全文获取类型
收费全文 | 1400篇 |
免费 | 43篇 |
国内免费 | 7篇 |
专业分类
化学 | 1028篇 |
晶体学 | 14篇 |
力学 | 17篇 |
数学 | 161篇 |
物理学 | 230篇 |
出版年
2022年 | 9篇 |
2021年 | 7篇 |
2020年 | 15篇 |
2019年 | 11篇 |
2017年 | 18篇 |
2016年 | 34篇 |
2015年 | 18篇 |
2014年 | 26篇 |
2013年 | 68篇 |
2012年 | 48篇 |
2011年 | 82篇 |
2010年 | 38篇 |
2009年 | 50篇 |
2008年 | 70篇 |
2007年 | 92篇 |
2006年 | 87篇 |
2005年 | 98篇 |
2004年 | 80篇 |
2003年 | 62篇 |
2002年 | 67篇 |
2001年 | 19篇 |
2000年 | 27篇 |
1999年 | 21篇 |
1998年 | 13篇 |
1997年 | 19篇 |
1996年 | 16篇 |
1995年 | 7篇 |
1994年 | 11篇 |
1992年 | 20篇 |
1991年 | 12篇 |
1990年 | 12篇 |
1989年 | 12篇 |
1988年 | 12篇 |
1987年 | 9篇 |
1986年 | 11篇 |
1985年 | 23篇 |
1984年 | 20篇 |
1983年 | 15篇 |
1982年 | 20篇 |
1981年 | 12篇 |
1980年 | 21篇 |
1979年 | 18篇 |
1978年 | 16篇 |
1977年 | 10篇 |
1976年 | 10篇 |
1975年 | 14篇 |
1974年 | 10篇 |
1973年 | 12篇 |
1967年 | 6篇 |
1966年 | 7篇 |
排序方式: 共有1450条查询结果,搜索用时 15 毫秒
21.
Takao K Yasui H Yamamoto S Sasaki D Kawasaki S Watanabe G Tadano K 《The Journal of organic chemistry》2004,69(25):8789-8795
The total syntheses of (+)-mycoepoxydiene and (-)-1893A have been completed. The present synthetic strategy features the use of one-pot ring-opening/cross metathesis (ROM/CM) followed by a ring-closing metathesis (RCM) reaction, allowing for the concise construction of the 9-oxabicyclo[4.2.1]nona-2,4-diene framework from a 7-oxabicyclo[2.2.1]hept-2-ene derivative and 1,3-butadiene. The sequential metathesis product was converted into (+)-mycoepoxydiene through the oxidative rearrangement of a furfuryl alcohol to a pyranone, thereby establishing its absolute stereochemistry. From the common intermediate, a structurally related natural product (-)-1893A was also synthesized via the vinylogous aldol reaction. 相似文献
22.
Dobashi T Nobe M Yoshihara H Yamamoto T Konno A 《Langmuir : the ACS journal of surfaces and colloids》2004,20(16):6530-6534
Curdlan dissolved in aqueous sodium hydroxide was dialyzed to aqueous calcium chloride to form a gel. Transparent and turbid concentric layers observed in the gel cross section perpendicular to the long axis of the dialysis tube were identified as liquid crystalline gels with refractive index gradient and amorphous gels, respectively. The thickness of each layer was proportional to the diameter of the dialysis tube, and the gelation proceeded in proportion to the root of time. The unique pattern formation was attributed to the change of curdlan conformation and calcium-induced cross-linking resulting from a diffusion of calcium cations and hydroxide anions through the dialysis tube. It is suggested that the orderedness of the curdlan molecules decreases by the increase of the curvature of the concentric liquid crystal layers as the layer comes toward the center of the dialysis tube. 相似文献
23.
Kubo Y Tokita S Kojima Y Osano YT Matsuzaki T 《The Journal of organic chemistry》1996,61(11):3758-3765
A new family of indoaniline-derived calix[4]arenes has been synthesized for the purpose of developing a new chromogenic receptor. A condensing reaction of calix[4]arene (1) with 4-(diethylamino)-2-methylaniline hydrochloride (2) in the presence of an oxidizing agent under alkaline conditions affords mono- (3), 1,2-bis- (4), 1,3-bis- (5), and tetrakisindoaniline-derived (6) calix[4]arenes after careful column chromatography. Compound 3 is crystallized from a CHCl(3)-MeOH solution, and the crystal structure was determined by X-ray analysis. The crystal is monoclinic, space group P2(1)/n, Z = 4, a = 19.507(6) ?, b = 18.591(6) ?, c = 8.524(2) ?, beta = 94.69(2) degrees. The final R value for 2406 reflections of F(o) > 3sigma(F(o)) is 0.085. A unique intramolecular hydrogen-bonding network involving the carbonyl oxygen of indoaniline for 3 implied that the quinone carbonyl group as an acceptor of the chromophore can easily be subjected to an electrostatic interaction in the lower rim. Indeed, 1,3-bis(indoaniline)-derived 2,4-bis((ethoxycarbonyl)methoxy)calix[4]arene 7, prepared by the reaction of 5 with ethyl bromoacetate in the presence of NaH, is capable of undergoing an efficient ion-dipole interaction between the binding cation and the two quinone carbonyl groups of the chromophores, so that a selective Ca(2+)-induced pronounced color change (wavelength change > 100 nm) occurs with an association constant on the order of 10(6) in 99% EtOH, making 7 of potential use as an optical sensor for Ca(2+) detection. The IR and NMR studies have indicated that Ca(2+) is encapsulated in the cavity made by the distally located OCH(2)CO(2) groups on the lower rim of the cone-shaped calix[4]arene segment. Interestingly, however, the shape of the cavity in which Ca(2+) has been encapsulated does not have a C(2) axis of symmetry, as inferred from the (1)H-(1)H COSY experiment. On the other hand, 1,2-bis(indoaniline)-derived analogue 8 shows no response with metal ions, which can be interpreted to mean the absence of a cavity for encapsulation on the lower rim. 相似文献
24.
Ichikawa S Tada M Iwasawa Y Ikariya T 《Chemical communications (Cambridge, England)》2005,(7):924-926
Chemoselective hydrogenation of halogenated nitrobenzenes over Pt/C catalysts proceeds effectively in supercritical carbon dioxide (scCO2) to produce halogenated anilines with excellent selectivity; the rate of the hydrogenation of nitro groups is markedly enhanced in scCO2 compared to the neat reaction, and the dehalogenation reaction is significantly suppressed. 相似文献
25.
Yuasa H Izumi T Mitsuhashi N Kajihara Y Hashimoto H 《Chemistry (Weinheim an der Bergstrasse, Germany)》2005,11(22):6478-6490
Hinged di- and trisaccharides incorporating 2,4-diamino-beta-D-xylopyranoside as a hinge unit (Hin) were synthesized. Bridging of the diamino group of Hin by carbonylation or chelation to a metal ion results in a conformational change from (4)C1 to (1)C4, which in turn causes a bending of the oligosaccharides. In this study, the bending abilities of the hinged oligosaccharides were compared, in terms of the reactivities toward carbonylation and chelation. Di- or trisaccharides containing a 6-O-glycosylated mannopyranoside or galactopyranoside at their reducing ends had bending abilities similar to that of the Hin monosaccharide, probably because there were neither attractive nor repulsive interactions between the reducing and nonreducing ends. However, when Hin was attached at O2 of methyl mannopyranoside (Man alphaMe), the bending ability was dependent on the nonreducing sugar and the reaction conditions. Typically, a disaccharide--Hin beta(1,2)Man alphaMe--was difficult to bend under all the tested reaction conditions, and the bent population in the presence of Zn(II) was only 4%. On the other hand, a trisaccharide--Man alpha(1,3)Hin beta(1,2)Man alphaMe--was bent immediately after the addition of Zn(II) or Hg(II), and the bent population reached 75%, much larger than those of all the other hinged trisaccharides ever tested (<40%). This excellent bending ability suggests an attractive interaction between the reducing and nonreducing ends. The extended conformation was recovered by the addition of triethylenetetramine, a metal ion chelator. Reversible, quick, and efficient bending of the hinged trisaccharide was thus achieved. 相似文献
26.
27.
An approach to analysis of pigment release from microcapsules with size distribution 总被引:2,自引:0,他引:2
Takao Yamamoto Toshiaki Dobashi Miho Kimura Chih Pong Chang 《Colloids and surfaces. B, Biointerfaces》2002,25(4):305-311
We have studied the release curve for microcapsules with size distribution. On the basis of an analogy to the relaxation phenomena with multiple characteristic times, we propose a stretched exponential release curve for the system with size distribution and relate the release curve to the size distribution function of the microcapsule. This method was successfully applied to the transfer of azo-pigments from inner medium of dioctyl phthalate to dispersing medium of methanol through poly(ureaurethane) microcapsule membrane. 相似文献
28.
Shogo Mitsuhashi Junko Kawai Tomofumi Santa Toshimasa Toyo’oka 《Analytica chimica acta》2006,562(1):36-43
Kynurenic acid (KYNA), an endogenous antagonist of ionotropic glutamate and α7 nicotinic receptors, was fluorometrically determined by column-switching high-performance liquid chromatography (HPLC) with fluorescence detection. The HPLC system consists of two octadecyl silica (ODS) columns, both of which are connected with an anion-exchange column (trapping column). Following sample injection onto the HPLC column, KYNA was separated on the first ODS column with a mobile phase of H2O/acetonitrile (95/5) containing 0.1% acetic acid. The peak fraction of KYNA was trapped on the anion-exchange column by changing the position of a six-port valve and then introduced into the second ODS column. Subsequently, KYNA was detected fluorometrically as a fluorescence complex formed with zinc ion which was pumped constantly. Instrumental limit of detection was approximately 0.16 nM, which corresponded to 8.0 fmol (per 50 μl injection, signal to noise ratio 3), and the limit of quantification was 0.53 nM (signal to noise ratio 10). Intra- and inter-day relative standard deviations were 1.1-3.9% (n = 3) and 3.0-5.3% (n = 3), respectively. The peak of KYNA in rat plasma was clearly detected by the proposed column-switching HPLC system after a facile pretreatment procedure. Intra- and inter-day relative mean errors were −1.6-1.4% (n = 3) and −2.4 to −0.4% (n = 3), respectively, with a satisfactory precision (within 5.0%). A calibration curve for the determination of KYNA showed a good linearity (r2 > 0.999) in the range of 25-200 nM. The KYNA concentrations in the plasma of male Sprague-Dawley rats (8-week-old) were 44 ± 5.5 nM (mean ± S.E., n = 5). In ketamine-treated rats, which are animal models of schizophrenia, the plasma KYNA concentrations were significantly increased compared with those in the control rats (p < 0.05). 相似文献
29.
Mugishima T Tsuda M Kasai Y Ishiyama H Fukushi E Kawabata J Watanabe M Akao K Kobayashi J 《The Journal of organic chemistry》2005,70(23):9430-9435
[Structure: see text]. Citrinadin A (2) is a pentacyclic indolinone alkaloid isolated from the cultured broth of a fungus, Penicillium citrinum, which was separated from a marine red alga. The absolute stereochemistry of the pentacyclic core in 2 and its new congener, citrinadin B (1), was elucidated by analysis of the ROESY spectrum for the chlorohydrin derivative (3) of 1 as well as comparison of the electronic circular dichroism (ECD) spectra for 1 and 2 with those of known spirooxiindole alkaloids. On the other hand, the absolute configuration at C-21 bearing an epoxide ring was assigned as S by comparison of the vibrational circular dichroism (VCD) spectra of 1 with those of model compounds 2S- and 2R-2,3-epoxy-3,3-dimethyl-1-phenylpropan-1-one (4a and 4b, respectively). 相似文献
30.
Kô Kaneko Mikako Tanaka Kimiaki Haruki Nobuaki Naruse Hiroshi Mitsuhashi 《Tetrahedron letters》1979,20(39):3737-3740
The 13C-NMR spectra of seven cavanine alkaloids isolated from Veratrum and Fritillaria plants were measured and their signals were assigned, and these results were applicated for structure elucidation of two new cevanine alkaloids, baimonidine and isoverticine, isolated from mature Fritillaria verticillata. 相似文献