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Deep Brain Photoreceptors and Photoperiodism in Vertebrates
Oishi, Tadashi,Haida, Yuka,Okano, Keiko,Yoshikawa, Tomoko,Kawano, Emi,Nagai, Kiyoko,Fukada, Yoshitaka,Tsutsui, Kazuyoshi,Tamotsu, Satoshi Korean Society of Photoscience 2002 Journal of Photosciences Vol.9 No.2
Photoperiodism is an important adaptive phenomenon in various physiological parameters including reproduction to cope with seasonal changes. Involvement of extraretinal photoreceptors in the photoperiodism in non-mammalian vertebrates has been well established. In addition, circadian clock system is known to be involved in the photoperiodic time measurement. The pathway consists of light-input system, time measurement system (circadian clock), gonadotropin releasing hormone (GnRH) production in the hypothalamus, luteinizing hormone (LH) and follicle stimulating hormone (FSH) production in the pituitary, and final gonadal development. Recently, several laboratories reported photopigments newly cloned in the pineal, eyes and deep brain in addition to already known visual pigments in the retina. These are pinopsin, parapinopsin, VA-opsin, melanopsin, etc. All these photopigments belong to the opsin family having retinal as the chromophore. However, the function of these photopigments remains unknown. I reviewed the studies on the location of the photopigments by immunocytochemistry. I also discussed the results on the action spectra for induction of gonadal development in relation with the location of the photoreceptors. Various physiologically active substances distribute in the vertebrate brain. Such substances are GnRH, GnIH, neuropeptide Y, vasoactive intestinal peptide, c-Fos, galanin, neurosteroids, etc. I summarized the immunhistochemical studies on the distribution and the photoperiodic changes of these substances and discussed the route from the deep brain photoreceptor to GnRH cells.
Kanezaki, Hiroshi,Nishimoto, Sei-Ichi,Tanabe, Kazuhito Korean Society of Photoscience 2014 Rapid communication in photoscience Vol.3 No.4
We characterized the one-electron reduction of oligodeoxynucleotides with a 2-oxopropyl group on a thymine base ($d^{oxo}T$) and applied the reaction to the radiolytic activation of DNAzyme function. We designed a system in which the DNAzyme function of cleaving mRNA was suppressed by introduction of $d^{oxo}T$ into the strand of DNAzyme. Hypoxic X-irradiation led to recovery of the cleavage ability because the 2-oxopropyl group was removed to form unmodified DNAzyme. We characterized the DNAzyme function by monitoring the fluorescence change of fluorophore- and quencher-labeled target strands. We confirmed that the DNAzyme function could be regulated by hypoxic X-irradiation and the reaction of $d^{oxo}T$.
Hirakawa, Kazutaka,Ito, Yusuke,Yamada, Takashi,Okazaki, Shigetoshi Korean Society of Photoscience 2014 Rapid communication in photoscience Vol.3 No.4
To examine the microenvironmental effect of DNA on the photosensitized reaction, the electron-donor-connecting porphyrin, meso-(9-phenanthryl)-tris(N-methyl-p-pyridinio) porphyrin (Phen-TMPyP), was synthesized. Phen-TMPyP can bind to oligonucleotides with two binding modes, depending on the DNA concentration. The fluorescence lifetime measurement of Phen-TMPyP shows a shorter component than that of the reference porphyrin without the phenanthryl moiety. However, the observed value is much longer than those of previously reported similar types of electron-donor-connecting porphyrins, suggesting that electron-transfer quenching by the phenanthryl moiety is not sufficient. The fluorescence quantum yield of Phen-TMPyP ($5{\mu}M$) decreased with an increase in DNA concentration of up to $5{\mu}M$ base pair (bp), possibly due to self-quenching through an aggregation along the DNA strand, increased with an increase in DNA concentration of more than $5{\mu}M$ bp and reached a plateau. The fluorescence quantum yield of Phen-TMPyP with a sufficient concentration of DNA was larger than that of the reference porphyrin. The singlet oxygen ($^1O_2$) generating activity of Phen-TMPyP was confirmed by the near-infrared emission spectrum measurement. The quantum yield of $^1O_2$ generation was decreased by a relatively small concentration of DNA, possibly due to the aggregation of Phen-TMPyP, and recovered with a sufficient concentration of DNA. The recovered quantum yield was rather smaller than that without DNA, indicating the quenching of $^1O_2$ by DNA. These results show that a DNA strand can stabilize the photoexcited state of a photosensitizer and, in a certain case, suppresses the $^1O_2$ generation.
Solvent effect on the excited state of stilbene dendrimers bearing phenylacetylene groups
Nishimura, Yoshinobu,Arai, Tatsuo Korean Society of Photoscience 2014 Rapid communication in photoscience Vol.3 No.4
We studied the characteristics of emissive state of the first (p-G1) and second (p-G2) generation of phenylacetylene dendrimers bearing stilbene as a core by using time-resolved fluorescence spectroscopy in cyclohexane (c-Hex) and N, N-dimethylformide (DMF), which are nonpolar and polar solvents, respectively. Time-dependent red-shift of emission spectra p-G2 both in c-Hex and DMF was observed in comparison with p-G1. Besides, the time constant of red-shift of spectra was found to be larger in DMF than in c-Hex. This indicates that the emissive state of p-G2 has a polar character in DMF as a result of charge delocalization from core to peripheral dendrons followed by stabilization of emissive state.
Shiragami, Tsutomu,Onitsuka, Dai,Matsumoto, Jin,Yasuda, Masahide Korean Society of Photoscience 2014 Rapid communication in photoscience Vol.3 No.4
Visible-light irradiation of MeCN solution containing di(hydroxo)metallo(tetraphenyl)porphyrin complex $(tppM(OH)_2$: 1a; $M=Sb(V)^+Br^-$, 1b; $M=P(V)^+Cl^-$, 1c; M=Ge(IV)) and 2-mercaptoethanol (2-ME) as a substrate under aerated condition gave bis(2-hydroxyethyl)disulfide (2-HEDS) as an oxidative product of 2-ME. It is indicated that the oxidation of 2-ME should proceed with a photocatalytic process by 1, because the turn over number (TON) for the formation of 2-HEDS was over unit. The TON was determined to be 642 as a maximum value when 1a was used as a sensitizer. The formation of 2-HDES was extremely slow under argon atmosphere. The fluorescence of 1 was not quenched by 2-ME at all, and the free energy change (${\Delta}G$) with electron transfer (ET) from 2-ME to excited triplet state of $1(^31^*)$ was estimated as a negative value. The quenching rate constant ($k_r$) of $^31^*$ by 2-ME, obtained by the kinetics for the formation of 2-HEDS, strongly depends on ${\Delta}G$. These findings indicate that 1-sensitized oxidation was initiated by photoinduced ET from 2-ME to $^31^*$ to generate both radical cation of 2-ME ($2-ME^{+\bulle}$) and porphyrin radical anion ($1^{-\bulle}$), resulting that the formation of 2-HEDS can be proceeded by the dimerization of $2-ME^{+\bulle}$, and through a catalytic cycle due to returning to 1 by the ET from $1^{-\bulle}$ to molecular oxygen.