全文获取类型
收费全文 | 1224篇 |
免费 | 11篇 |
国内免费 | 5篇 |
专业分类
化学 | 881篇 |
晶体学 | 28篇 |
力学 | 19篇 |
数学 | 76篇 |
物理学 | 236篇 |
出版年
2020年 | 5篇 |
2019年 | 7篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 10篇 |
2015年 | 8篇 |
2014年 | 13篇 |
2013年 | 64篇 |
2012年 | 50篇 |
2011年 | 53篇 |
2010年 | 42篇 |
2009年 | 36篇 |
2008年 | 79篇 |
2007年 | 60篇 |
2006年 | 53篇 |
2005年 | 65篇 |
2004年 | 59篇 |
2003年 | 59篇 |
2002年 | 55篇 |
2001年 | 33篇 |
2000年 | 16篇 |
1999年 | 11篇 |
1998年 | 11篇 |
1997年 | 23篇 |
1996年 | 24篇 |
1995年 | 12篇 |
1994年 | 8篇 |
1993年 | 18篇 |
1992年 | 19篇 |
1991年 | 7篇 |
1990年 | 12篇 |
1989年 | 8篇 |
1988年 | 19篇 |
1987年 | 8篇 |
1986年 | 11篇 |
1985年 | 24篇 |
1984年 | 21篇 |
1983年 | 20篇 |
1982年 | 24篇 |
1981年 | 21篇 |
1980年 | 24篇 |
1979年 | 19篇 |
1978年 | 20篇 |
1977年 | 14篇 |
1976年 | 6篇 |
1975年 | 9篇 |
1974年 | 10篇 |
1969年 | 5篇 |
1968年 | 7篇 |
1966年 | 6篇 |
排序方式: 共有1240条查询结果,搜索用时 15 毫秒
101.
Komoto A Maenosono S Yamaguchi Y 《Langmuir : the ACS journal of surfaces and colloids》2004,20(20):8916-8923
Fluorescence oscillation is observed in an ensemble of colloidal CdSe/ZnS core/shell quantum dots (QDs) dispersed in nonpolar solvent under continuous irradiation. The QDs dispersed in toluene gradually aggregate and change their fluorescence intensity, even in the dark. During the aggregation, the QD/toluene suspension is unstable, that is, overdispersed. The fluorescence oscillation is found only in this unstable state before the system reaches steady state. In addition, the aggregation rate is promoted by irradiation and strongly correlates with the oscillation amplitude. Our experimental results indicate that the dispersion instability plays an important role in both linear and nonlinear dynamics of the fluorescence. It is inferred from the experimental results and previous studies that the complex time evolution of fluorescence in the QD/toluene dispersion is possibly due to adsorption and desorption of surface ligand molecules over the course of QD aggregation. 相似文献
102.
Wada K Mizutani T Matsuoka H Kitagawa S 《Chemistry (Weinheim an der Bergstrasse, Germany)》2003,9(10):2368-2380
Water-soluble zinc bisporphyrin receptors 1 and 2 having two Lewis acidic sites (zinc) in the hydrophobic environment consisting of alkyl chains and a bisporphyrin framework, and covered with hydrophilic exterior (twelve or eighteen carboxyl groups) were prepared. The receptors show high affinity for diamines and DNA intercalators in water where the binding constants K(a) are of the order of 10(7) and 10(8) M(-1), respectively. Diamines and DNA intercalators are bound to the receptor through different mechanisms. Diamines are bound through hydrophobic interactions and zinc-nitrogen interactions, while DNA intercalators are bound through hydrophobic interactions and charge-transfer interactions. Flexible alkyl chains can make van der Waals contact with guests and create a hydrophobic environment around the bound guest by an induced-fit-type mechanism. For the binding of DNA intercalators, the following features are noteworthy: 1). Binding constants are similar between the zinc porphyrins and zinc-free porphyrins; 2). the binding constant is larger for the guest having the lower LUMO; this indicates the important contribution of charge-transfer interactions to binding; 3). the hydrophobic and cationic nature of DNA intercalators is substantially important, and 4). higher ionic strength reduced the binding affinities; this shows a moderate contribution of electrostatic interactions. The conformational instability of the receptors also contributes to the tight binding: hydrophobic and electrostatic interactions cannot both be favorable at the same time in the guest-free receptor. Enthalpy-entropy compensation observed for the binding of diamines and DNA intercalators is characterized by a relatively small slope (alpha=0.74) and a large intercept (beta=7.75 kcal mol(-1)) in the DeltaH degrees versus TDeltaS degrees plot; this shows that a conformational change of receptors and a significant desolvation occur upon binding. The receptor can competitively bind to propidium iodide to deprive DNA of the intercalated propidium iodide. These features of water-soluble receptors consisting of a rigid framework and flexible side chains with a large solvent-accessible area are in contrast to highly preorganized rigid receptors, and they can provide useful guidelines for rational design of induced-fit artificial receptors in water. 相似文献
103.
Single puffs of cigarette smoke with a wide continuous range of volatility are directly analyzed using a new system. The system consists of a smoking machine, an online thermal desorption system (TDS), and a multidimensional gas chromatograph-mass spectrometer (MDGC-MS) system. The online TDS with the smoking machine collects the single-puff cigarette smoke with glass beads as the cryogenic adsorbent. The MDGC is composed of three capillary columns, Poraplot Q, and DB-WAX for separation and a deactivated capillary column for pressure balance, which enables simultaneous separation of the two different phases. The smoke desorbed from the TDS is divided into vapor and semivolatile phases and analyzed individually with each column by the MDGC. Thus, the system enables the overall analysis of the two phases simultaneously, including acetaldehyde and 1,4-benzenediol. This system also provides more appropriate analysis for compounds crossing the two phases such as toluene and pyridine. For the approach of introducing internal standards, a gas mixture of toluene-d(8) and o-xylene-d(10) is applied and the compounds are detected in the vapor and semivolatile phases, respectively. 相似文献
104.
Okamura H Kawahara J Nanba T Kimura S Soda K Mizutani U Nishino Y Kato M Shimoyama I Miura H Fukui K Nakagawa K Nakagawa H Kinoshita T 《Physical review letters》2000,84(16):3674-3677
Optical conductivity data of the intermetallic compounds (Fe1-xVx)3Al ( 0=x=0.33) reveal that their density of states around the Fermi energy ( E(F)) is strongly reduced as x is increased. In particular, Fe2VAl ( x = 0.33) has a deep, well-developed pseudogap of 0.1-0.2 eV at E(F) and a small density ( approximately 5x10(20) cm(-3)) of carriers, which is highly unusual for intermetallic compounds. It is shown that the pseudogap results from the band structure of Fe2VAl, rather than from temperature-dependent correlation effects. Based on the present results, we propose a simple model that consistently explains both the semiconductorlike transport and the metallic photoemission results previously observed for Fe2VAl. 相似文献
105.
Yukio Yoshimura 《Journal of polymer science. Part A, Polymer chemistry》1986,24(9):2085-2099
Formaldehyde was reacted with both 2,4-dimethylphenol(2,4-xyenol) and 2,6-dimethylphenol(2,6-xylenol), which are model compounds of monofunctional phenols, and the reaction products were subjected to HLC analysis to elucidate details of the formation process and bonding manner of a formal group, which can greatly affect the performance of phenol–formaldehyde resins. As a result, formal compounds of dimethylphenols were successfully separated by HLC. It was further found, as a result of tracing the reactions by HLC, that the formation of a formal group occurs at either position of the ortho and para positions, and that methylol compounds were formed following formation of the formal compounds. Furthermore, as a result of NMR analysis as well as consideration of solvation on the basis of the relative elution volumes of the nonacetylated and acetylated reaction products it was found that the formal group was added to the phenol nuclei. 相似文献
106.
Atsuhiro Fujimori Hiroko Hoshizawa Satoshi Kobayashi Kaname Kanai Yukio Ouchi Kazuhiko Seki 《Journal of Polymer Science.Polymer Physics》2008,46(5):534-546
Comb copolymers containing both hydrogenated and fluorinated side‐chains were prepared by copolymerization using acrylic or methacrylic monomers in several ratios. The crystal structures of these copolymers and layer structures of their organized molecular films were investigated by wide‐angle X‐ray diffraction (WAXD), small‐angle X‐ray scattering (SAXS), and out‐of plane X‐ray diffraction. Further, to selectively estimate the regularity of shorter fluorocarbon side‐chains, organized molecular films of copolymers were investigated by polarized near‐edge X‐ray adsorption fine structure (NEXAFS) spectroscopy. From the results of these measurements, it was inferred that these copolymers formed highly ordered layer structures, and a long spacing was predominantly determined by the arrangement of hydrogenated side‐chains, except in copolymers having extremely high fluorocarbon contents. In the case of the organized molecular films, the fluorinated side‐chains of methacrylate copolymers cannot form a highly ordered arrangement, whereas those of acrylate copolymers were oriented on monolayers. However, in both cases, the hydrogenated side‐chains predominantly formed layer structures in the organized films, and the fluorinated side‐chains did not contribute to the formation of the layer structures. © 2008 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 46: 534–546, 2008 相似文献
107.
S. Iijima F. Mizutani O. Niwa N. Matsumoto Y. Sunatsuki M. Kojima 《Hyperfine Interactions》2005,166(1-4):397-402
The spin-crossover behaviors of mixed-valence iron compounds [FeIIH3L][FeIIIL](NO3)2 (1) and [FeIIH3LMe][FeIIILMe](NO3)2 (2) have been investigated by 57Fe Mössbauer spectroscopy, where H3L is a hexadentate N6 tripod ligand containing three imidazole groups and H3LMe is its 2-methylimidazole derivative. Deconvolution analyses of the Mössbauer spectra revealed that a two-step SCO (LS FeII–LS FeIII→HS FeII–LS FeIII→HS FeII–HS FeIII) proceeds in each compound on elevating the temperature. Compound 2 exhibited lower spin-transition temperatures than 1. “Frozen-in effect” was observed below 120 and 50 K for 1 and 2, respectively. 相似文献
108.
109.
Nonlinear resonances and self-excited oscillations of a rotor caused by radial clearance and collision 总被引:1,自引:0,他引:1
This paper investigates oscillations in a flexible rotor system with radial clearance between an outer ring of the bearing
and a casing by experiments and numerical simulations. The mathematical model considers the collisions of the bearing with
the casing. The following phenomena are found: (1) Nonlinear resonances of subharmonic, super-subharmonic and combination
oscillation occur. (2) Self-excited oscillation of a forward whirling mode occurs in a wide range above the major critical
speed. (3) Entrainment phenomena from self-excited oscillation to nonlinear forced oscillation occur at these nonlinear resonance
ranges. Moreover, this study analyzes periodic solutions of the mathematical model by the Harmonic Balance Method (HBM). As
the results, the nonlinear resonances of subharmonic oscillation and its entrainment phenomenon can be explained theoretically
by investigating the stability of the periodic solutions. The influence of the static force and the bearing damping on these
oscillation are also clarified. 相似文献
110.
Optically driven actuators have a feature of a non-contact method supplied by light energy. A new method is proposed with
three poly(vinylidene difluoride) (PVDF) cantilevers as the legs and a polymer film as the body. The PVDF cantilevers are
coated with silver on one surface. When one side of the cantilever is irradiated by a laser beam, an electric field is produced
along a cross-section of the cantilever by the pyroelectric effect and a mechanical displacement occurs by the piezoelectric
effect. Its response time and its generated force are measured experimentally. Two types of optically driven actuators using
PVDF film are proposed to move using different characteristics. 相似文献