Phosphorescent Ruthenium Complexes with a Nitroimidazole Unit that Image Oxygen Fluctuation in Tumor Tissue

Understanding oxygen fluctuation in a cancerous tumor is important for effective treatment, especially during radiotherapy. In this paper, ruthenium complexes bearing a nitroimidazole group are shown to report the oxygen status in tumor tissue directly. The nitroimidazole group was known to be accumulated in hypoxic tumor tissues. On the other hand, the ruthenium complex showed strong phosphorescence around 600 nm. The emission of ruthenium is quenched instantaneously by molecular oxygen due to energy transfer between triplet states of oxygen and ruthenium complex, but the emission is then recovered by the removal of oxygen. Thus, we could observe oxygen fluctuation in tumor tissue in a real‐time manner by monitoring the phosphorescence of the ruthenium complex. The versatility of the probe is demonstrated by monitoring oxygen fluctuation in living cells and tumor tissue planted in mice. The ruthenium complex promptly penetrated plasma membrane and accumulated in cells to emit its oxygen‐dependent phosphorescence. In vivo experiments revealed that the oxygen level in tumor tissue seems to fluctuate at the sub‐minute timescale.     

Silver-catalyzed synthesis of disubstituted isoxazoles by cyclization of alkynyl oxime ethers

A facile and practical synthesis of 3,5-disubstituted isoxazoles via a silver-catalyzed cyclization and subsequent protonation of alkynyl oxime ethers has been developed. The methodology was successfully applied to the synthesis of a biologically active isoxazolecarboxylic acid.     

Red and blue pulse timing control for pulse width modulation light dimming of light emitting diodes for plant cultivation

A pulse width modulation (PWM) light dimming system containing red and blue light emitting diodes was designed and constructed. Cultivation of the plant Arabidopsis thaliana under various light dimming wave patterns was compared. Control of the pulse timing (phase of wave pattern) between red and blue light in PWM light dimming was examined. Different plant growth was obtained by changing the phase of red and blue pulses. Pulse timing control of PWM light dimming for plant cultivation has the potential to act as a method for probing photosynthesis.     

Palladium-catalyzed cross coupling reaction of N-alkoxyimidoyl bromides and its application to one-pot synthesis of N-arylamines

The synthetic utility of N-alkoxyimidoyl halides is demonstrated using the palladium-catalyzed cross-coupling reaction. The Sonogashira and Suzuki-Miyaura coupling reactions of N-alkoxyimidoyl bromides produced versatile ketoxime ethers in good to excellent yields. A one-pot reaction of the imidoyl bromides with arylboronic acid and allylmagnesium bromide to produce N-arylamines via Suzuki-Miyaura coupling followed by domino reaction involving sequential addition-eliminative rearrangement-addition reactions was developed.     

Biodegradable polymers based on renewable resources. VII. Novel random and alternating copolycarbonates from 1,4:3,6‐dianhydrohexitols and aliphatic diols

Novel copolycarbonates containing 1,4:3,6‐dianhydro‐D ‐glucitol or 1,4:3,6‐dianhydro‐D ‐mannitol units, with various methylene chain lengths, were synthesized by bulk and solution polycondensations, of several combinations of carbonate‐modified sugar derivatives and aliphatic diols. Bulk polycondensations of 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(phenoxycarbonyl)‐D ‐glucitol or 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(phenoxycarbonyl)‐D ‐mannitol with four α,ω‐alkanediols having methylene chain lengths of 4, 6, 8, and 10, respectively, at 180 °C afforded the corresponding copolycarbonates with number‐average molecular weight (M_n) values up to 19.₂ × 10³. ¹³C NMR analysis disclosed that these polymers had scrambled structures in which the sugar carbonate and aliphatic carbonate moieties were nearly randomly distributed along a polymer chain. However, solution polycondensations between 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(p‐nitrophenoxycarbonyl)‐D ‐glucitol or 1,4:3,6‐dianhydro‐2,5‐bis‐O‐(p‐nitrophenoxycarbonyl)‐D ‐mannitol, and the α,ω‐alkanediols in sulfolane or dimethyl sulfoxide at 60 °C gave well‐defined copolycarbonates having regular structures consisting of alternating sugar carbonate and aliphatic carbonate moieties with M_n values up to 33.₈ × 10³. Differential scanning calorimetry demonstrated that all the copolycarbonates were amorphous with glass‐transition temperatures ranging from 1 to 65 °C, which decreased with increasing lengths of the methylene chain of the aliphatic diols. Additionally, all the copolycarbonates were stable up to 310–330 °C as estimated by thermogravimetric analysis. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 2312–2321, 2003     

Study of Tensor Correlations in 4He via the 4He(p, dp)d and 4He(p, dp)pn Reactions

Tensor correlations in ⁴He were studied via the (p, dp) reaction at the incident energy of 392 MeV with a focus on spin configurations of correlated pn pairs in ⁴He at high relative momenta ${(P_{\rm rel}^{\rm cor})}$ . The preliminary results show that the correlated pn pair at ${P_{\rm rel}^{\rm cor} = 310 {\rm MeV/c}}$ predominantly has the channel spin S = 1, which is consistent with the characteristics of tensor correlations.     

The N = 16 Spherical Shell Closure in 24O

The unbound excited states of the most neutron-rich dripline oxygen isotope, ²⁴O, have been investigated by using the ²⁴O(p,p′)²⁴O^* reaction at the beam energy of 62 MeV/nucleon in inverse kinematics. The first and second unbound excited states of ²⁴O have been observed at ${E_{\rm x}= 4.63_{-0.14}^{+0.30}}$  MeV and ${E_{\rm x}= 5.13_{-0.24}^{+0.19}}$  MeV (preliminary) along with the evidence for another higher lying state at around 7.3 MeV. The quadrupole deformation parameter ${\beta_{2^+}}$ was deduced to be ${0.15_{-0.03}^{+0.08}}$ (preliminary) for the first time. The systematics of the ${\beta_{2^+}}$ and the ${E_{\rm x}(2_1^+)}$ in the Z = 8 isotopes shows the N = 16 spherical shell closure in ²⁴O.     

Spectroscopic Measurement in 9He and 12Be

Spectroscopy for neutron-rich nuclei ⁹He and ¹²Be has been performed by means of heavy-ion double charge exchange (HIDCX) (¹⁸O, ¹⁸Ne) reaction on stable target nuclei ⁹Be and ¹²C, respectively. Several clear peaks in ¹²Be at low excitation energy region even above neutron separation energy have been observed in one-shot measurement, whereas no prominent signals of ⁹He have been observed owing to the small cross section. It is shown that the HIDCX reaction is a new powerful spectroscopic tool for study of unstable neutron-rich nuclei.