全文获取类型
收费全文 | 562篇 |
免费 | 11篇 |
专业分类
化学 | 389篇 |
晶体学 | 2篇 |
力学 | 6篇 |
数学 | 12篇 |
物理学 | 164篇 |
出版年
2024年 | 2篇 |
2023年 | 4篇 |
2022年 | 12篇 |
2021年 | 10篇 |
2020年 | 10篇 |
2019年 | 18篇 |
2018年 | 13篇 |
2017年 | 8篇 |
2016年 | 18篇 |
2015年 | 15篇 |
2014年 | 24篇 |
2013年 | 37篇 |
2012年 | 21篇 |
2011年 | 36篇 |
2010年 | 29篇 |
2009年 | 15篇 |
2008年 | 32篇 |
2007年 | 24篇 |
2006年 | 25篇 |
2005年 | 31篇 |
2004年 | 27篇 |
2003年 | 24篇 |
2002年 | 31篇 |
2001年 | 8篇 |
2000年 | 6篇 |
1999年 | 9篇 |
1998年 | 3篇 |
1997年 | 2篇 |
1996年 | 10篇 |
1995年 | 16篇 |
1994年 | 7篇 |
1993年 | 3篇 |
1992年 | 8篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 2篇 |
1987年 | 5篇 |
1985年 | 4篇 |
1984年 | 1篇 |
1982年 | 2篇 |
1981年 | 2篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1974年 | 2篇 |
1973年 | 1篇 |
1969年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
排序方式: 共有573条查询结果,搜索用时 15 毫秒
121.
Partial etherification of phenolic-OH groups of calix[4]arenes with various alkyl halides/tosylates and K2CO3 under microwave irradiation afforded 1,3-dialkoxycalix[4]arenes in their cone conformation only as predominant/sole product in good yields (71–85%). The protocol was found to be much superior to conventional heating both in terms of yield and reaction time. Some of the 1,3-dialkoxycalix[4]arenes were elaborated further to the syntheses of cesium selective calix[4]crown-6 ionophores. 相似文献
122.
Krow GR Shoulders MD Edupuganti R Gandla D Yu F Sonnet PE Sender M Choudhary A DeBrosse C Ross CW Carroll P Raines RT 《The Journal of organic chemistry》2012,77(12):5331-5344
Proline derivatives with a C(γ)-exo pucker typically display a high amide bond trans/cis (K(T/C)) ratio. This pucker enhances n→π* overlap of the amide oxygen and ester carbonyl carbon, which favors a trans amide bond. If there were no difference in n→π* interaction between the ring puckers, then the correlation between ring pucker and K(T/C) might be broken. To explore this possibility, proline conformations were constrained using a methylene bridge. We synthesized discrete gauche and anti 5-fluoro- and 5-hydroxy-N-acetylmethanoproline methyl esters from 3-syn and 3-anti fluoro- and hydroxymethanopyrrolidines using directed α-metalation to introduce the α-ester group. NBO calculations reveal minimal n→π* orbital interactions, so contributions from other forces might be of greater importance in determining K(T/C) for the methanoprolines. Consistent with this hypothesis, greater trans amide preferences were found in CDCl(3) for anti isomers en-MetFlp and en-MetHyp (72-78% trans) than for the syn stereoisomers ex-MetFlp and ex-MetHyp (54-67% trans). These, and other, K(T/C) results that we report here indicate how substituents on proline analogues can affect amide preferences by pathways other than ring puckering and n→π* overlap and suggest that caution should be exercised in assigning enhanced pyrrolidine C(γ)-exo ring puckering based solely on enhanced trans amide preference. 相似文献
123.
The disturbance caused by the application of continuous mechanical source on the free surface of a homogeneous, isotropic
elastic half space in the context of the theory of generalized thermoelastic diffusion with one relaxation time parameter
is investigated in the Laplace-Fourier transform domain for a two dimensional problem using eigenvalue approach. The integral
transforms are inverted by using a numerical technique. The expressions for displacement components, stresses, temperature
field, concentration and chemical potential so obtained in the physical domain are computed numerically and illustrated graphically
at different times, for copper like material. As a special case the effect of diffusion on various expressions has also been
obtained analytically and depicted graphically. 相似文献
124.
Masood Parvez Atta‐ur‐Rahman M. Iqbal Choudhary Shehnaz Parveen Syed Abdul Majid Ayatollahi 《Acta Crystallographica. Section C, Structural Chemistry》2000,56(2):233-234
In the title compound, 3β‐(dimethylamino)‐16α‐hydroxy‐14‐methyl‐4‐methylene‐9,19‐cyclo‐5α‐pregnan‐20‐one monohydrate, C25H39NO2·H2O, the pentacyclo steroidal alkaloid is composed of three six‐membered, one five‐membered and one three‐membered ring. The molecular dimensions are as expected. The structure is stabilized by hydrogen bonds involving H and O atoms of water and the alkaloid molecules, with strong N?O [2.829 (7) Å] and O?O [2.790 (6) and 2.949 (7) Å] interactions. 相似文献
125.
Developing more efficient catalytic processes using abundant and low toxicity transition metals is key to enable their mainstream use in synthetic chemistry. We have rationally designed a new Mn(i)-catalyst for hydroarylation reactions that displays much improved catalytic activity over the commonly used MnBr(CO)5. Our catalyst, MnBr(CO)3(MeCN)2, avoids the formation of the off-cycle manganacycle-(CO)4 species responsible for low catalyst activity, allowing near room temperature hydroarylation of alkenes and alkynes with broad functional group tolerance including late stage functionalisation and diversification of bioactive molecules.A Mn(i)-catalyst for hydroarylation reactions, MnBr(CO)3(MeCN)2, avoids the formation of the off-cycle manganacycle-(CO)4 species responsible for low catalyst activity typical of MnBr(CO)5, leading to mild and broad scope hydroarylation. 相似文献
126.
Sarosh Iqbal Nimra Naveed Shaikh Khalid Mohammed Khan Shumaila Kiran Sehrish Naz Zaheer Ul-Haq Shahnaz Perveen M. Iqbal Choudhary 《Molecules (Basel, Switzerland)》2022,27(22)
Currently the discovery and development of potent β-glucuronidase inhibitors is an active area of research due to the observation that increased activity of this enzyme is associated with many pathological conditions, such as colon cancer, renal diseases, and infections of the urinary tract. In this study, twenty-seven 2-aminopyrimidine derivatives 1–27 were synthesized by fusion of 2-amino-4,6-dichloropyrimidine with a variety of amines in the presence of triethylamine without using any solvent and catalyst, in good to excellent yields. All synthesized compounds were characterized by EI-MS, HREI-MS and NMR spectroscopy. Compounds 1–27 were then evaluated for their β-glucuronidase inhibitory activity, and among them, compound 24 (IC50 = 2.8 ± 0.10 µM) showed an activity much superior to standard D-saccharic acid 1,4-lactone (IC50 = 45.75 ± 2.16 µM). To predict the binding mode of the substrate and β-glucuronidase, in silico study was performed. Conclusively, this study has identified a potent β-glucuronidase inhibitor that deserves to be further studied for the development of pharmaceutical products. 相似文献
127.
PbBi2Ta2O9 ceramic samples were fabricated by high-temperature mixed oxide method. X-ray diffraction determines the structure as orthorhombic. The scanning electron microscopy confirms the formation of densely packed grains in the sample. The dielectric measurements, complex impedance and complex modulus study were carried out in a frequency range of 1?kHz–1?MHz and a temperature rangeof 25–500°C. The conduction mechanism of the material is discussed in details using variable range hoping, nearest neighbor hopping relaxation model and dc activation energy at two different temperature regimes. From the J-E characteristics studies, the occurrence of non-linear curves endorses the non-Ohmic nature of the material. 相似文献
128.
129.
The polycrystalline samples of Pb(Li1/4Dy1/4W1/2)O3 have been synthesized by high-temperature solid-state reaction techniques. Room temperature X-ray diffraction (XRD) studies
of the compound provided preliminary structural data, and hence formation of a single phase desired material was confirmed.
Detailed studies of dielectric constant (ε) and loss (tanδ) as a function of frequency (100 Hz to 10 kHz) at room temperature (298 K) and also as a function of temperature (liquid
nitrogen to 403 K) at 10 kHz suggest that the compound undergoes a ferroelectric phase transition of diffuse type. 相似文献
130.
The present paper is concerned with the dynamic problem of a homogeneous isotropic half-space with voids subjected to a set of normal point sources. The integral transforms have been inverted by using a numerical technique to obtain the normal force stress, normal displacement, tangential couple stress and volume fraction field in the physical domain for the two different sources. The expressions of these quantities have been given and illustrated graphically to depict the effect of micropolarity and voids. 相似文献