全文获取类型
收费全文 | 1918篇 |
免费 | 85篇 |
国内免费 | 16篇 |
专业分类
化学 | 1359篇 |
晶体学 | 16篇 |
力学 | 42篇 |
数学 | 344篇 |
物理学 | 258篇 |
出版年
2023年 | 16篇 |
2022年 | 7篇 |
2021年 | 17篇 |
2020年 | 33篇 |
2019年 | 32篇 |
2018年 | 31篇 |
2017年 | 30篇 |
2016年 | 61篇 |
2015年 | 56篇 |
2014年 | 52篇 |
2013年 | 117篇 |
2012年 | 130篇 |
2011年 | 125篇 |
2010年 | 66篇 |
2009年 | 76篇 |
2008年 | 127篇 |
2007年 | 146篇 |
2006年 | 141篇 |
2005年 | 102篇 |
2004年 | 94篇 |
2003年 | 67篇 |
2002年 | 80篇 |
2001年 | 45篇 |
2000年 | 48篇 |
1999年 | 27篇 |
1998年 | 22篇 |
1997年 | 24篇 |
1996年 | 32篇 |
1995年 | 19篇 |
1994年 | 25篇 |
1993年 | 17篇 |
1992年 | 16篇 |
1991年 | 15篇 |
1990年 | 13篇 |
1989年 | 9篇 |
1988年 | 10篇 |
1987年 | 7篇 |
1986年 | 3篇 |
1985年 | 17篇 |
1984年 | 9篇 |
1982年 | 4篇 |
1980年 | 5篇 |
1979年 | 4篇 |
1978年 | 4篇 |
1977年 | 4篇 |
1976年 | 5篇 |
1974年 | 5篇 |
1973年 | 4篇 |
1971年 | 5篇 |
1962年 | 3篇 |
排序方式: 共有2019条查询结果,搜索用时 328 毫秒
51.
Physical and electrochemical characterizations of microwave-assisted polyol preparation of carbon-supported PtRu nanoparticles 总被引:9,自引:0,他引:9
Liu Z Lee JY Chen W Han M Gan LM 《Langmuir : the ACS journal of surfaces and colloids》2004,20(1):181-187
PtRu nanoparticles supported on Vulcan XC-72 carbon and carbon nanotubes were prepared by a microwave-assisted polyol process. The catalysts were characterized by transmission electron microscopy, X-ray diffraction, and X-ray photoelectron spectroscopy (XPS). The PtRu nanoparticles, which were uniformly dispersed on carbon, were 2-6 nm in diameter. All PtRu/C catalysts prepared as such displayed the characteristic diffraction peaks of a Pt face-centered cubic structure, excepting that the 2theta values were shifted to slightly higher values. XPS analysis revealed that the catalysts contained mostly Pt(0) and Ru(0), with traces of Pt(II), Pt(IV), and Ru(IV). The electro-oxidation of methanol was studied by cyclic voltammetry, linear sweep voltammetry, and chronoamperometry. It was found that both PtRu/C catalysts had high and more durable electrocatalytic activities for methanol oxidation than a comparative Pt/C catalyst. Preliminary data from a direct methanol fuel cell single stack test cell using the Vulcan-carbon-supported PtRu alloy as the anode catalyst showed high power density. 相似文献
52.
3-(5'-tetrazolylazo)-2,6-Diaminotoluene (TEADAT, H(3)L(2+)) forms stable 1:1 and 1:2 (metal:ligand) pink-red complexes (lambda(max) 506 and 536 nm) with palladium(II). The apparent molar absorptivity of 1:2 complex is 5.2 x 10(4) 1.mol(-1). cm(-1) at 536 nm. Equilibrium constants beta*(nl) for reactions PdCl(2-)(4) + nH(3)L(2+) right harpoon over left harpoonright harpoon over left harpoon PdCl(4-n) (H(2)L)(2n-2)(n) + n Cl(-) + n H(+) were determined: logbeta*(1) = 4.09 +/- 0.05, logbeta*(2) = 8.40 +/- 0.02, corresponding stability conditional constants of PdCl(3)(H(2)L) and PdCl(2)(H(2)L)(2+)(2) were log beta(1) = 19.03, log beta(2) = 26.74. The formation of complexes was rather slow but could be speeded up considerably by the catalytic effect of trace amounts of thiocyanate. Constant absorbance values were thus reached in 2-5 min. A rapid, sensitive and highly specific method for the determination of palladium(II) at pH 1.42 in 0.25M NACl has been worked out with a detection limit of 0.54 mug. Interference of precious and common metal ions have been studied and the method has been applied for the determination of palladium in Pd asbestos, oakay alloys and various catalysts and for the determination of palladium in precious metals. 相似文献
53.
Spectrofluorimetric methods to determine cisatracurium and mivacurium are proposed and applied to the determination of both substances in human serum and to the determination of mivacurium in pharmaceuticals. The fluorimetric methods allow the determination of 5-500 ng ml(-1) of mivacurium in aqueous solutions and 5-500 ng ml(-1) of cisatracurium in water-acetonitrile solutions, both containing acetic acid-sodium acetate buffer (pH 5.5) with lambda(exc)=230 nm and lambda(em)=324 nm. 相似文献
54.
Limited flexibility of lactose detected from residual dipolar couplings using molecular dynamics simulations and steric alignment methods 总被引:1,自引:0,他引:1
Martín-Pastor M Canales A Corzana F Asensio JL Jiménez-Barbero J 《Journal of the American Chemical Society》2005,127(10):3589-3595
The conformational flexibility of lactose in solution has been investigated by residual dipolar couplings (RDCs). One-bond carbon-proton and proton-proton coupling constants have been measured in two oriented media and interpreted in combination with molecular dynamics simulations (MD). Two different approaches, known as PALES (Zweckstetter et al., J. Am. Chem. Soc. 2000, 122, 3791-3792) and TRAMITE (Azurmendi et al., J. Am. Chem. Soc. 2002, 124, 2426-2427), have been used to determine the alignment tensor from a shape-induced alignment model with the oriented medium. The steric alignment of the structures from several MD trajectories has provided ensemble averaged RDCs that have been compared with the experimental ones. The obtained results reveal the almost exclusive presence of a major low energy region defined as syn-phi/syn-psi (> 97%), for which sampling occurs in a dynamic manner. This result satisfactorily agrees with that determined by standard NOE-based methods. 相似文献
55.
The thermodynamic functions Gibbs energy, enthalpy and entropy of solution, mixing and solvation of acetaminophen in propylene
glycol (PG) + ethanol (EtOH) cosolvent mixtures were evaluated from solubility data measured at several temperatures, using
the van't Hoff and Gibbs equations. The solubility was greater at 50% m/m of PG at 20.0^C, while it was greater at 80% of
PG at 40.0 ^C where m/m refers to mass percent. The solvation of this drug is appreciably greater in the mixtures than in
the pure solvents. By means of an enthalpy–entropy compensation analysis, complex behavior was found for the solution. From
0 up to 20% of PG and from 60 up to 100% of PG the solution process is enthalpy driven, whereas from 20 up to 60% of PG it
is entropy driven. These facts can be explained in terms of a decrease in the energy required for cavity formation in the
solvent for mixtures containing 20–60% of PG. 相似文献
56.
Mineral content and botanical origin of Spanish honeys 总被引:2,自引:0,他引:2
Fernández-Torres R Pérez-Bernal JL Bello-López MA Callejón-Mochón M Jiménez-Sánchez JC Guiraúm-Pérez A 《Talanta》2005,65(3):686-691
Eleven elements (Zn, P, B, Mn, Mg, Cu, Ca, Ba, Sr, Na and K) were determined by inductively plasma coupled spectrometry in 40 honey samples from different places of Spain and four different botanical origins: Eucalyptus (Eucalyptus sp.), Heather (Erica sp.), Orange-blossom (Citrus sinensis) and Rosemary (Rosmarinus officinalis). K, Ca and P show the higher levels with average concentrations ranged between 434.1-1935 mg kg−1 for K; 42.59-341.0 mg kg−1 for Ca and 51.17-154.3 mg kg−1 for P. Levels of Cu (0.531-2.117 mg kg−1), Ba (0.106-1.264 mg kg−1) and Sr (0.257-1.462 mg kg−1) are the lowest in all honey samples. Zn (1.332-7.825 mg kg−1), Mn (0.133-9.471 mg kg−1), Mg (13.26-74.38 mg kg−1) and Na (11.69-218.5 mg kg−1) concentrations were found strongly dependent on the kind of botanical origin.Results were submitted to pattern recognition procedures, unsupervised methods such as cluster and principal components analysis and supervised learning methods like linear discriminant analysis in order to evaluate the existence of data patterns and the possibility of differentiation of Spanish honeys from different botanical origins according to their mineral content. Cluster analysis shows four clusters corresponding to the four botanical origins of honey and PCA explained 71% of the variance with the first two PC variables. The best-grouped honeys were those from heather; eucalyptus honeys formed a more dispersed group and finally orange-blossom and rosemary honeys formed a less distinguishable group. 相似文献
57.
Graeme B Bolger Angela McCahill Stephen J Yarwood Michael R Steele Jim Warwicker Miles D Houslay 《BMC biochemistry》2002,3(1):24-11
Background
The cyclic AMP specific phosphodiesterase, PDE4D5 interacts with the β-propeller protein RACK1 to form a signaling scaffold complex in cells. Two-hybrid analysis of truncation and mutant constructs of the unique N-terminal region of the cAMP-specific phosphodiesterase, PDE4D5 were used to define a domain conferring interaction with the signaling scaffold protein, RACK1. 相似文献58.
Jiménez-Hernández ME Orellana G Montero F Portolés MT 《Photochemistry and photobiology》2000,72(1):28-34
The capability of the new luminescent probe (dibenzo[h,j] dipyrido[3,2-a:2',3'-c]phenazine)bis(2,2'-bipyridine)ruthenium(II) dication, (RB2Z), to discriminate live and dead cells has been tested on rat hepatocytes and mouse lymphocytes. RB2Z-stained cells were analyzed using flow cytometry, fluorescence (confocal) microscopy and time-resolved luminescence measurements. The established viability probes propidium iodide (PI) and SYTOX green (SG) were used as controls. The intense luminescence of RB2Z at 606 nm is localized in the nucleus of nonviable cells. Viability measurements by flow cytometry and fluorescence microscopy using RB2Z as dead-cell marker yield the same results as PI and SG. The luminescence lifetime of RB2Z also displays sensitivity to cell viability (0.45 and 0.82 microsecond in presence of fully viable and dead cells, respectively). This ruthenium complex is photostable under laser sources and its 200 nm Stokes shift facilitates multicolor labeling experiments in flow cytometry and fluorescence microscopy. Unlike the currently available probes, the long-lived excited state of RB2Z also allows assays based on luminescence decay measurements. 相似文献
59.
1,3-Cyclopentanedione bis(4-methylthiosemicarbazone) monohydrochloride produces colored solutions with chlorate ions in strongly acid medium. The yellow color obtained has been used to propose a spectrophotometric method of C103? determination in the concentration range 0.5–6.0 ppm (molar absorptivity 1.26 × 104 liters mol?1 cm?1 at a wavelength of 397 nm). 相似文献
60.
Martin JN Muñoz EM Schwergold C Souard F Asensio JL Jiménez-Barbero J Cañada J Vicent C 《Journal of the American Chemical Society》2005,127(26):9518-9533
Sugar-oligoamides have been designed and synthesized as structurally simple carbohydrate-based ligands to study carbohydrate-DNA interactions. The general design of the ligands 1-3 has been done as to favor the bound conformation of Distamycin-type gamma-linked covalent dimers which is a hairpin conformation. Indeed, NMR analysis of the sugar-oligoamides in the free state has indicated the presence of a percentage of a hairpin conformation in aqueous solution. The DNA binding activity of compounds 1-3 was confirmed by calf thymus DNA (ct-DNA) NMR titration. Interestingly, the binding of the different sugar-oligoamides seems to be modulated by the sugar configuration. Semiquantitative structural information about the DNA ligand complexes has been derived from NMR data. A competition experiment with Netropsin suggested that the sugar-oligoamide 3 bind to DNA in the minor groove. The NMR titrations of 1-3 with poly(dA-dT) and poly(dG-dC) suggested preferential binding to the ATAT sequence. TR-NOE NMR experiments for the sugar-oligoamide 3-ct-DNA complex both in D(2)O and H(2)O have confirmed the complex formation and given information on the conformation of the ligand in the bound state. The data confirmed that the sugar-oligoamide ligand is a hairpin in the bound state. Even more relevant to our goal, structural information on the conformation around the N-glycosidic linkage has been accessed. Thus, the sugar asymmetric centers pointing to the NH-amide and N-methyl rims of the molecule have been characterized. 相似文献