全文获取类型
收费全文 | 1747篇 |
免费 | 98篇 |
国内免费 | 12篇 |
专业分类
化学 | 1210篇 |
晶体学 | 3篇 |
力学 | 56篇 |
数学 | 229篇 |
物理学 | 359篇 |
出版年
2024年 | 3篇 |
2023年 | 20篇 |
2022年 | 46篇 |
2021年 | 57篇 |
2020年 | 66篇 |
2019年 | 61篇 |
2018年 | 40篇 |
2017年 | 34篇 |
2016年 | 87篇 |
2015年 | 68篇 |
2014年 | 74篇 |
2013年 | 104篇 |
2012年 | 119篇 |
2011年 | 144篇 |
2010年 | 68篇 |
2009年 | 92篇 |
2008年 | 121篇 |
2007年 | 113篇 |
2006年 | 105篇 |
2005年 | 95篇 |
2004年 | 64篇 |
2003年 | 43篇 |
2002年 | 54篇 |
2001年 | 15篇 |
2000年 | 26篇 |
1999年 | 14篇 |
1998年 | 8篇 |
1997年 | 11篇 |
1996年 | 15篇 |
1995年 | 9篇 |
1994年 | 8篇 |
1993年 | 8篇 |
1992年 | 2篇 |
1991年 | 3篇 |
1990年 | 6篇 |
1989年 | 6篇 |
1988年 | 4篇 |
1987年 | 8篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1981年 | 4篇 |
1979年 | 2篇 |
1976年 | 3篇 |
1974年 | 1篇 |
1973年 | 3篇 |
1972年 | 1篇 |
1971年 | 2篇 |
1969年 | 1篇 |
1944年 | 1篇 |
1925年 | 1篇 |
排序方式: 共有1857条查询结果,搜索用时 62 毫秒
51.
Hernández-Borges J Rodríguez-Delgado MA García-Montelongo FJ Cifuentes A 《Electrophoresis》2005,26(20):3799-3813
Chiral separation of enantiomers is one of the most challenging tasks for any analytical technique including CE. Since the first report in 1985 showing the great possibilities of CE for the separation of chiral compounds, the amount of publications concerning this topic has quickly increased. Although chiral electromigration methods have mainly been used for enantioseparation of drugs and pharmaceuticals, they have also been applied to analyze chiral pollutants. This article intends to provide an updated overview, including works published till January 2005, on the principal applications of CE to the chiral analysis of pollutants and their metabolites, with special emphasis on articles published in the last 10 years. The main advantages and drawbacks regarding the use of CE for chiral separation of pollutants are addressed including some discussion on the foreseen trends of electromigration procedures applied to chiral analysis of contaminants. 相似文献
52.
Principal oscillation pattern (POP) analysis was recently introduced into climatology to analyze multivariate time series xi(t) produced by systems whose dynamics are described by a linear Markov process x=Bx + . The matrixB gives the deterministic feedback and is a white noise vector with covariances (t)
j
(t*Q
ij
(t–t. The POP method is applied to data from a direct simulation Monte Carlo program. The system is a dilute gas with 50,000 particles in a Rayleigh-Bénard configuration. The POP analysis correctly reproduces the linearized Navier-Stokes equations (in the matrixB) and the stochastic fluxes (in the matrixQ) as given by Landau-Lifschitz fluctuating hydrodynamics. Using this method, we find the Landau-Lifschitz theory to be valid both in equilibrium and near the critical point of Rayleigh-Bénard convection. 相似文献
53.
Alejandro Colina Betzabé Sulbarán-de-Ferrer Cateryna Aiello Alexis Ferrer 《Applied biochemistry and biotechnology》2003,108(1-3):715-724
Xylanase production of Trichoderma reesei Rut C-30 was examined at different initial pH values (4.8, 5.9, and 7.0) on rice straw in shake flasks, and in a fermentor,
for the best pH condition. Enzyme performance was tested on ammonia-treated dwarf elephant grass. The maximum xylanase activities,
92 and 122 IU/mL, were obtained at pH 4.8 in the shake flasks and fermentor, respectively, in which good growth of the fungus
was observed during the first 24 h and consumption of proteins dissolved from the rice straw caused the pH to rise later to
values between 6.4 and 6.7 (optimal for xylanase production). The xylanases from T. reesei were as effective as Multifect XL, a commercial enzyme preparation, in hydrolyzing ammonia-treated elephant grass. 相似文献
54.
Vicente M Bastida R Lodeiro C Macías A Parola AJ Valencia L Spey SE 《Inorganic chemistry》2003,42(21):6768-6779
The synthesis of a new oxaaza macrocyclic ligand, L, derived from O(1),O(7)-bis(2-formylphenyl)-1,4,7-trioxaheptane and tren containing an amine terminal pendant arm, and its metal complexation with alkaline earth (M = Ca(2+), Sr(2+), Ba(2+)), transition (M = Co(2+), Ni(2+), Cu(2+), Zn(2+), Cd(2+)), post-transition (M = Pb(2+)), and Y(3+) and lanthanide (M = La(3+), Er(3+)) metal ions are reported. Crystal structures of [H(2)L](ClO(4))(2).3H(2)O, [PbL](ClO(4))(2), and [ZnLCl](ClO(4)).H(2)O are also reported. In the [PbL] complex, the metal ion is located inside the macrocyclic cavity coordinated by all N(4)O(3) donor atoms while, in the [ZnLCl] complex, the metal ion is encapsulated only by the nitrogen atoms present in the ligand. pi-pi interactions in the [H(2)L](ClO(4))(2).3H(2)O and [PbL](ClO(4))(2) structures are observed. Protonation and Zn(2+), Cd(2+), and Cu(2+) complexation were studied by means of potentiometric, UV-vis, and fluorescent emission measurements. The 10-fold fluorescence emission increase observed in the pH range 7-9 in the presence of Zn(2+) leads to L as a good sensor for this biological metal in water solution. 相似文献
55.
In this work, different extracts from the microalga Spirulina platensis are obtained using pressurized liquid extraction (PLE) and four different solvents (hexane, light petroleum, ethanol and water). Different extraction temperatures (115 and 170 degrees C) were tested using extraction times ranging from 9 to 15 min. The antioxidant activity of the different extracts is determined by means of an in vitro assay using a free radical method. Moreover, a new and fast method is developed using micellar electrokinetic chromatography with diode array detection (MEKC-DAD) to provide a preliminary analysis on the composition of the extracts. This combined application (i.e., in vitro assays plus MEKC-DAD) allowed the fast characterization of the extracts based on their antioxidant activity and the UV-vis spectra of the different compounds found in the extracts. To our knowledge, this work shows for the first time the great possibilities of the combined use of PLE-in vitro assay-MEKC-DAD to investigate natural sources of antioxidants. 相似文献
56.
David Molnar Christian Niedermeier Alejandro Mora Peter Binkele Siegfried Schmauder 《Continuum Mechanics and Thermodynamics》2012,24(4-6):607-617
Kinetic Monte-Carlo (KMC) methods are used as an approach to simulate precipitation in Cu-alloyed bcc Fe. In order to characterize the process, transformed fractions, that is, the precipitated atoms, are related to Johnson-Mehl-Avrami-Kolmogorov theory. However, simulated data often deviate from corresponding fit curves and so does the resulting growth exponent when compared to theoretical expectations. Furthermore, some data may suggest the development of a metastable phase. In our study, we show that the characteristics of the transformed fraction and, as a consequence, the derived growth exponents sensitively depend on the number of atoms that are considered to form a particle and hence contribute to the transformed fraction. With a temperature dependence of the critical cluster size and additionally accounting for severe impingement of the particles, we obtain growth exponents which lie close to the expected range between n = 1.5 and n = 2.5 for pre-existing nuclei or continuous nucleation, respectively. From these, we obtain activation energies for nucleation and growth of precipitates. In this way, atomistic KMC simulations yield thermodynamical quantities, which can be valuable input parameters for larger length scale simulation methods, for example, for Phase Field Method simulations. 相似文献
57.
58.
Alejandro Ortega Moñux Steve Greedy Ginés Lifante 《Optical and Quantum Electronics》2013,45(4):307-307
59.
Dr. Xavier Just-Baringo Alejandro Yeste-Vázquez Javier Moreno-Morales Dr. Clara Ballesté-Delpierre Prof. Jordi Vila Prof. Ernest Giralt 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(51):12987-12991
The introduction of a novel tetra-ortho-chloroazobenzene amino acid (CEBA) has enabled photoswitching of the antimicrobial activity of tyrocidine A analogues by using exclusively visible light, granting spatiotemporal control under benign conditions. Compounds bearing this photoswitchable amino acid become active upon irradiation with red light, but quickly turn-off upon exposure to other visible light wavelengths. Critically, sunlight quickly triggers isomerisation of the red light-activated compounds into their original trans form, offering an ideal platform for self-deactivation upon release into the environment. Linear analogues of tyrocidine A were found to provide the best photocontrol of their antimicrobial activity, leading to compounds active against Acinetobacter baumannii upon isomerisation. Exploration of their N- and C-termini has provided insights into key elements of their structure and has allowed obtaining new antimicrobials displaying excellent strain selectivity and photocontrol. 相似文献
60.
Montecrinanes A–C: Triterpenes with an Unprecedented Rearranged Tetracyclic Skeleton from Celastrus vulcanicola. Insights into Triterpenoid Biosynthesis Based on DFT Calculations
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Martín Purino Dr. Alejandro E. Ardiles Dr. Oliver Callies Dr. Ignacio A. Jiménez Prof. Isabel L. Bazzocchi 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(22):7582-7591
Three new triterpenoids with an unprecedented 6/6/6/6‐fused tetracyclic carbon skeleton, montecrinanes A–C ( 1 – 3 ), were isolated from the root bark of Celastrus vulcanicola, along with known D:B‐friedobaccharanes ( 4 – 6 ), and lupane‐type triterpenes ( 7 – 12 ). The stereostructures of the new metabolites were elucidated based on spectroscopic (1D and 2D NMR) and spectrometric (HR‐EIMS and HR‐ESIMS) techniques. Their absolute configurations were determined by both NMR spectroscopy, with (R)‐(?)‐α‐methoxyphenylacetic acid as a chiral derivatizing agent, and biogenetic considerations. Biogenetic pathways for montecrinane and D:B‐friedobaccharane skeletons were proposed and studied by DFT methods. The theoretical results support the energetic feasibility of the putative biogenetic pathways, in which the 1,2‐methyl shift from the secondary baccharenyl cation represents a novel and key reaction step for a new montecrinane skeleton. 相似文献