Effects of butylated hydroxytoluene upon PUVA-tumorigenesis and induction of ornithine decarboxylase activity in the mouse

Psoralen photochemotherapy (PUVA) is widely used in the treatment of psoriasis. Some therapy regimen have been associated with increased risk of skin cancer. Free radical species are thought to play a role in psoralen phototoxicity and photocarcinogenesis. It has been reported that the antioxidant butylated hydroxytoluene (BHT) inhibits acute phototoxicity by PUVA but does not reduce therapeutic efficacy. It has also been shown that BHT inhibits UVB-induced erythema, tumorigenesis and induction of ornithine decarboxylase (ODC) activity--ODC activity is thought by some to be associated with tumor promotion. Therefore, we have investigated the effect of BHT on psoralen tumorigenesis and PUVA-induced epidermal ODC activity. SKH-Hr-1 hairless albino mice were treated with topically applied 8-MOP and exposed to UVA (3X weekly) for 31 weeks with and without BHT administered either in the diet or topically. Induction of ODC activity was determined in similar experimental groups 24 h after a single exposure to UVA. Neither route of BHT administration had any effect on 8-MOP phototumorigenesis. However, BHT when administered in the diet reduced induction of ODC activity by 40% (p less than 0.05). These data indicate different mechanisms for UVB- and PUVA-induced carcinogenesis and again bring into question the relationship between induction of ODC activity and photocarcinogenesis.     

Dose-response of electromagnetic field-enhanced ornithine decarboxylase activity

Alteration of ODC activity in animals or cultured cells exposed to extremely low frequency electromagnetic fields, or to modulated microwave fields, has been documented by several laboratories. However, an evaluation of the dose-response relationship in these experiments has not been done. We examined ODC activity in L929 fibroblasts exposed for 4 h to 60 Hz magnetic fields of different amplitudes. Our results show a clear threshold response which could be fitted to a sigmoidal function, with the 50% point occurring at approximately 5 microT. This sigmoidal response is characteristic of biological responses which are governed by ligand-receptor binding, and has been previously observed in the incidence of magnetic-field induced morphological abnormalities in chick embryos. The implications of this study are discussed in terms of environmental exposures to EM fields.     

Simple and rapid enzymatic assay of ornithine decarboxylase activity

Since the induction of putrescine synthesis by ornithine decarboxylase (ODC) is observed in many pathological and physiological processes, a useful and simple method to assay this enzyme activity should be an interesting tool to quantify the biological importance of its induction. An enzymatic method to assay ODC is reported here. This method is based on the reaction between putrescine and soya diamine oxidase. The reaction releases H(2)O(2), which is measured by a colorimetric method. The validation of this method showed good accuracy (98+/-5% of recovery). High precision and reproducibility were obtained. A linearity with a correlation coefficient of 0.999 in the range of 2.5-25 nmol was obtained. This method is also rugged and specific. The application of the assay of ODC activity showed that it is useful as a rapid and simple tool for assaying ODC activity in vitro. Comparison with the HPLC determination of ODC activity shows strong correlation along with the high accuracy of the two methods.     

Assay of ornithine decarboxylase activity by reversed-phase high-performance liquid chromatography

Ornithine decarboxylase (L-ornithine carboxylase; EC 4.1.1.17; ODCase) is a key enzyme in the biosynthesis of polyamines. It catalyzes the decarboxylation of L-ornithine to putrescine. The high-performance liquid chromatographic (HPLC) method described here for determining ODCase activity combines the sensitivity of radiochemical detection with the separative capacity of HPLC without the necessity of generating a pre-column derivative. In this study, [1,2-3H]putrescine was separated from L-[2,3-3H]ornithine using reversed-phase HPLC eluted isocratically. This method was used to study ODCase from both prokaryotic and mammalian sources. With the ODCase from Escherichia coli we found the reaction rates to be linear for 5 min with an apparent Michaelis constant (KM) of 20 mM. After 1 h this activity had produced approximately four-fold more product at pH 5.0 than at pH 7.3. In contrast, the initial rate of ODCase from submandibular glands was linear for 60 min. Also, the rate of putrescine synthesis was ten-fold higher in the embryonic gland than in the adult which was 8-80 times lower than that of E. coli.     

Wavelength dependence of laser polymerization of acrylic monomers

Photopolymerization of multifunctional acrylic monomers using excimer and Nd: YAG lasers operated at five different UV wavelengths is reported. The effects of different wavelengths on the surface and bulk cure both in air and under argon are investigated and discussed.     

Wavelength dependence of mycosporine-like amino acid synthesis in Gyrodinium dorsum

The synthesis or accumulation of mycosporine-like amino acids (MAAs) is an important UV tolerance mechanism in aquatic organisms. To investigate the wavelength dependence of MAA synthesis in the marine dinoflagellate Gyrodinium dorsum, the organism was exposed to polychromatic radiation (PAR and UV) from a solar simulator for up to 72 h. Different irradiance spectra were produced by inserting various cut-off filters between lamp and samples. A polychromatic action spectrum for the synthesis of MAA synthesis was constructed. PAR and long wavelength UV-A radiation showed almost no effect while the most effective wavelength range was around 310 nm. Shorter wavelengths where less effective in the induction of MAA synthesis. Wavelengths below 300 nm damaged the organisms severely as indicated by a decrease in chlorophyll a absorption.     

Wavelength dependence of HCO formation in the photolysis of acetaldehyde

The wavelength dependence of HCO(0,0,0) formation in the photodissociation of acetaldehyde was measured using narrow (0.1 nm) bandwidth laser excitation and time-resolved intracavity laser detection (TRILD). A sharp energetic onset at 320 ± 1 nm (89.3 ± 0.3 kcal) for HCO(0,0,0) formation was found. The maximum concentration of HCO(0,0,0) occurs between 100 and 250 μs after excitation depending on the wavelength of excitation     

Wavelength dependence of first molecular hyperpolarizability of a dendrimer in solution

The frequency dependence of the first molecular hyperpolarizability of a dendrimer incorporated with thiophene-stilbene based charge-transfer chromophores is investigated by using a nanosecond 1907 nm laser and a number of wavelengths ranging from 1160 to 1760 nm emitted from an optical parametric amplifier pumped by a 1 kHz 130 fs Ti:sapphire laser. The measured hyperpolarizabilities are compared with those calculated from the charge-transfer absorption spectrum involving a Kramers-Kronig transformation scheme. The Kramers-Kronig transformation analysis provides a satisfactory account of the dispersion of the first molecular hyperpolarizability over the entire excitation wavelength range measured. The Kramers-Kronig technique extends the Oudar-Chemla two-level model previously proposed for the first molecular hyperpolarizability and it can be used in the nonresonance as well as the resonance region where the Oudar-Chemla model fails. The Kramers-Kronig transformation scheme allows a consistent intrinsic hyperpolarizability beta(0) to be obtained from the measured beta(HRS) using different excitation wavelengths for the dendrimer. The comparison of beta(0) for the dendrimer, which contains three chromophores, with that of corresponding monomer chromophore suggests that the chromophores inside the dendrimer are independent. This gives the evidence of the site isolation effect of the dendrimer and substantiates the larger macroscopic optical nonlinearity recently obtained for the dendrimer.     

Hydroxydibenzoylmethane induces apoptosis through repressing ornithine decarboxylase in human promyelocytic leukemia HL-60 cells

Ornithine decarboxylase (ODC) is the rate-limiting enzyme in polyamine biosynthesis and a target for chemoprevention. Hydroxydibenzoylmethane (HDB), a derivative of dibenzoylmethane of licorice, is a promising chemopreventive agent. In this paper, we investigated whether HDB would inhibit the ODC pathway to enhance apoptosis in human promyelocytic leukemia HL-60 cells. We found ODC enzyme activity was reduced during HDB treatment. Overexpression of ODC in HL-60 parental cells could reduce HDB-induced apoptosis, which leads to loss of mitochondrial membrane potential (Δψ(m)), through lessening intracellular ROS. Furthermore, ODC overexpression protected cytochrome c release and the activation of caspase-3 following HDB treatment. The results demonstrated HDB-induced apoptosis was through a mechanism of down-regulation of ODC and occurred along a ROS-dependent mitochondria-mediated pathway.     

Infrared-induced conformer interconversion processes for allylamine in argon matrices: Wavelength dependence on the kinetics

Infrared photoisomerization of allylamine trapped in solid argon is studied by irradiation either at specific wavelengths emitted by a CO₂ laser in coincidence with bands of the three conformers (S⁺ G⁺, ST and CT) or in several mid- or near-IR domains using broad band filters. Upon irradiation with broad band filters the CT → ST process is mainly observed whatever the frequency domain, with only a slight intensity increase of the S⁺ G⁺ bands. Upon irradiation with CO₂ lines in coincidence with CT bands the conversion CT → ST is observed; the reverse process is evidenced by irradiation at ST frequencies. Irradiation at S⁺ G⁺ frequency shows no effect on the conformational equilibrium. Kinetic rate constants are measured and normalized to constant light power absorbed by the sample. They are compared with those calculated by the RRKM theory of first-order processes, assuming the same torsional barrier around the C---C bond as in the gas phase. The good agreement between experimental and calculated values suggests the absence of vibrational selectivity in this photoisomerization process.     

Wavelength dependence of the surface photo-oxidation of Bisphenol A polycarbonate

ESCA and difference uv techniques have been used to monitor the changes which take place in the surface and bulk chemistry, during photo-oxidation of Bisphenol A polycarbonate, as a function of irradiation wavelength over the range 280–330 nm. Whereas for the surface, the maximum change is observed at 280 nm, in the bulk this occurs at 290 nm. Irradiation at 310 nm, which gives bulk changes similar to natural weathering, does not involve the carbonate group in the surface so that the initial photo-instability of polycarbonate cannot be attributed to a photo-Fries rearrangement of this moiety. The surface photo-reactions are consistent with photo-oxidation.     

Wavelength dependence in photochemical vapor deposition of aluminum film using dimethylaluminum hydride

In photochemical vapor deposition of aluminum film on silicon using dimethylaluminum hydride, (CH₃)₂AlH, a surface reaction dominated below a (CH₃)₂AlH pressure of 0.3 m Torr at 200°C, which was induced only with the 160 nm band emitted from a deuterium lamp. A gas-phase reaction occurred above 0.3 mTorr at 200°C, which could be induced by both 160 nm and 240 nm emission bands from the lamp. To distinguish between surface ad gas-phase reactions, a thickness profile was used. At 240°C the surface reaction could be induced even by the 240 nm band, while the deposits formed under illumination of the two bands were thinner than those obtained with only the 240 nm band, indicating occurrence of vacuum ultraviolet (VUV)-enhanced desorption. The mechanism responsible for the observed wavelength dependence in unclear. The electrical resistivity of the films deposited at 200°C was 4.5 μΩ cm, which did not change with wavelength.     

Wavelength dependence of the suppressed ionization of molecules in strong laser fields

We study ionization of molecules by an intense laser field over a broad wavelength regime, ranging from 0.8 to 1.5 μm experimentally and from 0.6 to 10 μm theoretically. A reaction microscope is combined with an optical parametric amplifier to achieve ionization yields in the near-infrared wavelength regime. Calculations are done using the strong-field S-matrix theory and agreement is found between experiment and theory, showing that ionization of many molecules is suppressed compared to the ionization of atoms with identical ionization potentials at near-infrared wavelengths at around 0.8 μm, but not at longest wavelengths (10 μm). This is due to interference effects in the electron emission that are effective at low photoelectron energies but tend to average out at higher energies. We observe the transition between suppression and nonsuppression of molecular ionization in the near-infrared wavelength regime (1-5 μm).     

Wavelength dependence of light-induced fading and free radical formation in azoreactive dyes

Light-induced stable free radicals (SFRs) were detected in azoreactive dyed cotton fabrics. Extremely slow photofading occurred under exposure to light of relatively long wavelength. The rate of photofading and SFR formation depend on the structure of the dye. Some of them show little drop in the rate of fading with the increasing wavelength, whereas others show nearly negligible changes under incident light of relatively long wavelength. In general a high rate of photofading was found when the SFR concentration was low.     

Wavelength dependence of the hyper Rayleigh scattering response from gold nanoparticles

The wavelength dependence of the quadratic hyperpolarizability of 11 nm diam gold nanoparticles, is reported as measured by hyper Rayleigh scattering. An important photoluminescence background underlying the hyper Rayleigh signal is observed, a contribution attributed to radiative electron-hole recombinations following multiphoton excitation favored by adsorbed organic compound like citrate on the surface of the nanoparticles. The absolute value of the quadratic hyperpolarizability of gold spherical nanoparticles is determined and a strong enhancement is observed for harmonic frequencies in resonance with the dipolar surface plasmon excitation. No contribution of the interband transition is observed. The absolute values reported, beta(C)=5.1x10(-26) esu at the second harmonic energy 2.39 eV, have been measured with femtosecond long laser pulse, and are 1 order of magnitude weaker that the one previously reported with nanosecond long pulses. This difference can be related to similar measurements performed on the second order hyperpolarizability of gold nanoparticles and may be attributed to different electronic relaxation regimes. Finally, the spectrum of the quadratic hyperpolarizability is compared to the theoretically expected one.     

Wavelength dependence of nanoscale photodegradation in poly(3-octylthiophene) thin films

The use of conducting polymers in optoelectronic devices is subject to the understanding of the electro-optical processes that take place at the nanoscale. One of the photo-induced processes that limit their application is the photodegradation, which reduces the device working life. In this work the photodegradation of poly(3-octylthiophene) thin films was studied by combining Kelvin probe microscopy and optical microscopy. In this way, a direct correlation between morphological and contact potential changes with optical density changes as a function of the irradiation wavelength and intensity can be made. These results, complemented with Raman spectra help to clarify the degradation processes that are taking place. We find that the photodegradation strongly depends on the irradiation wavelength blue light being much more aggressive than UV. In addition, the optical properties change abruptly before any substantial change in the morphology is observed.     

Wavelength and metal dependence in the photofragmentation of a gas-phase lanthanide beta-diketonate complex

The time-of-flight mass spectra of tris(2,2,6,6-tetramethyl-3,5-heptanedionato) lanthanide(III) [or Ln(thd)3 with Ln = Eu, Tb, Gd] produced by laser-induced multiphoton ionization in a supersonic expansion were studied as a function of laser excitation wavelength. Resonance-enhanced multiphoton ionization (REMPI), monitoring the Eu(I) ion signal from gas-phase Eu(thd)3, was observed in three distinct visible-excitation regions, corresponding to electronic absorption transitions on neutral Eu(0) atoms. The confirmation of the presence of Eu(0) atoms in the beam supports the proposed mechanism for the production of Ln atoms through sequential dissociation of neutral thd ligands from the metal following photoexcitation into ligand-to-metal charge-transfer (LMCT) states. Evidence is also presented that the LnO+ and LnOH+ fragments observed in the mass spectrum are produced via a separate, competing fragmentation pathway. The branching ratios between the two fragmentation pathways are compared for Ln(thd)3 (Ln = Eu, Tb, Gd). The ligand-dissociation pathway that produces Ln atoms appears to be more favorable in Ln(thd)3 complexes with low-lying LMCT states. Finally, the observation of the Tb2(thd)6+ dimer and its associated fragmentation pattern, as well as the presence of metal carbides, which are relevant to carbon contamination in chemical vapor deposition, is discussed.