law Kiwi Y. W. Chan Eddy W. Y. Ng Sai‐Ming Ngai Joseph J. Y. Sung Henry L. Y. Chan 《Electrophoresis》2010,31(10):1721-1730
ProteinChip surface‐enhanced laser desorption/ionization technology and magnetic beads‐based ClinProt system are commonly used for semi‐quantitative profiling of plasma proteome in biomarker discovery. Unfortunately, the proteins/peptides detected by MS are non‐recoverable. To obtain the protein identity of a MS peak, additional time‐consuming and material‐consuming purification steps have to be done. In this study, we developed a magnetic beads‐based proteomic fingerprinting method that allowed semi‐quantitative proteomic profiling and micropreparative purification of the profiled proteins in parallel. The use of different chromatographic magnetic beads allowed us to obtain different proteomic profiles, which were comparable to those obtained by the ProteinChip surface‐enhanced laser desorption/ionization technology. Our assays were semi‐quantitative. The normalized peak intensity was proportional to concentration measured by immunoassay. Both intra‐assay and inter‐assay coefficients of variation of the normalized peak intensities were in the range of 4–30%. Our method only required 2 μL of serum or plasma for generating enough proteins for semi‐quantitative profiling by MALDI‐TOF‐MS as well as for gel electrophoresis and subsequent protein identification. The protein peaks and corresponding gel spots could be easily matched by comparing their intensities and masses. Because of its high efficiency and reproducibility, our method has great potentials in clinical research, especially in biomarker discovery. 相似文献
128.
Chun‐Ho Wong Lai‐Sheung Choi Sui‐Lung Yim Dr. Kwun‐Ngai Lau Prof. Dr. Hak‐Fun Chow Sin‐Kam Hui Prof. Dr. Kong‐Hung Sze 《化学:亚洲杂志》2010,5(10):2249-2257
Two series of aliphatic hydrocarbon‐based G1–G3 dendritic 2‐ureido‐4‐pyrimidinones (UPy) ( S‐Gn )2 and ( L‐Gn )2, differing from one another by the distance between the branching juncture to the urea end, were prepared and characterized. These hydrocarbon dendrons were also appended to a p‐aminonitrobenzene solvatochromic chromophore in order to probe their microenvironment polarity. While positive solvatochromism was observed which indicated the chromophore was solvent accessible, there was no significant difference between the microenvironment polarities on going from the G1 to the G3 dendrons. The self‐assembling behavior and tautomeric preference of the dendritic UPy derviatives were examined by 1H NMR spectroscopy. The dimerization constants (Kdim*) of the DDAA tautomers were unchanged at 107 M ?1 in CDCl3 at both 25 and 50 °C, which were comparable to those of UPy compounds bearing other nonpolar substitutents. Furthermore, the lower limits on the K′dim* of the DADA tautomeric forms of the ( S‐Gn )2 and ( L‐Gn )2 series were determined to be 106 and 105 M ?1 in CDCl3, respectively. It was found that a closer proximity of the dendron branching juncture to the UPy unit could lead to a destabilization effect on the dimeric states. Hence, the ( L‐Gn )2 dimers are more stable than those of ( S‐Gn )2 in the DDAA form, but the latter are more stable than the former in the tautomeric DADA state. This study showed that both the highly nonpolar microenvironment and the proximity of the dendritic branching juncture to the UPy motif could alter the strength and profile of the hydrogen bond‐mediated self‐assembling process. 相似文献
129.
Ding F Rosén A Campbell EE Falk LK Bolton K 《The journal of physical chemistry. B》2006,110(15):7666-7670
A new model is proposed for the encapsulation of catalyst metal particles by graphite layers that are obtained, for example, in low-temperature chemical vapor deposition production of carbon nanotubes (CNTs). In this model graphite layers are primarily formed from the dissolved carbon atoms in the metal-carbide particle when the particle cools. This mechanism is in good agreement with molecular dynamics simulations (which show that precipitated carbon atoms preferentially form graphite sheets instead of CNTs at low temperatures) and experimental results (e.g., encapsulated metal particles are found in low-temperature zones and CNTs in high-temperature regions of production apparatus, very small catalyst particles are generally not encapsulated, and the ratio of the number of graphitic layers to the diameter of the catalyst particle is typically 0.25 nm(-1)). 相似文献
130.
Calorimetry is the method first used by Jackson and McKenna to study the effect of finite-size on the molecular dynamics of glass-formers confined in nano-meter scale pores. It was found that the glass transition is shifted to lower temperature as pore size decreases. Since then, other spectroscopic techniques have corroborated this finding and given more information on the molecular dynamics. These results are used to compare with the predictions of several theories of glass transition, and in particular the coupling model of the author.This revised version was published online in November 2005 with corrections to the Cover Date. 相似文献