全文获取类型
收费全文 | 413篇 |
免费 | 19篇 |
国内免费 | 4篇 |
专业分类
化学 | 303篇 |
晶体学 | 10篇 |
力学 | 13篇 |
数学 | 53篇 |
物理学 | 57篇 |
出版年
2023年 | 9篇 |
2022年 | 18篇 |
2021年 | 24篇 |
2020年 | 17篇 |
2019年 | 9篇 |
2018年 | 19篇 |
2017年 | 7篇 |
2016年 | 27篇 |
2015年 | 16篇 |
2014年 | 11篇 |
2013年 | 34篇 |
2012年 | 28篇 |
2011年 | 34篇 |
2010年 | 18篇 |
2009年 | 19篇 |
2008年 | 13篇 |
2007年 | 23篇 |
2006年 | 13篇 |
2005年 | 19篇 |
2004年 | 23篇 |
2003年 | 11篇 |
2002年 | 4篇 |
2001年 | 5篇 |
2000年 | 3篇 |
1999年 | 4篇 |
1997年 | 2篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1994年 | 3篇 |
1993年 | 1篇 |
1991年 | 2篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1984年 | 1篇 |
1978年 | 2篇 |
1976年 | 1篇 |
1974年 | 1篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1969年 | 2篇 |
1961年 | 1篇 |
1915年 | 1篇 |
1890年 | 2篇 |
排序方式: 共有436条查询结果,搜索用时 15 毫秒
1.
M.V. Nazarov J.H. Kang E.-J. Popovici B.S. Tsukerblat 《Solid State Communications》2005,133(3):183-186
Samples of yttrium oxide doped with trivalent europium have been prepared by ceramic techniques, under different synthesis conditions; barium chloride (BaCl2) and sodium tetraborate (Na2B4O7) were tested as flux. The improvement of luminescence properties in dependence on substitution of Eu3+ for Y3+ in the host lattice, under electron and UV excitations is demonstrated. The lattice parameter as a quantitative assessment of activator incorporation degree is proposed. The obtained results are discussed with respect to the employed processing method. 相似文献
2.
Dan Popovici 《Comptes Rendus Mathematique》2004,338(1):59-64
Let (X,ω) be a compact complex Hermitian manifold, and let T?γ be a d-closed (1,1) almost positive current on X. A variant of Demailly's regularization-of-currents theorem states that T is the weak limit of a sequence of (1,1)-currents Tm with analytic singularities of coefficient 1/m, lying in the same cohomology class as T, whose Lelong numbers converge to those of T, and with a loss of positivity decaying to zero. We prove that if the (1,1)-form γ is assumed to be closed and C∞, the regularizing currents Tm can be chosen such that for a constant C>0 independent of m. To cite this article: D. Popovici, C. R. Acad. Sci. Paris, Ser. I 338 (2004). 相似文献
3.
Summary Complexes of CoII, NiII, CuII, PdII, and PtIV with 2,4,5-trihydroxybenzoic acid and its substituted phenylazoderivatives have been prepared, together with some mixed-metal (Co, Cu or Ni, Cu) complexes of itsm-nitro,m-carboxy andm-hydroxyarylazo derivatives. The stereochemistries and the modes of bonding of the complexes were elucidated by spectral and magnetic susceptibility measurements.Abstracted from her Ph.D. thesis. 相似文献
4.
Ji QC Zhang J Rodila R Watson P El-Shourbagy T 《Rapid communications in mass spectrometry : RCM》2004,18(19):2293-2298
Quantitative determination of drug concentrations in tissue samples can provide critical information for drug metabolism, kinetics, and toxicity evaluations. For analysis of tissue samples using liquid chromatography/tandem mass spectrometric (LC/MS/MS) detection, homogenization is a critical step in achieving good assay performance. Assay performance can be closely evaluated by spiking the drug directly into tissue samples prior to homogenization. It is especially important to include this assay evaluation for the analysis of artery tissue samples because artery tissue is very elastic, making it quite a challenge to develop an effective procedure for homogenization. An LC/MS/MS assay in 96-well format using liquid-liquid extraction was developed for analyzing ABT-578 in rabbit artery samples. Tissue quality control samples were prepared by spiking ABT-578 stock solutions directly into the tissue before homogenization. The usage of the tissue control samples gives a thorough evaluation of the sample preparation process that includes both homogenization and sample extraction. A 20% blood in saline solution was used as a homogenization solution. Calibration standards were made by spiking ABT-578 into rabbit whole blood. Blood quality control samples were also prepared by spiking ABT-578 into rabbit whole blood. These blood QC samples were used to confirm the validity of the calibration curve. A lower limit of quantitation of 0.050 ng/mL was achieved. The linear dynamic range of blood standards was from 0.050-30.3 ng/mL with the correlation coefficient (r) ranging from 0.9969-0.9996. Overall %CV was between 1.3 and 7.0%, and analytical recovery was between 98.2 and 105.8% for blood QC samples. The %CVs for tissue QC samples were between 6.7 and 13.0%, and analytical recovery after correction was between 93.5 and 114.3%. 相似文献
5.
Winter B Weber R Hertel IV Faubel M Jungwirth P Brown EC Bradforth SE 《Journal of the American Chemical Society》2005,127(19):7203-7214
Photoelectron spectroscopy combined with the liquid microjet technique enables the direct probing of the electronic structure of aqueous solutions. We report measured and calculated lowest vertical electron binding energies of aqueous alkali cations and halide anions. In some cases, ejection from deeper electronic levels of the solute could be observed. Electron binding energies of a given aqueous ion are found to be independent of the counterion and the salt concentration. The experimental results are complemented by ab initio calculations, at the MP2 and CCSD(T) level, of the ionization energies of these prototype ions in the aqueous phase. The solvent effect was accounted for in the electronic structure calculations in two ways. An explicit inclusion of discrete water molecules using a set of snapshots from an equilibrium classical molecular dynamics simulations and a fractional charge representation of solvent molecules give good results for halide ions. The electron binding energies of alkali cations computed with this approach tend to be overestimated. On the other hand, the polarizable continuum model, which strictly provides adiabatic binding energies, performs well for the alkali cations but fails for the halides. Photon energies in the experiment were in the EUV region (typically 100 eV) for which the technique is probing the top layers of the liquid sample. Hence, the reported energies of aqueous ions are closely connected with both structures and chemical reactivity at the liquid interface, for example, in atmospheric aerosol particles, as well as fundamental bulk solvation properties. 相似文献
6.
A polarographic procedure is described for the determination of paracetamol (acetaminophen) and salicylamide after treatment with nitrous acid. The different experimental parameters affecting the derivatization process and the polarographic analysis were studied. The derivatization products were found to be reduced at the dropping mercury electrode over the whole pH range in Britton-Robinson buffers. At pH 7.0, well defined diffusion-controlled cathodic waves were produced for both compounds. Plots of limiting current vs. concentration were linear over the ranges 0.05–0.75 and 0.25–1.5mM for paracetamol and salicylamide, respectively, in the d.c. mode, with minimum detectability of 2.5 × 10–6 and 1.25 × 10–5
M, respectively. The procedure was applied to the analysis of some pharmaceutical dosage forms and the results were in good agreement with those obtained by official and compendial methods. 相似文献
7.
4-Amino-3-hydroxy-2-(2-chlorobenzene)-azo-1-naphthalene sulfonic acid (AHCANSA) was used as a chelating modifier to improve the reactivity of the silica gel surface in terms of selective binding and extraction of heavy metal ions. The surface coverage values were found to be 0.488 and 0.473mmolg–1 for the newly modified physically adsorbed silica gel phase (I) and chemically immobilized-AHCANSA phase (II), respectively. The modified silica gel phases (I, II) were tested for stability in different acidic buffer solutions (pH 1–6) and found to be highly resistant to hydrolysis and leaching by buffer solutions above pH 2. The application of these two phases as solid extractors for a series of mono-, di-, and tri-valent metal ions from aqueous solutions was also performed with different controlling factors such as the pH value of metal ion solutions and equilibrium shaking time. The mmolg–1 metal capacity values determined by silica gel phases (I, II) were found to confirm high affinity and selectivity characters for binding with heavy metal ions such as Cr3+, Ni2+, Cu2+, Zn2+, Cd2+ and Pb2+ in a range of 0.250–0.483. The tested alkali and alkaline earth metals, Na+, K+, Mg2+ and Ca2+, were found to exhibit little interaction and binding ability with the modified silica gel phases. The selectivity characters incorporated into the modified silica gel phases were further utilized and applied in solid phase extraction and pre-concentration of trace concentration levels (1.0µgmL–1 and 2.00–2.50ngmL–1) from real seawater samples. The percentage recovery values determined for Cr3+, Cu2+, Zn2+, Cd2+ and Pb2+ were found to be in the range of 95.2–98.1±2.0–5.0%, and the pre-concentration recovery values for the same tested heavy metal ions were found to be in the range of 92.5–97.1±3.0–6.0% for the two newly modified silica gel phases with a pre-concentration factor of 500.Received December 20, 2002; accepted May 14, 2003
published online September 1, 2003 相似文献
8.
Slaughter BD Unruh JR Price ES Huynh JL Bieber Urbauer RJ Johnson CK 《Journal of the American Chemical Society》2005,127(34):12107-12114
We used single-pair fluorescence resonance energy transfer (spFRET) measurements to characterize denatured and partially denatured states of the multidomain calcium signaling protein calmodulin (CaM) in both its apo and Ca(2+)-bound forms. The results demonstrate the existence of an unfolding intermediate. A CaM mutant (CaM-T34C-T110C) was doubly labeled with fluorescent probes AlexaFlour 488 and Texas Red at opposing globular domains. Single-molecule distributions of the distance between fluorophores were obtained by spFRET at varying levels of the denaturant urea. Multiple conformational states of CaM were observed, and the amplitude of each conformation was dependent on urea concentration, with the amplitude of an extended conformation increasing upon denaturation. The distributions at intermediate urea concentrations could not be adequately described as a combination of native and denatured conformations, showing that CaM does not denature via a two-state process and demonstrating that at least one intermediate is present. The intermediate conformations formed upon addition of urea were different for Ca(2+)-CaM and apoCaM. An increase in the amplitude of a compact conformation in CaM was observed for apoCaM but not for Ca(2+)-CAM upon the addition of urea. The changes in the single-molecule distributions of CaM upon denaturation can be described by either a range of intermediate structures or by the presence of a single unfolding intermediate that grows in amplitude upon denaturation. A model for stepwise unfolding of CaM is suggested in which the domains of CaM unfold sequentially. 相似文献
9.
Berrichi Amina Bailiche Zahra Bachir Redouane 《Research on Chemical Intermediates》2022,48(10):4119-4134
The AHA coupling of amines, haloalkane and alkynes under UV visible light was achieved with a higher yield in the presence of Au/Fe2O3. The catalyst was prepared by two methods using different gold content and then characterized by XRD, UV–vis, BET, TEM, ICP-OES and TPR spectroscopies. A comparative study of the ordinary and photocatalytic conditions, showed that the UV visible light could activate the gold nanoparticles and lead to the formation of CH2Cl? and Cl? radicals through CH2Cl2 fragmentation. The propargylamine was afforded at low temperature and a short time using 2% Au/Fe2O3. The catalyst was stable for five cycles with good photoactivity.
Graphical abstract10.