全文获取类型
收费全文 | 1655篇 |
免费 | 30篇 |
国内免费 | 4篇 |
专业分类
化学 | 1276篇 |
晶体学 | 14篇 |
力学 | 9篇 |
数学 | 91篇 |
物理学 | 299篇 |
出版年
2023年 | 7篇 |
2022年 | 14篇 |
2021年 | 12篇 |
2020年 | 12篇 |
2019年 | 23篇 |
2018年 | 12篇 |
2017年 | 14篇 |
2016年 | 19篇 |
2015年 | 23篇 |
2014年 | 42篇 |
2013年 | 86篇 |
2012年 | 72篇 |
2011年 | 126篇 |
2010年 | 47篇 |
2009年 | 66篇 |
2008年 | 106篇 |
2007年 | 94篇 |
2006年 | 74篇 |
2005年 | 96篇 |
2004年 | 85篇 |
2003年 | 82篇 |
2002年 | 79篇 |
2001年 | 34篇 |
2000年 | 29篇 |
1999年 | 12篇 |
1998年 | 12篇 |
1997年 | 6篇 |
1996年 | 24篇 |
1995年 | 21篇 |
1994年 | 20篇 |
1993年 | 22篇 |
1992年 | 16篇 |
1991年 | 14篇 |
1990年 | 12篇 |
1989年 | 11篇 |
1988年 | 12篇 |
1987年 | 13篇 |
1986年 | 20篇 |
1985年 | 32篇 |
1984年 | 25篇 |
1983年 | 10篇 |
1982年 | 16篇 |
1981年 | 13篇 |
1980年 | 15篇 |
1979年 | 25篇 |
1978年 | 11篇 |
1977年 | 23篇 |
1976年 | 16篇 |
1975年 | 9篇 |
1973年 | 8篇 |
排序方式: 共有1689条查询结果,搜索用时 15 毫秒
71.
Hydroxyapatite (HAp) films were deposited by electron cyclotron resonance plasma sputtering under a simultaneous flow of H2O vapor gas. Crystallization during sputter-deposition at elevated temperatures and solid-phase crystallization of amorphous films were compared in terms of film properties. When HAp films were deposited with Ar sputtering gas at temperatures above 460 °C, CaO byproducts precipitated with HAp crystallites. Using Xe instead of Ar resolved the compositional problem, yielding a single HAp phase. Preferentially c-axis-oriented HAp films were obtained at substrate temperatures between 460 and 500 °C and H2O pressures higher than 1×10−2 Pa. The absorption signal of the asymmetric stretching mode of the PO43− unit (ν3) in the Fourier-transform infrared absorption (FT-IR) spectra was the narrowest for films as-crystallized during deposition with Xe, but widest for solid-phase crystallized films. While the symmetric stretching mode of PO43− (ν1) is theoretically IR-inactive, this signal emerged in the FT-IR spectra of solid-phase crystallized films, but was absent for as-crystallized films, indicating superior crystallinity for the latter. The Raman scattering signal corresponding to ν1 PO43− sensitively reflected this crystallinity. The surface hardness of as-crystallized films evaluated by a pencil hardness test was higher than that of solid-phase crystallized films. 相似文献
72.
Keigo?SuzukiEmail author Nobuhiko?Tanaka Akira?Ando Hiroshi?Takagi 《Journal of nanoparticle research》2012,14(5):863
Size-tuned copper oxide nanoparticles with sizes of 9, 12, and 15 nm were fabricated by laser ablation and on-line size selection
using a differential mobility analyzer at a gas pressure of 666 Pa. The dependence of the particle properties on the in situ
annealing temperatures and selection sizes was investigated. The crystalline phases of the nanoparticles fabricated at temperatures
below 973 K were assigned to monoclinic cupric oxide (CuO) which converted into cubic cuprous oxide (Cu2O) when the annealing temperature was above 1,173 K. This indicates that the crystalline phases can be easily controlled by
changing the annealing temperature. TEM images confirmed that well-crystallized and well-dispersed CuO and Cu2O nanoparticles with narrow size distributions were obtained using this method. This fabrication process is useful and promising
for the future investigation of the intrinsic size-dependent properties of CuO and Cu2O. 相似文献
73.
Application of the muramyldipeptide derivative B30-MDP to liposomal vaccines will aid in the development of improved high immunogenicity vaccines. To give full play to the effectiveness of B30-MDP as a liposomal vaccine, it is important to evaluate the effect of cholesterol, dimyristoylphosphatidylcholine (DMPC) or distearoylphosphatidylcholine (DSPC) incorporation on the chemical stability of B30-MDP and physicochemical properties of B30-MDP/lipid mixed vesicles from the view point of pharmaceutics.The observed degradation rate constants of B30-MDP by hydrolysis in B30-MDP/cholesterol mixed vesicles were increased with increasing concentration of cholesterol, however, those in B30-MDP/DMPC and B30-MDP/DSPC mixed vesicles were unchanged with increasing concentration of DMPC and DSPC. The degradation behavior of B30-MDP was then compared with physicochemical properties of B30-MDP/lipid mixed vesicles, such as membrane fluidity and particle size. It was apparent that the degradation of B30-MDP in B30-MDP/cholesterol mixed vesicles was influenced by the particle size, but not by the fluidity of the membranes. In the case of B30-MDP/phospholipid mixed vesicles, MDP/phospholipid mixed vesicles, the degradation of B30-MDP was not influenced by either the membranes' fluidity or the particle size of the mixed vesicles.It is considered that the degradation of B30-MDP in the mixed vesicles is dependent on the membrane state, and the addition of cholesterol to B30-MDP vesicle inhibits the mutual interaction of MDP regions, whereas the addition of phospholipids hardly influences the mutual interaction of MDP regions, possibly owing to phase separation between B30-MDP and phospholipids. 相似文献
74.
Retro-allylation of homoallyl alcohol by rhodium catalysis occurs to generate allylrhodium species. This allylrhodium reacts with aldehydes to give the corresponding secondary alcohols in situ. Isomerization of these alcohols proceeds in the same pots to furnish the corresponding saturated ketones in good yields. [reaction: see text] 相似文献
75.
Uchiyama S Matsushima E Tokunaga H Otsubo Y Ando M 《Journal of chromatography. A》2006,1116(1-2):165-171
A new method is described for the determination of orthophthalaldehyde in air which is used for the disinfection of various instruments (e.g. endoscopes) in hospital. Orthophthalaldehyde in air was collected with a silica gel cartridge impregnated with acidified 2,4-dinitrophenylhydrazine (DNPH-cartridge) and derivatives were analyzed by high-performance liquid chromatography (HPLC). In this study, the derivatization was examined by comparing the process with three phthalaldehyde isomers (ortho-, iso- and tere-). In the case of iso- and tere-phthalaldehyde, derivatives synthesized with excess of aldehyde consisted mainly of mono-derivatives, and derivatives synthesized with excess of DNPH consisted mainly of bis-derivative. In the case of orthophthalaldehyde, derivative consisted of only bis-derivative and mono-derivative was never observed under any conditions. Orthophthalaldehyde was completely retained by the DNPH-cartridge during air sampling, however, the derivatization reaction was incomplete and unreacted orthophthalaldehyde was flushed from the cartridge during the subsequent solvent extraction process. Unreacted orthophthalaldehyde and DNPH reacted again in the extraction solvent solution. Immediately after the solvent extraction, both mono- and bis-DNPhydrazone derivatives of orthophthalaldehyde were present in the solution. However, over time, the mono-derivative decreased and bis-derivative increased until only the bis-derivative was left allowing accurate determination of the orthophthalaldehyde concentration. The transformation of mono-derivative to bis-derivative was faster in polar aprotic solvents such as acetonitrile, dimethyl sulfoxide and ethyl acetate. Transformation was found to occur most quickly in acetonitrile solvent and was completed in 4 h in this case. It was possible to measure orthophthalaldehyde in air as bis-derivative using a DNPH impregnated silica cartridge and HPLC analysis. 相似文献
76.
Moriyuki Sato Miyuki Notsu Shinji Nakashima Yuko Uemoto 《Macromolecular rapid communications》2001,22(9):681-686
New semi‐rigid thermotropic liquid crystalline (LC) polyesters composed of a quaterphenyl analogue of 2,2′‐bis(1,3,4‐thiadiazole) were synthesized by high‐temperature solution polycondensation of a dioxydiundecanol derivative of 5,5′‐diphenyl‐2,2′‐bis(1,3,4‐thiadiazole) with four diacyl chlorides, whose structures were characterized by FT‐IR and 13C NMR spectroscopy, as well as elemental analysis. Differential scanning calorimetry (DSC) measurements and texture observations using polarizing microscopy displayed that all the polyesters form stable enantiotropic smectic and/or nematic LC phases. Solution and solid state absorption and fluorescence spectra indicated that the polyesters show absorption maxima arising from the 2,2′‐bis(1,3,4‐thiadiazole) moiety and emit bluish green light, the Stokes shifts being 129 nm in solution and 60–64 nm in the solid state. Band gap energies of the polyesters calculated from the solid state absorption spectra were 2.67–2.82 eV. 相似文献
77.
To provide theoretical insight into the structures and properties of Sc3N@C80, which has been isolated in high yield and purity as a new stable endohedral metallofullerene, density functional calculations are carried out for the Sc3?nLanN@C80 (n=0–3) series. Because of electron transfer from Sc3N to C80, the electronic structure of Sc3N@C80 is formally described as (Sc3N)6+C$_{80}^{6-}$. The encapsulated Sc3N cluster takes a planar structure with long Sc–Sc distances and is highly stabilized inside the Ih cage of C80, which rotates rapidly. As the number of La atoms increases, the Sc3?nLanN cluster is forced to maintain a pyramidal structure in Sc3?nLanN@C80. In addition, the C80 cage takes an open‐shell electronic structure due to an increase in the number of electrons transferring from Sc3?nLanN. These make the endohedral structure less stable and more reactive. © 2001 John Wiley & Sons, Inc. J Comput Chem 22: 1353–1358, 2001 相似文献
78.
Kiyoharu Tadanaga Akira Miyata Daisuke Ando Naoko Yamaguchi Masahiro Tatsumisago 《Journal of Sol-Gel Science and Technology》2012,62(1):111-116
Using hot water treatment of sol–gel derived precursor gel films, Co–Al and Ni–Al layered double hydroxide (LDH) thin films
were prepared. The precursor gel films of Al2O3–CoO or Al2O3–NiO were prepared from cobalt or nickel nitrates and aluminum tri-sec-butoxide using the sol–gel method. Then, the precursor gel films were immersed in a NaOH aqueous solution of 100 °C. Nanocrystallites
of Co–Al and Ni–Al LDH were precipitated with the hot water treatment with NaOH solution. The largest amounts of nanocrystals
were obtained with a solution of pH = 10 for Co–Al LDH, and with that of pH = 9 for Ni–Al LDH. X-ray diffraction measurements
confirmed that this process formed CO3
2− intercalated LDHs. Both Co–Al and Ni–Al LDH thin films were confirmed to work as electrodes for electrochemical devices by
cyclic voltammogram measurements. 相似文献
79.
The elution behaviors of the biogenic amines, histamine (HA) and its metabolite methyl histamine (MHA), were evaluated by means of on-column derivatization (OCD)-capillary electrochromatography (CEC) which employed a monolithic octadecylsilica (ODS) capillary column (20 cm of effective length x 50 microm of inner diameter). Five kinds of alkylthiols, e.g., 2- hydroxyethylthiol (or 2-mercaptoethanol (2-ME)), ethanethiol (ET), 1-propanethiol (1-PT), 2-methyl-1-propanethiol (2-MPT) and 1-butanethiol (1-BT) were separately presented at 5 mM each in the OCD-CEC separation run buffer consisting of 60% acetonitrile in 5 mM o-phthalaldehyde (OPA)-10 mM borate buffer (pH 10). When 2-ME was present in the run buffer solution, both derivatives corresponding to HA and MHA migrated separately, but closely together through the capillary column. Replacement of 2-ME with 1-BT in the run buffer solution caused a delay in their elution profiles on the electrochromatogram and the separation between those two peaks became remarkably improved. The elution times of HA and MHA followed the increase in alkyl chain length or hydrophobicity of thiol, 1-BT > 2-MPT > 1-PT > ET > 2-ME. Performance of on-line preconcentrations of HA and MHA was also evaluated by varying the electrokinetic injection voltage from 1 kV to 8 kV. The peak area counts corresponding to HA recorded about 50 times higher when 2 kV was applied for 240 s to a 0.1 mM HA solution than when 8 kV was applied for 5 s. This method was next applied to a sample of human urine spiked with HA and MHA at levels of 0.1 microM each. Although HA and MHA peaks were not identifiable among the peaks corresponding to the materials in the urine matrix when OPA/2-ME was employed in a run buffer for the OCD-CEC, the separation and identification of their peaks became possible by replacing 2-ME with 1-BT in the run buffer solution. 相似文献
80.
Harumi Sato Rumi Murakami Katsuhito Mori Yuriko Ando Isao Takahashi Isao Noda Yukihiro Ozaki 《Vibrational Spectroscopy》2009,51(1):132-135
Infrared reflection–absorption (IR-RAS) and transmission spectra were measured for poly(3-hydroxybutyrate) (PHB) thin films to explore its specific crystal structure in the surface region. As IR-RAS is sensitive to the vibration mode of perpendicular orientation of the surface, differences between IR-RAS and transmission spectra indicate an orientation of the lamella structure in the surface of PHB thin films. The relative intensity of the crystalline CO stretching band in the IR-RAS spectrum is significantly weaker than that in the transmission spectrum. It may be concluded that the transient dipole moment of the CO stretching mode of the crystalline state is not oriented perpendicular but nearly parallel to the substrate surface. On the other hand, the relative intensity of the band at 3009 cm−1 due to the C–H stretching mode of the C–HOC hydrogen bonding is similar between the IR-RAS and transmission spectra, suggesting that the C–H bond is oriented neither perpendicular nor parallel to the substrate surface but in an intermediate direction. Since the CO group of the C–HOC hydrogen bonding is oriented nearly parallel to the surface and its C–H group is in the intermediate direction, it is very likely that the C–HOC hydrogen bonding has a somewhat bent structure. These results are in good agreement with our previous conclusion that the C–HOC hydrogen bonding of PHB exists along the a-axis (not the b-axis) between the CH3 group of one helix and the CO group of another helix. 相似文献