全文获取类型
收费全文 | 317篇 |
免费 | 10篇 |
专业分类
化学 | 186篇 |
晶体学 | 3篇 |
力学 | 15篇 |
数学 | 25篇 |
物理学 | 98篇 |
出版年
2022年 | 2篇 |
2020年 | 4篇 |
2019年 | 3篇 |
2018年 | 7篇 |
2017年 | 9篇 |
2016年 | 13篇 |
2015年 | 8篇 |
2014年 | 8篇 |
2013年 | 19篇 |
2012年 | 18篇 |
2011年 | 21篇 |
2010年 | 15篇 |
2009年 | 14篇 |
2008年 | 11篇 |
2007年 | 7篇 |
2006年 | 12篇 |
2005年 | 11篇 |
2004年 | 10篇 |
2003年 | 13篇 |
2002年 | 9篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 6篇 |
1998年 | 4篇 |
1997年 | 3篇 |
1996年 | 5篇 |
1992年 | 4篇 |
1991年 | 6篇 |
1990年 | 4篇 |
1989年 | 2篇 |
1988年 | 2篇 |
1987年 | 3篇 |
1986年 | 2篇 |
1985年 | 5篇 |
1984年 | 4篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 4篇 |
1977年 | 3篇 |
1975年 | 2篇 |
1974年 | 2篇 |
1968年 | 7篇 |
1961年 | 2篇 |
1957年 | 2篇 |
1944年 | 2篇 |
1939年 | 3篇 |
1938年 | 2篇 |
1936年 | 2篇 |
1934年 | 2篇 |
排序方式: 共有327条查询结果,搜索用时 31 毫秒
91.
Hans‐Peter Sieper Hans‐Joachim Kupka Lutz Lange Andreas Roßmann Nicole Tanz Hanns‐Ludwig Schmidt 《Rapid communications in mass spectrometry : RCM》2010,24(19):2849-2858
The quantitative conversion of organically bound oxygen into CO, a prerequisite for the 18O/16O analysis of organic compounds, is generally performed by high‐temperature conversion in the presence of carbon at ~1450°C. Since this high‐temperature procedure demands complicated and expensive equipment, a lower temperature method that could be utilized on standard elemental analyzers was evaluated. By substituting glassy carbon with carbon black, the conversion temperature could be reduced to 1170°C. However, regardless of the temperature, N‐containing compounds yielded incorrect results, despite quantitative conversion of the bound oxygen into CO. We believe that the problems were partially caused by interfering gases produced by a secondary decomposition of N‐ and C‐containing polymers formed during the decomposition of the analyte. In order to overcome the interference, we replaced the gas chromatographic (GC) separation of CO and N2 by reversible CO adsorption, yielding the possibility of collecting and purifying the CO more efficiently. After CO collection, the interfering gases were vented by means of a specific stream diverter, thus preventing them from entering the trap and the mass spectrometer. Simultaneously, a make‐up He flow was used to purge the gas‐specific trap before the desorption of the CO and its subsequent mass spectrometric analysis. Furthermore, the formation of interfering gases was reduced by the use of polyethylene as an additive for analytes with a N:O ratio greater than 1. These methodological modifications to the thermal conversion of N‐containing analytes, depending on their structure or O:N ratio, led to satisfactory results and showed that it was possible to optimize the conditions for their individual oxygen isotope ratio analysis, even at 1170°C. With these methodological modifications, correct and precise δ18O results were obtained on N‐containing analytes even at 1170°C. Differences from the expected standard values were below ±1‰ with standard deviations of the analysis <0.2‰. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
92.
93.
A simple and rapid reversed-phase HPLC-UV method was developed for the determination of triterpenic acids in the crude extract of Prunellae Spica. Five triterpenic acids were extracted and isolated from P. Spica as marker compounds for use in the quality control of herbal medicines. Various solvent extraction techniques were evaluated, and the greatest efficiency was observed with sonication in 100% ethanol. Elemental compositions of the five marker compounds were determined by high-resolution mass spectroscopy. The dynamic range of the HPLC-UV method depended on the specific analyte, and acceptable quantitation was obtained between 10 and 250 μg mL−1 for oleanolic acid, between 10 and 300 μg mL−1 for ursolic acid, between 3 and 75 μg mL−1 for 2α,3α,24-trihydroxyolean-12en-28oic acid, between 5 and 100 μg mL−1 for euscaphic acid, and between 5 and 100 μg mL−1 for 2α,3α-dihydroxyurs-12en-28oic acid. The method was deemed satisfactory by inter- and intra-day validation and exhibited both high accuracy and precision (relative standard deviation <9.4%). Overall limits of quantitation and detection were approximately 0.5-2.5 μg mL−1 at a signal-to-noise ratio (S/N) of 3 and were about 3.0-10.0 μg mL−1 at a S/N of 10. In addition, principal component analysis (PCA) was performed on the analytical data of 15 different P. Spica samples in order to classify samples collected from different regions. 相似文献
94.
Plastic microchip liquid chromatography-matrix-assisted laser desorption/ionization mass spectrometry using monolithic columns 总被引:1,自引:0,他引:1
A prototype array of monolithic liquid chromatography (LC) columns was prepared in a plastic microfluidic device for the off-line interface with matrix assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF-MS). The microfluidic channels were fabricated on a cyclic olefin copolymer (COC) plate by hot embossing. An array of methacrylate monolithic columns was prepared in the microfluidic channels by UV-initiated polymerization. The deposition system employed a pulsed electric field to transfer the effluents from multiple columns directly onto MALDI targets with a non-contact deposition method reported by Ericson et al. [C. Ericson, Q.T. Phung, D.M. Horn, E.C. Peters, J.R. Fitchett, S.B. Ficarro, A.R. Salmon, L.M. Brill, A. Brock, Anal. Chem. 75 (2003) 2309]. To characterize the off-line interface of the multiple-channel microchip LC and the MALDI-MS for the analysis of peptide mixtures, the separation efficiency and reproducibility tests in each column were carried out by separating a peptide mixture from tryptic digested proteins and depositing the multiple effluents simultaneously on the MALDI target plate. Using a MALDI-TOF mass spectrometer with a mass accuracy of +/-1 Da for peptide assignments of digested bovine serum albumin (BSA), amino acid sequence coverage of around 59% was obtained for the microchip LC-MALDI-MS compared to 23% obtained by the MALDI-MS method without LC separation. In sensitivity tests for the detection of low abundance proteins in the presence of high concentration protein mixtures, as low as 10 fmol/mul (S/N = 10) of a spiked peptide in 1 microg of digested BSA could be detected. In the analysis of a mixture of three digested proteins (BSA, myoglobin, and cytochrome c), more than twice the amino acid sequence coverage was obtained for the microchip LC-MALDI-MS compared to MALDI-MS alone. 相似文献
95.
T. Rożek D. Grzonka H.-H. Adam A. Budzanowski R. Czyżykiewicz M. Janusz L. Jarczyk B. Kamys A. Khoukaz K. Kilian P. Klaja P. Kowina P. Moskal W. Oelert C. Piskor-Ignatowicz J. Przerwa J. Ritman T. Sefzick M. Siemaszko J. Smyrski A. Täschner P. Winter M. Wolke P. Wüstner Z. Zhang W. Zipper 《Physics letters. [Part B]》2006
96.
An equality constrained optimization problem with a deterministic objective function and constraints in the form of mathematical expectation is considered. The constraints are transformed into the Sample Average Approximation form resulting in deterministic problem. A method which combines a variable sample size procedure with line search is applied to a penalty reformulation. The method generates a sequence that converges towards first-order critical points. The final stage of the optimization procedure employs the full sample and the SAA problem is eventually solved with significantly smaller cost. Preliminary numerical results show that the proposed method can produce significant savings compared to SAA method and some heuristic sample update counterparts while generating a solution of the same quality. 相似文献
97.
Md. Shakilur Rahman Kyung-Sook Kim Manwoo Lee Guinyun Kim Youngdo Oh Hee-Seock Lee Moo-Hyun Cho In Soo Ko Won Namkung Van Do Nguyen Duc Khue Pham Tien Thanh Kim Tae-Ik Ro 《Journal of Radioanalytical and Nuclear Chemistry》2010,283(2):519-525
We measured isomeric-yield ratios for the 197Au(γ,n)196m,gAu reactions with bremsstrahlung energies of 50-, 60-, 70- MeV, and 2.5-GeV at the two different electron linac of the Pohang accelerator laboratory by using the activation method. The photons were produced when a pulsed electron beam hit a thin tungsten target. The well-known photoactivation method was used and hence the induced activities in the irradiated foils were measured with the high-resolution γ-ray spectrometric system consisting of lithium drifted high-purity Germanium detector and a multichannel analyzer. The measured isomeric-yield ratios for the 197Au(γ,n)196m,gAu reactions were (4.95 ± 0.51) × 10?4, (5.72 ± 0.72) × 10?4, (6.03 ± 0.50) × 10?4, and (9.27 ± 0.83) × 10?4 for 50-, 60-, 70-MeV, and 2.5-GeV bremsstrahlung energies, respectively. The present results measured with the bremsstrahlung energy higher than 60-MeV are the first measurement. 相似文献
98.
In the presence of a photomediator such as benzophenone, alkynes with electron-withdrawing groups react with cycloalkanes to give vinyl cycloalkanes. The reaction involves the regiospecific addition of a photochemically generated cycloalkyl radical to the beta-carbon of the alkyne. The stereochemical outcome of the reaction depends on the nature of the photomediator and alkyne used. 相似文献
99.
Ro YT Kim EJ Lee HI Saiz M Carrion R Patterson JL 《Experimental & molecular medicine》2004,36(2):145-156
In this study, Leishmania RNA virus 1-4 (LRV1-4) particles purified from host Leishmania guyanensis promastigotes were examined for capsid endoribonuclease. Temperature optimum for the endoribonuclease activity was found to be at 37(O)C to 42(O)C and the activity was specifically inhibited by the aminoglycoside antibiotics, neomycin, kanamycin, and hygromycin and by 100 mM levels of NaCl or KCl. To determine the catalytic domain of the capsid endoribonuclease activity, three point-mutation at cysteine residues at C47S (P1), C128/ 133S (P2), and C194R (P3) were prepared and each gene was constructed into baculoviruses and expressed in Sf9 insect cells. LRV1-4 capsid N- terminus (N2 and N3) and C-terminus (C1 and C2) deletion mutants (Cadd et al., 1994) were also examined by in vitro RNA cleavage assay. The results showed that the capsid mutants; C1, C2, N3, P1, and P2 were capable of forming proper virus-like particles (VLPs) and they all possessed the specific endoribonuclease activity. However, two assembly-defective capsid mutants, N2 (N- terminus 24-amino acids deletion) and P3 mutants, did not retain the specific endoribonuclease activity. Taken together, the results suggest that at least 24 amino acids from the N-terminal region and C194 residue in LRV1-4 capsid protein are functionally important for LRV1-4 viral assembly and the capsid endoribonuclease activity may be dependent upon the properly assembled LRV1-4 virus particles. 相似文献
100.
Rozman M 《Journal of the American Society for Mass Spectrometry》2005,16(11):1846-1852
A mass spectrometry and Density Functional Theory study of gas-phase H/D exchange in protonated Ala, Cys, Ile, Leu, Met, and Val is reported. Site-specific rate constants were determined and results identify the alpha-amino group as the protonation site. Lack of exchange on the Cys thiol group is explained by the absence of strong intramolecular hydrogen bonding within the reaction complex. In aliphatic amino acids the presence of a methyl group at the beta-C atom was found to lower the site-specific H/D exchange rate for amino hydrogens. Study of the exchange mechanism showed that isotopic exchange occurs in two independent reactions: in one, only the carboxylic hydrogen is exchanged and in the other, both carboxylic and amino group hydrogens exchange. The proposed reaction mechanisms, calculated structures of various species, and a number of structural findings are consistent with experimental data. 相似文献