Biological Impact of Shorter Wavelength Ultraviolet Radiation-C†

Life on earth has constantly coped with the impact of solar radiation, especially solar ultraviolet radiation (solar UV). Various biological mechanisms protect us from solar UV. New devices emitting shorter wavelengths UV-C, i.e. <254 nm emitted by conventional UV germicidal lamps, have emerged. These shorter wavelength UV-C emitting devices are useful for various purposes, including microorganism inactivation. However, as solar UV-C does not reach the earth surface, biological impacts of UV-C has been studied using 254 nm germicidal lamps, and those using shorter wavelength UV-C is rarely known. To balance the utility and risk of UV-C, the biological effect of these new UV-C emitting devices must be investigated. In addition, our knowledge of biological impacts of the wavelength-dependent entire UV (100–400 nm) must be enhanced. In this review, we briefly summarize the biological impacts of shorter wavelength UV-C. Mechanisms of UV-C-induced cellular damage and factors affecting the microorganism inactivation efficiency of UV-C have been discussed. In addition, we theoretically estimate the probable photocarcinogenic action spectrum of shorter wavelength UV-C. We propose that increasing the knowledge on UV-C will facilitate the adoption of shorter wavelength UV-C emitting new devices in an optimal and appropriate manner.     

Control of aqueous droplets using magnetic and electrostatic forces

Basic control operations were successfully performed on an aqueous droplet using both magnetic and electrostatic forces. In our droplet-based microfluidics, magnetic beads were incorporated in an aqueous droplet as a force mediator. This report describes droplet anchoring and separation of the beads from the droplet using a combination of magnetic and electrostatic forces. When an aqueous droplet is placed in an oil-filled reservoir, the droplet sinks to the bottom, under which an electrode had been placed. The droplet was adsorbed (or anchored) to the bottom surface on the electrode when a DC voltage was applied to the electrode. The magnetic beads were removed with magnetic force after the droplet had been anchored. Surfactant addition into droplet solution was very effective for the elimination of electric charge, which resulted in the stable adsorption of a droplet to hydrophobic substrate under an applied voltage of DC 0.5-3 kV. In a sequential process, small volume of aqueous liquid was successfully transferred using both magnetic and electrostatic forces.     

Development of Donor-π-Acceptor-Type Fluorinated Tolanes as Compact Condensed Phase Luminophores and Applications in Photoluminescent Liquid-Crystalline Molecules

Fluorinated tolanes, produced by introducing fluorine atoms into one of the aromatic rings of tolane, emitted almost no fluorescence in a solution state, but the fluorescence intensity increased dramatically in the crystalline state because of intermolecular H⋅⋅⋅F hydrogen bonds. The photoluminescent (PL) colors depend on the molecular orbitals, dipole moments, and molecular aggregated structures can be varied by controlling terminal substituents along the major molecular axis. The introduction of a long alkoxy or semifluoroalkoxy unit as a flexible chain into the terminal positions along the major molecular axis induced the formation of a liquid-crystalline (LC) phase; fluorinated tolanes act both as luminophores and as mesogens, leading to the molecular design of new photoluminescent LC molecules (PLLCs). The results also indicated that a fluorinated tolane dimer, which consists of two fluorinated tolanes linked by a flexible alkylene spacer, also becomes a novel PLLC.     

An efficient unnatural base pair for PCR amplification

Expansion of the genetic alphabet by an unnatural base pair system provides a powerful tool for modern biotechnology. As an alternative to previous unnatural base pairs, we have developed a new pair between 7-(2-thienyl)imidazo[4,5-b]pyridine (Ds) and 2-nitropyrrole (Pn), which functions in DNA amplification. Pn more selectively pairs with Ds in replication than another previously reported pairing partner, pyrrole-2-carbaldehyde (Pa). The nitro group of Pn efficiently prevented the mispairing with A. High efficiency and selectivity of the Ds-Pn pair in PCR amplification were achieved by using a substrate mixture of the gamma-amidotriphosphate of Ds and the usual triphosphates of Pn and the natural bases, with Vent DNA polymerase as a 3' to 5' exonuclease-proficient polymerase. After 20 cycles of PCR, the total mutation rate of the Ds-Pn site in an amplified DNA fragment was approximately 1%. PCR amplification of DNA fragments containing the unnatural Ds-Pn pair would be useful for expanded genetic systems in DNA-based biotechnology.     

Synthesis of the entire carbon framework of the kedarcidin chromophore aglycon

In advanced studies directed toward the total synthesis of the kedarcidin chromophore, we have successfully achieved the late-stage installation of the nine-membered diyne ring in the presence of the highly functionalised ansamacrocyclic bridge.     

"Pocket dendrimers" as nanoscale receptors for bimolecular guest accommodation

A new series of dendrimer receptors was prepared by combining a (tetraphenylporphinato)zinc(II) core and benzyl ether type dendritic substituents. Since one direction of the (tetraphenylporphinato)zinc(II) was not substituted by a dendritic residue, the resulting unsymmetrical dendrimers have "pockets" available for access of external substrates. Molecular modeling, NMR measurements, and zinc-coordination experiments revealed that the third-generation dendrimer of this type exhibited characteristic inclusion of coordinative pyridine guests. When diamidopyridine moiety was introduced into the dendrimer pocket, a thymine derivative was bound through complementary hydrogen bonding. Two different kinds of substrates, pyridine and thymine derivatives, were simultaneously accommodated in the nanoscale pocket and bimolecular guest accommodation was realized with the designed dendrimer receptor.     

Linear metal-metal-bonded tetranuclear M-Mo-Mo-M complexes (M = Ir and Rh): oxidative metal-metal bond formation in a tetrametallic system and 1,4-addition reaction of alkyl halides

Reaction of Mo2(pyphos)4 (1) with [MCl(CO)2]2 (M = Ir and Rh) afforded linear tetranuclear complexes of a formula Mo2M2(CO)2(Cl)2(pyphos)4 (2, M = Ir; 3, M = Rh). X-ray diffraction studies confirmed that two "MCl(CO)" fragments are introduced into both axial sites of the Mo2 core in 1 and coordinated by two PPh2 groups in a trans fashion, thereby forming a square-planar geometry around each M(I) metal. Treatment of 2 and 3 with an excess amount of tBuNC and XylNC induced dissociation of the carbonyl and chloride ligands to yield the corresponding dicationic complexes [Mo2M2(pyphos)4(tBuNC)4](Cl)2 (5a, M = Ir; 6a, M = Rh) and [Mo2M2(pyphos)4(XylNC)4](Cl)2 (7, M = Ir; 8, M = Rh). Their molecular structures were characterized by spectroscopic data as well as X-ray diffraction studies of BPh4 derivatives [Mo2M2(pyphos)4(tBuNC)4](BPh4)2 (5b, M = Ir; 6c, M = Rh), which confirmed that there is no direct sigma-bonding interaction between the M(I) atom and the Mo2 core. The M(I) atom in 5 and 6 can be oxidized by either 2 equiv of [Cp2Fe][PF6] or an equimolar amount of I2 to afford Mo(II)2M(II)2 complexes, [Mo2M2(X)2(tBuNC)4(pyphos)4]2+ in which two Mo-M(II) single bonds are formed and the bond order of the Mo-Mo moiety has been decreased to three. The Ir(I) complex 5a reacted not only with methyl iodide but also with dichloromethane to afford the 1,4-oxidative addition products [Mo2Ir2(CH3)(I)(tBuNC)4(pyphos)4](Cl)2 (13) and [Mo2Ir2(CH2Cl)(Cl)(tBuNC)4(pyphos)4](Cl)2 (15), respectively, although the corresponding reactions using the Rh(I) analogue 6 did not proceed. Kinetic analysis of the reaction with CH3I suggested that the 1,4-oxidative addition to the Ir(I) complex occurs in an SN2 reaction mechanism.     

Determination of vanillin and related flavor compounds in cocoa drink by capillary electrophoresis

In the first part of this study, the stability of five terpenes (alpha-pinene, limonene, camphor, citronellol, and carvacrol) under subcritical water conditions was investigated. The stability studies were carried out at four different temperatures (100, 150, 200, and 250 degrees C) with two different heating times (30 and 300 min). When water temperature was increased, the degradation of terpenes became more serious. Prolonged exposure time to each heating temperature also caused decreased terpene stability. The terpene recoveries were determined by conducting subcritical water extraction of sand spiked with terpenes. The recoveries are typically around 70 to 80% for extractions at 100 degrees C. Terpene recoveries were decreased with increasing water temperature due to poorer stability of terpenes. After the degradation and recovery studies, basil and oregano leaves were extracted using water at both 100 and 150 degrees C. The concentrations of each individual terpene in the water extract generally ranged from trace quantity to 65 microg terpene/g herb. However, the concentration of carvacrol in the oregano-water extract at 150 degrees C was found to be as high as 4270 microg carvacrol/g oregano.     

On the Kodaira Dimension of the Moduli Space of K3 Surfaces II

We show that the Kodaira dimension of the moduli space of polarized K3 surfaces of degree 2n in non negative if n = 42, 43, 51, 53, 55, 57, 59, 61, 66, 67, 69, 74, 83, 85, 105, 119 or 133. We use an automorphic form associated with the fake monster Lie algebra constructed by Borcherds.     

Effect of Substrates on the Addition Polymerization of 1,4-Benzenedithiol to 1,4-Diethynylbenzene in the Solid State and the Electronic Properties of the Resulting Polymer

The effect of substrates on the addition polymerization of 1,4-benzenedithiol (BDT) to 1,4-diethynylbenzene (DEB) in the solid state and the electronic properties of the polymers obtained were studied. As the substrate polymer sheets, for instance, PET (poly (ethylene terephthalate)) sheet, ON-6 (oriented nylon-6) sheet and so on having surface free energies Γ_s from 27.4 to 55.0 erg/cm² were used. At the monomer sublimation temperature of 60°C, the S wt% (sulfur content) and the cis content of the polymers were not affected by the kind of polymer sheets. However, the molecular weights, M¯_n of the polymers polymerized on the polymer sheets were 13,000–30,000, and the values were several times higher than the molecular weight of the polymers polymerized on glass plate. On the other hand, at the sublimation temperature of 82°C, the cis content of the polymers apparently increased with decreasing d-value of the polymer sheets. On X-ray diffraction patterns of monomer mixtures sublimed onto polymer sheets, the diffraction intensities and the diffraction peak positions were concerned with the d-value of the polymer sheets. Using polymer sheets, the diffraction peak intensities of the monomer mixture at 7.73 and 7.58 Å decreased compared with those on glass plate. In contrast, the peak at 3.65 Å, which is a negligibly small peak on glass plate, obviously increased. However, as the d-value of the polymer sheets (PET 3.45 Å; OPP (oriented polypropylene) 5.2 Å) increased, the diffraction peak intensities at 7.73 Å and 7.58 Å gradually increased and the diffraction peak intensity at 3.65 Å gradually decreased. The parallel electrical conductivities (σ_||) toward the layered structural polymer on PET, ON-6 and glass plate under air atmosphere were 10⁻⁷, 10⁻⁹ and 10⁻¹¹ S/cm, respectively. Under a reduced pressure of 10⁻³ mmHg, the σ_|| values of each polymer lowered by one or two orders of magnitude. On the other hand, the σ_|| values of the nonlayered structural polymers under air atmosphere were about 10⁻¹¹–10⁻¹² S/cm and were independent of the substrates. Even under a reduced pressure of 10⁻³ mmHg, the σ_|| values hardly changed and remained at 10⁻¹¹–10⁻¹² S/cm. The vertical electrical conductivities (σ_⟂) of the layered structural polymers on conductive PET sheet coated by indium tin oxide or NESA glass plates were independent of the substrates and were 10⁻¹⁴ S/cm under air atmosphere. The σ_⟂ values of the nonlayered structural polymers also exhibited the same values. The reversible change of the amount of the layered structural polymer on PET sheet was also caused by irradiation of the photo-light which is the effective wavelength for the phase transition of the polymers mounted on glass plate. The σ_|| value of the layered structural polymer on ON-6 sheet reversibly changed with the amount of the layer structure controlled by the photo-light, that is, the σ_|| increased up to about one order of magnitude by the photo-light at 545.6 nm. On the other hand, the _|| decreased to about one order of magnitude by the photo-light at 539.6 nm. Anisotropic conductivity with respect to σ_|| and σ_⟂, and oxygen doping mechanisms were discussed in relation to the layer structure of polymers. © 1997 John Wiley & Sons, Ltd.