全文获取类型
收费全文 | 1844篇 |
免费 | 86篇 |
国内免费 | 8篇 |
专业分类
化学 | 1158篇 |
晶体学 | 12篇 |
力学 | 109篇 |
数学 | 327篇 |
物理学 | 332篇 |
出版年
2023年 | 12篇 |
2022年 | 28篇 |
2021年 | 52篇 |
2020年 | 49篇 |
2019年 | 37篇 |
2018年 | 33篇 |
2017年 | 37篇 |
2016年 | 71篇 |
2015年 | 76篇 |
2014年 | 63篇 |
2013年 | 106篇 |
2012年 | 121篇 |
2011年 | 150篇 |
2010年 | 69篇 |
2009年 | 83篇 |
2008年 | 134篇 |
2007年 | 107篇 |
2006年 | 90篇 |
2005年 | 91篇 |
2004年 | 78篇 |
2003年 | 58篇 |
2002年 | 52篇 |
2001年 | 22篇 |
2000年 | 26篇 |
1999年 | 11篇 |
1998年 | 12篇 |
1997年 | 20篇 |
1996年 | 15篇 |
1995年 | 11篇 |
1994年 | 15篇 |
1993年 | 15篇 |
1992年 | 11篇 |
1991年 | 13篇 |
1990年 | 13篇 |
1989年 | 16篇 |
1988年 | 12篇 |
1987年 | 5篇 |
1986年 | 7篇 |
1985年 | 9篇 |
1984年 | 11篇 |
1983年 | 8篇 |
1982年 | 9篇 |
1981年 | 14篇 |
1980年 | 9篇 |
1979年 | 11篇 |
1977年 | 4篇 |
1975年 | 3篇 |
1974年 | 5篇 |
1973年 | 3篇 |
1970年 | 3篇 |
排序方式: 共有1938条查询结果,搜索用时 312 毫秒
101.
Chencheng Dai Yuanmiao Sun Gao Chen Adrian C. Fisher Zhichuan J. Xu 《Angewandte Chemie (International ed. in English)》2020,59(24):9418-9422
Nitrates are widely used as fertilizer and oxidizing agents. Commercial nitrate production from nitrogen involves high‐temperature‐high‐pressure multi‐step processes. Therefore, an alternative nitrate production method under ambient environment is of importance. Herein, an electrochemical nitrogen oxidation reaction (NOR) approach is developed to produce nitrate catalyzed by ZnFexCo2?xO4 spinel oxides. Theoretical and experimental results show Fe aids the formation of the first N?O bond on the *N site, while high oxidation state Co assists in stabilizing the absorbed OH? for the generation of the second and third N?O bonds. Owing to the concerted catalysis, the ZnFe0.4Co1.6O4 oxide demonstrates the highest nitrate production rate of 130±12 μmol h?1 gMO?1 at an applied potential of 1.6 V versus the reversible hydrogen electrode (RHE). 相似文献
102.
Dendrimers are three dimensional nanosized synthetic molecules that have internal cavities and numerous surface groups. In recent times they have received increased attention in sensing applications. For dendrimers to be used as sensors, they most commonly require functionalization at their surface. This is because the surface is generally the first point of contact between the dendrimer and the outside world, hence surface functionalization serves to selectively home in on the target analyte. Further, sensor signals may be transmitted through surface functionalities e.g. fluorochromic molecules. It is therefore important to document surface functionalization approaches. Dendrimers with amine surface groups have the advantage of being able to be conjugated to other molecules via an amide linkage, which is one of the most fundamental and widespread chemical bonds in nature. In this paper we demonstrate the properties of dendrimers that make them so applicable to sensing. We review several methods for functionalizing dendrimers via an amide linkage, as well as present a review of surface functionalized polyamidoamine, polyamine, and polypeptide dendrimers that have been employed for biological, chemical and molecular sensing. 相似文献
103.
Gheorghe A van Nuijs A Pecceu B Bervoets L Jorens PG Blust R Neels H Covaci A 《Analytical and bioanalytical chemistry》2008,391(4):1309-1319
A validated method based on solid-phase extraction (SPE) and liquid chromatography-ion trap tandem mass spectrometry (LC-MS/MS) is described for the determination of cocaine (COC) and its principal metabolites, benzoylecgonine (BE) and ecgonine methyl ester (EME), in waste and surface water. Several SPE adsorbents were investigated and the highest recoveries (95.7 +/- 5.5, 91.8 +/- 2.2 and 72.5 +/- 5.3% for COC, BE and EME, respectively) were obtained for OASIS HLB(R) cartridges (6 mL/500 mg) using 100 mL of waste water or 500 mL of surface water. Extracts were analysed by reversed-phase (RP) or hydrophilic interaction (HILIC) LC-MS/MS in positive ion mode with multiple reactions monitoring (MRM); the latter is the first reported application of the HILIC technique for drugs of abuse in water samples. Corresponding deuterated internal standards were used for quantification. The method limits of quantification (LOQs) for COC and BE were 4 and 2 ng L(-1), respectively, when RPLC was used and 1, 0.5 and 20 ng L(-1) for COC, BE and EME, respectively, with the HILIC setup. For COC and BE, the LOQs were below the concentrations measured in real water samples. Stability tests were conducted to establish the optimal conditions for sample storage (pH, temperature and time). The degradation of COC was minimal at -20 degrees C and pH = 2, but it was substantial at +20 degrees C and pH = 6. The validated method was applied to a set of waste and surface water samples collected in Belgium. 相似文献
104.
Stereoscopic particle image velocimetry applied to liquid flows 总被引:7,自引:5,他引:7
A twin-camera stereoscopic system has been developed to extend conventional high image-density Particle Image Velocimetry (PIV) to three-dimensional vectors on planar domains. The stereoscopic velocimeter performs with extremely high accuracy. Translation tests have yielded errors (rms) of 0.2% of full-scale for the in-plane displacement, and 0.8% of full-scale for the out-of-plane component, both of which agree with the errors predicted by an uncertainty analysis. In addition, modified techniques in hardware and software have enabled the stereoscopic system to perform successfully when acquiring images through a thick liquid layer, wherein previously the aberrations arising due to the liquid-air interface have restricted the use of such systems. With these techniques, the stereoscopic system, in combination with a simple method for image-shifting, is able to accurately measure threedimensional velocity fields in liquids. This is demonstrated by measurements of the helical, three-dimensional flow induced by a rotating disk in glycerine. 相似文献
105.
Raluca Pele Gabriel Marc Anca Stana Ioana Ionu Cristina Nastas Brîndua Tiperciuc Ilioara Oniga Adrian Pîrnu Laurian Vlase Ovidiu Oniga 《Molecules (Basel, Switzerland)》2022,27(8)
Considering the important damage caused by the reactive oxygen (ROS) and nitrogen (RNS) species in the human organism, the need for new therapeutic agents, with superior efficacy to the known natural and synthetic antioxidants, is crucial. Quinazolin-4-ones are known for their wide range of biological activities, and phenolic compounds display an important antioxidant effect. Linking the two active pharmacophores may lead to an increase of the antioxidant activity. Therefore, we synthesized four series of new hybrid molecules bearing the quinazolin-4-one and phenol scaffolds. Their antioxidant potential was evaluated in vitro, considering different possible mechanisms of action: hydrogen atom transfer, ability to donate electrons and metal ions chelation. Theoretical quantum and thermodynamical calculations were also performed. Some compounds, especially the ortho diphenolic ones, exerted a stronger antioxidant effect than ascorbic acid and Trolox. 相似文献
106.
A study of the effect of step excrescences and free‐stream disturbances on boundary layer stability 下载免费PDF全文
In this work, a study of the mechanism by which free‐stream acoustic and vorticity disturbances interact with a boundary layer flow developing over a flat plate featuring a step excrescence located at a certain distance from a blunt leading edge is included. The numerical tool is a high‐fidelity implicit numerical algorithm solving for the unsteady, compressible form of the Navier–Stokes equations in a body‐fitted curvilinear coordinates and employing high‐accurate compact differencing schemes with Pade‐type filters. Acoustic and vorticity waves are generated using a source term in the momentum and energy equations, as opposed to using inflow boundary conditions, to avoid spurious waves that may propagate from boundaries. The results show that the receptivity to surface step excrescences is largely the result of an overall adverse pressure gradient posed by the step, and that the free‐stream disturbances accelerate the generation of instabilities in the downstream. As expected, it is found that the acoustic disturbance interacting with the surface imperfection is more efficient in exciting the Tollmien–Schlichting waves than the vorticity disturbance. The latter generates Tollmien–Schlichting waves that are grouped in wave packets consistent with the wavelength of the free‐stream disturbance. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
107.
108.
Sonic boom focusing phenomenon can be predicted using the solution to the nonlinear Tricomi equation which is a hybrid (hyperbolic‐elliptic) second‐order partial differential equation. In this paper, the hyperbolic conservation law form is derived, which is valid in the entire domain. In this manner, the presence of two regions where the equation behaves differently (hyperbolic in the upper and elliptic in the lower half‐plane) is avoided. On the upper boundary, a new mixed boundary condition for the acoustic pressure is employed. The discretization is carried out using a discontinuous Galerkin (DG) method combined with a Runge–Kutta total‐variation diminishing scheme. The results show the accuracy of DG methods to solve problems involving sharp gradients and discontinuities. Comparisons with analytical results for the linear case, and other numerical results using classical explicit and compact finite difference schemes and weighted essentially non‐oscillatory schemes are included. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献
109.
Ciprian Dragan Adrian Samuila Subhankar Das Dan Iancu Mihai Bilici Lucian Dascalescu 《Journal of Electrostatics》2009,67(2-3):184-188
The aim of this study is to refine the understanding of the tribo-electrostatic phenomena that can affect the efficiency of suction-type dilute-phase transport systems. The study was conducted with mm-size ABS-PC particles, a granular material originating from genuine information technology wastes. The tribo-charging process was modelled using the response surface method of experimental design. The controlled variables were the granular material feed rate and the aspirating air speed rate. The monitored variable was the charge imparted to a well-defined section of the duct and which is equal to the charge transferred to the particles passing through that section of the pneumatic transport system. An induction type sensor connected to an electrometer has been employed for the measurements. The data were processed by a virtual instrument developed in LabView. A commercial software package was employed for estimating the effects of the various factors and predicting the optimum operating conditions, which were then confirmed by a final experiment. 相似文献
110.
Adrian K. Y. Lam Craig A. Hutton Richard A. J. O'Hair 《Rapid communications in mass spectrometry : RCM》2010,24(17):2591-2604
A combination of electrospray ionisation (ESI), multistage and high‐resolution mass spectrometry experiments was used to compare the gas‐phase chemistry of the amino acids histidine (1), 2‐oxo‐histidine (2), and 2‐thioxo‐histidine (3). Collision‐induced dissociation (CID) of all three different proton‐bound heterodimers of these amino acids led to the relative gas‐phase proton affinity order of: histidine >2‐thioxo‐histidine >2‐oxo‐histidine. Density functional theory (DFT) calculations confirm this order, with the lower proton affinities of the oxidised histidine derivatives arising from their ability to adopt the more stable keto/thioketo tautomeric forms. All protonated amino acids predominately fragment via the combined loss of H2O and CO to yield a1 ions. Protonated 2 and 3 also undergo other small molecule losses including NH3 and the imine HN=CHCO2H. The observed differences in the fragmentation pathways are rationalised through DFT calculations, which reveal that while modification of histidine via the introduction of the oxygen atom in 2 or the sulfur atom in 3 does not affect the barriers against the loss of H2O+CO, barriers against the losses of NH3 and HN=CHCO2H are lowered relative to protonated histidine. Copyright © 2010 John Wiley & Sons, Ltd. 相似文献