全文获取类型
收费全文 | 336篇 |
免费 | 14篇 |
国内免费 | 2篇 |
专业分类
化学 | 270篇 |
晶体学 | 9篇 |
数学 | 16篇 |
物理学 | 57篇 |
出版年
2023年 | 2篇 |
2022年 | 1篇 |
2021年 | 2篇 |
2020年 | 9篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2017年 | 7篇 |
2016年 | 4篇 |
2015年 | 10篇 |
2014年 | 6篇 |
2013年 | 13篇 |
2012年 | 19篇 |
2011年 | 27篇 |
2010年 | 14篇 |
2009年 | 13篇 |
2008年 | 31篇 |
2007年 | 13篇 |
2006年 | 25篇 |
2005年 | 25篇 |
2004年 | 22篇 |
2003年 | 29篇 |
2002年 | 16篇 |
2001年 | 3篇 |
2000年 | 14篇 |
1999年 | 5篇 |
1998年 | 2篇 |
1997年 | 3篇 |
1996年 | 3篇 |
1995年 | 1篇 |
1993年 | 3篇 |
1992年 | 1篇 |
1990年 | 1篇 |
1989年 | 2篇 |
1986年 | 2篇 |
1985年 | 3篇 |
1984年 | 1篇 |
1982年 | 1篇 |
1981年 | 2篇 |
1980年 | 2篇 |
1979年 | 1篇 |
1976年 | 1篇 |
排序方式: 共有352条查询结果,搜索用时 31 毫秒
41.
We have observed a non-periodic diameter modulation in SiC nanowire growth. The modulation was tentatively attributed to a stick-slip motion in a self-organized vapor-liquid-solid (VLS) growth, and was characterized by methods of time-series analysis. From the power-law decay behavior of a fat tail of the probability distribution of increments with the exponent 2.1±0.2, the modulation was interpreted as a Lévy flight. The degree of determinism is also discussed. 相似文献
42.
A generalized technique for the encapsulation of nano‐sized NiO particles by styrene‐2‐hydroxyethyl methacrylate copolymer 下载免费PDF全文
M. Shamim Hossan M. Abdur Rahman Klaus Tauer Hideto Minami Hasan Ahmad 《先进技术聚合物》2015,26(9):1047-1052
Encapsulation of nickel oxide (NiO) particles is of great interest to the researchers as such modification produces remarkable improvement in properties and versatility in application potential. In this investigation, nanosized NiO particles were first prepared by calcination of nickel hydroxide precursor obtained using a simple liquid‐phase process. The produced NiO particles were stabilized with oleic acid and then treated with tetraethylorthosilicate to produce NiO/SiO2 composite seed particles. Finally tri‐layered inorganic/organic composite particles were prepared by seeded copolymerization of styrene and 2‐hydroxyethyl methacrylate (HEMA) in the presence of NiO/SiO2 composite seed particles. The produced composite particles named as NiO/SiO2/P(S‐HEMA) were colloidally stable, and the obtained particles were characterized by Fourier transform infrared spectroscopy, scanning electron microscopy, X‐ray diffraction, X‐ray photoelectron spectroscopy and thermogravimetric analyses. Copyright © 2015 John Wiley & Sons, Ltd. 相似文献
43.
We give an easier way to calculate a bijection from the set of isoclasses of tilted algebras of Dynkin type Δ to the set of configurations on the translation quiver ?Δ. 相似文献
44.
Miyabe K 《Analytical sciences》2011,27(10):1007-1017
New moment equations were developed for chromatography using superficially porous (shell-type) spherical particles, which have recently attracted much attention as one of separation media for fast separation with high efficiency. At first, the moment equations of the first absolute and second central moments in the real time domain were derived from the analytical solution in the Laplace domain of a set of basic equations of the general rate model of chromatography, which represent the mass balance, mass-transfer rate, and reaction kinetics in the column packed with shell-type particles. Then, the moment equations were used for analyzing the experimental data of chromatography of kallidin in a Halo column, which were published in a previous paper written by other researchers. It was tried to predict the chromatographic behavior of shell-type particles having different shell thicknesses. The new moment equations are useful for a detailed analysis of the chromatographic behavior of shell-type spherical particles. It is also concluded that they can be used for the preliminarily optimization of their structural characteristics. 相似文献
45.
Ujiie K Kanayama N Asai K Kishimoto M Ohara Y Akashi Y Yamada K Hashimoto S Oda T Ohkohchi N Yanagihara H Kita E Yamaguchi M Fujii H Nagasaki Y 《Colloids and surfaces. B, Biointerfaces》2011,88(2):771-778
This paper describes the preparation of iron oxide nanoparticles, surface of which was coated with extremely high immobilization stability and relatively higher density of poly(ethylene glycol) (PEG), which are referred to as PEG protected iron oxide nanoparticles (PEG-PIONs). The PEG-PIONs were obtained through alkali coprecipitation of iron salts in the presence of the PEG-poly(4-vinylbenzylphosphonate) block copolymer (PEG-b-PVBP). In this system, PEG-b-PVBP served as a surface coating that was bound to the iron oxide surface via multipoint anchoring of the phosphonate groups in the PVBP segment of PEG-b-PVBP. The binding of PEG-b-PVBP onto the iron oxide nanoparticle surface and the subsequent formation of a PEG brush layer were proved by FT-IR, zeta potential, and thermogravimetric measurements. The surface PEG-chain density of the PEG-PIONs varied depending on the [PEG-b-PVBP]/[iron salts] feed-weight ratio in the coprecipitation reaction. PEG-PIONs prepared at an optimal feed-weight ratio in this study showed a high surface PEG-chain surface density (≈0.8 chainsnm(-2)) and small hydrodynamic diameter (<50 nm). Furthermore, these PEG-PIONs could be dispersed in phosphate-buffered saline (PBS) that contains 10% serum without any change in their hydrodynamic diameters over a period of one week, indicating that PEG-PIONs would provide high dispersion stability under in vivo physiological conditions as well as excellent anti-biofouling properties. In fact we have confirmed the prolong blood circulation time and facilitate tumor accumulation (more than 15% IDg(-1) tumor) of PEG-PIONs without the aid of any target ligand in mouse tumor models. The majority of the PEG-PIONs accumulated in the tumor by 96 h after administration, whereas those in normal tissues were smoothly eliminated by 96 h, proving the enhancement of tumor selectivity in the PEG-PION localization. The results obtained here strongly suggest that originally synthesized PEG-b-PVBP, having multipoint anchoring character by the phosphonate groups, is rational design for improvement in nanoparticle as in vivo application. Two major points, viz., extremely stable anchoring character and dense PEG chains tethered on the nanoparticle surface, worked simultaneously to become PEG-PIONs as an ideal biomedical devices intact for prolonged periods in harsh biological environments. 相似文献
46.
Yasuda M Nakajima H Takeda R Yoshioka S Yamasaki S Chiba K Baba A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(14):3856-3867
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity. 相似文献
47.
Matsuoka H Shen JR Kawamori A Nishiyama K Ohba Y Yamauchi S 《Journal of the American Chemical Society》2011,133(12):4655-4660
The oxidation of a redox-active tyrosine residue Y(Z) in photosystem II (PSII) is coupled with proton transfer to a hydrogen-bonded D1-His190 residue. Because of the apparent proximity of Y(Z) to the water-oxidizing complex and its redox activity, it is believed that Y(Z) plays a significant role in water oxidation in PSII. We investigated the g-anisotropy of the tyrosine radical Y(Z)(?) to provide insight into the mechanism of Y(Z)(?) proton-coupled electron transfer in Mn-depleted PSII. The anisotropy was highly resolved by electron paramagnetic resonance spectroscopy at the W-band (94.9 GHz) using PSII single crystals. The g(X)-component along the phenolic C-O bond of Y(Z)(?) was calculated by density functional theory (DFT). It was concluded from the highly resolved g-anisotropy that Y(Z) loses a phenol proton to D1-His190 upon tyrosine oxidation, and D1-His190 redonates the same proton back to Y(Z)(?) upon reduction. 相似文献
48.
Miyabe K 《Journal of separation science》2011,34(19):2674-2679
It was tried to estimate the molecular diffusivity (D(m)) of solutes in the mixtures of acetonitrile (ACN) and water by the Wilke-Chang equation. Although the information about association coefficient (α) is necessary for the calculation, it has never been proposed for ACN. The value of α was estimated as 1.37 from D(m) of benzene in ACN at 303 K experimentally measured by the peak parking method. The values of α, i.e. 2.6, 1.9, 1.5, and 1.0, which have respectively been proposed for four solvents, i.e. water, methanol, ethanol, and benzene, were correlated with two physico-chemical parameters of the solvents, i.e. solubility parameter and E(T) value. The α value for ACN was plotted around the two correlations, indicating its appropriateness. The values of D(m) calculated by the Wilke-Chang equation using the α value for ACN were compared with those measured by the peak parking method and the Aris-Taylor method in aqueous solutions of ACN. The mean square deviation of the estimation of D(m) was calculated as 8.8 and 14%. It was demonstrated that the Wilke-Chang equation can be used for estimating D(m) with a reasonable accuracy in the mixtures consisting of ACN and water. 相似文献
49.
Sogawa K Watanabe M Sato K Segawa S Ishii C Miyabe A Murata S Saito T Nomura F 《Analytical and bioanalytical chemistry》2011,400(7):1905-1911
In a clinical diagnosis microbiology laboratory, the current method of identifying bacterial isolates is based mainly on phenotypic
characteristics, for example growth pattern on different media, colony morphology, Gram stain, and various biochemical reactions.
These techniques collectively enable great accuracy in identifying most bacterial isolates, but are costly and time-consuming.
In our clinical microbiology laboratory, we prospectively assessed the ability of matrix-assisted laser desorption ionization–time
of flight mass spectrometry (MALDI–TOF MS) to identify bacterial strains that were routinely isolated from clinical samples.
Bacterial colonies obtained from a total of 468 strains of 92 bacterial species isolated at the Department of Clinical Laboratory
at Chiba University were directly placed on target MALDI plates followed by addition of CHCA matrix solution. The plates were
then subjected to MALDI–TOF MS measurement and the microorganisms were identified by pattern matching with the libraries in
the BioTyper 2.0 software. Identification success at the species and genus levels was 91.7% (429/468) and 97.0% (454/468),
respectively. MALDI–TOF MS is a rapid, simple, and high-throughput proteomic technique for identification of a variety of
bacterial species. Because colony-to-colony differences and effects of culture duration on the results are minimal, it can
be implemented in a conventional laboratory setting. Although for some pathogens, preanalytical processes should be refined,
and the current database should be improved to obtain more accurate results, the MALDI–TOF MS based method performs, in general,
as well as conventional methods and is a promising technology in clinical laboratories. 相似文献
50.
The utility of hydroxylamines as nitrogen nucleophiles was investigated in the iridium-catalyzed regio- and enantioselective allylic substitution. Allylic substitution with hydroxylamines proceeded with good enantioselectivities by using the iridium-complex of bis(oxazolinyl)pyridine ligand. The good regio- and enantioselectivities were also achieved in the reaction with alkylamines, p-anisidine, and 4-methoxyphenol. 相似文献