全文获取类型
收费全文 | 4918篇 |
免费 | 124篇 |
国内免费 | 36篇 |
专业分类
化学 | 3226篇 |
晶体学 | 36篇 |
力学 | 244篇 |
数学 | 867篇 |
物理学 | 705篇 |
出版年
2022年 | 40篇 |
2021年 | 49篇 |
2020年 | 56篇 |
2019年 | 38篇 |
2018年 | 59篇 |
2017年 | 43篇 |
2016年 | 101篇 |
2015年 | 90篇 |
2014年 | 100篇 |
2013年 | 269篇 |
2012年 | 209篇 |
2011年 | 275篇 |
2010年 | 159篇 |
2009年 | 144篇 |
2008年 | 234篇 |
2007年 | 219篇 |
2006年 | 219篇 |
2005年 | 233篇 |
2004年 | 233篇 |
2003年 | 223篇 |
2002年 | 207篇 |
2001年 | 92篇 |
2000年 | 97篇 |
1999年 | 55篇 |
1998年 | 47篇 |
1997年 | 52篇 |
1996年 | 73篇 |
1995年 | 60篇 |
1994年 | 62篇 |
1993年 | 60篇 |
1992年 | 51篇 |
1991年 | 48篇 |
1990年 | 46篇 |
1989年 | 48篇 |
1988年 | 44篇 |
1987年 | 41篇 |
1986年 | 43篇 |
1985年 | 66篇 |
1984年 | 80篇 |
1983年 | 58篇 |
1982年 | 69篇 |
1981年 | 62篇 |
1980年 | 75篇 |
1979年 | 70篇 |
1978年 | 59篇 |
1977年 | 54篇 |
1976年 | 49篇 |
1975年 | 49篇 |
1974年 | 58篇 |
1973年 | 39篇 |
排序方式: 共有5078条查询结果,搜索用时 15 毫秒
951.
An interlaboratory study was performed on behalf of the UK Food Standards Agency to evaluate the effectiveness of an immunoaffinity column cleanup liquid chromatographic (LC) method for the determination of deoxynivalenol in a variety of cereals and cereal products at proposed European regulatory limits. The test portion was extracted with water. The sample extract was filtered a applied to an immunoaffinity column. After being washed with water, the deoxynivalenol was eluted with acetonitrile or methanol. Deoxynivalenol was quantitated by reversed-phase LC with UV determination. Samples of artificially contaminated wheat-flour, rice flour, oat flour, polenta, and wheat based breakfast cereal, naturally contaminated wheat flour, and blank (very low level) samples of each matrix were sent to 13 collaborators in 7 European countries. Participants were asked to spike test portions of all samples at a range of deoxynivalenol concentrations equivalent to 200-2000 ng/g deoxynivalenol. Average recoveries ranged from 78 to 87%. Based on results for 6 artificially contaminated samples (blind duplicates), the relative standard deviation for repeatability (RSDr) ranged from 3.1 to 14.1%, and the relative standard deviation for reproducibility (RSDR) ranged from 11.5 to 26.3%. The method showed acceptable within-laboratory and between-laboratory precision for all 5 matrixes, as evidenced by HorRat values < 1.3. 相似文献
952.
Majedi FS Hasani-Sadrabadi MM Emami SH Taghipoor M Dashtimoghadam E Bertsch A Moaddel H Renaud P 《Chemical communications (Cambridge, England)》2012,48(62):7744-7746
A microfluidic platform is developed for the synthesis of monodisperse, 100 nm, chitosan based nanoparticles using nanogelation with ATP. The resulting nanoparticles tuned and enhanced transport and electrochemical properties of Nafion based nanocomposite membranes, which is highly favorable for fuel cell applications. 相似文献
953.
Russell J. Waugh John H. Bowie Roger N. Hayes 《Journal of mass spectrometry : JMS》1991,26(4):250-256
Deprotonated dipeptides, on collisional activation, fragment by the characteristic process NH2CH(R1) CONHCH(R2)CO2? → NH2?C(R1)CONHCH(R2)CO2H → ?NHCH(R2)CO2H + NH2C(R1)?C?O, when R1 and R2 = H or alkyl. However, when one of the constituent amino acids is either aspartic acid or glutamic acid, the standard cleavage becomes minor in comparison with fragmentation through the α-side-chain of Asp or Glu. For example, [Asp-Leu - H]? and [Leu-Asp - H]? both fragment principally by loss of water, a fragmentation not normally noted for peptides. In addition, [Leu-Asp - H]? loses CO2 and also forms HO2CCH?CHCO2?˙. These fragmentations establish that Asp is the C-terminal amino acid. In contrast, isomeric Glu dipeptides, e.g. [Glu-Ala - H]? and [Ala-Glu - H]? undergo similar fragmentation, both competitively losing H2O and CO2. Both spectra also contain a product ion at m/z 128, identified as the pyroglutamate anion. Product ion and deuterium-labelling studies have been used in an attempt to elucidate the complex fragmentation mechanisms in these systems. 相似文献
954.
A Frisch-Newton Algorithm for Sparse Quantile Regression 总被引:3,自引:0,他引:3
RogerKoenker PinNg 《应用数学学报(英文版)》2005,21(2):225-236
Recent experience has shown that interior-point methods using a log barrier approach are far superior to classical simplex methods for computing solutions to large parametric quantile regression problems. In many large empirical applications, the design matrix has a very sparse structure. A typical example is the classical fixed-effect model for panel data where the parametric dimension of the model can be quite large, but the number of non-zero elements is quite small. Adopting recent developments in sparse linear algebra we introduce a modified version of the Prisch-Newton algorithm for quantile regression described in Portnoy and Koenker~([28]). The new algorithm substantially reduces the storage (memory) requirements and increases computational speed. The modified algorithm also facilitates the development of nonparametric quantile regression methods. The pseudo design matrices employed in nonparametric quantile regression smoothing are inherently sparse in both the fidelity and roughness penalty components. Exploiting the sparse structure of these problems opens up a whole range of new possibilities for multivariate smoothing on large data sets via ANOVA-type decomposition and partial linear models. 相似文献
955.
Roger C. Alperin 《Proceedings of the American Mathematical Society》1996,124(10):2935-2941
We classify the normal subgroups of of index less than 960; they are all congruence subgroups.
956.
Vasilyev S Schiller S Nevsky A Grisard A Faye D Lallier E Zhang Z Boyland AJ Sahu JK Ibsen M Clarkson WA 《Optics letters》2008,33(13):1413-1415
A narrow-linewidth mid-IR source based on difference-frequency generation of an amplified 1.5 microm diode laser and a cw Tm-doped fiber laser in orientation-patterned (OP) GaAs has been developed and evaluated for spectroscopic applications. The source can be tuned to any frequency in the 7.6-8.2 microm range with an output power of 0.5 mW. The measured characteristics of the OP-GaAs sample demonstrate a high quality of the material. 相似文献
957.
Bruna Tischer Raquel G. Vendruscolo Roger Wagner Cristiano R. Menezes Cláudia S. Barin Sandro R. Giacomelli Jane M. Budel Juliano S. Barin 《Chemical Papers》2017,71(4):753-761
Grinding methods were evaluated aiming to determine yield and composition of essential oils (EOs) from Baccharis articulata (Lam) Pers., called as carqueja, a native plant from South Brazil. Cryogenic, knife (with and without cooling) and ball mills were used. The major constituents found in EOs were β-pinene, caryophyllene, spathulenol and caryophyllene oxide, but differences in 21 compounds were observed. All grinding processes reduced monoterpenes and oxygenated sesquiterpenes with concentration of hydrocarbon sesquiterpenes. The sesquiterpenes (hydrocarbons and oxygenated) were found from 63.55 to 86.02% while the monoterpene hydrocarbons’ concentration ranged from 13.98 to 36.45%. Plants milled with knife mill provided EOs with profile similar to those not grinded. Despite the lower working temperature, cryogenic milling resulted in smaller EO yield (0.40 ± 0.03%) in comparison to other grinding methods (yields from 0.50 ± 0.02 to 0.56 ± 0.03%) and different chromatographic profile. Microscopic analysis showed the smaller particle size provided by cryogenic grinding, which leads to glandular trichome rupture and consequently to loss of EOs. This study showed that grinding should be carefully evaluated to provide reproducible results in essential oil analysis. 相似文献
958.
Geert Silversmit Hilde Poelman Philippe M. Heynderickx Sergey Nikitenko Philippe F. Smet Roger De Gryse Guy B. Marin 《Journal of Physics and Chemistry of Solids》2009,70(9):1274-88
The redox behaviour of a CuO-CeO2/Al2O3 catalyst is studied under propane reduction and re-oxidation. The evolution of the local Cu and Ce structure is studied with in-situ transmission X-ray absorption spectroscopy (XAS) at the Cu K and Ce L3 absorption edges.CuO and CeO2 structures are present in the catalyst as such. No structural effect on the local Cu structure is observed upon heating in He up to 873 K or after pre-oxidation at 423 K.Exposure to propane at reaction temperature (600-763 K) fully reduces the Cu2+ cations towards metallic Cu0. Quick EXAFS spectra taken during reduction show a small amount of intermediate Cu1+ species. Parallel to the CuO reduction, CeO2 is also reduced in the same temperature range. About 25% of the Ce4+ reduces rapidly to Ce3+ in the 610-640 K temperature interval, while beyond 640 K a further slower reduction of Ce4+ to Ce3+ occurs. At 763 K, Ce reduction is still incomplete with 32% of Ce3+.Re-oxidation of Cu and Ce is fast and brings back the original oxides.The propane reduction of the CuO-CeO2/Al2O3 catalyst involves both CuO and CeO2 reduction at similar temperatures, which is ascribed to an interaction between the two compounds. 相似文献
959.
Sandra M. Meyers Cornelia Laule Irene M. Vavasour Shannon H. Kolind Burkhard Mädler Roger Tam Anthony L. Traboulsee Jimmy Lee David K.B. Li Alex L. MacKay 《Magnetic resonance imaging》2009
This study compared region of interest (ROI) and voxel-based analysis (VBA) methods to determine the optimal method of myelin water fraction (MWF) analysis. Twenty healthy controls were scanned twice using a multi-echo T2 relaxation sequence and ROIs were drawn in white and grey matter. MWF was defined as the fractional signal from 15 to 40 ms in the T2 distribution. For ROI analysis, the mean intensity of voxels within an ROI was fit using non-negative least squares. For VBA, MWF was obtained for each voxel and the mean and median values within an ROI were calculated. There was a slightly higher correlation between Scan 1 and 2 for the VBA method (R2=0.98) relative to the ROI method (R2=0.95), and the VBA mean square difference between scans was 300% lower, indicating VBA was the most consistent between scans. For the VBA method, mean MWF was found to be more reproducible than median MWF. As the VBA method is more reproducible and gives more options for visualization and analysis of MWF, it is recommended over the ROI method of MWF analysis. 相似文献
960.
Joy Ann Panis Prof. Marine Louis Arnaud Brosseau Shouhei Katao Florencio de los Reyes Prof. Takuya Nakashima Dr. Rémi Métivier Dr. Clémence Allain Prof. Tsuyoshi Kawai 《Chemistry (Weinheim an der Bergstrasse, Germany)》2022,28(44):e202201012
We synthesized two bichromophoric difluoroboron-β-diketonates (DFB) connected in para and meta positions by using cyclohexane diamine as a chiral bridge ( para and meta (R/S)-CyDFB ). TD-DFT calculations revealed that the variation in connectivity of the DFB units leads to different spatial arrangements and a chirality inversion of the bichromophoric DFB. Higher gabs values were obtained in (R/S)-CyDFB connected in para as compared to meta position. Aggregation of para (R/S)-CyDFB in mixture of solvents increase the glum values as compared to its monomeric form. Ultrasonication and heating induced the formation of highly ordered nano-helical wires of para (R/S)-CyDFB that increased the glum values to 0.015. On the other hand, meta (R/S)-CyDFB failed to form highly ordered self-assembled wires due to hindered H-binding sites. These observations indicate that the chiroptical properties of DFB bi-chromophore system can be modulated with self-assembly and spatial arrangement of the chromophores. 相似文献