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11.
Danuta Frackowiak Mamoru Minuro Iwao Yamazaki† Naoto Tamai† Yoshihiko Fujita 《Photochemistry and photobiology》1989,50(4):563-570
–Time-resolved fluorescence spectra in the ps time range were measured on phycobilisome (PBS) embedded in poly(vinyl alcohol) films. The cyanobacterium Tolypothrix tenuis was used as a source of PBS because the pigment composition and the structure of the PBS are well defined. Isotropic PBS in the unstretched film and PBS uniaxially oriented in the stretched film were investigated. Diameters of PBS hemidiscs were oriented parallel to the film-stretching direction. The time-resolved fluorescence spectra of the unstretched sample and of the two polarized components in the stretched samples showed several differences in the rise and decay. The delay time, estimated from the time span between the maximum laser pulse and maximal intensity of the phycocyanin and allophycocyanin fluorescence, was much longer than that reported in the aqueous media. This suggests occurrence of a higher thermal deactivation of PBS in polymer film than in aqueous media. The excitation energy transfer from excited phycocrythrin to allophycocyanin was more efficient in the unstretched than in the stretched samples, and it was greater in the parallel polarized component of the stretched sample than in the perpendicular component. The present results are in agreement with a previous suggestion which states that there are two independent pathways of excitation energy transfer in PBS and that there is more than one final emitter of fluorescence. The molecules taking part in various pathways of energy transfer differ in their orientation within PBS. 相似文献
12.
Ishikawa N Sugita M Tanaka N Ishikawa T Koshihara SY Kaizu Y 《Inorganic chemistry》2004,43(18):5498-5500
An alternating-current (ac) magnetic susceptibility measurement for the [(Pc)(2)Tb(III)](0) complex (Pc = phthalocyaninato) has shown that ligand oxidation of the anionic [(Pc)(2)Tb(III)](-) complex gives rise to a significant upward shift of the temperature range where the magnetization response shows a phase lag behind the time-varying external magnetic field. The peaks of the out-of-phase component of the ac susceptibility of the pi-radical [(Pc)(2)Tb(III)](0) were observed at 50, 43, and 36 K with ac magnetic fields of 10(3), 10(2), and 10 Hz, respectively, which were more than 10 K higher than the corresponding values of the anionic complex with a closed-shell pi-system. The ac susceptibility measurements on the complex with octa(dodecoxy)-substituted Pc ligand, which is readily dilutable in diamagnetic media, proved that the significant rise of the temperatures occurs as an intrinsic single-molecular property of the complex possessing both J = 6 and S = (1)/(2) systems, and is not due to long-range magnetic order or interactions between adjacent unpaired pi-electrons. 相似文献
13.
Kazuharu Sugawara Tatsuya Shirotori Naoto Kamiya Shunitz Tanaka 《Analytica chimica acta》2004,523(1):75-80
Formation of avidin-biotin complex was investigated using bisbiotinyl thionine (BBT) by means of voltammetric techniques. Thionine is an electroactive compound and has two amino groups that are necessary for the reaction with a biotinylation reagent. The biotinylation of thionine produces a new reagent with two biotin moieties at each end of thionine. Three BBTs of different lengths of the spacer that connects the biotin moiety to the thionine moiety were prepared. The avidin-biotin binding assay was achieved by measuring the electrode response of the thionine moiety in BBT. The binding affinity and the conformation of complex, which depended on the length of spacer, are discussed. BBT in which the spacer is shortest (BBT-S, distance between carbonyl group of the two biotin moieties: 11 Å) binds with only one avidin molecule. BBT with medium length of spacer (BBT-M, 28.8 Å) forms the complex with two avidin molecules. BBT with the longest spacer (BBT-L, 46.6 Å) allows binding with two avidin molecules as well as intramolecular binding within one avidin molecule. The affinity constants of BBT-S, BBT-M and BBT-L for avidin were estimated to be 7.0 × 1012 M−1, 3.2 × 1012 M−1 and 4.0 × 1012 M−1, respectively. 相似文献
14.
Chatani N Amako K Tobisu M Asaumi T Fukumoto Y Murai S 《The Journal of organic chemistry》2003,68(4):1591-1593
The reaction of benzofuran-2,3-dione derivatives 1 with CO and alkenes (or alkynes) results in a carbonylative [2+2+1] cycloaddition in which the ester-carbonyl group is incorporated into a two-atom assembling unit to give spirolactone derivatives 2. This reaction provides the first example of an ester-carbonyl group participating in a carbonylative cycloaddition reaction. 相似文献
15.
The reaction of alpha,beta-unsaturated imines with CO and alkenes in the presence of Ru(3)(CO)(12) as a catalyst results in a three-component coupling reaction that gives alpha,alpha-disubstituted beta,gamma-unsaturated gamma-butyrolactams. The reaction proceeds via a two-step sequence involving the initial formation of ketone derivatives by catalytic carbonylation at the beta-olefinic C-H bonds of alpha,beta-unsaturated imines, followed by the (uncatalyzed) intramolecular nucleophilic attack of the imine nitrogen on the ketonic carbon to generate a tetrahedral intermediate, which then undergoes a 1,2-ethyl migration. The reaction of a cyclic unsaturated imine, derived from the reaction of (1R)-(-)-myrtenal with tert-butylamine, gives a beta-aminocyclopentene derivative, which is formed by an aldol-type condensation of the initially formed ketone, indicating the initial formation of ethyl ketone. 相似文献
16.
The dynamic behavior of the reaction-diffusion system, composed of glucose oxidase (EC 1.1.3.4) immobilized at a uniform concentration in a membrane, used as a glucose electrode is represented by a diffusion equation with a nonlinear reaction-term in one-dimensional space. The mathematical model is analyzed by computer simulation, that is, numerical integration of the equation under various initial and boundary conditions, to examine the effect of enzyme concentration on the response characteristics (responsiveness and linearity in response) of the electrode. The analysis of the responses of the system to stepwise changes in the boundary value (glucose concentration in simple solution) infers that the enzyme concentration governs the patterns of the spatial distributions of the substrates (glucose and dissolved oxygen) in steady states and transient responses. It is also revealed that the response characteristics of the electrode are optimized with concentration of immobilized enzyme and that the system establishes the steady states at the same spatial distributions of the substrates, regardless of the boundary value. The diffusion of the substrates and the oxygen concentration also have significant effects on the response characteristics of the electrode. 相似文献
17.
Akhtaruzzaman M Kamata N Nishida J Ando S Tada H Tomura M Yamashita Y 《Chemical communications (Cambridge, England)》2005,(25):3183-3185
Dithiazolylbenzothiadiazoles easily obtained have high electron affinity and the FET device of a trifluoromethylphenyl derivative exhibited a good n-type performance with high electron mobility. 相似文献
18.
Takimiya K Kunugi Y Konda Y Niihara N Otsubo T 《Journal of the American Chemical Society》2004,126(16):5084-5085
2,6-Diphenylbenzo[1,2-b:4,5-b']dichalcogenophenes including thiophene, selenophene, and tellurophene analogues as organic semiconductors for field-effect transistors were effectively synthesized in three steps from commercially available 1,4-dibromobenzene. All three benzodichalcogenophenes acted as good p-type semiconductors, and particularly the selenophene analogue, 2,6-diphenylbenzo[1,2-b:4,5-b']diselenophene, showed high FET mobility of 0.17 cm2 V-1 s-1. 相似文献
19.
Kakiuchi F Kan S Igi K Chatani N Murai S 《Journal of the American Chemical Society》2003,125(7):1698-1699
The ruthenium-catalyzed reaction of aromatic ketones with arylboronic acid esters (arylboronates) gave the ortho arylation product. For this coupling reaction, a RuH2(CO)(PPh3)3 complex exhibited the highest catalytic activity among the complexes screened. Several aromatic ketones, for example, acetophenones, acetonaphthone, alpha-tetralone, and benzosuberone, can be used in this coupling reaction. A variety of arylboronates containing electron-donating (OMe and NMe2) and -withdrawing (F and CF3) groups were found to react with aromatic ketones to give the corresponding aylation products. The corresponding arylboronic acids could be used in this coupling reaction, but the yields were slightly lower, as compared to those of the reaction using the corresponding arylboronates. 相似文献
20.
Yoshiaki Sugihara Naoto Inai Masayasu Taki Thomas Baumgartner Ryosuke Kawakami Takashi Saitou Takeshi Imamura Takeshi Yanai Shigehiro Yamaguchi 《Chemical science》2021,12(18):6333
The use of donor–π–acceptor (D–π–A) skeletons is an effective strategy for the design of fluorophores with red-shifted emission. In particular, the use of amino and boryl moieties as the electron-donating and -accepting groups, respectively, can produce dyes that exhibit high fluorescence and solvatochromism. Herein, we introduce a dithienophosphole P-oxide scaffold as an acceptor–spacer to produce a boryl- and amino-substituted donor–acceptor–acceptor (D–A–A) π-system. The thus obtained fluorophores exhibit emission in the near-infrared (NIR) region, while maintaining high fluorescence quantum yields even in polar solvents (e.g. λem = 704 nm and ΦF = 0.69 in CH3CN). A comparison of these compounds with their formyl- or cyano-substituted counterparts demonstrated the importance of the boryl group for generating intense emission. The differences among these electron-accepting substituents were examined in detail using theoretical calculations, which revealed the crucial role of the boryl group in lowering the nonradiative decay rate constant by decreasing the non-adiabatic coupling in the internal conversion process. The D–A–A framework was further fine-tuned to improve the photostability. One of these D–A–A dyes was successfully used in bioimaging to visualize the blood vessels of Japanese medaka larvae and mouse brain.Combination of electron-accepting diarylboryl terminal groups and dithienophosphole oxide spacers with electron-donating triarylamine moieties produces donor–acceptor–acceptor type π-systems, which exhibit emissions in the near-infrared region. 相似文献