全文获取类型
收费全文 | 1031篇 |
免费 | 43篇 |
国内免费 | 6篇 |
专业分类
化学 | 818篇 |
晶体学 | 36篇 |
力学 | 24篇 |
数学 | 33篇 |
物理学 | 169篇 |
出版年
2023年 | 8篇 |
2022年 | 22篇 |
2021年 | 32篇 |
2020年 | 16篇 |
2019年 | 36篇 |
2018年 | 32篇 |
2017年 | 37篇 |
2016年 | 44篇 |
2015年 | 25篇 |
2014年 | 45篇 |
2013年 | 103篇 |
2012年 | 81篇 |
2011年 | 84篇 |
2010年 | 48篇 |
2009年 | 48篇 |
2008年 | 69篇 |
2007年 | 60篇 |
2006年 | 72篇 |
2005年 | 48篇 |
2004年 | 39篇 |
2003年 | 25篇 |
2002年 | 23篇 |
2001年 | 5篇 |
2000年 | 5篇 |
1999年 | 5篇 |
1998年 | 5篇 |
1997年 | 6篇 |
1996年 | 6篇 |
1995年 | 6篇 |
1994年 | 4篇 |
1993年 | 3篇 |
1991年 | 1篇 |
1990年 | 1篇 |
1989年 | 1篇 |
1987年 | 3篇 |
1986年 | 4篇 |
1985年 | 2篇 |
1984年 | 3篇 |
1983年 | 2篇 |
1982年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1978年 | 2篇 |
1976年 | 2篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1969年 | 1篇 |
1967年 | 2篇 |
1959年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有1080条查询结果,搜索用时 484 毫秒
191.
The kinetics of the oxidation of 2-methyl cyclohexanone and cycloheptanone with Fe(CN)6
3− catalyzed by RhCl3 in alkaline medium was investigated at four temperatures. The rate follows direct proportionality with respect to lower concentrations
of hexacyanoferrate(III) ion, but tends to become zero order at higher concentrations of the oxidant, while the reaction shows
first-order kinetics with respect to hydroxide ion and cyclic ketone concentrations. The rate shows a peculiar nature with
respect to RhCl3 concentrations in that it increases with increase in catalyst at low catalyst concentrations but after reaching a maximum,
further increase in concentration retards the rate. An increase in the ionic strength of the medium increases the rate, while
increase in the Fe(CN)6
4− concentration decreases the rate. 相似文献
192.
C. Praveen 《Tetrahedron letters》2009,50(6):644-647
An efficient synthesis of bis(indolyl)methanes and di(indolyl)indolin-2-ones has been developed by a sequential approach involving gold(I)-catalyzed cycloisomerization/bis-addition of o-ethynylanilines with various aldehydes and isatins, respectively. This methodology opens clean and synthetically competitive alternative to the already established procedures of the synthesis of bis(indolyl)methanes and di(indolyl)indolin-2-ones. 相似文献
193.
Manfred Martin Richard Dronskowski Jürgen Janek Klaus-Dieter Becker Daniel Roehrens Jochen Brendt Marck W. Lumey Lakshmi Nagarajan Ilia Valov Alexander Börger 《Progress in Solid State Chemistry》2009,37(2-3):132-152
Within the ternary system Ga–O–N we performed experimental and theoretical investigations on the thermodynamics, structure and kinetics of new stable and metastable compounds.We studied the ammonolysis of β-Ga2O3 at elevated temperatures by means of ex situ X-ray diffraction, ex situ neutron diffraction, and in situ X-ray absorption spectroscopy (XAS). From total diffraction pattern refinement with the Rietveld method we analyzed the anionic occupancy factors and the lattice parameters of β-Ga2O3 during the reaction. Within the detection limits of these methods, we can rule out the existence of a crystalline oxynitride phase that is not derived from wurtzite-type GaN. The nitrogen solubility in β-Ga2O3 was found to be below the detection limit of about 2–3 at.% in the anionic sublattice. The kinetics of the ammonolysis of β-Ga2O3 to α-GaN and of the oxidation of α-GaN to β-Ga2O3 was studied by means of in situ X-ray absorption spectroscopy. In both cases the reaction kinetics could be described well by fitting linear combinations of β-Ga2O3 and α-GaN spectra only, excluding that other crystalline or amorphous phases appear during these reactions. The kinetics of the ammonolysis can be described well by an extended Johnson–Mehl–Avrami–Kolmogorow model with nucleation and growth of GaN nuclei, while the oxidation kinetics can be modeled by a shrinking core model where Ga2O3 grows as a layer. Investigations by means of TEM and SEM support the assumptions in both models.To investigate the structure and energetics of spinel-type gallium oxynitrides (γ-galons) we performed first-principles calculations using density-functional theory. In addition to the ideal cubic γ-Ga3O3N we studied gallium deficient γ-galons within the Constant-Anion-Model.In highly non-stoichiometric, amorphous gallium oxide of approximate composition GaO1.2 we found at a temperature around 670 K an insulator–metal transition, with a conductivity jump of seven orders of magnitude. We demonstrate through experimental studies and density-functional theory calculations that the conductivity jump takes place at a critical gallium concentration and is induced by crystallization of stoichiometric β-Ga2O3 within the metastable oxide matrix. By doping with nitrogen the critical temperature and the conductivity in the highly conducting state can be tuned. 相似文献
194.
Rabindra N. Roy Lakshmi N. Roy Shahaf Ashkenazi Joshua T. Wollen Craig D. Dunseth Michael S. Fuge Jared L. Durden Chandra N. Roy Hannah M. Hughes Brett T. Morris Kevin L. Cline 《Journal of solution chemistry》2009,38(4):449-458
The values of the second dissociation constant, pK
2, of N-(2-hydroxyethyl) piperazine-N′-2-ethanesulfonic acid (HEPES) have been reported at twelve temperatures over the temperature range 5 to 55 °C, including
37 °C. This paper reports the results for the pa
H of eight isotonic saline buffer solutions with an I=0.16 mol⋅kg−1 including compositions: (a) HEPES (0.01 mol⋅kg−1) + NaHEPES (0.01 mol⋅kg−1) + NaCl (0.15 mol⋅kg−1); (b) HEPES (0.02 mol⋅kg−1) + NaHEPES (0.02 mol⋅kg−1) + NaCl (0.14 mol⋅kg−1); (c) HEPES (0.03 mol⋅kg−1) + NaHEPES (0.03 mol⋅kg−1) + NaCl (0.13 mol⋅kg−1); (d) HEPES (0.04 mol⋅kg−1) + NaHEPES (0.04 mol⋅kg−1) + NaCl (0.12 mol⋅kg−1); (e) HEPES (0.05 mol⋅kg−1) + NaHEPES (0.05 mol⋅kg−1) + NaCl (0.11 mol⋅kg−1); (f) HEPES (0.06 mol⋅kg−1) + NaHEPES (0.06 mol⋅kg−1) + NaCl (0.10 mol⋅kg−1); (g) HEPES (0.07 mol⋅kg−1) + NaHEPES (0.07 mol⋅kg−1) + NaCl (0.09 mol⋅kg−1); and (h) HEPES (0.08 mol⋅kg−1) + NaHEPES (0.08 mol⋅kg−1) + NaCl (0.08 mol⋅kg−1). Conventional pa
H values, for all eight buffer solutions from 5 to 55 °C, have been calculated. The operational pH values with liquid junction
corrections, at 25 and 37 °C have been determined based on the NBS/NIST standard between the physiological phosphate standard
and four buffer solutions. These are recommended as pH standards for physiological fluids in the range of pH = 7.3 to 7.5
at I=0.16 mol⋅kg−1. 相似文献
195.
David L. Mitchell Lakshmi Paniker Thierry Douki 《Photochemistry and photobiology》2009,85(6):1384-1390
Exposure to sunlight is responsible for most cutaneous malignant melanomas in the human population. It is very likely that DNA damage is an initial event in melanomagenesis, however, the role played by this damage is an open question. To this end, we used a hemipigmented F1 hybrid of the fish genus Xiphophorus and HPLC tandem mass spectrometry to examine the effects of melanin on the induction and repair of the predominant UV-induced photoproducts formed in skin cell DNA. We found that heavily pigmented skin cells had about half the damage of nonpigmented cells and the relative induction of the major photoproducts was independent of the degree of pigmentation. The efficiency of photoenzymatic repair was the same in nonpigmented and pigmented areas of the fish. We found no evidence of residual damage at 10 days after the last exposure. Most striking was that repeated exposure to multiple doses of UVB caused a very significant photoadaptive response. Rather than an accumulation of damage after five doses of UVB we saw a significant reduction in the amount of damage induced after the final dose compared with the initial dose. The relevance of these observations is discussed in the context of melanoma susceptibility and UVB thresholds. 相似文献
196.
Anne M. Shearrow Glenn A. Harris Li Fang Praveen K. Sekhar Ly T. Nguyen Erica B. Turner Shekhar Bhansali Abdul Malik 《Journal of chromatography. A》2009,1216(29):5449-5458
Ionic liquid (IL)-mediated sol–gel hybrid organic–inorganic materials present enormous potential for effective use in analytical microextraction. This opportunity, however, has not yet been explored. One obstacle to materializing this prospect arises from high viscosity of ILs significantly slowing down sol–gel reactions. In this work, we developed a method that overcomes this hurdle and provides IL-mediated advanced sol–gel materials for capillary microextraction (CME). We examined two different ILs: (a) a phosphonium-based IL, trihexyltetradecylphosphonium tetrafluoroborate, and (b) a pyridinium-based ionic liquid, N-butyl-4-methylpyridinium tetrafluoroborate. These ILs were evaluated in conjunction with two types of hydroxy-terminated polymers: (a) two Si–OH terminated polymers (PDMS and BMPO), and (b) two C–OH terminated polymers (PEG and polyTHF) that differ in their sol–gel reactivity. Scanning electron microscopy results demonstrate that ILs can serve as porogenic agents in sol–gel reactions. The IL-mediated sol–gel coatings prepared with silanol-terminated polymers provided up to 28 times higher extractions in off-line CME-GC compared to analogous sol–gel coatings prepared without any IL in the sol solution. Contrary to this, the IL-mediated sol–gel coatings prepared with C–OH terminated polymers provided lower extraction efficiencies compared to their IL-free counterparts. These observations were explained by (a) lower sol–gel reactivity of C–OH groups in PEG and polyTHF compared to Si–OH groups in PDMS and in hydrolyzed alkoxysilane precursors and (b) extremely high viscosity of ionic liquids. This study shows that IL-generated porous morphology alone is not enough to provide effective extraction media: careful choice of the organic polymer and the precursor with close sol–gel reactivity must be made to ensure effective chemical bonding of the organic polymer to the created sol–gel material to be able to provide the desired sorbent characteristics. Additionally, IL-mediated sol–gel PDMS coatings provided run-to-run RSD values of 4.2–5.0% and detection limits ranging from 3.2 ng/L to 17.4 ng/L. PDMS sol–gels prepared without ILs provided RSD values of 2.8–14.1%, and detection limits ranging from 4.9 ng/L to 487.0 ng/L. 相似文献
197.
Shubhra Mathur Rishi Vyas Rohit Jain Praveen Kumar K. Sachdev S.K. Sharma 《Journal of Non》2011,357(16-17):3084-3087
Potentiodynamic polarization studies were carried out on nanocrystalline I, nanocrystalline II and nanocrystalline III states having crystallite size 35 ± 5 nm, 18 ± 2 nm and 10 ± 2 nm of the alloy Ti60Ni40 in 1 M H2SO4 aqueous medium. It was observed that the nanocrystalline III state exhibits superior corrosion resistance as compared to the nanocrystalline II and nanocrystalline I states of the alloy Ti60Ni40. XPS studies were also performed after corrosion test and it was observed that nanocrystalline III state contains only Ti2+ and Ti4+ species whereas nanocrystalline I and nanocrystalline II state contains Ti2+, Ti3+and Ti4+ along with some unoxidized metallic Ti0 in the case of nanocrystalline I state. Thus the small crystallite size and the presence of only Ti2+ and Ti4+ species in the form of TiO and TiO2 leads to the formation of a protective oxide film which is adherent, stable and improves the corrosion resistance of the nanocrystalline III state of the alloy Ti60Ni40. 相似文献
198.
Lakshmi VV Murty MR Reddy TJ Ravikumar M Prabhakar S Vairamani M 《Rapid communications in mass spectrometry : RCM》2006,20(6):981-986
Off-site detection of the hydrolysed products of sulfur mustards in aqueous samples is an important task in the verification of Chemical Weapons Convention (CWC)-related chemicals. The hydrolysed products of sulfur mustards are studied under positive and negative electrospray ionisation (ESI) conditions using an additive with a view to detecting them at trace levels. In the presence of cations (Li(+), Na(+), K(+) and NH(4) (+)), the positive ion ESI mass spectra of all the compounds include the corresponding cationised species; however, only the [M+NH(4)](+) ions form [M+H](+) ions upon decomposition. The tandem mass (MS/MS) spectra of [M+H](+) ions from all the hydrolysed products of the sulfur mustard homologues were distinct and allowed these compounds to be characterised unambiguously. Similarly, the negative ion ESI mass spectra of all the compounds show prominent adducts with added anions (F(-), Cl(-), Br(-), and I(-)), but the [M-H](-) ion can only be generated by decomposition of an [M+F](-) ion. The MS/MS spectra of the [M-H](-) ions from all the compounds result in a common product ion at m/z 77. A precursor ion scan of m/z 77 is shown to be useful in the rapid screening of these compounds in aqueous samples at trace levels, even in the presence of complex masking agents, without the use of time-consuming sample preparation and chromatography steps. An MS/MS method developed to measure the detection limits of the hydrolysed products of sulfur mustards found these to be in the range of 10-500 ppb. 相似文献
199.
Methanol-swollen Nafion beads were used as microreactors to control the photochemical reaction pathways. Product selectivity in three unimolecular reactions, namely, the photo-Fries rearrangement of naphthyl esters, Norrish Type I reaction of 1-phenyl-3-p-tolyl-propan-2-one and Norrish Type I and Type II reactions of benzoin alkyl ethers were examined. The influence of cations over the photodimerization of acenaphthylene and cross-photodimerization between acenaphthylene and N-benzyl maleimide included within Nafion were also examined. The photochemical behaviors of the above substrates were significantly altered within Nafion compared with their solution photochemistry. Of particular interest, the product distributions were found to depend on the counter cations of Nafion. 相似文献
200.
Two new glycosides, named Firmacosides A and B, together with known fatty esters, batyl alcohol, Delta(5,20) sterol and sphingosine derivatives have been isolated from the soft coral Sinularia firma TIX-DUR. On the basis of spectroscopic analysis ((1)H-NMR, (13)C-NMR, (1)H-(1)H COSY, HMQC, HMBC and FAB-MS), Firmacoside A was established as hexadecanyl-1-O-alpha-D-arabinopyranosyloxy (1-->4)-alpha-D-arabinopyranosyloxy (1-->4)-alpha-D-arabinopyranoside (1), and firmacoside B was elucidated as docosanyl-1-O-alpha-D-arabinopyranosyloxy (1-->4)-3-O-acetyl-alpha-arabinopyranosyloxy (1-->4)-alpha-D-arabinopyranoside (2). 相似文献