全文获取类型
收费全文 | 1112篇 |
免费 | 43篇 |
国内免费 | 6篇 |
专业分类
化学 | 843篇 |
晶体学 | 15篇 |
力学 | 16篇 |
数学 | 77篇 |
物理学 | 210篇 |
出版年
2023年 | 10篇 |
2022年 | 9篇 |
2021年 | 15篇 |
2020年 | 12篇 |
2019年 | 20篇 |
2018年 | 19篇 |
2017年 | 15篇 |
2016年 | 24篇 |
2015年 | 36篇 |
2014年 | 32篇 |
2013年 | 56篇 |
2012年 | 91篇 |
2011年 | 101篇 |
2010年 | 41篇 |
2009年 | 42篇 |
2008年 | 80篇 |
2007年 | 63篇 |
2006年 | 64篇 |
2005年 | 70篇 |
2004年 | 58篇 |
2003年 | 46篇 |
2002年 | 55篇 |
2001年 | 10篇 |
2000年 | 13篇 |
1999年 | 8篇 |
1998年 | 5篇 |
1997年 | 13篇 |
1996年 | 16篇 |
1995年 | 9篇 |
1994年 | 11篇 |
1993年 | 8篇 |
1992年 | 9篇 |
1991年 | 4篇 |
1990年 | 8篇 |
1988年 | 4篇 |
1987年 | 4篇 |
1986年 | 4篇 |
1985年 | 12篇 |
1984年 | 6篇 |
1983年 | 5篇 |
1982年 | 3篇 |
1981年 | 9篇 |
1979年 | 4篇 |
1978年 | 6篇 |
1977年 | 7篇 |
1974年 | 2篇 |
1971年 | 2篇 |
1968年 | 2篇 |
1961年 | 2篇 |
1960年 | 2篇 |
排序方式: 共有1161条查询结果,搜索用时 15 毫秒
71.
Yamaguchi K Ueki R Nonaka H Sugihara F Matsuda T Sando S 《Journal of the American Chemical Society》2011,133(36):14208-14211
Monoamine oxidase (MAO) A is a flavoenzyme that catalyzes the oxidation of biologically important monoamines and is thought to be associated with psychiatric disorders. Here, we report a strategy for rationally designing a (19)F magnetic resonance imaging probe for the specific detection of human MAO-A (hMAO-A) activity. Our designed (19)F probe was oxidized expeditiously by hMAO-A to produce 2-fluoro-4-nitrophenol via a spontaneous β-elimination mechanism. Concomitant with the structural change of the probe to the product, the (19)F chemical shift changed by 4.2 ppm, which was enough to visualize the probe and enzymatic product separately. Importantly, our probe achieved excellent discrimination of hMAO-A from its isoform hMAO-B. 相似文献
72.
Tatsuya Sakakura Assoc. Prof. Naoya Murakami Dr. Yoshiyuki Takatsuji Masayuki Morimoto Prof. Tetsuya Haruyama 《Chemphyschem》2019,20(11):1467-1474
Electric-discharge nitrogen comprises three main types of excited nitrogen species-atomic nitrogen (Natom), excited nitrogen molecules (N2*), and nitrogen ions (N2+) – which have different lifetimes and reactivities. In particular, the interfacial reaction locus between the discharged nitrogen and the water phase produces nitrogen compounds such as ammonia and nitrate ions (denoted as N-compounds generically); this is referred to as the plasma/liquid interfacial (P/L) reaction. The Natom amount was analyzed quantitatively to clarify the contribution of Natom to the P/L reaction. We focused on the quantitative relationship between Natom and the produced N-compounds, and found that both N2* and N2+, which are active species other than Natom, contributed to P/L reaction. The production of N-compounds from N2* and N2+ was enhanced upon UV irradiation of the water phase, but the production of N-compounds from Natom did not increase by UV irradiation. These results revealed that the P/L reactions starting from Natom and those starting from N2* and N2+ follow different mechanisms. 相似文献
73.
Shinya Hayami Yasuka Komatsu Tetsuya Shimizu Hidenobu Kamihata Young Hoon Lee 《Coordination chemistry reviews》2011,255(17-18):1981-1990
In this review article we discuss the unique and novel magnetic properties for the cobalt(II) compounds with a variety of terpy derivatives including substituents at the 4-position. These are also compared with the unsubstituted terpy cobalt(II) complex. Since the first SCO cobalt(II) complex with terpy ligand was reported, this system has been widely studied. SCO cobalt(II) complexes possessing terpy or OH-terpy ligand reveal incomplete or gradual SCO behavior. The pyterpy-appended cobalt(II) complex shows SCO depending on the guest molecules involved. Cobalt(II) complexes with long-alkylated terpy ligands, [Co(Cn-terpy)2](BF4)2 (n = 16, 14 and 12) have been synthesized and some were characterized by single crystal X-ray analysis. Furthermore, variable-temperature magnetic susceptibility indicated that the non-solvated compounds [Co(Cn-terpy)2](BF4)2 (n = 16, 14 and 12) exhibit “reverse spin transition” phenomenon with wide thermal hysteresis around room temperature. In addition, the solvated compound [Co(C12-terpy)2](BF4)2·EtOH·0.5H2O shows “re-entrant SCO” behavior. The long alkyl chains in SCO cobalt(II) complexes can lead to novel physical properties resulting from a synergetic effect between SCO and response of the flexibility toward external stimuli. 相似文献
74.
Adsorption and photochemical behaviors of the novel cationic xanthene derivative on the clay surface
Yuta Ohtani Yohei Ishida Yuka Ando Hiroshi Tachibana Tetsuya Shimada Shinsuke Takagi 《Tetrahedron letters》2014
Novel tetra-cationic xanthene derivative (Flu) was synthesized. Its adsorption and photochemical behaviors on the clay surface were investigated. Fluorescence quantum yield (?f) and fluorescence lifetime were 0.50 and 2.9 ns for Flu/clay complex. ?f of Flu was enough high (>0.1) even at high density conditions (0.080 molecules nm−2). It is supposed that the strong interaction between clay and Flu by the ‘Size-Matching Effect’ realizes the highly emissive clay complexes at high density adsorption condition by a suppression of a molecular aggregation, which tends to decrease the photochemical activity. 相似文献
75.
Tetsuya Noda 《European Polymer Journal》2007,43(6):2321-2330
Continuous ATRP of MMA was carried out in a flow tubular reactor with varying flow rate, temperature, and [monomer]/[initiator] ratios. Changing the flow rate directly relates to the reaction time. This process produces polymer continuously with the conversion increasing with decreasing flow rate. The molecular weight (relating to the flow rate) increases linearly with conversion which is also observed when the [monomer]/[initiator] ratio was changed. The effect of altering the reaction temperature was studied and the apparent activation energy of the propagation reaction of MMA in this system was calculated to be ∼56.9 kJ mol−1, close to the values reported previously. Preparation of diblock copolymers is also reported with varying comonomers and the conversion, and SEC results suggested that this continuous system is an excellent and facile way to have a continuous ATRP process. 相似文献
76.
Murahashi T Higuchi Y Katoh T Kurosawa H 《Journal of the American Chemical Society》2002,124(48):14288-14289
The linear sandwich tripalladium complexes [Pd3{Ar(CH=CH)4Ar}2[BArf]2 (Ar = Ph, p-t-Bu-C6H4, p-styryl-C6H4) undergo photoinduced isomerization involving face-inversion of the tetraene ligands. Irradiation of these complexes with visible light (>510 nm) resulted in rac (staggered sandwich) to meso (eclipsed sandwich) isomerization. The structures of rac and meso isomers are determined by X-ray crystallographic analyses. 相似文献
77.
Tetsuya Okuyama Masaru Nakayama Yoshitsugu Tomokiyo Omer Van Der Biest 《Microscopy and microanalysis》2002,8(1):11-15
Lattice strains around a platelet oxygen precipitate in Si wafer is studied by energy filtering convergent-beam electron diffraction (CBED) and calculations based on the finite element method (FEM). Local lattice strains are measured from CBD patterns obtained with a probe size less than 2 nm in a specimen thicker than 450 nm. Strains measured are compressive along a direction normal to a plate of the precipitation and tensile along a direction parallel to the plate. Two-dimensional stress fields near the precipitate are obtained with FEM computer analyses by fitting the measured strains. It appears that shear stresses are concentrated at the end of the precipitate edge and the maximum shear stress at an interface between the precipitate and the Si-matrix is 1.9 GPa. It is demonstrated that a combination of the energy filtering CBED and FEM is very useful for the study of local strains near interfaces in semiconductor devices, in particular for the study of stress fields that are too steep for application of the conventional CBED technique. 相似文献
78.
Iwanaga A Asakawa H Fukuma T Nakamichi M Shigematsu S Linder MB Haruyama T 《Colloids and surfaces. B, Biointerfaces》2011,84(2):3020-399
A groundbreaking method for ordered molecular layer preparation on a solid surface employing the drop-stamp method has been developed by us taking advantage of the characteristics of the HFB molecule as a self-organizer/adsorption carrier. It is a smart method which can be used to prepare a self-organized protein layer on a solid surface without unspecific adsorption or defects. In our previous report, we clarified the self-organizing nature of HFB-tagged protein molecules on a surface of a solution droplet. In this report, a protein layer was prepared on a HOPG surface by using the drop-stamp method with a maltose binding protein (MBP)-tagged HFBII molecule. The structure of the stamped protein layer was investigated using frequency modulation atomic force microscopy (FM-AFM) in a liquid condition. The FM-AFM images show that the drop-stamp method can prepare an ordered protein layer on a solid surface smartly. The drop-stamp method using a HFB carrier is a practical method which can be used to prepare an ordered protein layer on a solid substrate surface without unspecific adsorption defects. 相似文献
79.
80.
Akagi M Omae D Tamura Y Ueda T Kumashiro T Urata H 《Chemical & pharmaceutical bulletin》2002,50(6):866-868
L-Ribose was synthesized by a simple four-step method with overall yield of 76.3% from a protected L-arabinose derivative, which is a compatible intermediate for the synthesis of L-deoxyribose. The key step of this strategy is the Swern oxidation and subsequent stereoselective reduction accompanied by inversion of the 2-hydroxy group of protected L-arabinose. 相似文献