全文获取类型
收费全文 | 82110篇 |
免费 | 442篇 |
国内免费 | 396篇 |
专业分类
化学 | 26998篇 |
晶体学 | 847篇 |
力学 | 6781篇 |
数学 | 32200篇 |
物理学 | 16122篇 |
出版年
2020年 | 63篇 |
2019年 | 71篇 |
2018年 | 10473篇 |
2017年 | 10287篇 |
2016年 | 6111篇 |
2015年 | 924篇 |
2014年 | 363篇 |
2013年 | 546篇 |
2012年 | 3976篇 |
2011年 | 10726篇 |
2010年 | 5754篇 |
2009年 | 6177篇 |
2008年 | 6824篇 |
2007年 | 8993篇 |
2006年 | 472篇 |
2005年 | 1497篇 |
2004年 | 1677篇 |
2003年 | 2119篇 |
2002年 | 1181篇 |
2001年 | 343篇 |
2000年 | 403篇 |
1999年 | 223篇 |
1998年 | 231篇 |
1997年 | 184篇 |
1996年 | 262篇 |
1995年 | 164篇 |
1994年 | 109篇 |
1993年 | 139篇 |
1992年 | 124篇 |
1991年 | 109篇 |
1990年 | 94篇 |
1989年 | 100篇 |
1988年 | 121篇 |
1987年 | 104篇 |
1986年 | 109篇 |
1985年 | 110篇 |
1984年 | 106篇 |
1983年 | 65篇 |
1982年 | 86篇 |
1981年 | 79篇 |
1980年 | 89篇 |
1979年 | 87篇 |
1978年 | 71篇 |
1977年 | 62篇 |
1976年 | 41篇 |
1975年 | 47篇 |
1974年 | 42篇 |
1973年 | 49篇 |
1914年 | 45篇 |
1909年 | 41篇 |
排序方式: 共有10000条查询结果,搜索用时 15 毫秒
991.
A method for the quantitation of polycyclic aromatic hydrocarbons (PAHs) in indoor and outdoor air by high-performance liquid chromatography (HPLC) with a spectrofluorometric detection and programmed excitation and emission wavelength pairs is proposed. The mobile phase is a linear gradient of methanol-water. The relative standard deviations (n = 5) are in the range 0.38-1.7% at concentration levels of 0.69-11.40 ng ml(-1). The determination limits (S N = 10 ) are 0.5-15.9 pg. The proposed method was successfully applied to quantitate 12 PAHs in gas phase and particulates in indoor and outdoor air. The recoveries of PAHs from gas phase and particulates were 95.7-117.5 and 94.8-112.4%, respectively. This highly sensitive automatic HPLC analysis for PAHs both in gas phase and particulates can be applied to indoor and outdoor survey. 相似文献
992.
Choji Kashima Katsumi Takahashi Kiyoshi Fukusaka Akira Hosomi 《Journal of heterocyclic chemistry》1998,35(3):503-511
The conjugate additions of N-(α,β-unsaturated)acylpyrazoles were carried out by the treatment with Grignard reagents in the presence of cuprous halides. The reaction of 2-(α,β-unsaturated)acyl-3-phenyl-l-menthopyrazoles 3a-h occurred in higher chemical yields and with asymmetric inductions on β-position, where the addition of magnesium bromide as a Lewis acid influenced to the yields and the diastereoselectivities. In the case of α-methylated 2-(α,β-unsaturated)acyl-3-phenyl-l-menthopyrazoles 3i-n , the excellent asymmetric induction on the α-position was also observed through the diastereofacial protonation. 相似文献
993.
Ya-Guang Chen Fan-Xia Meng Hai-Jun Pang Dong-Mei Shi Yu Sun 《Journal of Cluster Science》2007,18(2):396-405
A novel uranyl complex with dimeric lacunary polyoxoanion like open-mouthed clam, Na5[(A-α-SiW9O33H3)2K{UO2(H2O)}2], was prepared and characterized by elemental analysis, infrared and ultraviolet–visible spectroscopy and single crystal
X-ray diffraction. In the anion, two A-α-SiW9O3410− groups share two terminal oxygen atoms Od′ derived from removal of three corner-shared W atoms from saturated α-Keggin anion, forming a dimeric anion with an open
mouth in which potassium ion and uranyl ions are coordinated. Uranium atom adopts a pentagonal bipyramidal geometry. The coordinating
anions are linked by sodium ions via coordination of terminal or bridging oxygen atoms, forming two-dimensional layer arrangement.
Between the layers are the hydrogen bonds from which a supramolecular architecture is created. UV–VIS spectrum gives W–O and
U–O charge transfer transitions at 230–265 and 432 nm, showing the change of geometry of the polyanion and weakening of the
U–O bonds of the uranyl cation.
Electronic supplementary material The online version of this article () contains supplementary material, which is available to authorized users. 相似文献
994.
Yan Xiao Jian Wang Wang Xia Guang Feng Huai You Wang 《Journal of Analytical Chemistry》2007,62(5):438-443
The maximum emission wavelength of dopamine is 317 nm with excitation at 290 nm. The relative fluorescence intensity of dopamine
decreased in the presence of enoxacin, which showed that fluorescence quenching occurred. The Stern-Volmer (S-V) plot showed
a nonlinear relationship between the relative fluorescence intensity of dopamine and the concentration of enoxain. The quenching
mechanism was studied and the results suggested that both dynamic and static quenching processes were responsible for the
observed positive deviation in the S-V plot. When the S-V plot was modified by logarithm, the linear relationship was obtained
between logF
0/F and C in the range of 0.10 to 13.0 μg/mL (where F
0 is the relative fluorescence intensity of dopamine, F is the relative fluorescence intensity of dopamine in the presence of enoxacin, and C is the concentration of enoxacin). The fluorescence quenching method for the determination of enoxacin was developed. The
linear regression equation of the calibration graph of enoxacin was C = 13.70 (logF
0/F) − 0.5836, with the correlation coefficient 0.9984. The detection limit was 2.0 ng/mL and the relative standard deviation
was 2.52%. The effects of pH, the stability of dopamine in the presence of enoxacin, and foreign ions on the determination
of enoxacin have been examined. The recovery of enoxacin was from 94.9 to 103.0% in a human serum sample and from 94.9 to
108.0% in a urine sample. The method is simple, rapid, and can be used for the determination of enoxacin in human serum and
urine samples with satisfactory results.
The text was submitted by the authors in English. 相似文献
995.
The factors influencing the electrochemical behaviour of a supercapacitor have been partly examined in this work. The effects
of so-called intrinsic parameters, i.e. exchange current density, unit cell length and double layer (DL) capacitance; as well
as the so-called application parameters, i.e. cell current, on the cell potential discharge time have been considered. The
contributions of each type of capacitors, DL capacitor and faradaic supercapacitor under various states of operation and material
have been analyzed, and the competing (compensating) effects of the two types of capacitors as regards to the discharge and
power characteristics manifested by current–potential and energy–power (Ragone plots) are elucidated. 相似文献
996.
Capillary electrophoresis with wavelength-resolved laser-induced fluorescence detection 总被引:5,自引:0,他引:5
Capillary electrophoresis (CE) enables rapid separations with high separation efficiency and compatibility with small sample volumes. Laser-induced fluorescence detection can result in extremely low limits of detection in CE. Single-channel fluorescence detection, however, furnishes little qualitative information about a species being detected, except for its CE migration time. Use of multidimensional information often enables unambiguous identification of analytes. Combination of CE with information-rich wavelength-resolved fluorescence detection is analogous with ultraviolet-visible diode-array detection and furnishes both qualitative and quantitative chemical information about target species. This review discusses recent advances in wavelength-resolved laser-induced fluorescence detection coupled with CE, with an emphasis on instrument design. 相似文献
997.
Metallic Na formation in/on NaCl crystals with irradiation by electron or vacuum ultraviolet photons
Shigehiro Owaki Shigeko Koyama Masao Takahashi Masao Kamada Ryouichi Suzuki 《Radiation Physics and Chemistry》1997,49(6):609-615
Metallic Na was formed in/on NaCl single crystals by irradiating them with a variety of radiation sources, namely, 21 MeV electron pulses, an electron beam of 30 keV and photon fluxes in the VUV region. The physical states were analysed using several methods, optical absorption, lifetime measurement of positron annihilation, Auger electron spectroscopy and UV photoelectron spectroscopy. Metallic Na was obtained in different physical states; clusters were formed in bulk, thin layers (islands) and thick layers on the surface. 相似文献
998.
A type of high visible-light active titanium oxinitride(TiO2-xNx) powder was prepared by a simple proc-ess:the calcination of the hydrated titanium dioxide at the atmosphere of ammonia-argon using a tu-bular electric furnace at high temperatures. The hydrated titanium dioxide was synthesized as the precursor of TiO2-xNx using titanic acid as raw material,which came from sulfate technique of produc-ing titanium white. The effects of temperature and reaction time on the nitrogen content,grain size and crystal structure were studied. The visible-light activity and photocatalysis capability of the powder were also investigated. 相似文献
999.
Okuyama Y Nakano H Takahashi K Hongo H Kabuto C 《Chemical communications (Cambridge, England)》2003,(4):524-525
Easily prepared, chiral sulfideoxathiane ligands are described which give excellent enantioselectivity (up to 99% ee) in the Pd-catalyzed allylic alkylation of 1,3-diphenyl-2-propenyl acetate with a range of alkyl malonate nucleophiles. 相似文献
1000.
Ooi T Takahashi M Yamada M Tayama E Omoto K Maruoka K 《Journal of the American Chemical Society》2004,126(4):1150-1160
A series of (2,7-disubstituted-1,8-biphenylenedioxy)bis(dimethylaluminum) (2) has been readily prepared in situ by treatment of the requisite 2,7-disubstituted-1,8-biphenylenediol (1) with Me3Al (2 equiv) in CH2Cl2 at room temperature; this primarily relies on the successful establishment of a new synthetic procedure of 1 starting from inexpensive m-anisidine. Evaluation of 2 as a bidentate organoaluminum Lewis acid has been performed by the reduction of ketonic substrates using Bu3SnH as a hydride source in comparison to the conventional monodentate Lewis acid dimethylaluminum 2,6-xylenoxide (11), uncovering the significantly high activation ability of 2 toward carbonyl. Particularly, (2,7-dimethyl-1,8-biphenylenedioxy)bis(dimethylaluminum) (2a) exerted the highest reactivity, which has also been emphasized in the Mukaiyama aldol reaction. The structure of the bidentate Lewis acid 2 was unambiguously determined by single-crystal X-ray diffraction analysis of 2g possessing a bulky 3,5-di-tert-butylphenyl substituent, revealing the rigid dimeric assembly in the solid state. The double electrophilic activation of carbonyl substrate by 2a has been supported by low-temperature 13C NMR analysis as well as theoretical study using the Gaussian 98 program. Moreover, unique stereoselectivity has been observed in the 2a-promoted Mukaiyama Michael addition, and highly chemoselective functionalization of carbonyl compounds in the presence of their acetal counterparts has been realized using 2a. Finally, the effectiveness of 2a for the activation of ether functionality has been demonstrated in the Claisen rearrangement of allyl vinyl ethers. 相似文献