全文获取类型
收费全文 | 275篇 |
免费 | 9篇 |
专业分类
化学 | 220篇 |
晶体学 | 2篇 |
力学 | 5篇 |
数学 | 6篇 |
物理学 | 51篇 |
出版年
2023年 | 1篇 |
2021年 | 4篇 |
2020年 | 3篇 |
2019年 | 2篇 |
2018年 | 3篇 |
2016年 | 7篇 |
2015年 | 7篇 |
2014年 | 8篇 |
2013年 | 10篇 |
2012年 | 15篇 |
2011年 | 19篇 |
2010年 | 5篇 |
2009年 | 12篇 |
2008年 | 24篇 |
2007年 | 18篇 |
2006年 | 17篇 |
2005年 | 13篇 |
2004年 | 19篇 |
2003年 | 10篇 |
2002年 | 6篇 |
2001年 | 4篇 |
2000年 | 5篇 |
1999年 | 10篇 |
1998年 | 6篇 |
1997年 | 2篇 |
1996年 | 1篇 |
1994年 | 2篇 |
1993年 | 3篇 |
1992年 | 3篇 |
1991年 | 3篇 |
1990年 | 1篇 |
1989年 | 4篇 |
1988年 | 3篇 |
1987年 | 3篇 |
1986年 | 3篇 |
1985年 | 2篇 |
1984年 | 1篇 |
1982年 | 5篇 |
1981年 | 3篇 |
1980年 | 3篇 |
1978年 | 2篇 |
1977年 | 3篇 |
1976年 | 4篇 |
1974年 | 3篇 |
1973年 | 2篇 |
排序方式: 共有284条查询结果,搜索用时 31 毫秒
91.
Naokazu Yoshikawa Takeko Matsumura-Inoue Nobuko Kanehisa Yasushi Kai Hiroshi Takashima Keiichi Tsukahara 《Analytical sciences》2004,20(12):1639-1644
Hexafluorophosphate salts of mononuclear complexes [Ru(II)Cl(L)(terpy)]+ (L = dmbpy (1); dpbpy (2), sambpy (3), and dpp (7), and binuclear complexes [Ru(II)2Cl2(dpp)(terpy)2]2+ (8) and [Ir(III)Ru(II)Cl2(dpp)(terpy)2]3+ (9) were prepared and characterized. Abbreviations of the ligands are bpy = 2,2'-bipyridine, dmbpy = 4,4'-dimethyl-2,2'-bipyridine, dpbpy = 4,4'-diphenyl-2,2'-bipyridine, dpp = 2,3-bis(2-pyridyl)pyrazine, sambpy = 4,4'-bis((S)-(+)-alpha-1-phenylethylamido)-2,2'-bipyridine, and terpy = 2,2':6',2'-terpyridine. The absorption spectra of 8 and 9 are dominated by ligand-centered bands in the UV region and by metal-to-ligand charge-transfer bands in the visible region. The details of their spectroscopic and electrochemical properties were investigated. In both binuclear complexes, it has been found that the HOMO is based on the Ru metal, and LUMO is dpp-based. [Ir(III)Ru(II)Cl2(dpp)(terpy)2]3+, indicating intense emission at room temperature, and a lifetime of 154 ns. The long lifetime of this bimetallic chromophore makes it a useful component in the design of supramolecular complexes. 相似文献
92.
Kohji Tashiro Keiko Ono Yasuhisa Minagawa Masamichi Kobayashi Tsuyoshi Kawai Katsumi Yoshino 《Journal of Polymer Science.Polymer Physics》1991,29(10):1223-1233
In order to clarify the structural changes that occur in the thermochromic phase transition of poly (3-dodecylthiophene) [P3DT] and poly (3-hexylthiophene) [P3HT], the temperature dependence of x-ray diffraction and Fourier transform infrared spectra was measured. (1) Orthogonal unit-cell parameters were determined at room temperature: a=25.83 Å, b=7.75 Å, c (fiber axis)=7.77 Å for P3DT and a=16.63 Å, b=7.75 Å, and c=7.77 Å for P3HT. A large variation of the a-axis length between P3DT and P3HT indicates the extended trans conformation for the alkyl side chains which are oriented along the lateral a-axis direction. (2) The interplanar spacing, intensity, and integral width of the x-ray (h00) and (00l) reflections were found to change drastically in the transition region. (3) Polarized infrared measurements at high temperature revealed a marked increase of the gauche band intensity for the alkyl side group modes followed by a decrease in the band intensity of the thiophene ring modes. (4) The layer reflections of the x-ray fiber diagram become diffuse at high temperatures, indicating that the transition occurs in a liquidcrystalline manner with the orientation of the main chain axes preserved but with almost no axial correlation between the neighboring main chains. These results provide experimental support for the structural model proposed earlier: as the temperature increases, the trans-type side chains begin to disorder by introduction of gauche bonds. This disordering disrupts the regularity of the main chain conformation and decreases the effective length of the polythiophene conjugated system. 相似文献
93.
Tisato Kajiyama Yasuhisa Nagata Shintaro Washizu Motowo Takayanagi 《Journal of membrane science》1982,11(1):39-52
Polymer/liquid crystal composite membranes were cast from a 1,2-dichloroethane solution of polycarbonate (PC) and N-(4-ethoxybenzylidene-4'-n- butylaniline) (EBBA). The mixing state of the polymer/liquid crystal composite membrane was investigated on the basis of differential scanning calorimetry, x-ray, density, sorption isotherm and sorption—desorption studies and also by electron microscopic observations. EBBA molecules in the composite membrane exist in an almost molecularly dispersed state up to an EBBA fraction of 30 wt%, and in the case of EBBA fractions above 30 wt% form a crystal domain as the mutual continuous phase among the network of polycarbonate fibrils. The composite membrane containing EBBA of 60 wt% can be handled as a homogeneous medium when considering gas permeation.The diffusive permeability coefficient to water reveals a distinct jump in the vicinity of the crystal—liquid crystal phase transition temperature of EBBA. The permeability coefficients, P, to hydrocarbon gases increases 100-200 times over several degrees in the phase transition temperature range. P for hydrocarbon gases decreases with increasing number of carbon atoms below the phase transition temperature, but increases with increasing number of carbon atoms above it. These results suggest that the permeation process is predominantly controlled by diffusion mechanism below the transition temperature of EBBA, while the solubility factor significantly affects gas permeation above it. 相似文献
94.
Takumi Goto Satoshi Matsuyama Hiroki Nakamori Yasuhisa Sano Yoshiki Kohmura Makina Yabashi 《Synchrotron Radiation News》2016,29(4):32-36
Ultra-bright and high-coherence X-rays are now being used in synchrotron radiation facilities and X-ray free electron laser facilities. X-ray focusing techniques are essential to take full advantage of these excellent X-ray light sources. To meet the strong demand, high-quality X-ray focusing optics have been developed owing to the advancement of ultraprecision machining and measurement. State-of-the-art refractive lenses [1], zone plates [2], and Laue lenses [3] can be used to achieve X-ray focusing to a spot a few tens of nanometers. 相似文献
95.
Ozawa K Yamamura Y Yasuzuka S Mori H Kutsumizu S Saito K 《The journal of physical chemistry. B》2008,112(39):12179-12181
Structure of a complex superstructure self-organized by thermotropic mesogen, 1,2-bis(4'- n-alkoxybenzoyl)hydrazine [BABH(n), where n is the number of carbon atoms in an alkoxy chain] was studied while paying special attention to the structure at the molecular level. Maximum entropy (MEM) analysis revealed that the molecular cores form two kinds of aggregates: Jungle gym with 3-fold junctions roughly on P minimal surface and spherical shells. 相似文献
96.
Dr. Alessa Hinzmann Dr. Tobias Betke Prof. Dr. Yasuhisa Asano Prof. Dr. Harald Gröger 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(17):5313-5321
While belonging to the most fundamental functional groups, nitriles represent a class of compound that still raises challenges in terms of an efficient, cost-effective, general and, at the same time, sustainable way for their synthesis. Complementing existing chemical routes, recently a cyanide-free enzymatic process technology based on the use of an aldoxime dehydratase (Oxd) as a biocatalyst component has been developed and successfully applied for the synthesis of a range of nitrile products. In these biotransformations, the Oxd enzymes catalyze the dehydration of aldoximes as readily available substrates to the nitrile products. Herein, these developments with such enzymes are summarized, with a strong focus on synthetic applications. It is demonstrated that this biocatalytic technology has the potential to “cross the bridge” between the production of fine chemicals and pharmaceuticals, on one hand, and bulk and commodity chemicals, on the other. 相似文献
97.
Mizuno M Hamada N Tokunaga F Mizutani Y 《The journal of physical chemistry. B》2007,111(23):6293-6296
Picosecond time-resolved ultraviolet resonance Raman (UVRR) spectra of photoactive yellow protein (PYP) were measured. UVRR bands attributed to the vibration of tyrosine and tryptophan residues showed a spectral change upon photoreaction. It was found that the hydrogen-bond strength between the chromophore and Y42 increases in the pG* state. The ultrafast change in the tryptophan band revealed that a photoinduced structural change of the chromophore had propagated to the W119 region, located 12 A from the chromophore, within picoseconds. 相似文献
98.
Prof. Dr. Muhammet Uyanik Dr. Naoto Sahara Mayuko Tsukahara Yuhei Hattori Prof. Dr. Kazuaki Ishihara 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2020,132(39):17258-17265
We report high-performance I+/H2O2 catalysis for the oxidative or decarboxylative oxidative α-azidation of carbonyl compounds by using sodium azide under biphasic neutral phase-transfer conditions. To induce higher reactivity especially for the α-azidation of 1,3-dicarbonyl compounds, we designed a structurally compact isoindoline-derived quaternary ammonium iodide catalyst bearing electron-withdrawing groups. The nonproductive decomposition pathways of I+/H2O2 catalysis could be suppressed by the use of a catalytic amount of a radical-trapping agent. This oxidative coupling tolerates a variety of functional groups and could be readily applied to the late-stage α-azidation of structurally diverse complex molecules. Moreover, we achieved the enantioselective α-azidation of 1,3-dicarbonyl compounds as the first successful example of enantioselective intermolecular oxidative coupling with a chiral hypoiodite catalyst. 相似文献
99.
Yamauchi K Mimura H Kimura T Yumoto H Handa S Matsuyama S Arima K Sano Y Yamamura K Inagaki K Nakamori H Kim J Tamasaku K Nishino Y Yabashi M Ishikawa T 《J Phys Condens Matter》2011,23(39):394206
We have constructed an extremely precise optical system for hard-x-ray nanofocusing in a synchrotron radiation beamline. Precision multilayer mirrors were fabricated, tested, and employed as Kirkpatrick-Baez mirrors with a novel phase error compensator. In the phase compensator, an at-wavelength wavefront error sensing method based on x-ray interferometry and an in situ phase compensator mirror, which adaptively deforms with nanometer precision, were developed to satisfy the Rayleigh criterion to achieve diffraction-limited focusing in a single-nanometer range. The performance of the optics was tested at BL29XUL of SPring-8 and was confirmed to realize a spot size of approximately 7 nm. 相似文献
100.
Morisue M Ueda S Kurasawa M Naito M Kuroda Y 《The journal of physical chemistry. A》2012,116(21):5139-5144
Supramolecular control of the π-stacked configuration of aqueous phthalocyanine (Zn[Pc(SO(3))(4)]) was achieved, allowing organization of a J-type slipped-cofacial dimer with per-O-methylated α-cyclodextrin (TMe-α-CDx) by the aid of host-guest interactions. Pristine Zn[Pc(SO(3))(4)] forms nonfluorescent face-to-face aggregates in water. The π-stacked configuration was controlled in the slipped-cofacial dimer, which was formed as a shallow inclusion complex with TMe-α-CDx, giving remarkably enhanced fluorescence with a very small Stokes shift. Organization of the J-type slipped-cofacial dimer as a 2:2 Zn[Pc(SO(3))(4)]-TMe-α-CDx complex was achieved through π-stacking of the unencapsulated segment of Zn[Pc(SO(3))(4)] shallowly encapsulated by a small TMe-α-CDx cavity. 相似文献