全文获取类型
收费全文 | 186篇 |
免费 | 2篇 |
国内免费 | 3篇 |
专业分类
化学 | 132篇 |
力学 | 3篇 |
数学 | 22篇 |
物理学 | 34篇 |
出版年
2022年 | 1篇 |
2020年 | 4篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 1篇 |
2016年 | 4篇 |
2015年 | 2篇 |
2014年 | 7篇 |
2013年 | 14篇 |
2012年 | 12篇 |
2011年 | 16篇 |
2010年 | 7篇 |
2009年 | 7篇 |
2008年 | 7篇 |
2007年 | 9篇 |
2006年 | 9篇 |
2005年 | 9篇 |
2004年 | 17篇 |
2003年 | 9篇 |
2002年 | 6篇 |
2001年 | 2篇 |
2000年 | 2篇 |
1999年 | 3篇 |
1998年 | 1篇 |
1997年 | 3篇 |
1996年 | 4篇 |
1995年 | 1篇 |
1993年 | 1篇 |
1992年 | 2篇 |
1991年 | 2篇 |
1990年 | 2篇 |
1989年 | 1篇 |
1988年 | 3篇 |
1986年 | 1篇 |
1985年 | 2篇 |
1982年 | 1篇 |
1979年 | 2篇 |
1978年 | 1篇 |
1976年 | 1篇 |
1974年 | 2篇 |
1968年 | 1篇 |
排序方式: 共有191条查询结果,搜索用时 15 毫秒
61.
Emiko Mouri Kozo Matsumoto Hideki Matsuoka 《Journal of Polymer Science.Polymer Physics》2003,41(16):1921-1928
A carpetlike dense‐layer formation between a hydrophobic layer and a polyelectrolyte brush layer has been found in the monolayers of an ionic amphiphilic diblock copolymer, poly(1,1‐diethylsilacyclobutane)m‐block‐poly(methacrylic acid)n, on a water surface by an X‐ray reflectivity technique. By detailed analysis, we have found that the hydrophilic layer under the water is not a simple layer but is divided into two layers, that is, a carpetlike dense methacrylic acid (MAA) layer near the hydrophobic layer and a polyelectrolyte brush layer. We have also confirmed that a well‐established polyelectrolyte brush is formed only for the m:n = 43:81 polymer monolayer: For m:n = 40:10 and m:n = 45:60 polymer monolayers, only a dense MAA layer is formed. This dense‐layer formation should be the origin of the interesting hydrophobic‐layer thickness variation previously reported; The hydrophobic‐layer thickness takes a minimum as a function of the hydrophilic chain length at any surface pressure studied. An overview of the data for three samples with different chain lengths (m:n = 40:10, 45:60, or 43:81) has shown that the thickness of this dense layer is 10–20 Å and is independent of the surface pressure and polymerization degree of poly(methacrylic acid) (PMAA) in the range studied. This dense‐layer formation is explained by the reasonable speculation that contact with PMAA is thermodynamically more stable than direct contact with water for the diethylsilacyclobutane (Et2SB) layer on water. In this sense, the dense layer acts like a carpet for the hydrophobic Et2SB layer, and a 10–20‐Å thickness could be a critical value for the carpet. © 2003 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 41: 1921–1928, 2003 相似文献
62.
Paredes-Gamero EJ França JP Moraes AA Aguilar MO Oshiro ME Ferreira AT 《Journal of fluorescence》2004,14(6):711-722
Fura-2 is one of the most used fluorophore for measuring intracellular calcium concentration ([Ca2+]i). In mouse bone marrow cell suspensions ATP produces a biphasic effect: till 1 mM, ATP produces increases in [Ca2+]i; from 1 mM on an increase is observed, that is followed by the decrease in the 340/380 nm ratio (R340/380). At high ATP (4 mM) concentration fura-2 leaked from loaded bone marrow cell suspensions. We observed that ATP decreases fluorescence in the absorption and excitation spectra of fura-2, consequently the emitted one is decreased including the isobestic point (360 nm). ATP analogs: BzATP, ATPyS and UTP, but not alphabetaATP, ADP or AMP, promote decrease of fluorescence in the isobestic point of fura-2. The physical/chemical process that reduces the absorption and excitation of fura-2 by ATP is unknown. The P2X7 inhibitors, Mg2+ (5 mM), OxATP (300 microM) and Brilliant Blue (100 nM), blocked the efflux of fura-2 and ATP-induced R340/380 decrease. The J774 cell line and mononuclear cells with a higher expression of P2X7 receptors show the same decrease in R340/380 as that induced by ATP. In the HL-60 cell line, myeloid cells and erythroblasts extracted from bone marrow, such effect does not occur. It is concluded that the use of the fluorescent Ca2+ indicator fura-2 does not allow the correct measurement of [Ca2+]i in these cells in the presence of a higher concentration of ATP which activated the P2X7 receptor. 相似文献
63.
Using (S)-benzyl 2,3-epoxypropyl ether (1), the first stereoselective synthesis of (+)-nuciferol (14) and (+)-nuciferal (16) has been achieved. Employing the same methodology an enantioselective synthesis of (+)--curcumene (17) is also described. 相似文献
64.
Ohne Zusammenfassung 相似文献
65.
Osamu Kujirai Takeshi Kobayashi Emiko Sudo 《Fresenius' Journal of Analytical Chemistry》1979,297(5):398-403
Summary A simple and rapid analytical method has been developed for the direct determination of trace quantities of thallium in nickel and cobalt-base heatresisting alloys by graphite furnace atomic absorption spectrometry. Hydrofluoric acid, sulphuric acid, and hydrogen peroxide were used for the dissolution of a wide variety of these alloys. The interferences of matrix elements and acids were eliminated. The absorbance of thallium is constant over a wide range of ashing temperatures. Synthetic standard solutions composed of nickel or cobalt matrix and thallium were used for calibration. The detection limit for thallium by this method is 0.2 ppm in the sample. Mechanisms of the interferences are discussed.
Schnelle Bestimmung von Thalliumspuren in hitzebeständigen Cobalt- und Nickellegierungen durch Atomabsorptions-Spektralphotometrie mit dem Graphitofen
Zusammenfassung Ein Verfahren zur AAS-Bestimmung von Thallium in verschiedenartigen Cobalt- und Nickellegierungen wird beschrieben. Zur Auflösung der Probe werden Flußsäure, Schwefelsäure und Wasserstoffperoxid verwendet. Störungen durch Matrixelemente und durch die Säuren konnten beseitigt werden. Die Thalliumabsorption ist über einen weiten Temperaturbereich bei der Veraschung konstant. Zur Eichung dienen synthetische Lösungen von Cobalt- bzw. Nikkelmatrix und Thallium. Die Nachweisgrenze für Thallium beträgt 0,2 ppm. Die Mechanismen der Störungen werden diskutiert.相似文献
66.
Natsuru Chikushi Emiko Ohara Ayako Hisama Hiroyuki Nishide 《Macromolecular rapid communications》2014,35(10):976-980
Network polymers of cobaltporphyrin derivatives are prepared by a facile click reaction via the Michael addition of acetoacetate‐substituted tetraphenyl cobaltporphyrin and tri‐ or tetra‐acrylates. The conversion is saturated for 1 h in the presence of a catalyst, which almost reaches the same gelation point of the formed network polymers. Deeply and homogeneously red‐colored membranes with a sub‐micrometer thickness are yielded on a porous supporting membrane. They are still tough even with a very high content of the rigid porphyrin residue. The oxygen permeability is high, at 10–100 Barrer, and the oxygen/nitrogen permselectivity (PO2/PN2) is significantly enhanced with the porphyrin content reaching 30, for the membranes with ca. 70 wt% porphyrin content.
67.
Gold nanoparticles were fabricated by reduction of highly concentrated Au(III) ions (200 mM) with casein proteins from milk. The gold nanoparticles were converted to nanoparticle-powders after washing and subsequent vacuum drying without aggregation. The nanoparticle-powders completely re-dispersed in aqueous solution, and stable colloidal gold nanoparticles were obtained. UV-vis extinction spectra and dynamic light scattering (DLS) measurements revealed that large assemblies (size, ca. 3 μm) and subaggregates (size, <0.5 μm) composed of gold nanoparticle-casein protein chain-Au(III) ion were dynamically formed and disintegrated over the course of the growth of the gold nanoparticles. Fourier transform infrared (FT-IR) spectra indicated conformational changes of casein proteins induced by the interaction of casein protein-Au(III) ion and -gold nanoparticle. Finally, rapid, one-pot, and highly concentrated synthetic procedures of gold and silver nanoparticle powders protected by casein (mean diameters below 10 nm) were successfully developed using 3-amino-1-propanol aqueous solutions as reaction media. Dense colloidal gold (40 g L(-1)) and silver (22 g L(-1)) nanoparticle aqueous solutions were obtained by re-dispersing the metal nanoparticle powders. 相似文献
68.
We have successfully applied electrospray ionization mass spectrometry (ESI-MS) and (1)H NMR analyses to study ligand substitution reactions of mu-oxo ruthenium bipyridine dimers cis,cis-[(bpy)(2)(L)RuORu(L')(bpy)(2)](n+) (bpy = 2,2'-bipyridine; L and L' = NH(3), H(2)O, and HO(-)) with solvent molecules, that is, acetonitrile, methanol, and acetone. The results clearly show that the ammine ligand is very stable and was not substituted by any solvents, while the aqua ligand was rapidly substituted by all the solvents. In acetonitrile and acetone solutions, the substitution reaction of the aqua ligand(s) competed with a deprotonation reaction from the ligand. The hydroxyl ligand was not substituted by acetonitrile or acetone, but it exchanged slowly with CH(3)O(-) in methanol. The substitution reaction of the aqua ligands in [(bpy)(2)(H(2)O)Ru(III)ORu(III)(H(2)O)(bpy)(2)](4+) was more rapid than that of the hydroxyl ligand in [(bpy)(2)(H(2)O)Ru(III)ORu(IV)(OH)(bpy)(2)](4+). In methanol, slow reduction of Ru(III) to Ru(II) was observed in all the mu-oxo dimers, and the Ru-O-Ru bridge was then cleaved to give mononuclear Ru(II) complexes. 相似文献
69.
Chi Zhang Emiko Kazuma Yousoo Kim 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(49):17900-17908
Dehalogenative cycloaddition reaction is a powerful strategy to generate new ring scaffolds with π‐conjugated features on a surface, and thus holds great promise toward atomically precise electronic devices or nanomaterials. The ortho‐dihalo substitution provides a good strategy to realize cycloaddition. However, the limited understanding of intermediate states involved hinders mechanistic exploration for further precise design and optimization of reaction products. Now, the evolutions of competing surface‐stabilized radicals and organometallic intermediates in real space were visualized toward the formation of dominant conjugated four‐membered ring connections. From the interplay of scanning tunneling microscopy and density functional theory calculations, the stepwise metal‐mediated dehalogenative cycloaddition pathway is elucidated both experimentally and theoretically. The results provide fundamental insights into the intermediate states involved in on‐surface synthesis. 相似文献
70.
Kohji Yoshinaga Shouhei Satoh Emiko Mouri Akemi Nakai 《Colloid and polymer science》2006,284(6):694-698
Immobilization of colloidal crystals by gelation of polymer-grafted silica suspension in acetonitrile with alkyl amides derived from amino acids was investigated. Addition of N-benzyloxycarbonyl-l-isoleucylaminooctadecane (Z-Ile-C18) and 1,12-bis(N-benzyloxycarbonyl-l-valylamino)dodecane [Bis(Z-Val)-C12] to poly(maleic anhydride-co-styrene)-grafted silica suspension in acetonitrile resulted in formation of physical gels preserved colloidal crystal structure. From the reflection spectra, intersphere distance and size of crystallite in the gel formed with Bis(Z-Val)-C12 were confirmed to be mostly same as those of colloidal crystals in suspension. 相似文献