全文获取类型
收费全文 | 2321篇 |
免费 | 158篇 |
国内免费 | 3篇 |
专业分类
化学 | 1774篇 |
晶体学 | 19篇 |
力学 | 37篇 |
数学 | 331篇 |
物理学 | 321篇 |
出版年
2023年 | 21篇 |
2022年 | 17篇 |
2021年 | 30篇 |
2020年 | 47篇 |
2019年 | 35篇 |
2018年 | 37篇 |
2017年 | 26篇 |
2016年 | 113篇 |
2015年 | 94篇 |
2014年 | 98篇 |
2013年 | 152篇 |
2012年 | 164篇 |
2011年 | 174篇 |
2010年 | 122篇 |
2009年 | 98篇 |
2008年 | 174篇 |
2007年 | 156篇 |
2006年 | 162篇 |
2005年 | 140篇 |
2004年 | 85篇 |
2003年 | 68篇 |
2002年 | 62篇 |
2001年 | 45篇 |
2000年 | 30篇 |
1999年 | 21篇 |
1998年 | 24篇 |
1997年 | 20篇 |
1996年 | 18篇 |
1995年 | 16篇 |
1994年 | 16篇 |
1993年 | 20篇 |
1992年 | 17篇 |
1991年 | 10篇 |
1990年 | 14篇 |
1989年 | 9篇 |
1988年 | 10篇 |
1987年 | 11篇 |
1986年 | 5篇 |
1985年 | 6篇 |
1984年 | 7篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1978年 | 6篇 |
1975年 | 4篇 |
1969年 | 4篇 |
1963年 | 5篇 |
1959年 | 11篇 |
1958年 | 8篇 |
1957年 | 11篇 |
1956年 | 9篇 |
排序方式: 共有2482条查询结果,搜索用时 15 毫秒
101.
Gil-Agustí M Capella-Peiró E Monferrer-Pons L García-Alvarez-Coque MC Esteve-Romero J 《The Analyst》2001,126(4):457-464
The chromatographic behaviour of binary and ternary mixtures of several phenethylamines (phenylephrine, phenylpropanolamine, ephedrine, pseudoephedrine and methoxyphenamine) and antihistamines (pheniramine, carbinoxamine, doxylamine, chlorpheniramine, dexchlorpheniramine, dexbrompheniramine, diphenhydramine, tripolidine, azatadine and phenyltoloxamine), found in cough-cold pharmaceutical preparations, was studied using C8, C18 and cyano columns, micellar mobile phases of sodium dodecyl sulfate (SDS) and pentanol and UV detection. Using a C8 column and mobile phases of 0.05 mol l-1 SDS-6% v/v pentanol or 0.15 mol l-1 SDS-2% v/v pentanol at pH 7, more than 30 different phenethylamine-antihistamine combinations can be resolved in < 15 min. Intra- and inter-day repeatabilities and reproducibilities evaluated at three different drug concentrations (0.5, 5 and 25 micrograms ml-1, n = 10) were below 1.6, 2.5 and 2.4%, respectively. The drug amounts found in 18 formulations agreed with those declared by the manufacturers within the tolerance limits, and with those obtained using a mobile phase of 55% v/v methanol at pH 7. No interference was observed from other accompanying drugs such as acetylsalicylic acid, ascorbic acid, betamethasone, bromhexine, caffeine, codeine, dextromethorphan, paracetamol, prednisolone, salicylamide and tartrazine. The proposed procedure has the advantage over the conventional aqueous-organic procedure of using a small amount of organic solvent, which is highly retained in the SDS solution. The efficiencies are also greater. On the other hand, in the micellar system, the retentions of phenethylamines and antihistamines are similar, although the compounds can be easily resolved. In contrast, using the methanol-water mobile phase, the phenethylamines are weakly retained, whereas the antihistamines usually show a high retention. 相似文献
102.
Portella G Poater J Bofill JM Alemany P Solà M 《The Journal of organic chemistry》2005,70(7):2509-2521
The local aromaticity of the six-membered rings in three series of benzenoid compounds, namely, the [n]acenes, [n]phenacenes, and [n]helicenes for n = 1-9, has been assessed by means of three probes of local aromaticity based on structural, magnetic, and electron delocalization properties. For [n]acenes our analysis shows that the more reactive inner rings are more aromatic than the outer rings. For [n]phenacenes, all indicators of aromaticity show that the external rings are the most aromatic. From the external to the central ring, the local aromaticity varies in a damped alternate way. The trends for the [n]helicene series are the same as those found for [n]phenacenes. Despite the departure from planarity in [n]helicenes, only a very slight loss of aromaticity is detected in [n]helicenes as compared to the corresponding [n]phenacenes. Finally, because of magnetic couplings between superimposed six-membered rings in the higher members of the [n]helicenes series, we have demonstrated that the NICS indicator of aromaticity artificially increases the local aromaticity of their most external rings. 相似文献
103.
YAG : Nd grown under 98% Ar 2% H2 protective atmosphere free of nitrogen or hydrocarbons showed after UV irradiation broad absorption peaked at 1·9×104 cm–1 which disappeared relatively slowly at room temperature. It was more intensive in oxygen treated samples than in those annealed in hydrogsn. Transient absorption suppresses laser output by the increase of absorption at 0·94×104 cm–1 (1064 nm) and, particularly in CW mode, by the anomalous rod deformation. YAG : Nd containing Fe ions (2·10–4 wt%) showed no transient absorption. 相似文献
104.
Jordi Badosa Josep Calbó Richard Mckenzie Ben Liley Josep‐Abel González Bruce Forgan Charles N. Long 《Photochemistry and photobiology》2014,90(4):941-951
Cloud effects on UV Index (UVI) and total solar radiation (TR) as a function of cloud cover and sunny conditions (from sky images) as well as of solar zenith angle (SZA) are assessed. These analyses are undertaken for a southern‐hemisphere mid‐latitude site where a 10‐years dataset is available. It is confirmed that clouds reduce TR more than UV, in particular for obscured Sun conditions, low cloud fraction (<60%) and large SZA (>60°). Similarly, local short‐time enhancement effects are stronger for TR than for UV, mainly for visible Sun conditions, large cloud fraction and large SZA. Two methods to estimate UVI are developed: (1) from sky imaging cloud cover and sunny conditions, and (2) from TR measurements. Both methods may be used in practical applications, although Method 2 shows overall the best performance, as TR allows considering cloud optical properties. The mean absolute (relative) differences of Method 2 estimations with respect to measured values are 0.17 UVI units (6.7%, for 1 min data) and 0.79 Standard Erythemal Dose (SED) units (3.9%, for daily integrations). Method 1 shows less accurate results but it is still suitable to estimate UVI: mean absolute differences are 0.37 UVI units (15%) and 1.6 SED (8.0%). 相似文献
105.
106.
107.
γ-Carboxylation of β-diketones, 1, can be improved using samples containing 100% of ketoenol tautomers, 3, prepared by mild hydrolysis of the corresponding copper(II) complexes 2. Cyclization of the so formed 4-alkyl-3,5-dioxohexanoic acids, 4, affords 5-alkyl-4-hydroxy-6-methyl-2-pyrones, 5. 相似文献
108.
Mesoporous molecular sieve SBA‐15 and conventional silica gel were grafted with 3‐[2‐(diethylamino)ethylamino]propyl groups and used as supports for the preparation of deposited palladium catalysts, which were subsequently evaluated in Stille cross‐coupling reaction of aryl bromides. The highest conversions were achieved with the metal‐saturated catalyst resulting from the modified SBA‐15. Influence of various reaction parameters (solvent, additive, temperature, etc.) on the overall yield and selectivity was studied. Copyright © 2013 John Wiley & Sons, Ltd. 相似文献
109.
Expanding the Scope of Hypervalent Iodine Reagents for Perfluoroalkylation: From Trifluoromethyl to Functionalized Perfluoroethyl
下载免费PDF全文
![点击此处可从《Chemistry (Weinheim an der Bergstrasse, Germany)》网站下载免费的PDF全文](/ch/ext_images/free.gif)
Dr. Václav Matoušek Jiří Václavík Peter Hájek Julie Charpentier Zsófia E. Blastik Ewa Pietrasiak Alena Budinská Prof. Dr. Antonio Togni Dr. Petr Beier 《Chemistry (Weinheim an der Bergstrasse, Germany)》2016,22(1):417-424
A series of new hypervalent iodine reagents based on the 1,3‐dihydro‐3,3‐dimethyl‐1,2‐benziodoxole and 1,2‐benziodoxol‐3‐(1H)‐one scaffolds, which contain a functionalized tetrafluoroethyl group, have been prepared, characterized, and used in synthetic applications. Their corresponding electrophilic fluoroalkylation reactions with various sulfur, oxygen, phosphorus, and carbon‐centered nucleophiles afford products that feature a tetrafluoroethylene unit, which connects two functional moieties. A related λ3‐iodane that contains a fluorophore was shown to react with a cysteine derivative under mild conditions to give a thiol‐tagged product that is stable in the presence of excess thiol. Therefore, these new reagents show a significant potential for applications in chemical biology as tools for fast, irreversible, and selective thiol bioconjugation. 相似文献
110.
In this article, an ALE finite element method to simulate the partial melting of a workpiece of metal is presented. The model includes the heat transport in both the solid and liquid part, fluid flow in the liquid phase by the Navier–Stokes equations, tracking of the melt interface solid/liquid by the Stefan condition, treatment of the capillary boundary accounting for surface tension effects and a radiative boundary condition. We show that an accurate treatment of the moving boundaries is crucial to resolve their respective influences on the flow field and thus on the overall energy transport correctly. This is achieved by a mesh‐moving method, which explicitly tracks the phase boundary and makes it possible to use a sharp interface model without singularities in the boundary conditions at the triple junction. A numerical example describing the welding of a thin‐steel wire end by a laser, where all aforementioned effects have to be taken into account, proves the effectiveness of the approach.Copyright © 2012 John Wiley & Sons, Ltd. 相似文献