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1.
Sensors (Basel) ; 16(8)2016 Jul 29.
Artigo em Inglês | MEDLINE | ID: mdl-27483279

RESUMO

Radio frequency identification (RFID) technology has already been explored for efficient self-localization of indoor mobile robots. A mobile robot equipped with RFID readers detects passive RFID tags installed on the floor in order to locate itself. The Monte-Carlo localization (MCL) method enables the localization of a mobile robot equipped with an RFID system with reasonable accuracy, sufficient robustness and low computational cost. The arrangements of RFID readers and tags and the size of antennas are important design parameters for realizing accurate and robust self-localization using a low-cost RFID system. The design of a likelihood model of RFID tag detection is also crucial for the accurate self-localization. This paper presents a novel design and arrangement of RFID readers and tags for indoor mobile robot self-localization. First, by considering small-sized and large-sized antennas of an RFID reader, we show how the design of the likelihood model affects the accuracy of self-localization. We also design a novel likelihood model by taking into consideration the characteristics of the communication range of an RFID system with a large antenna. Second, we propose a novel arrangement of RFID tags with eight RFID readers, which results in the RFID system configuration requiring much fewer readers and tags while retaining reasonable accuracy of self-localization. We verify the performances of MCL-based self-localization realized using the high-frequency (HF)-band RFID system with eight RFID readers and a lower density of RFID tags installed on the floor based on MCL in simulated and real environments. The results of simulations and real environment experiments demonstrate that our proposed low-cost HF-band RFID system realizes accurate and robust self-localization of an indoor mobile robot.

2.
J Am Chem Soc ; 130(8): 2466-72, 2008 Feb 27.
Artigo em Inglês | MEDLINE | ID: mdl-18237165

RESUMO

Product analyses and nanosecond time-resolved spectroscopy on laser flash photolysis were studied for the photoinduced electron-transfer reaction of 3,4-di(alpha-styryl)furan (6a). A combination of these results, kinetic, density functional theoretical (DFT), and time-dependent DFT analyses enabled assignment of the absorption to the tetramethyleneethane (TME)-type radical cation (7a*+, lambda(max) = 392 nm) and the corresponding singlet biradical ((1)7a**, lambda(max) = 661 nm). These two intermediates were mechanistically linked to each other with a facile back electron-transfer reaction. The present studies provide a new method for the generation of aryl-substituted TME-type intermediates.


Assuntos
Alcenos/química , Elétrons , Etano/análogos & derivados , Furanos/química , Alcenos/efeitos da radiação , Cátions/química , Cátions/efeitos da radiação , Etano/química , Etano/efeitos da radiação , Radicais Livres/química , Radicais Livres/efeitos da radiação , Furanos/efeitos da radiação , Lasers , Espectroscopia de Ressonância Magnética/métodos , Espectroscopia de Ressonância Magnética/normas , Modelos Químicos , Estrutura Molecular , Fotoquímica , Fotólise , Teoria Quântica , Padrões de Referência
3.
J Org Chem ; 64(5): 1640-1649, 1999 Mar 05.
Artigo em Inglês | MEDLINE | ID: mdl-11674231

RESUMO

Under the 9,10-dicyanoanthracene-sensitized photoinduced electron-transfer conditions, (Z,Z)-, (E,E)-, (E,Z)-3,6-diaryl-2,6-octadiene and (d,l),(meso)-2,5-diaryl-3,4-dimethyl-1,5-hexadiene stereospecifically undergo the Cope rearrangement to give a Cope photostationary mixture. Remarkably, the photoinduced electron-transfer Cope rearrangements of the 4-methylphenyl derivatives are concurrent with the formation of trans- or endo,cis-1,4-bis(4-methylphenyl)-2,3-dimethylbicyclo[2.2.0]hexane in a Cope photostationary mixture. Observed stereospecificity of the Cope rearrangement and the formation of the bicyclo[2.2.0]hexane derivatives demonstrate the intermediacies of both the chair and boat 1,4-diaryl-1,2-dimethylcyclohexane-1,4-diyl and cation radical intermediates in a Cope rearrangement cycle. Photoreactions of trans- and exo,cis-1,4-diaryl-5,6-dimethyl-2,3-diazabicyclo[2.2.2]oct-2-enes further support the interventions of the diyl intermediates in the Cope rearrangement cycle. By photoacoustic analysis, a cation radical cyclization-diradical cleavage mechanism is proposed for the photoinduced electron-transfer Cope rearrangement of the title dienes.

4.
J Phys Chem A ; 110(8): 2595-600, 2006 Mar 02.
Artigo em Inglês | MEDLINE | ID: mdl-16494367

RESUMO

To make the effects of molecular size on photoinduced electron-transfer (ET) reactions clear, the ET fluorescence quenching of aromatic hydrocarbons by trivalent lanthanide ions M3+ (europium ion Eu3+ and ytterbium ion Yb3+) and the following ET reactions such as the geminate and free radical recombination were studied in acetonitrile. The rate constant k(q) of fluorescence quenching, the yields of free radical (phi(R)) and fluorescer triplet (phi(T)) in fluorescence quenching, and the rate constant k(rec) of free radical recombination were measured. Upon analysis of the free energy dependence of k(q), phi(R), phi(T), and k(rec), it was found that the switchover of the fluorescence quenching mechanism occurs at deltaG(fet) = -1.4 to -1.6 eV: When deltaG(fet) < -1.6 eV, the fluorescence quenching by M3+ is induced by a long-distance ET yielding the geminate radical ion pairs. When deltaG(fet) > -1.4 eV, it is induced by an exciplex formation. The exciplex dissociates rapidly to yield either the fluorescer triplet or the geminate radical ion pairs. The large shift of switchover deltaG(fet) from -0.5 eV for aromatic quenchers to -1.4 to -1.6 eV for lanthanide ions is almost attributed to the difference in the molecular size of the quenchers. Furthermore, it was substantiated that the free energy dependence of ET rates for the geminate and free radical recombination is satisfactorily interpreted within the limits of the Marcus theory.


Assuntos
Acetonitrilas/química , Európio/química , Fluorescência , Hidrocarbonetos Aromáticos/química , Itérbio/química , Transporte de Elétrons , Radicais Livres/química , Íons , Cinética , Espectrometria de Fluorescência
5.
J Org Chem ; 70(14): 5592-8, 2005 Jul 08.
Artigo em Inglês | MEDLINE | ID: mdl-15989341

RESUMO

[reaction: see text] A series of butterfly-shaped tetracyanoanthraquinodimethanes (TCNAQs) with a chiral amide auxiliary 1a-f were prepared from the corresponding anthraquinones. They are stronger acceptors than the unsubstituted derivative and undergo one-wave two-electron reduction. They form weak electron-donor-acceptor (EDA) complexes with the title pinacol 2. Upon charge-transfer excitation of these complexes, dihydro-TCNAQs 3 and 1,8-dianisoylnaphthalene 4 were efficiently formed, the latter of which is the product of a retropinacol reaction via 2+*. Partial enantiodifferentiation of rac-2 was realized during the photoreactions with 2-[(R)-1-phenylethylcarbamoyl]-TCNAQ 1ain CD3CN. Thus, optically active (S,S)-(+)-pinacol 2 (12.3% ee at 54% conversion; 21.5% ee at 70% conversion) was recovered from the photolyzates. This reaction represents a new and rare example of the pseudokinetic resolution of tert-alcohol accompanied by C-C bond fission. Significant differences in the association constants for the diastereomeric EDA complexes are responsible for the observed enantiodifferentiation.

6.
J Am Chem Soc ; 125(30): 9147-57, 2003 Jul 30.
Artigo em Inglês | MEDLINE | ID: mdl-15369372

RESUMO

2-(dideuteriomethylene)-1,1-bis(4-methoxyphenyl)cyclopropane (d(2)-1) undergoes degenerate rearrangement in both singlet- and triplet-sensitized electron-transfer photoreactions. Nanosecond time-resolved absorption spectroscopy on laser flash photolysis of the unlabeled 1 with 9,10-dicyanoanthracene, 1,2,4,5-tetracyanobenzene, or N-methylquinolinium tetrafluoroborate as an electron-accepting photosensitizer gives rise to two transients with lambda(max) at 500 and 350 nm assigned to the dianisyl-substituted largely twisted trimethylenemethane cation radical (6.+) and the corresponding diradical (6..), respectively. These intermediates are also detected, respectively, by steady state and nanosecond time-resolved EPR with chloranil or anthraquinone as a sensitizer. The degenerate rearrangement of d(2)-1 thus proceeds via these two different types of intermediates in a cation radical cleavage-diradical cyclization mechanism. Energetics based on nanosecond time-resolved photoacoustic calorimetry support this mechanism. A comparison of the reactivities and the spectroscopic results of 1, 1,1-bis(4-methoxyphenyl)-2-methylenespiro[2.2]pentane (2), and 1-cyclopropylidene-2,2-bis(4-methoxyphenyl)cyclopropane (3) suggest that the reversible methylenecyclopropane rearrangement between 2 and 3 proceeds via a similar mechanism.

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