全文获取类型
收费全文 | 322篇 |
免费 | 6篇 |
国内免费 | 1篇 |
学科分类
数理化 | 329篇 |
出版年
2022年 | 2篇 |
2020年 | 4篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 2篇 |
2016年 | 7篇 |
2015年 | 10篇 |
2014年 | 5篇 |
2013年 | 18篇 |
2012年 | 17篇 |
2011年 | 18篇 |
2010年 | 21篇 |
2009年 | 11篇 |
2008年 | 24篇 |
2007年 | 15篇 |
2006年 | 22篇 |
2005年 | 12篇 |
2004年 | 7篇 |
2003年 | 20篇 |
2002年 | 9篇 |
2001年 | 6篇 |
2000年 | 4篇 |
1999年 | 4篇 |
1997年 | 2篇 |
1996年 | 5篇 |
1995年 | 4篇 |
1993年 | 5篇 |
1992年 | 2篇 |
1991年 | 5篇 |
1990年 | 3篇 |
1989年 | 2篇 |
1988年 | 7篇 |
1986年 | 4篇 |
1985年 | 3篇 |
1984年 | 4篇 |
1982年 | 2篇 |
1981年 | 3篇 |
1979年 | 3篇 |
1978年 | 2篇 |
1977年 | 2篇 |
1976年 | 2篇 |
1974年 | 2篇 |
1973年 | 2篇 |
1968年 | 1篇 |
1967年 | 1篇 |
1966年 | 1篇 |
1965年 | 1篇 |
1964年 | 1篇 |
1961年 | 2篇 |
1958年 | 1篇 |
排序方式: 共有329条查询结果,搜索用时 15 毫秒
1.
Takashi Yoshitake Ryuji Iizuka Kaoru Fujino Osamu Inoue Kenji Yamagata Hitoshi Nohta Masatoshi Yamaguchi 《Analytical sciences》2004,20(12):1687-1690
An improved high-performance liquid-chromatographic (HPLC) assay for the simultaneous determination of serotonin (5-HT) and 5-hydroxyindole-3-acetic acid (5-HIAA) in human urine is reported. Following the automated precolumn derivatization of urinary 5-HT and 5-HIAA with benzylamine, the derivatives are separated by isocratic elution on a reversed-phase C18 semi-microbore column, and are fluorometrically detected at an excitation wavelength of 345 nm and an emission wavelength of 480 nm. The detection limits of 5-HT and 5-HIAA are 7 and 5 nmol/l in urine (0.7 and 0.5 fmol/20-microl injection). The proposed automatic method permits a highly selective and sensitive determination of 5-HT and 5-HIAA in human urine without any sample purification. 相似文献
2.
An InGaAs/InAlAs five-layer asymmetric coupled quantum well (FACQW) is expected to show very large electrorefractive index change. n in a wideband transparency region. Band structures of the FACQW are analyzed with Luttinger-Kohn Hamiltonian. The electrorefractive characteristics of the FACQW are discussed. 相似文献
3.
4.
Thirty three compounds were obtained from the bulbs of Urginea maritima (Liliaceae). The compounds were identified by means of fast atom bombardment mass spectrometry (FAB-MS), nuclear magnetic resonance (1H-NMR), (13C-NMR), nuclear overhauser effects (NOE) and two dimensional (2D) NMR. Ten of them were new natural compounds. Nine were bufadienolides and only one was lignan in these compounds. 相似文献
5.
The α,β-unsaturated γ,δ-epoxyketone 7 is isomerized almost exclusively to the δ-diketone 9 both upon irradiation in the n → π* absorption band with light of wavelengths above 310 nm (in anhydrous dioxane or benzene solutions) and upon triplet sensitization using acetophenone in benzene. The reaction may be formulated by the cleavage of the Cγ? O oxide bond and the shift of the δ-hydrogen to the γ-position, and thus bears a formal “double bond homology” to the photochemical α,β-epoxyketone rearrangement. Excitation in the π → π* absorption band of 7 with light of wavelength 253,7 nm (in anhydrous dioxane solution) leads to the formation of product 10 as well as to the triplet rearrangement to 9 . With this result a novel partial synthesis of O-acetyl-B-nortestosterone has been accomplished, which has the advantages of fewer steps and higher product yield ( 7 → 10 : ~30% yield) than previously published syntheses. On the basis of the presently available experiments, the mechanism of the transformation 7 → 10 , which constitutes one of the still few examples of enone photoreactions induced selectively from the π,π* excited singlet, remains unknown. 相似文献
6.
Nakanishi I Miyazaki K Shimada T Iizuka Y Inami K Mochizuki M Urano S Okuda H Ozawa T Fukuzumi S Ikota N Fukuhara K 《Organic & biomolecular chemistry》2003,1(22):4085-4088
Electron-transfer reduction of molecular oxygen (O2) by the phenolate anion (1-) of a vitamin E model, 2,2,5,7,8-pentamethylchroman-6-ol (1H), occurred to produce superoxide anion, which could be directly detected by a low-temperature EPR measurement. The rate of electron transfer from 1- to O2 was relatively slow, since this process is energetically unfavourable. The one-electron oxidation potential of 1- determined by cyclic voltammetric measurements is sufficiently negative to reduce 2,2-bis(4-tert-octylphenyl)-1-picrylhydrazyl radical (DOPPH*) to the corresponding one-electron reduced anion, DOPPH-, suggesting that 1- can also act as an efficient radical scavenger. 相似文献
7.
Yamanaka N Kawano R Kubo W Kitamura T Wada Y Watanabe M Yanagida S 《Chemical communications (Cambridge, England)》2005,(6):740-742
Use of a new ionic liquid crystal, 1-dodecyl-3-methylimidazolium iodide, and iodine as an electrolyte of dye-sensitized solar cells leads to a high short circuit photocurrent density and a high light-to-electricity conversion efficiency, due to a self-assembled structure of the imidazolium cations, resulting in high conductivity of the electrolyte. 相似文献
8.
H Harada K Iizuka T Kamijo K Akahane R Yamamoto Y Nakano A Tsubaki T Kubota I Shimaoka H Umeyama 《Chemical & pharmaceutical bulletin》1990,38(11):3042-3047
The experimental details for the synthesis of human renin inhibitors are described. In order to avoid metabolic degradation of the Phe-His (P3-P2) amide bond in transition-state analogs, structurally modified acyl residues (P4-P3) were incorporated into the inhibitors. Compound 1a, which contained 2-(1-naphthylmethyl)-3-(N-phenethylcarbamoyl)propionyl residue (P4-P3) with a retro-inverso amide bond, L-histidine, and norstatine isoamylamide residue (P1-P1) as a transition-state mimic, had potent human renin inhibitory activity, and it lowered blood pressure when administered orally to common marmosets. 相似文献
9.
Yokozawa T Ogawa M Sekino A Sugi R Yokoyama A 《Journal of the American Chemical Society》2002,124(51):15158-15159
Poly(p-benzamide) with a defined molecular weight and a low polydispersity and a block copolymer containing this well-defined aramide was synthesized. Phenyl 4-aminobenzoate, which would yield poly(p-benzamide), did not polymerize under the conditions of chain-growth polycondensation. However, phenyl 4-(4-octyloxybenzylamino)benzoate (1b) polymerized at room temperature in the presence of base and phenyl 4-nitrobenzoate (2) as an initiator in a chain-growth polycondensation manner to give well-defined aromatic polyamides having the 4-octyloxybenzyl groups as a protecting group on nitrogen in an amide. It was confirmed by a model reaction that deprotection of this protecting group proceeded completely with trifluoroacetic acid (TFA) without breaking the amide linkage. The utility of this approach to poly(p-benzamide) with a low polydispersity was demonstrated by the synthesis of block copolymers. Thus, phenyl 4-(octylamino)benzoate (1a) polymerized in the presence of 2 and base, followed by addition of 1b and base to the reaction mixture of the prepolymer to yield the block copolymer of 1a and 1b with a controlled molecular weight and a low polydispersity. The block copolymer was treated with TFA, resulting in a soluble block copolymer of poly(N-octyl-p-benzamide) and poly(p-benzamide). The SEM images of the supramolecular assemblies of the block copolymer showed mum-sized bundles and aggregates of flake structures. 相似文献
10.
Crown ether dyes with pendent anionic side-arms were synthesized for extractionspectrophotometry of alkali and alkaline earth metal ions. Dramatic changes in metal selectivity were obtained simply by changing the nature of the anionic side-arm on the same crown ether skeleton. A structure/metal selectivity relationship is discussed in detail in terms of “chelate” and “intramolecular ion-pair” formation. Small metal cations (high charge density) are preferred in the extraction by a crown ether reagent with a charge-localized anionic side-arm through the formation of a “chelate”. Large metal cations (low charge density) are preferred in the extraction by reagents with a charge-delocalized anionic side-arm through the formation of an “intramolecular ion-pair”. Steric restrictions imposed by the side-arm on the metal ion approaching the crown ether are also important factor in controlling the selectivity of these reagents. 相似文献