全文获取类型
收费全文 | 470篇 |
免费 | 15篇 |
国内免费 | 1篇 |
专业分类
化学 | 320篇 |
晶体学 | 9篇 |
力学 | 42篇 |
数学 | 29篇 |
物理学 | 86篇 |
出版年
2024年 | 5篇 |
2023年 | 7篇 |
2022年 | 10篇 |
2021年 | 17篇 |
2020年 | 29篇 |
2019年 | 27篇 |
2018年 | 26篇 |
2017年 | 23篇 |
2016年 | 17篇 |
2015年 | 18篇 |
2014年 | 17篇 |
2013年 | 46篇 |
2012年 | 39篇 |
2011年 | 38篇 |
2010年 | 14篇 |
2009年 | 24篇 |
2008年 | 15篇 |
2007年 | 8篇 |
2006年 | 4篇 |
2005年 | 2篇 |
2004年 | 8篇 |
2003年 | 5篇 |
2002年 | 6篇 |
2001年 | 3篇 |
2000年 | 2篇 |
1999年 | 2篇 |
1998年 | 3篇 |
1997年 | 5篇 |
1996年 | 3篇 |
1995年 | 3篇 |
1994年 | 9篇 |
1993年 | 5篇 |
1992年 | 4篇 |
1991年 | 2篇 |
1990年 | 4篇 |
1989年 | 3篇 |
1988年 | 4篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 2篇 |
1983年 | 3篇 |
1981年 | 2篇 |
1974年 | 1篇 |
1973年 | 4篇 |
1971年 | 1篇 |
1969年 | 3篇 |
1966年 | 1篇 |
1960年 | 1篇 |
1959年 | 2篇 |
1948年 | 1篇 |
排序方式: 共有486条查询结果,搜索用时 15 毫秒
51.
The reactions of dimeric complex [Rh(CO)2Cl]2 with hemilabile ether‐phosphine ligands Ph2P(CH2) nOR [n = 1, R = CH3 (a); n = 2, R = C2H5 (b)] yield cis‐[Rh(CO)2Cl(P ~ O)] (1) [P ~ O = η 1‐(P) coordinated]. Halide abstraction reactions of 1 with AgClO4 produce cis‐[Rh(CO)2(P ∩ O)]ClO4 (2) [P ∩ O = η 2‐(P,O)chelated]. Oxidative addition reactions of 1 with CH3I and I2 give rhodium(III) complexes [Rh(CO)(COCH3)ClI(P ∩ O)] (3) and [Rh(CO)ClI2(P ∩ O)] (4) respectively. The complexes have been characterized by elemental analyses, IR, 1H, 13C and 31P NMR spectroscopy. The catalytic activity of 1 for carbonylation of methanol is higher than that of the well‐known [Rh(CO)2I2]? species. Copyright © 2002 John Wiley & Sons, Ltd. 相似文献
52.
The combined effects of the permeability of the medium, magnetic field, buoyancy forces and dissipation on the unsteady mixed convection flow over a horizontal cylinder and a sphere embedded in a porous medium have been studied. The nonlinear coupled partial differential equations with three independent variables have been solved numerically using an implicit finite-difference scheme in combination with the quasilinearization technique. The skin friction, heat transfer and mass transfer increase with the permeability of the medium, magnetic field and buoyancy parameter. The heat and mass transfer continuously decrease with the stream-wise distance, whereas the skin friction increases from zero, attains a maximum and then decreases to zero. The skin friction, heat transfer and mass transfer are significantly affected by the free stream velocity distribution. The effect of dissipation parameter is found to be more pronounced on the heat transfer than on the skin friction and mass transfer.Untersucht wurden kombinierte Effekte der Permeabilität des Mediums, des magnetischen Feldes, der Auftriebskräfte und der Dissipation auf die instationäre Mischkonvektions-Strömung über einen horizontalen Zylinder und eine Kugel, die in einem porösen Medium eingebettet sind. Die nichtlinearen gekoppelten partiellen Differentialgleichungen mit drei unabhängigen Variablen wurden numerisch unter Benutzung eines impliziten Finite-Differenzen-Verfahrens in Verbindung mit der Quasi-Linearisierungstechnik gelöst. Die Oberflächenreibung und die Wärme- und Stoffübertragung steigen mit der Permeabilität des Mediums, dem magnetischen Feld und dem Auftriebsparameter an. Die Wärme- und Stoffübertragung fällt stetig in Strömungsrichtung ab, wohingegen die Oberflächenreibung von Null ansteigt, ein Maximum erreicht und wieder auf Null abfällt. Die Oberflächenreibung und die Wärme- und Stoffübertragung werden signifikant von der Verteilung der Freistromgeschwindigkeit beeinflut. Es wurde festgestellt, das der Dissipations-Parameter stärker die Wärmeübertragung als die Oberflächenreibung und die Stoffübertragung beeinflut. 相似文献
53.
Gayatri Kumari N. R. Patil Venkata Srinu Bhadram Ritesh Haldar Satyanarayana Bonakala Tapas Kumar Maji Chandrabhas Narayana 《Journal of Raman spectroscopy : JRS》2016,47(2):149-155
Interpenetrating metal organic frameworks are interesting functional materials exhibiting exceptional framework properties. Uptake or exclusion of guest molecules can induce sliding in the framework making it porous or non‐porous. To understand this dynamic nature and how framework interaction changes during sliding, metal organic framework (MOF) 508 {Zn(BDC)( 4,4′‐Bipy)0.5 · DMF(H2O)0.5} was selected for study. We have investigated structural transformation in MOF‐508 under variable conditions of temperature, pressure and gas loading using Raman spectroscopy and substantiated it with IR studies and density functional theory (DFT) calculations. Conformational changes in the organic linkers leading to the sliding of the framework result in changes in Raman spectra. These changes in the organic linkers are measured as a function of high pressure and low temperature, suggesting that the dynamism in MOF‐508 framework is driven by ligand conformation change and inter‐linker interactions. The presence of Raman signatures of adsorbed CO2 and its librational mode at 149 cm−1 suggests cooperative adsorption of CO2 in the MOF‐508 framework, which is also confirmed from DFT calculations that give a binding energy of 34 kJ/mol. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
54.
Kalawati Meena Sudesh Kumari Jitender M. Khurana Amita Malik Chetan Sharma Harsh Panwar 《中国化学快报》2017,28(1):136-142
A simple and efficient three component procedure has been developed for the synthesis of highly substituted spiro[indolo-3,10'-indeno[1,2-b]quinolin]-2,4,11'-triones by one pot three component condensation of enaminones, isatin and indane-1,3-dione in ethanol:water (1:1) in presence of ceric ammonium nitrate (CAN) as catalyst. This method provides several advantages such as lesser reaction time, high yield of products and operational simplicity. The antimicrobial activity of some of the compounds has been investigated against six microbial strains, some of the tested compounds showed good antimicrobial activity. 相似文献
55.
Sagar Suman Panda Khusbu Sharma Bijeta Mohanty Ravi Kumar Venkata Varaha Bera Sasmita Kumari Acharjya Sarwar Beg 《液相色谱法及相关技术杂志》2017,40(19):951-958
An ultrafast liquid chromatographic bioanalytical method was developed and validated for the determination of telaprevir in Wistar albino rat serum. Principles of quality by design (QbD) were implemented for enhancing the bioanalytical liquid–liquid extraction of telaprevir from rat serum. A Box–Behnken design was utilized in the studies by selecting extraction time, centrifugation speed, and vortex time as the critical method variables for evaluating their effect on the critical analytical attribute, i.e., %recovery of telaprevir. Chromatographic separation was achieved within a run time of 10?min using a C-18 column and mobile phase comprising of methanol:borate buffer of pH 9 (90:10 v/v) flowing at 1.2?mL/min. Photodiode array detection was performed at 270?nm. Results of validation studies were satisfactory. The method was linear over a concentration of 25–10,000?ng/mL. Limit of detection for the developed method was 10?ng/mL. Further, design of experiments (DoE) used for inter-day accuracy and precision study suggested superior method reliability. This integrated QbD- and DoE-based approach ensured the development of a validated and reliable analytical method for optimum bioanalysis of telaprevir in biological matrix. 相似文献
56.
The unsteady laminar incompressible boundary layer flow due to a two-dimensional slot jet on a flat plate at an angle of attack
has been studied. The unsteadiness in the flow field is due to the free stream velocity distribution or wall temperature (concentration)
which varies with time. The governing partial differential equations in primitive variables have been solved numerically using
an implicit finite-difference scheme in combination with the quasilinearization technique. The effect of the variation of
the free stream velocity distribution with time is found to be more pronounced on the skin friction than on the heat or mass
transfer. The Prandtl number and the variation of the wall temperature with time strongly affect the heat transfer. Similarly,
the Schmidt number and the variation of the concentration at the wall with time strongly affect the mass transfer. Beyond
a certain critical value of the viscous dissipation parameter, the plate gets heated instead of being cooled. 相似文献
57.
Solid-supported nano and microparticles of Pd(0) (SS-Pd) were prepared and used as heterogeneous catalysts for Suzuki-Miyaura cross coupling reactions of aryl halides (chloro, bromo and iodo) and phenyl boronic acid under mild and ligand-free conditions. Scanning electron microscope (SEM) and UV-vis based studies were performed to observe the distribution of nano and microparticles of palladium over solid surface and their oxidation states. In addition, the catalyst could be reused up to seven runs without significant loss of activity and stable enough under moist conditions. 相似文献
58.
Neelam?Kumari D.?R.?Prabhu P.?N.?PathakEmail author A.?S.?Kanekar V.?K.?Manchanda 《Journal of Radioanalytical and Nuclear Chemistry》2011,289(3):835-843
Extraction behavior of 1 × 10−2–0.1 M U(VI) from aqueous phases containing 0.86 M Th(IV) at 4 M HNO3 in 1.1 M tributyl phosphate (TBP) and 1.1 M N,N-dihexyl octanamide (DHOA) solutions in different diluents viz. n-dodecane, 10% 1-octanol + n-dodecane, and decahydronaphthalene (decalin) was studied. Third-phase formation was observed in both the extractants using
n-dodecane as diluent. There was a gradual decrease in Th(IV) concentration in the third-phase (heavy organic phase, HOP) with
increased aqueous U(VI) concentration [0.71 M (no U(VI))–0.61 M (0.1 M U(VI)) for TBP; 0.27 M (no U(VI))–0.22 M (0.1 M U(VI))
for DHOA]. The HOP volume in case of DHOA was ~2.2 times of that of TBP. Uranium concentration in HOP increased with its initial
concentration in the aqueous phase [from 1.8 × 10−2 M (0.01 M U(VI))–0.162 M (0.1 M U(VI)) for TBP; from 1.4 × 10−2 M (0.01 M U(VI))–0.14 M (0.1 M U(VI)) for DHOA] suggesting that Th(IV) was being replaced by U(VI). An empirical correlation
was developed for predicting the concentrations of uranium and thorium in HOP for both the extractants. No third-phase appeared
during the extraction of uranium and thorium from the aqueous phases employing 10% 1-octanol + n-dodecane, or decalin as diluents, and therefore, were better choices as diluent for alleviating the third-phase formation
during the reprocessing of spent thorium based fuels, and for the recovery of thorium from high-level waste solutions. 相似文献
59.
60.
The structural characterization of different kinds of zigzag and chiral single-walled carbon nanotubes (SWNTs) has been investigated theoretically using (19)F NMR spectroscopy. The chemical shift anisotropy (CSA) tensor is computed at different levels of theory for the (19)F nuclei in different forms of functionalized fluorinated carbon nanotubes (CNT). A set of fluorine CSA parameters comprising the span, skew, and isotropic chemical shift is computed for each form of the fluoronanotubes and multidimensional CSA parameter correlation maps are constructed. We show that these correlations are able to clearly distinguish between the chiral and zigzag forms of fluorinated carbon nanotubes (F-SWNTs). Implications for solid-state and liquid-state NMR experiments are discussed. 相似文献