全文获取类型
收费全文 | 714篇 |
免费 | 106篇 |
国内免费 | 69篇 |
专业分类
化学 | 613篇 |
晶体学 | 4篇 |
力学 | 96篇 |
综合类 | 19篇 |
数学 | 30篇 |
物理学 | 127篇 |
出版年
2024年 | 1篇 |
2023年 | 9篇 |
2022年 | 28篇 |
2021年 | 39篇 |
2020年 | 42篇 |
2019年 | 29篇 |
2018年 | 33篇 |
2017年 | 27篇 |
2016年 | 33篇 |
2015年 | 34篇 |
2014年 | 36篇 |
2013年 | 31篇 |
2012年 | 38篇 |
2011年 | 43篇 |
2010年 | 41篇 |
2009年 | 40篇 |
2008年 | 35篇 |
2007年 | 37篇 |
2006年 | 43篇 |
2005年 | 47篇 |
2004年 | 42篇 |
2003年 | 24篇 |
2002年 | 21篇 |
2001年 | 18篇 |
2000年 | 14篇 |
1999年 | 20篇 |
1998年 | 9篇 |
1997年 | 16篇 |
1996年 | 10篇 |
1995年 | 6篇 |
1994年 | 6篇 |
1993年 | 4篇 |
1992年 | 5篇 |
1991年 | 3篇 |
1990年 | 3篇 |
1989年 | 5篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 3篇 |
1984年 | 2篇 |
1982年 | 2篇 |
1981年 | 1篇 |
1957年 | 1篇 |
排序方式: 共有889条查询结果,搜索用时 687 毫秒
11.
Bromine Superoxide: Generation and Photoisomerization into Bromine Dioxide Flash pyrolysis of a gas mixture containing bromine, oxygen and argon yields bromine superoxide, which can be identified IR- and UV-spectroscopically after trapping the pyrolysate at 12 K. Matrix irradiation transfers bromine superoxide into bromine dioxide. The backreaction can be induced by changing the wavelength. Even at room temperature a detectable amount of bromine superoxide is formed upon preparing a mixture of gaseous bromine, oxygen and argon. 相似文献
12.
海洋天然产物研究新进展 总被引:12,自引:0,他引:12
海洋天然产物化学是目前天然产物化学中最活跃的研究领域之一。近年来,从海洋生物中分离到非常多的化学结构和生理活性上令人注目的新化合物,引起了有机化学家和药物化学家的关注。本文按萜类、太环内酯、聚醚类、生物碱,环肽、含氰化合物、甾醇、聚丙酸酯类化合物等化学结构来概述海洋天然产物研究近年来的进展。 相似文献
13.
Summary Optically pure (+)-beta-eudesmol is a possible starting material for the synthesis of several termite defense compounds. A
two step procedure for the isolation of gram quantities of (+)-beta-eudesmol from commercially availableAmyris balsamifera oil (syn. West Indian sandalwood oil), containing 8% beta-eudesmol, was developed. Step one consisted of an efficient vacuum
distillation of the total oil. Step two was a medium pressure LC separation with an AgNO3 impregnated silica gel stationary phase. Several other separation procedures failed due to the presence of many closely related
sesquiterpene alcohols (75% of the oil). 相似文献
14.
Isolation of lipase producer and its performance in enantioselective hydrolysis of glycidyl butyrate
A racemic glycidyl butyrate resolving strain, preliminarily identified as a Rhizopus sp., had been isolated from soil. Its extracellular lipase was found to enantioselectively hydrolyze the (S)-enantiomer of
the chiral ester, with optimal activities at pH 5.3 and 42°C. Higher en antioselectivity of theenzyme was observed at lower
temperatures, while the best anantioselectivity was obtained at pH 5.5–6.0, with an, E value (enantiomeric ratio) of 57. 相似文献
15.
16.
D. A. Rakhimov A. S. Shashkov K. S. Zhauynbaeva M. Kh. Malikova N. D. Abdullaev 《Chemistry of Natural Compounds》2004,40(4):358-361
Native acetylated glucomannan of molecular weight (MW) 32000 with a glucose:mannose ratio 1:30 was isolated from bulbs of Narcissus poeticus. Glucomannan was depolymerized to a fragment of MW 15000 with an unchanged primary structure and was studied using PMR and 13C NMR spectroscopy. It was found that the linear chain of the biopolymer consists of 1-4-bound D-gluco- and D-mannopyranose units and the O-Ac groups are localized on C-2, C-3, and C-6 hydroxyls in certain anhydromannose units. 相似文献
17.
Yevgen Posokhov Alexander Gorski Jens Spanget-Larsen Fritz Duus Poul Erik Hansen Jacek Waluk 《Chemphyschem》2004,5(4):495-502
Thioacetylacetone and its variously deuterated isotopomers have been investigated using electronic and vibrational spectroscopy combined with quantum chemical calculations. Thioacetylacetone is known for its photochromic properties, but the structures of the initial and final forms have been the subject of a long debate. Analysis of the IR spectra recorded in low-temperature argon and xenon matrices, room-temperature solutions, and in the gas phase has allowed us to establish the nature of the photochromic species and of its precursor. Similar to the case of another beta-thioxoketone, monothiodibenzoylmethane, the photo-product has been assigned to the nonchelated SH exo-rotamer of the (Z)-enethiol tautomeric form, whereas the dominant ground-state species corresponds to the chelated (Z)-enol tautomeric form. Detailed vibrational assignments have been proposed for both forms based on quantum chemical calculations and polarization experiments. In the case of the chelated (Z)-enol species prevailing in the ground state, a second-order perturbative anharmonic analysis at the B3LYP/cc-pVTZ level indicated strong anharmonic effects associated with the intramolecular hydrogen bond, leading to a shift of more than 600 cm-1 of the wavenumber of the OH-stretching vibration. A small fraction of the SH endo-rotameric chelated (Z)-enethiol form was also detected under unperturbed conditions. The (Z)-enethiol form can be converted into the (Z)-enol form by irradiation at 290 nm. 相似文献
18.
Ernst Berger David W. T. Griffith Gerhard Schuster Stephen R. Wilson 《Mikrochimica acta》1988,95(1-6):239-241
The use of an integrating sphere for the measurement of absorption spectra of thin films is described. The thin film (for example a rare gas matrix) is grown directly on the inside surface of the sphere. Multiple reflections inside the integrating sphere lead to significant enhancement of weak absorptions of the film, increasing the sensitivity of such measurements. 相似文献
19.
E. Yu. Yagudaeva M. R. Muidinov D. V. Kapustin V. P. Zubov 《Russian Chemical Bulletin》2007,56(6):1166-1173
Polyaniline coatings of the cation-exchange resin Dowex and a synthetic composite material based on silica gel surface-modified
by a sulfated styrene-divinylbenzene copolymer were prepared by precipitative polymerization of aniline on the surface of
the supports. The optimal conditions for the preparation of the polyaniline-containing material providing the formation of
a thin polymeric coating on the support surface were determined. Aniline is predominantly consumed to the formation of a uniform
polymeric coating about 3 nm thick with an increase in the concentration of sulfo groups on the support surface. The efficiency
of using the polyaniline-containing sorbents for the preparative isolation of DNA from plant tissue lysates was demonstrated.
Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 6, pp. 1123–1130, June, 2007. 相似文献
20.
Matrix isolation infrared studies of complexes formed between substituted phenols and trimethylamine
Infrared spectroscopy and matrix isolation technique have been used to study the 1 : 1 complexes formed between 2,4,5-trichlorophenol (TCP), pentachlorophenol (PCP) or 2-chloro-4,6-dinitrophenol (CNP) and trimethylamine (TMA) isolated in solid argon. The results were analyzed in relation to the type of complex formed. Depending on the proton-donor ability of the phenol three different types of hydrogen bonded complexes have been identified in argon matrices. The weakest phenol in the series, TCP (pKa = 6.72), forms a strong molecular hydrogen bonded complex with TMA as indicated by the broad ν(OHN) absorption with a maximum at 2490 cm−1 and a band at 811 cm−1 due to the νs(C3N) mode of the perturbed amine. The strongest phenol, CNP (pKa = 2.01), interacts with TMA in an argon matrix to form ionic complex with the proton transferred to the base molecule. This is evidenced by the presence of the ν(NH+---O−) absorption between 3000−1800 cm−1, by the νas(C3N+) and νs(C3N+) absorptions due to the protonated amine and by numerous product bands due to the relatively strongly perturbed modes of the phenol ring. The interaction between TMA and a phenol of intermediate strength, PCP (pKa = 4.74), in solid argon probably leads to the formation of two types of hydrogen bonded complexes: an ionic complex with the proton transferred to the amine molecule and a pseudosymmetric one with the proton more or less equally shared between the phenol and amine molecules. In this case the protonic absorption consists of two broad features situated in the 3000–1600 cm−1 and 950–400 cm−1 regions due to the ν(NH+O−) and ν(OHN) modes, respectively. 相似文献