全文获取类型
收费全文 | 5622篇 |
免费 | 154篇 |
国内免费 | 20篇 |
专业分类
化学 | 3987篇 |
晶体学 | 73篇 |
力学 | 74篇 |
数学 | 229篇 |
物理学 | 1433篇 |
出版年
2022年 | 31篇 |
2021年 | 33篇 |
2020年 | 60篇 |
2019年 | 67篇 |
2018年 | 50篇 |
2017年 | 36篇 |
2016年 | 87篇 |
2015年 | 94篇 |
2014年 | 120篇 |
2013年 | 266篇 |
2012年 | 261篇 |
2011年 | 276篇 |
2010年 | 157篇 |
2009年 | 165篇 |
2008年 | 297篇 |
2007年 | 254篇 |
2006年 | 276篇 |
2005年 | 262篇 |
2004年 | 258篇 |
2003年 | 202篇 |
2002年 | 212篇 |
2001年 | 153篇 |
2000年 | 164篇 |
1999年 | 94篇 |
1998年 | 67篇 |
1997年 | 64篇 |
1996年 | 68篇 |
1995年 | 44篇 |
1994年 | 70篇 |
1993年 | 91篇 |
1992年 | 93篇 |
1991年 | 76篇 |
1990年 | 66篇 |
1989年 | 56篇 |
1988年 | 74篇 |
1987年 | 73篇 |
1986年 | 76篇 |
1985年 | 105篇 |
1984年 | 98篇 |
1983年 | 43篇 |
1982年 | 77篇 |
1981年 | 80篇 |
1980年 | 69篇 |
1979年 | 66篇 |
1978年 | 54篇 |
1977年 | 66篇 |
1976年 | 56篇 |
1975年 | 42篇 |
1974年 | 52篇 |
1973年 | 33篇 |
排序方式: 共有5796条查询结果,搜索用时 15 毫秒
221.
Detection of ethanol in human body fluids by headspace solid-phase micro extraction (SPME)/capillary gas chromatography 总被引:1,自引:0,他引:1
Summary Ethanol has been found extractable from human whole blood and urine samples by headspace solid-phase micro extraction (SPME) with a Carbowax/divinylbenzene-coated fiber. After heating a vial containing the body fluid sample with ethanol, and isobutanol as internal standard (IS) at 70°C in the presence of (NH4)2SO4, a Carbowax/divinylbenzene-coated SPME fiber was exposed in the headspace of the vial to allow adsorption of the compounds. The fiber needle was then injected into a middle-bore capillary gas chromatography (GC) port. The headspace SPME-GC gave intense peaks for both compounds; a small amount of background noises appeared, but did not interfere with the detection of the compounds. Recoveries of ethanol and IS were 0.049 and 0.026% for whole blood, respectively, and 0.054 and 0.085% for urine, respectively. The calibration curves for ethanol showed excellent linearity in the range of 80–5000 mg L–1 for whole blood and 40–5000 mg L–1 for urine; the detection limits for both samples were 20 and 10 mg L–1, respectively. The data on actual determination of ethanol after the drinking of beer are also presented for two subjects. 相似文献
222.
Ken-ichi Sato Shoji AkaiToshiyuki Hiroshima Hidenori AokiMayumi Sakuma Ken-ju Suzuki 《Tetrahedron letters》2003,44(17):3513-3516
The chemoenzymatic synthesis of 13C-labeled sialic acid (NeuAc) and 3-deoxy-d-glycero-d-galacto-2-nonulosonic acid (KDN) as useful molecular probes for studying the conformation of sialyl or KDN oligosaccharides attached to proteins was performed by using [6-13C]-ManNAc, [6-13C]-Man and [3-13C]-pyruvic acid sodium salt. In the synthesis of the compounds, 5,6-anhydro intermediates were found to easily provide not only 6-13C-labeled but also 5-, and 6-modified NeuAc and KDN analogs. Furthermore, it was demonstrated that identical results are obtained by NMR for both [3,9-13C]-NeuAc and 1:1 mixtures of [3-13C]- and [9-13C]-NeuAc. 相似文献
223.
Combination of ()-4--butyldimethylsiloxy-2-cyclopentenone, ()-()-3--butyldimethylsiloxy-1-iodo-1-octene, and 6-methoxycarbonyl-2-hexynal via the tandem organo-copper conjugate addition—aldol reaction procedure leads directly to a 5,6-dehydroprostaglandin E2 derivative, which can be transformed to a variety of chiral primary prostaglandins in a stereoselective manner. 相似文献
224.
A method is described for the determination of trace selenium (impurities in medicinal organic compounds) by ion chromatography (IC) after oxygen flask combustion. All selenium compounds formed by oxygen flask combustion are converted to selenate ion by heating with nitric acid and potassium permanganate. The selenate ion is then determined by IC, using a simple recycle system to eliminate interfering ions. The detection limit of selenium is 0.4 nmol in 50 mg of sample. The recoveries of selenium added to seven drugs are ca. 95-103% with relative standard deviations of 1-6%. 相似文献
225.
T. Tanaka A. Hazato K. Bannai N. Okamura S. Sugiura K. Manabe S. Kurozumi M. Suzuki R. Noyori 《Tetrahedron letters》1984,25(43):4947-4950
6-Oxoprostaglandin E1 methyl ester was synthesized in a single pot from ()-4--butyldimethylsiloxy-2-cyclopentenone by organocopper conjugate addition with an ω side-chain unit, trapping of the resulting enolate with 6-methoxycarbonyl-2-nitrohex-1-ene, and treatment with aqueous titanium(III) trichloride. Hydrolysis of the methyl ester was accomplished by porcine liver esterase. 6-Oxoprostaglandin F1α, was obtained from 6-nitroprostaglandin E1 methyl ester in four steps. 相似文献
226.
Emiko Uchida Yoshikimi Uyama Yoshito Ikada 《Journal of polymer science. Part A, Polymer chemistry》1989,27(2):527-537
To improve the low water wettability of poly(ethylene terephthalate) (PET), graft polymerization of acrylamide (AAm) by UV irradiation was performed onto the surface of a PET film with the simultaneous irradiation method without using a photo sensitizer. The PET film immersed in a 10 wt % deaerated aqueous solution of AAm was found to become highly hydrophilic upon UV irradiation. Optical microscopy on cross sections of grafted films showed that localization of the graft polymerization was restricted to a thin surface region of the film. Both the low concentration of polymer radicals formed by UV irradiation and the monomer penetration limited to the film surface would be responsible for localization of the grafted layer to the film surface region. Pretreatment of the PET film with benzyl alcohol was effective for enhancement of the graft polymerization. Retention of high hydrophilicity of the surface even after rigorous extraction of homopolymer and a comparative study of polymerization without UV irradiation strongly suggested that UV irradiation of the PET film under immersion in the deaerated AAm aqueous solution would lead to formation of the true graft copolymer. 相似文献
227.
Junji Furukawa Eiichi Kobayashi Yoshihiro Arai Toshimitsu Suzuki Yoshinobu Takegami 《Journal of polymer science. Part A, Polymer chemistry》1976,14(10):2553-2563
An investigation by 220-MHz NMR spectroscopy was carried out on the alternating copolymers of acrylic monomer with 2-substituted 1,3-diolefin. The chain structures were determined. The acrylic monomers used were methyl methacrylate (MMA), acrylonitrile (AN), and methacrylonitrile (MAN); isoprene (IP) and chloroprene (CLP) were the 1,3-diolefins. In the MAN–IP alternating copolymer, the 1-position methylene protons of IP showed an AB quartet peak, confirming the α-1 linkage structure. Similarly, in the MMA–CLP and AN–CLP copolymers, the 1-position methylene protons of CLP showed and AB quartet and an ABX pattern, respectively, confirming the α-1 linkage structure in both these cases also. The α-1 linkage structure was also revealed by the decoupling technique in the MAN–CLP alternating copolymer. The AN–IP and MMA–IP alternating copolymers also possess a bond between the α-position of the acrylic monomer and the 1-position of IP. The monomeric units in the alternating copolymers of acrylic monomers with 2-substituted 1,3-diolefins were generally linked at the α-position of acrylic monomer and the 1-position of 1,3-diolefin. On the other hand, in the Diels-Alder adducts of acrylic monomer with 2-substituted 1,3-diolefin, the reaction takes place between the α-position of acrylic monomer and the 4-position of 1,3-diolefin. The regioselectivity of the alternating copolymers and the Diels-Alder adducts is quite compatible with the expectations from molecular orbital theory. 相似文献
228.
S. Sawamura M. Tsuchiya T. Ishigami Y. Taniguchi K. Suzuki 《Journal of solution chemistry》1993,22(8):727-732
Solubility of naphthalene in water was measured at 25°C and pressures up to 200 MPa. The solubility decreased with increasing pressure. From the pressure coefficient of the solubility, the volume change V accompanying the dissolution was estimated as 13.8±0.4 cm
3
-mol
–1
. Further we estimated the volume change V
CH
accompanying hydrophobic hydration as –0.1±0.6 cm
3
-mol
–1
using the V value, the molar volume of crystalline naphthalene, and the partial molar volume of naphthalene in n-heptane. This V
CH
is much larger (i.e., less negative) than that for hydrophobic hydration of alkyl-chain compounds and suggests that the hydration structure of naphthalene differs from that of alkyl-chain compounds. 相似文献
229.
Tomoya Kitazume Zaiju Jiang Kana Kasai Yuma Mihara Mamie Suzuki 《Journal of fluorine chemistry》2003,121(2):205-212
The utility of reusable ionic liquid-proline (or aldolase antibody 38C2) reaction system, proceeding the aldol reactions, is described. Further, obtained α-chloro-β-hydroxy compounds were transformed to the optically active α,β-epoxy carbonyl compounds. The aldolase antibody 38C2-ionic liquid system was able to reuse in Michael additions and the reaction of fluoromethylated imines. 相似文献
230.
Tobe Y Utsumi N Kawabata K Nagano A Adachi K Araki S Sonoda M Hirose K Naemura K 《Journal of the American Chemical Society》2002,124(19):5350-5364
m-Diethynylbenzene macrocycles (DBMs), buta-1,3-diyne-bridged [4(n)]metacyclophanes, have been synthesized and their self-association behaviors in solution were investigated. Cyclic tetramers, hexamers, and octamers of DBMs having exo-annular octyl, hexadecyl, and 3,6,9-trioxadecyl ester groups were prepared by intermolecular oxidative coupling of dimer units or intramolecular cyclization of the corresponding open-chain oligomers. The aggregation properties were investigated by two methods, the (1)H NMR spectra and the vapor pressure osmometry (VPO). Although some discrepancies were observed between the association constants obtained from the two methods, the qualitative view was consistent with each other. The analysis of self-aggregation by VPO revealed unique aggregation behavior of DBMs in acetone and toluene, which was not elucidated by the NMR method. Namely, the association constants for infinite association are several times larger than the dimerization constant, suggesting that the aggregation is enhanced by the formation of dimers (a nucleation mechanism). In polar solvents, DBMs aggregate more strongly than in chloroform due to the solvophobic interactions between the macrocyclic framework and the solvents. Moreover, DBMs self-associate in aromatic solvents such as toluene and o-xylene more readily than in chloroform. In particular, the hexameric DBM having a large macrocyclic cavity exhibits extremely large association constants in aromatic solvents. By comparing the aggregation properties of DBMs with the corresponding acyclic oligomers, the effect of the macrocyclic structure on the aggregation propensity was clarified. Finally, it turned out that DBMs tend to aggregate more readily than the corresponding phenylacetylene macrocycles, acetylene-bridged [2(n)]metacyclophanes, owing to the withdrawal of the electron density from the aromatic rings by the butadiyne linkages which facilitates pi-pi stacking interactions. 相似文献