全文获取类型
收费全文 | 238篇 |
免费 | 8篇 |
专业分类
化学 | 191篇 |
晶体学 | 7篇 |
力学 | 6篇 |
数学 | 10篇 |
物理学 | 32篇 |
出版年
2023年 | 1篇 |
2022年 | 1篇 |
2021年 | 6篇 |
2020年 | 2篇 |
2019年 | 7篇 |
2018年 | 3篇 |
2017年 | 1篇 |
2016年 | 5篇 |
2015年 | 8篇 |
2014年 | 5篇 |
2013年 | 10篇 |
2012年 | 3篇 |
2011年 | 17篇 |
2010年 | 8篇 |
2009年 | 9篇 |
2008年 | 11篇 |
2007年 | 13篇 |
2006年 | 19篇 |
2005年 | 15篇 |
2004年 | 20篇 |
2003年 | 11篇 |
2002年 | 7篇 |
2001年 | 1篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1998年 | 2篇 |
1997年 | 2篇 |
1996年 | 2篇 |
1995年 | 3篇 |
1994年 | 3篇 |
1993年 | 2篇 |
1992年 | 1篇 |
1989年 | 2篇 |
1987年 | 1篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1983年 | 1篇 |
1982年 | 1篇 |
1981年 | 3篇 |
1980年 | 7篇 |
1979年 | 3篇 |
1978年 | 5篇 |
1977年 | 1篇 |
1976年 | 1篇 |
1975年 | 2篇 |
1973年 | 2篇 |
1972年 | 1篇 |
1970年 | 2篇 |
1968年 | 2篇 |
1966年 | 1篇 |
排序方式: 共有246条查询结果,搜索用时 15 毫秒
51.
Ishikawa T Aikawa T Ohata E Iseki T Maeda S Matsuo T Fujino T Saito S 《The Journal of organic chemistry》2007,72(2):435-441
Enolate generated from O-(tetrahydropyran-2-yl)hydroxyacetone under thermodynamically controlled conditions (1.3 equiv of NaH, THF, 0 degrees C to rt) was allylated at the carbon bearing the protected hydroxy group with very high regioselectively. When tert-BuOH, equivalent to the excessive portion of initially added NaH, was introduced into the mixture followed by addition of aldehyde, aldol reaction took place on the methyl group to give 1-substituted 4-hydroxy-(1E),6-heptadien-3-one in acceptable yields after acidic treatment of the mixture for dehydration and deprotection. Introducing a chiral auxiliary protecting group into hydroxyacetone led to asymmetric allylation though stereoselectivity was around 50% ee. Thus, the hidden aspect of the chemoselective nature of protected hydroxyacetone-derived enolate generated under thermodynamically controlled conditions has opened a new avenue for two-directional elaboration of hydroxyacetone that should be potentially useful in organic synthesis. 相似文献
52.
Kobayashi K Kitagawa R Yamada Y Yamanaka M Suematsu T Sei Y Yamaguchi K 《The Journal of organic chemistry》2007,72(9):3242-3246
Tetrakis(4-hydroxyphenyl)-cavitand 1 and tetra(4-pyridyl)-cavitand 2 self-assemble into a heterodimeric capsule 1.2 via four ArOH...pyridyl hydrogen bonds in CDCl3. The 1.2 expresses the orientational isomerism of an encapsulated unsymmetrical guest with high orientational selectivity because the electronic environment of the 1 unit is different from that of the 2 unit. For p-ethoxyiodobenzene and 2-iodo-6-methoxynaphthalene encapsulated in 1.2, the iodo group is specifically oriented to the cavity of the 2 unit. The orientational isomeric selectivity for methyl p-acetoxybenzoate and methyl p-ethoxybenzoate within 1.2 is 1:0.11 and 1:<0.05, respectively, wherein the methyl ester group is preferentially oriented to the cavity of the 2 unit. The delicate balance among electrostatic potential repulsion, CH-pi interaction, or CH-halogen (halogen-pi) interaction, in 1.2-guest assembly influences the orientational isomeric selectivity of unsymmetrical guests within 1.2. 相似文献
53.
Nonequilibrium radiation phenomena behind strong shock waves in low-density air are observed by using a couple of CCD camera systems in a shock tube experiment. The simultaneous observation for total radiation and its spectral radiation is carried out in order to elucidate spaced-ependent contribution of an individual radiation spectrum to the total radiation intensity. The results are shown for the shock velocity range from 9.0 km/s to 12.1 km/s at the initial pressure 13.3 Pa. Wavelength range is selected from 300 nm to 445 nm to investigate mainly the contributions from UV radiation. It is found that the band spectra due to the molecular species N2+ and CN mainly contribute to the first-peak, while the spectra due to the atomic species O+ and N mainly contribute to the formation of the second-peak. It is also found that the Balmer series in H spectra strongly contributes to the second-peak. The radiation along the tube wall surfaces is composed of the same constituents as those around the tube axis as well as the spectra coming from the impurities. 相似文献
54.
55.
Ryosuke Nakahara Satomi Kashitani Kumi Hayakawa Yuuki Kitani Takako Yamaguchi Yoshikazu Fujita 《Journal of fluorescence》2009,19(5):769-775
A fluorophotometric method for the determination of hydrogen peroxide (H2O2) using fluorescin was developed. This method was based on the oxidative reaction of fluorescin, a colorless, non-fluorescent
lactoid fluorescein, by H2O2 to give highly fluorescein fluorescence emission. In the determination of H2O2, the calibration curve exhibited linearity over the H2O2 concentration range of 1.5–310 ng mL−1 at an emission wavelength of 525 nm with an excitation of 500 nm and with relative standard deviations (n = 6) of 2.51%, 2.48%, and 1.31% for 3.1 ng mL−1, 30.8 ng mL−1, and for 308 ng mL−1 of H2O2, respectively. The detection limit for H2O2 was 1.9 ng mL−1 six blank determinations was performed (ρ = 6). This proposed method was applied to detection of other reactive oxygen species and nitrogen species (ROS/RNS) such
as singlet oxygen (1O2), hydroxyl radical (•OH), peroxynitrite (ONOO−) etc., and it was possible to detect them with a high sensitivity. In addition, this proposed method was applied to the recovery
tests of H2O2 in calf serum, human saliva, rain water, and wheat noodles; the results were satisfactory. 相似文献
56.
Toshihiko Myojo Takako Oyabu Kenichiro Nishi Chikara Kadoya Isamu Tanaka Mariko Ono-Ogasawara Hirokazu Sakae Tadashi Shirai 《Journal of nanoparticle research》2009,11(1):91-99
Mass production of some kinds of carbon nanotubes (CNT) is now imminent, but little is known about the risk associated with
their exposure. It is important to assess the propensity of the CNT to release particles into air for its risk assessment.
In this study, we conducted aerosolization of a multi-walled CNT (MWCNT) to assess several aerosol measuring instruments.
A Palas RBG-1000 aerosol generator applied mechanical stress to the MWCNT by a rotating brush at feed rates ranging from 2
to 20 mm/h, which the MWCNT was fed to a two-component fluidized bed. The fluidized bed aerosol generator was used to disperse
the MWCNT aerosol once more. We monitored the generated MWCNT aerosol concentrations based on number, area, and mass using
a condensation particle counter and nanoparticle surface area monitor. Also we quantified carbon mass in MWCNT aerosol samples
by a carbon monitor. The shape of aerosolized MWCNT fibers was observed by a scanning electron microscope (SEM). The MWCNT
was well dispersed by our system. We found isolated MWCNT fibers in the aerosols by SEM and the count median lengths of MWCNT
fibers were 4–6 μm. The MWCNT was quantified by the carbon monitor with a modified condition based on the NIOSH analytical
manual. The MWCNT aerosol concentration (EC mass base) was 4 mg/m3 at 2 mm/h in this study. 相似文献
57.
Kei-Ichi Kitahara Shuji Okuya Isao Yoshihama Takako Hanada Kunio Nagashima Sadao Arai 《Journal of chromatography. A》2009,1216(44):7409-7414
For the separation of aromatic amines, two types of monodispersed porous polymer resins were prepared by the copolymerization of 2-vinylpyridine and 4-vinylpyridine with divinylbenzene in the presence of template silica gel particles (particle size 5 μm), followed by dissolution of the template silica gel in an alkaline solution. The transmission electron micrographs and the scanning electron micrograph revealed that these templated polymer resins have a spherical morphology with a good monodispersity and porous structure. Using these monodispersed polymer resins, the high-performance liquid chromatographic separation of aromatic amines in the mobile phases of pHs 2.0, 2.9, 4.1, 7.2 and 11.7 were carried out. The 2-vinylpyridine–divinylbenzene copolymer resins showed slightly stronger retentions for aromatic amines than the 4-vinylpyridine–divinylbenzene copolymer resins. Under acidic conditions (around pH 2.0), aniline and the toluidines showed no retention on these copolymer resins due to the repulsion between the cationic forms of these amines and pyridinium cations in the stationary phase, whereas less basic aromatic amines or non-basic acetanilide showed slight retentions. Above pH 4.1, the separation of aromatic amines with these polymer resins showed a typical reversed-phase mode separation. Therefore, the separation patterns of aromatic amines are effectively tunable by changing the pH value of the mobile phases. A good separation of eight aromatic amines was achieved at pH 2.9 using the 2-vinylpyridine–divinylbenzene copolymer resins. 相似文献
58.
In order to quickly confirm a potentially hazardous psychoactive designer drug (a compound in which part of the molecular structure of a stimulant or narcotic has been modified), we created a psychoactive drugs data library by performing analysis using liquid chromatography with photodiode array spectrophotometry (LC/PDA) and gas chromatography-mass spectrometry (GC/MS). The data in this library consist of the LC capacity factor (k′) ratios in relation to the internal standard, the ultraviolet (UV) spectra and the MS spectra of 104 compounds. By performing a comparative study of the data in this report with the analytical data for commercial and illegal drug products, it is possible to quickly identify the psychoactive designer drugs in 205 purchased products by using the library. Further, it is possible to analogize the structure of drugs for which there is no matching data in the library using similar data.Furthermore, when structural isomers of controlled substances have detected from the presented library, similarity of their biological effects on human will be predicted, thus leading to regulate their public circulation. Examples of these types of isomers include, for instance, the narcotic 3,4,5-trimethoxyamphetamine (TMA) and its positional isomers 2,4,5-trimethoxyamphetamine (TMA-2) and 2,4,6-trimethoxyamphetamine (TMA-6), or the narcotic 1-(3-chlorophenyl)piperazine (3CPP) and its isomers 1-(o-chlorophenyl)piperazine (2CPP) and 1-(p-chlorophenyl)piperazine (4CPP). Differentiation of these compounds is necessary in regulating them, and we report here the results of a study of a method to confirm these compounds using the present library. 相似文献
59.
Oxygenation of a series of p-substituted phenols to the corresponding catechols (phenolase activity) by the (mu-eta2:eta2-peroxo)dicopper(II) species of Octopus hemocyanin has been directly examined for the first time by using a UV-vis spectroscopic method in a 0.5 M borate buffer solution containing 8 M urea under anaerobic conditions. Preliminary kinetic studies have indicated that the reaction involves an electrophilic aromatic substitution mechanism as in the case of phenolase reaction of tyrosinase. The oxygenation of phenols by hemocyanin also proceeded catalytically when the reaction was carried out under aerobic conditions. 相似文献
60.
Diamond is a promising candidate for bioapplications. Properties of hybridized DNA arrays on single-crystalline diamond are studied on a microscopic level by atomic force microscopy (AFM) in buffer solutions. Compact DNA layers in a thickness of 76 A are resolved by optimizing phase and height contrast in AFM. The height shows some long-range (30 nm) undulations of +/-5 A due to tip and DNA interactions. The axis of double helix DNA is oriented at about 36 degrees with respect to the diamond surface. DNA molecules can be removed by contact-mode AFM with forces >45 nN, indicating stronger DNA bonding than on gold substrates. 相似文献