全文获取类型
收费全文 | 855篇 |
免费 | 28篇 |
国内免费 | 10篇 |
专业分类
化学 | 632篇 |
晶体学 | 8篇 |
力学 | 7篇 |
数学 | 39篇 |
物理学 | 207篇 |
出版年
2021年 | 7篇 |
2020年 | 9篇 |
2019年 | 8篇 |
2018年 | 5篇 |
2017年 | 9篇 |
2016年 | 16篇 |
2015年 | 6篇 |
2014年 | 20篇 |
2013年 | 42篇 |
2012年 | 31篇 |
2011年 | 49篇 |
2010年 | 21篇 |
2009年 | 23篇 |
2008年 | 53篇 |
2007年 | 45篇 |
2006年 | 62篇 |
2005年 | 51篇 |
2004年 | 44篇 |
2003年 | 20篇 |
2002年 | 24篇 |
2001年 | 31篇 |
2000年 | 15篇 |
1999年 | 22篇 |
1998年 | 7篇 |
1997年 | 6篇 |
1996年 | 11篇 |
1995年 | 10篇 |
1994年 | 6篇 |
1993年 | 11篇 |
1992年 | 7篇 |
1991年 | 13篇 |
1990年 | 10篇 |
1989年 | 8篇 |
1988年 | 6篇 |
1987年 | 8篇 |
1986年 | 7篇 |
1985年 | 16篇 |
1984年 | 25篇 |
1983年 | 11篇 |
1982年 | 8篇 |
1981年 | 6篇 |
1980年 | 10篇 |
1979年 | 12篇 |
1978年 | 13篇 |
1977年 | 9篇 |
1976年 | 17篇 |
1975年 | 7篇 |
1974年 | 13篇 |
1973年 | 9篇 |
1939年 | 3篇 |
排序方式: 共有893条查询结果,搜索用时 140 毫秒
91.
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
92.
93.
Nakajima K Baba Y Noma R Kitano M Kondo JN Hayashi S Hara M 《Journal of the American Chemical Society》2011,133(12):4224-4227
Niobic acid, Nb(2)O(5)·nH(2)O, has been studied as a heterogeneous Lewis acid catalyst. NbO(4) tetrahedra, Lewis acid sites, on Nb(2)O(5)·nH(2)O surface immediately form NbO(4)-H(2)O adducts in the presence of water. However, a part of the adducts can still function as effective Lewis acid sites, catalyzing the allylation of benzaldehyde with tetraallyl tin and the conversion of glucose into 5-(hydroxymethyl)furfural in water. 相似文献
94.
Cho KR Huang Y Yu S Yin S Plomp M Qiu SR Lakshminarayanan R Moradian-Oldak J Sy MS De Yoreo JJ 《Journal of the American Chemical Society》2011,133(22):8586-8593
Aberrant protein aggregation causes numerous neurological diseases including Creutzfeldt-Jakob disease (CJD), but the aggregation mechanisms remain poorly understood. Here, we report AFM results on the formation pathways of β-oligomers and nonfibrillar aggregates from wild-type full-length recombinant human prion protein (WT) and an insertion mutant (10OR) with five additional octapeptide repeats linked to familial CJD. Upon partial denaturing, seeds consisting of 3-4 monomers quickly appeared. Oligomers of ~11-22 monomers then formed through direct interaction of seeds, rather than by subsequent monomer attachment. All larger aggregates formed through association of these β-oligomers. Although both WT and 10OR exhibited identical aggregation mechanisms, the latter oligomerized faster due to lower solubility and, hence, thermodynamic stability. This novel aggregation pathway has implications for prion diseases as well as others caused by protein aggregation. 相似文献
95.
Tachi T Hase T Okamoto Y Kaji N Arima T Matsumoto H Kondo M Tokeshi M Hasegawa Y Baba Y 《Analytical and bioanalytical chemistry》2011,401(7):2301-2305
Microchip analysis is a promising method for therapeutic drug monitoring. This led us to evaluate a microchip-based fluorescence
polarization immunoassay (FPIA) system for point-of-care testing on patients being treated with theophylline. The sera were
collected from 20 patients being treated with theophylline. Fluorescence polarization was measured on the microchip and theophylline
concentrations in serum were obtained. Regression analysis of the correlations was done between the results given by the microchip-based
FPIA and the conventional cloned enzyme donor immunoassay (CEDIA), and between the results given by the microchip-based FPIA
and the conventional particle-enhanced turbidimetric inhibition immunoassay (PETINIA). We successfully carried out a quantitative
analysis of theophylline in serum at values near its therapeutic range in 65 s. The results obtained by the microchip-based
FPIA correlated well with CEDIA and PETINIA results; the correlation coefficients (R
2) were 0.986 and 0.989, respectively. The FPIA system is a simple and rapid method for point-of-care testing of drugs in serum,
and its accuracy is the same as the conventional CEDIA and PETINIA. It is essential to use real samples from patients and
to confirm good correlations with conventional methods for a study on the realization of microchip. 相似文献
96.
Mohamedou Ould HayeAnne Philippe 《Statistics & probability letters》2011,81(9):1354-1364
Some convergence results on the kernel density estimator are proven for a class of linear processes with cyclic effects. In particular, we extend the results of Ho and Hsing (1996), Mielniczuk (1997) and Hall and Hart (1990) to the stationary processes for which the singularities of the spectral density are not limited to the origin. We show that the convergence rates and the limiting distribution may be different in this context. 相似文献
97.
We present a reaction scheme of silver containing 5-substituted uracils (N) bridge formation with two silver ions to a silver-mediated base pair [N-Ag(2)-N] by using the conductor-like polarizable continuum model (CPCM)-B3LYP/aug-cc-pVDZ level of theory. The whole reaction scheme is divided into the following three steps: (1) silver ion binding and deprotonation, (2) silver ion transfer, and (3) dimer formation and structural fluctuation. With a new pK(a) computing scheme proposed in our previous studies, it is found that a silver coordination decreases the pK(a) of N by 2.5-3.0 pK(a) units, which is an important clue for silver-ion selectivity by N. Judging from the calculation, we revealed that the silver ion transfer reaction and the dimerization reaction occur spontaneously. Moreover, both reactions are independent of the C5 ligand in N so that the deprotonation reaction, which is the first step of this scheme, plays a key role in forming the [N-Ag(2)-N] pairing. 相似文献
98.
R. A. Ganeev M. Suzuki M. Baba H. Kuroda 《The European Physical Journal D - Atomic, Molecular, Optical and Plasma Physics》2006,37(2):255-259
The high-order harmonic generation from boron plasma was studied using the
longitudinal pump scheme. The harmonics up to the 57th order (λ=13.96
nm) were observed. The characteristics of plateau in the range of 15th
to 57th harmonics were analyzed depending on fundamental radiation
intensity and the saturation of harmonic cutoff was observed. The harmonic
cutoff energy was restricted by the self-defocusing of femtosecond
radiation. A comparison of longitudinal and orthogonal pump schemes of boron
plasma excitation was presented. 相似文献
99.
Mohammad Jabasini Ashraf A Ewis Feng Xu Guichen Ping Maged Fouad Toshikatsu Shinka Yutaka Nakahori Mitsuru Ishikawa Yoshinobu Baba 《Analytical sciences》2005,21(12):1537-1539
For the diagnosis of unexplained male infertility a multiplex PCR for 6 markers, which are well-known as candidate genes for studying male infertility and located on the human Y-chromosome, has been designed. The multiplex PCR products have been separated on a 12 channel microchip electrophoresis system, which can analyze different samples simultaneously. By combining the technologies of multiplex PCR with multichannel microchip electrophoresis, the number of the DNA markers that can be screened simultaneously is increased to be 72 marker (12 x 6) in a single run while the electrophoresis analysis time is reduced to be only 180 s. 相似文献
100.
This work deals with the global existence of weak solutions for a Kazhikhov–Smagulov type system with a density which may or not vanish. Our model is formally equivalent to the physical compressible model with Fick’s law, in contrast to those in previous works. This model may be used for addressing environmental problems such as propagation of pollutants and avalanche modelling. We also explain why this system may be seen as a physical regularization of the standard nonhomogeneous incompressible Navier–Stokes equations and we give an existence result with an initial density less regular but away from the vacuum. 相似文献