全文获取类型
收费全文 | 489篇 |
免费 | 18篇 |
国内免费 | 6篇 |
专业分类
化学 | 278篇 |
晶体学 | 1篇 |
力学 | 4篇 |
数学 | 178篇 |
物理学 | 52篇 |
出版年
2023年 | 2篇 |
2022年 | 6篇 |
2021年 | 16篇 |
2020年 | 4篇 |
2019年 | 10篇 |
2018年 | 16篇 |
2017年 | 18篇 |
2016年 | 20篇 |
2015年 | 24篇 |
2014年 | 16篇 |
2013年 | 35篇 |
2012年 | 39篇 |
2011年 | 26篇 |
2010年 | 27篇 |
2009年 | 16篇 |
2008年 | 32篇 |
2007年 | 29篇 |
2006年 | 19篇 |
2005年 | 20篇 |
2004年 | 19篇 |
2003年 | 15篇 |
2002年 | 14篇 |
2001年 | 10篇 |
2000年 | 3篇 |
1999年 | 2篇 |
1998年 | 4篇 |
1997年 | 10篇 |
1996年 | 9篇 |
1995年 | 7篇 |
1994年 | 4篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 7篇 |
1989年 | 4篇 |
1988年 | 5篇 |
1987年 | 4篇 |
1986年 | 1篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1979年 | 1篇 |
排序方式: 共有513条查询结果,搜索用时 15 毫秒
491.
A multi-element graphite furnace atomic absorption spectrometry (GFAAS) method was elaborated for the simultaneous determination of As, Cd, Cu, and Pb in wine samples of various sugar contents using the transversally heated graphite atomizer (THGA) with end-capped tubes and integrated graphite platforms (IGPs). For comparative GFAAS analyses, direct injection (i.e., dispensing the sample onto the IGP) and digestion-based (i.e., adding oxidizing agents, such as HNO(3) and/or H(2)O(2) to the sample solutions) methods were optimized with the application of chemical modifiers. The mixture of 5 microg Pd (applied as nitrate) plus 3 microg Mg(NO(3))(2) chemical modifier was proven to be optimal for the present set of analytes and matrix, it allowing the optimal 600 degrees C pyrolysis and 2200 degrees C atomization temperatures, respectively. The IGP of the THGA was pre-heated at 70 degrees C to prevent the sputtering and/or foaming of sample solutions with a high organic content, dispensed together with the modifier solution, which method also improved the reproducibility of the determinations. With the digestion-based method, the recovery ranged between 87 and 122%, while with the direct injection method it was between 96 and 102% for Cd, Cu, and Pb, whereas a lower, compromise recovery of 45-85% was realized for As. The detection limits (LODs) were found to be 5.0, 0.03, 1.2, and 0.8 microg l(-1) for As, Cd, Cu, and Pb, respectively. The characteristic mass (m(0)) data were 24 pg As, 1.3 pg Cd, 13 pg Cu, and 35 pg Pb. The upper limits of the linear calibration range were 100, 2, 100, and 200 microg l(-1) for As, Cd, Cu, and Pb, respectively. The precisions were not worse than 4.8, 3.1, 3.7, and 2.3% for As, Cd, Cu, and Pb, respectively. For arsenic, a higher amount of the modifier (e.g., 20 microg Pd plus 12 microg Mg(NO(3))(2)) could be recommended to overcome the interference from the presence of sulphate and phosphate in wines. Although this method increased the sensitivity for As (m(0)=20 pg), it also enhanced the background noise, thus only a slight improvement in the LOD of As (3.9 microg l(-1)) was realized. For the 35 red and white wine samples studied, the highest metal contents were observed for Cu ranging from 20 to 640 microg l(-1) (average: 148 microg l(-1)), followed by Pb from 6 to 90 microg l(-1) (average: 32.3 microg l(-1)), and Cd from 0.05 to 16.5 microg l(-1) (average: 1.06 microg l(-1)), whereas the As content was below the LOD. This wide fluctuation in the trace metal content could be associated with the origin of wines from various regions (i.e., different trace metal level and/or quality of soil, and/or anthropogenic impact), and with diverse materials (e.g., additives and containers) involved in the wine production processes. The Cu content of wine samples was significantly correlated with Pb, whereas its weak anti-correlation was found with Cd. Interestingly, the level of Pb was anti-correlated with the year of production of the wines. This is likely due to the gradual decrease in the Pb content of soils of vineyards by time, which certainly causes less Pb-uptake of the grape plant, thus a decrease in the Pb content of wines as well. 相似文献
492.
Callahan MP Gengeliczki Z Svadlenak N Valdes H Hobza P de Vries MS 《Physical chemistry chemical physics : PCCP》2008,10(19):2819-2826
We present resonant two-photon ionization and IR-UV double resonance spectra of methylated xanthine derivatives including 7-methylxanthine dimer and theobromine dimer seeded in a supersonic jet by laser desorption. For 7-methylxanthine, theophylline and theobromine monomer we assign the lowest energy tautomer based on comparison with IR-UV double resonance spectra and calculated IR frequencies. For the 7-methylxanthine dimer, we observe hydrogen bonding on the N3H position suggesting 3 possible combinations, one that is reverse Watson-Crick type and two that are reverse Hoogsteen type. For the theobromine dimer, we observe a stacked structure. For trimethylxanthine dimers we infer a stacked structure as well. 相似文献
493.
High-efficiency aminocarbonylation by introducing CO to a pressurized continuous flow reactor 总被引:1,自引:0,他引:1
Csajági C Borcsek B Niesz K Kovács I Székelyhidi Z Bajkó Z Urge L Darvas F 《Organic letters》2008,10(8):1589-1592
Halogenated aryl carboxylic acids were efficiently converted to the corresponding dicarboxylic acid monoamides by a one-step Pd-catalyzed aminocarbonylation in a micro/meso fluidic continuous flow reactor (X-Cube) operated at high pressure and high temperature with CO gas introduction. Reaction parameters (solvent, base, catalyst, pressure, temperature) were rapidly optimized in the reactions, which required less than 2 min. The method gave improved results over comparable batch techniques and is also suited to automated parallel syntheses of compound libraries. 相似文献
494.
The best approximation algorithm for Max Cut in graphs of maximum degree 3 uses semidefinite programming, has approximation ratio 0.9326, and its running time is Θ(n3.5logn); but the best combinatorial algorithms have approximation ratio 4/5 only, achieved in O(n2) time [J.A. Bondy, S.C. Locke, J. Graph Theory 10 (1986) 477–504; E. Halperin, et al., J. Algorithms 53 (2004) 169–185]. Here we present an improved combinatorial approximation, which is a 5/6-approximation algorithm that runs in O(n2) time, perhaps improvable even to O(n). Our main tool is a new type of vertex decomposition for graphs of maximum degree 3. 相似文献
495.
László Bencs Krisztina György Márta Kardos János Osán Bálint Alföldy Imre Varga Zsolt Ajtony Norbert Szoboszlai Zsolt Stefánka Éva Széles László Kovács 《Analytica chimica acta》2012
Solid sampling (SS) graphite furnace atomic absorption spectrometry (GFAAS) and solution-based (SB) methods of GFAAS, flame atomic absorption spectrometry (FAAS), inductively coupled plasma optical emission spectrometry (ICP-OES) and inductively coupled plasma mass spectrometry (ICP-MS) were elaborated and/or optimized for the determination of Cr, Fe and Mn trace elements used as dopants in lithium niobate optical crystals. 相似文献
496.
Rojas-Quijano FA Tircsó G Tircsóné Benyó E Baranyai Z Tran Hoang H Kálmán FK Gulaka PK Kodibagkar VD Aime S Kovács Z Sherry AD 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(31):9669-9676
Tissue hypoxia occurs in pathologic conditions, such as cancer, ischemic heart disease and stroke when oxygen demand is greater than oxygen supply. An imaging method that can differentiate hypoxic versus normoxic tissue could have an immediate impact on therapy choices. In this work, the gadolinium(III) complex of 1,4,7,10-tetraazacyclododecane-1,4,7,10-tetraacetic acid (DOTA) with a 2-nitroimidazole attached to one carboxyl group via an amide linkage was prepared, characterized and tested as a hypoxia-sensitive MRI agent. A control complex, Gd(DO3A-monobutylamide), was also prepared in order to test whether the nitroimidazole side-chain alters either the water proton T(1) relaxivity or the thermodynamic stability of the complex. The stabilities of these complexes were lower than that of Gd(DOTA)(-) as expected for mono-amide derivatives. The water proton T(1) relaxivity (r(1)), bound water residence lifetime (τ(M)) and rotational correlation time (τ(R)) of both complexes was determined by relaxivity measurements, variable temperature (17) O?NMR spectroscopy and proton nuclear magnetic relaxation dispersion (NMRD) studies. The resulting parameters (r(1) =6.38?mM(-1) s(-1) at 20?MHz, τ(M) =0.71?μs, τ(R) =141?ps) determined for the nitroimidazole derivative closely parallel to those of other Gd(DO3A-monoamide) complexes of similar molecular size. In vitro MR imaging experiments with 9L rat glioma cells maintained under nitrogen (hypoxic) versus oxygen (normoxic) gas showed that both agents enter cells but only the nitroimidazole derivative was trapped in cells maintained under N(2) as evidenced by an approximately twofold decrease in T(1) measured for hypoxic cells versus normoxic cells exposed to this agent. These results suggest that the nitroimidazole derivative might serve as a molecular reporter for discriminating hypoxic versus normoxic tissues by MRI. 相似文献
497.
Dr. Federico A. Rojas‐Quijano Dr. Gyula Tircsó Enikő Tircsóné Benyó Dr. Zsolt Baranyai Huan Tran Hoang Dr. Ferenc K. Kálmán Dr. Praveen K. Gulaka Prof. Vikram D. Kodibagkar Prof. Silvio Aime Prof. Zoltán Kovács Prof. A. Dean Sherry 《Chemistry (Weinheim an der Bergstrasse, Germany)》2012,18(31):9669-9676
Tissue hypoxia occurs in pathologic conditions, such as cancer, ischemic heart disease and stroke when oxygen demand is greater than oxygen supply. An imaging method that can differentiate hypoxic versus normoxic tissue could have an immediate impact on therapy choices. In this work, the gadolinium(III) complex of 1,4,7,10‐tetraazacyclododecane‐1,4,7,10‐tetraacetic acid (DOTA) with a 2‐nitroimidazole attached to one carboxyl group via an amide linkage was prepared, characterized and tested as a hypoxia‐sensitive MRI agent. A control complex, Gd(DO3A‐monobutylamide), was also prepared in order to test whether the nitroimidazole side‐chain alters either the water proton T1 relaxivity or the thermodynamic stability of the complex. The stabilities of these complexes were lower than that of Gd(DOTA)? as expected for mono‐amide derivatives. The water proton T1 relaxivity (r1), bound water residence lifetime (τM) and rotational correlation time (τR) of both complexes was determined by relaxivity measurements, variable temperature 17O NMR spectroscopy and proton nuclear magnetic relaxation dispersion (NMRD) studies. The resulting parameters (r1=6.38 mM ?1 s?1 at 20 MHz , τM=0.71 μs, τR=141 ps) determined for the nitroimidazole derivative closely parallel to those of other Gd(DO3A‐monoamide) complexes of similar molecular size. In vitro MR imaging experiments with 9L rat glioma cells maintained under nitrogen (hypoxic) versus oxygen (normoxic) gas showed that both agents enter cells but only the nitroimidazole derivative was trapped in cells maintained under N2 as evidenced by an approximately twofold decrease in T1 measured for hypoxic cells versus normoxic cells exposed to this agent. These results suggest that the nitroimidazole derivative might serve as a molecular reporter for discriminating hypoxic versus normoxic tissues by MRI. 相似文献
498.
Istvn Orbn Bertalan Varga Pter Bagi Lszl Hegeds Pter Bak Zsolt Rapi 《Molecules (Basel, Switzerland)》2021,26(15)
Carbohydrate-based crown ethers have been reported to be able to generate asymmetric induction in certain reactions. Previously, it was proved that the monosaccharide unit, the anomeric substituent, and the sidearm could influence the catalytic activity of the monoaza-15-crown-5 macrocycles derived from sugars. In order to gain information about the effect of the flexibility, 4,6-di-O-ethyl-glucoside-based crown compounds were synthesized, and their efficiency was compared to the 4,6-O-benzylidene analogues. It was found that the absence of the two-ring annulation has a negative effect on the enantioselectivity in liquid-liquid two-phase reactions: in the Darzens condensation of 2-chloroacetophenone and in the epoxidation of chalcone. The same trend was observed in the solid-liquid phase Michael addition of diethyl acetamidomalonate. Surprisingly, in the solid-liquid phase cyclopropanation of benzylidenemalononitrile, one of the new catalysts was highly enantioselective (99% ee). 相似文献
499.
Viktória Vargha Avashnee Chetty Zsolt Sulyok Judith Mihály Zsófia Keresztes András Tóth István Sajó László Korecz Rajesh Anandjiwala Lydia Boguslavsky 《Journal of Thermal Analysis and Calorimetry》2012,109(2):1019-1032
Surface oxyfluorination had been carried out on polypropylene non-woven fabric (PP NWF) samples of different morphologies and pore sizes. The modified surfaces were characterised by Attenuated Total Reflectance Fourier Transform InfraRed (ATR-FTIR)-spectroscopy, FTIR imaging microscopy, X-Ray Photoelectron Spectroscopy (XPS), Electron Spin Resonance (ESR) spectroscopy, Differential Scanning Calorimetry (DSC), X-Ray Diffraction (XRD) analysis, Scanning Electron Microscopy (SEM), dynamic rheometry and Thermo-Gravimetry (TG). ATR-FTIR and XPS techniques revealed the presence of ?CCF, ?CCF2, ?CCHF and ?CC(O)F groups. The formed ?CC(O)F groups mostly got hydrolysed to ?CCOOH groups. The C=O groups of alpha-haloester, and the C=C stretching of the formed ?CCF=C(OH)?C groups could also be detected. Long-lived radicals could be detected on the functionalised surfaces as middle-chain peroxy radicals by ESR spectroscopy. SEM micrographs showed slight roughening of the oxyfluorinated surfaces. Oxyfluorination had no significant effect on the crystalline structure and phase composition of the PP NWF samples supported by DSC and XRD measurements. The molecular mass of the samples were unaffected by the oxyfluorination treatment as proved by oscillating rheometry. The surface modification, however, significantly affected the thermal decomposition but not affected the thermo-oxidative decomposition of PP NWFs. Different morphologies and pore sizes of PP NWF samples resulted in reproducibility of the findings, although did not substantially affect surface functionalisation. 相似文献
500.
Zsolt Balogh 《Journal of Pure and Applied Algebra》2012,216(6):1282-1287
Let be a group such that the set of -elements of forms a finite nonabelian subgroup, where is an odd prime, and let be a field of characteristic . In this paper we prove that the lower bound of the Lie derived length of the group algebra given by Shalev in [11] is also a lower bound for the Lie derived length of the set of symmetric elements of for every involution which is linear extension of an involutive anti-automorphism of . Furthermore, we provide counterexamples to the interesting cases which are not covered by the main theorem. 相似文献