全文获取类型
收费全文 | 585篇 |
免费 | 19篇 |
国内免费 | 1篇 |
专业分类
化学 | 433篇 |
晶体学 | 2篇 |
力学 | 92篇 |
数学 | 49篇 |
物理学 | 29篇 |
出版年
2023年 | 8篇 |
2022年 | 20篇 |
2021年 | 13篇 |
2020年 | 11篇 |
2019年 | 10篇 |
2018年 | 6篇 |
2017年 | 7篇 |
2016年 | 17篇 |
2015年 | 24篇 |
2014年 | 25篇 |
2013年 | 29篇 |
2012年 | 34篇 |
2011年 | 47篇 |
2010年 | 33篇 |
2009年 | 24篇 |
2008年 | 47篇 |
2007年 | 37篇 |
2006年 | 25篇 |
2005年 | 26篇 |
2004年 | 24篇 |
2003年 | 22篇 |
2002年 | 11篇 |
2001年 | 6篇 |
2000年 | 7篇 |
1999年 | 7篇 |
1998年 | 7篇 |
1997年 | 4篇 |
1996年 | 9篇 |
1995年 | 8篇 |
1994年 | 3篇 |
1993年 | 11篇 |
1992年 | 3篇 |
1991年 | 2篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 7篇 |
1986年 | 1篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1983年 | 2篇 |
1981年 | 3篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1977年 | 1篇 |
1976年 | 3篇 |
1973年 | 1篇 |
1972年 | 1篇 |
1921年 | 1篇 |
排序方式: 共有605条查询结果,搜索用时 15 毫秒
101.
Antonia Neels Helen Stoeckli-Evans Burhkard Costisella Harald Jancke Kenneth D. Knudsen Philip Pattison 《Helvetica chimica acta》1999,82(1):35-43
The structure of [(dimethylamino)methylene]bis[phosphonic acid] dihydrate (C3H11NO6P2⋅2 H2O; 1 ) was solved ab initio from synchrotron powder X-ray diffraction data. The structure determination was based on direct methods combined with difference Fourier techniques, and the refinement was carried out using the Rietveld method. Using this high-quality diffraction pattern, it was possible to index a second phase which corresponds to the structure of the known [(dimethylamino)methylene]bis[phosphonic acid] monohydrate ( 2 ). [(Dimethylamino)methylene]bis[phosphonic acid] dihydrate ( 1 ) is monoclinic, space group P21/c, Z=4, with a=10.6644(1), b=9.1599(1), c=10.5213(1) Å, and β=98.353(1)°. The structure analysis indicates two non-equivalent P-atoms in the molecule of 1 which are also observed in the corresponding monohydrate 2 and unhydrated form 3 . All three compounds exhibit extended H-bonding networks which result in remarkably different 31P-NMR spectra. The [(dimethylamino)methylene]bis[phosphonic acids] 1 – 3 crystallize in the betaine-type structure which, therefore, contains two nonequivalent P-atoms. The −P(=O)(OH)2 and −P(=O)(OH)O− groups of 1 – 3 are involved in a number of strong H-bonds which can be characterized by the different 31P-NMR chemical shifts of the two P-atoms of 1 – 3 . 相似文献
102.
Antonia Di Mola Francesco Ferdinando Summa Patrizia Oliva Francesco Lelj Stefano Remiddi Ludovica Silvani Antonio Massa 《Molecules (Basel, Switzerland)》2021,26(23)
The properties of mixtures of two polysaccharides, arabinogalactan (AG) and hyaluronic acid (HA), were investigated in solution by the measurement of diffusion coefficients D of water protons by DOSY (Diffusion Ordered SpectroscopY), by the determination of viscosity and by the investigation of the affinity of a small molecule molecular probe versus AG/HA mixtures in the presence of bovine submaxillary mucin (BSM) by 1HNMR spectroscopy. Enhanced mucoadhesive properties, decreased mobility of water and decreased viscosity were observed at the increase of AG/HA ratio and of total concentration of AG. This unusual combination of properties can lead to more effective and long-lasting hydration of certain tissues (inflamed skin, dry eye corneal surface, etc.) and can be useful in the preparation of new formulations of cosmetics and of drug release systems, with the advantage of reducing the viscosity of the solutions. 相似文献
103.
104.
105.
106.
Danilo Antonio Giarola Paulo Rogério Catarini da Silva Alexandre Urbano Fernanda Midori de Oliveira César Ricardo Texeira Tarley Luiz Henrique Dall’Antonia 《Journal of Solid State Electrochemistry》2014,18(2):497-504
Nickel hydroxide films were electrosynthesized in the presence of different diluted surfactant solutions by galvanostatic electroprecipitation. Lamellar α-Ni(OH)2 films are obtained using cationic surfactant cetyltrimethylammonium bromide (CTAB), anionic surfactant sodium dodecyl sulfate (SDS), and also neutral surfactant Tween® 80. The films were structurally and morphologically characterized by X-ray diffraction, thermal gravimetric analysis, Fourier transform infrared spectroscopy, and scanning electron microscopy, and electrochemically by cyclic voltammetry and electrochemical quartz crystal microbalance (EQCM). The results evidenced that SDS remains intercalated between the lamellae of α-Ni(OH)2. Albeit the presence of CTAB and Tween® 80, it was noticed in FTIR spectra that the surfactants did not intercalate. The morphology was affected by the presence of different surfactants. All studied surfactants displaced the oxidation potential (E O) of Ni2+/Ni3+ process to less positive values. Also, the presence of surfactants improved the electrode charge efficiency and the charge response for the same number of moles of nickel ions deposited. The ratio of the charge and frequency change is 4.4 times bigger for films deposited with SDS when compared with pure α-Ni(OH)2 films. 相似文献
107.
Victoria F. Samanidou Dimitrios E. Giannakis Antonia Papadaki 《Journal of separation science》2009,32(9):1302-1311
Herein a quantitative method for the determination of seven penicillins in bovine plasma and veterinary drugs has been developed. Amoxicillin (AMO), ampicillin (AMP), penicillin G (PENG), penicillin V (PENV), oxacillin (OXA), cloxacillin (CLO) and dicloxacillin (DICLO) were separated on a Perfectsil ODS‐2 (250×4 mm, 5 μm) column, using gradient elution, with a mobile phase of 0.1% v/v TFA and ACN–methanol (90:10 v/v). PDA detection was used at 240 nm. Penicillins were isolated from bovine plasma by SPE on Lichrolut RP‐18 cartridges with mean recoveries from 85.7 to 113.5%. Colchicine (3 ng/μL) was used as an internal standard. The developed method was validated in terms of selectivity, linearity, accuracy, precision, stability and sensitivity. Repeatability (n = 5) and between‐day precision (n = 5) revealed RSD < 12%. The detection limits in the bovine plasma were estimated as 18 ng for AMO and AMP, 25 for PENG, PENV and OXA, 3 ng for CLO and 12 ng for DICLO. Spiked plasma samples were stable for 1 wk, except for AMP and CLO, which were stable for 3 wk and OXA for 4 wk. AMO, PENG and PENV were stable for two freeze–thaw cycles, OXA, CLO and DICLO for four, while AMP only for one. 相似文献
108.
Percolation theory is a multidisciplinary theory that studies chaotic systems. It has been applied in the pharmaceutical field since 1987. The application of this theory to study the release and hydration rate of hydrophilic matrices allowed for first time to explain the changes in release and hydration kinetic of swellable matrices type controlled delivery systems. The objective of the present paper is to estimate the percolation threshold of HPMC K4M in matrices of lobenzarit disodium and to apply the obtained result to the design of hydrophilic matrices for the controlled delivery of this drug. The materials used to prepare the tablets were Lobenzarit disodium (LBD) and HPMC of viscosity grade K4M. The drug mean particle size was 42+/-0.61 mum and the polymer was sieved and 150-200 microm granulometric fraction was selected. The formulations studied were prepared with different excipient contents in the range of 10-80% w/w. Dissolution studies were carried out using the paddle method and the water uptake measurements were performed using a modified Enslin apparatus. In order to estimate the percolation threshold, the behaviour of the kinetic parameters with respect to the volumetric fraction of each component at time zero, was studied. According to percolation theory, the critical points observed in dissolution and water uptake studies are attributed to the existence of an excipient percolation threshold. This threshold was situated between (18.58 to 24.33% v/v of HPMC). Therefore, the LBD-HPMC K4M matrices with a relative HPMC particle size of should be formulated with an excipient content above 24.33% v/v of HPMC, to obtain a control of the drug release from these systems. 相似文献
109.
We present an empirical but simple and practical spectral chart method for determining the mean turbulent kinetic energy dissipation rate $ \left\langle \varepsilon \right\rangle $ in a variety of turbulent flows. The method relies on the validity of the first similarity hypothesis of Kolmogorov (C R (Doklady) Acad Sci R R SS, NS 30:301–305, 1941) (or K41) which implies that spectra of velocity fluctuations scale on the kinematic viscosity ν and $ \left\langle \varepsilon \right\rangle $ at large Reynolds numbers. However, the evidence, based on the DNS spectra, points to this scaling being also valid at small Reynolds numbers, provided effects due to inhomogeneities in the flow are negligible. The methods avoid the difficulty associated with estimating time or spatial derivatives of the velocity fluctuations. It also avoids using the second hypothesis of K41, which implies the existence of a ?5/3 inertial subrange only when the Taylor microscale Reynods number R λ is sufficiently large. The method is in fact applied to the lower wavenumber end of the dissipative range thus avoiding most of the problems due to inadequate spatial resolution of the velocity sensors and noise associated with the higher wavenumber end of this range.The use of spectral data (30?≤?R λ?≤?400) in both passive and active grid turbulence, a turbulent mixing layer and the turbulent wake of a circular cylinder indicates that the method is robust and should lead to reliable estimates of $ \left\langle \varepsilon \right\rangle $ in flows or flow regions where the first similarity hypothesis should hold; this would exclude, for example, the region near a wall. 相似文献
110.
Nostro A Filocamo A Giovannini A Catania S Costa C Marino A Bisignano G 《Natural product research》2012,26(22):2132-2136
This study reported the antimicrobial activity and phenolic content of natural site and micropropagated Limonium avei (De Not.) Brullo & Erben inflorescences. The minimum inhibitory concentration (MIC) and minimum bactericidal concentration (MBC) of ethanolic extracts were determined according to the Clinical Laboratory Standards Institute guidelines. Individual phenolic acids and flavonoids were detected by a high performance liquid chromatography (HPLC-DAD) method. The samples showed a comparable antimicrobial activity, although the natural site extract possessed the lower MIC values. The best activity was detected against Gram-positive bacteria, such as Staphylococcus aureus including methicillin resistant strains (MIC and MBC values ranging from 7.81 to 62.50?μg?mL(-1) and from 500 to 2000?μg?mL(-1) respectively). In contrast, a low activity was found on Gram-negative bacteria and Candida albicans. The HPLC-DAD analysis revealed ten phenolic acids and four flavonoids with a major amount of m-coumaric acid, naringin and quercetin in the natural site extract. 相似文献