Interference, fluctuation, and alternation of electron tunneling in protein media. 2. Non-condon theory for the energy gap dependence of electron transfer rate

Developing the quantum transition rate theory of Prezhdo and Rossky (J. Chem. Phys. 1997, 107, 5863), we produced a new non-Condon theory of the rate of electron transfer (ET) which happens through a protein medium with conformational fluctuation. The new theory is expressed by a convolution form of the power spectrum for the autocorrelation function of the electronic tunneling matrix element T(DA)(t) with quantum correction and the ordinary Franck-Condon factor. The new theory satisfies the detailed balance condition for the forward and backward ET rates. The ET rate formula is divided into two terms of elastic and inelastic tunneling mechanisms on the mathematical basis. The present theory is applied to the ET from Bph(-) to Q(A) in the reaction center of Rhodobacter sphaeroides. Numerical calculations of T(DA)(t) were made by a combined method of molecular dynamics simulations and quantum chemistry calculations. We showed that the normalized autocorrelation function of T(DA)(t) is almost expressed by exponential forms. The calculated energy gap law of the ET rate is nearly Marcus' parabola in most of the normal region and around the maximum region, but it does not decay substantially in the inverted region, which is called the anomalous inverted region. We also showed that the energy gap law at the high uphill energy gap in the normal region is elevated considerably from the Marcus' parabola, which is called the anomalous normal region. Those anomalous energy gap laws are due to the inelastic tunneling mechanism which works actively at the energy gap far from zero. We presented an empirical formula for easily calculating the non-Condon ET rate, which is usable by many researchers. We provided experimental evidence for the anomalous inverted region which was basically reproduced by the present theory. The present theory was extensively compared with the previous non-Condon theories.     

Radiative heat transfer analysis in pure water heater used for semiconductor processing

A simplified one-dimensional model is presented to analyze the non-gray radiative transfer in pure water heater used in the rinsing processes within semiconductor production lines, and the ray-tracing method is extended to simulate the radiative heat transfer. To examine the accuracy of the simplified model, the distribution of radiation absorption is determined by the ray-tracing method based the simplified model and compared with the data obtained by three-dimensional non-gray model in combination with Monte Carlo method in reference, and the effects of the water thickness on the radiation absorption are analyzed. The results show that the simplified model has a good accuracy in solving the radiation absorption in the pure water heater. The radiation absorption increases with the water thickness, but when the water thickness is greater than , the radiation absorption increases very slowly with the water thickness.     

Stabilization of enhanced chirality from pyrene-containing l-glutamide lipid in methyl methacrylate by photo-induced polymerization

Enhanced CD spectra based on chirally-oriented structures of pyrene-containing L-glutamic acid-derived lipid were observed in polymerizable monomers and CD strength was maintained after photo-induced polymerization of the monomer solvents.     

An HPLC assay of hydroxyl radicals by the hydroxylation reaction of terephthalic acid

An HPLC assay for hydroxyl radicals is described. The hydroxyl radical was trapped by terephthalic acid (non-fluorescent), and 2-hydroxyl terephthalic acid (fluorescent) was quantitated by HPLC-fluorescence detection. At a terephthalic acid concentration of 4.25 mmol/L, the hydroxyl radical formed in the Fenton reaction was successfully assayed in the concentration range of hydrogen peroxide of 2.5-50 micro mol/L, where the concentration of Fe(II) was 50 micro mol/L. The fluorescence of 2-hydroxy terephthalate was stable at 24 h, and its detection limit by this method was 5 nmol/L (100 fmol).     

Discovery of temperature-dependent phenomena of muon-catalyzed fusion in solid deuterium and tritium mixtures

A systematic experimental study on muon-catalyzed fusion was conducted using a series of solid deuterium and tritium mixtures. A variety of conditions were investigated, i.e., tritium concentrations from 20% to 70%, and temperatures from 5 to 16 K. With decreasing temperature, we observed an unexpected decrease in the muon cycling rate (lambda(c)) and an increase in the muon loss probability (W). The origins of these observed changes were interpreted by the temperature-dependence in the dt mu formation process for lambda(c) and that in the muon reactivation process after muon-to-alpha sticking for W.     

Long-term effects of UV light on contractility of rat arteries in vivo

Several studies have shown that UV irradiation may be effective for preventing vascular restenosis or vasopasm. However, the long-term effects of UV light on the physiological properties of vessels such as arterial tension have not been elucidated. We therefore studied the long-term effects of UV using rat carotid arteries treated with UV-B light (wavelength = 313 nm, total energy = 14 mJ/mm2). The animals were sacrificed at 1, 7 and 14 days after UV light exposure, and the carotid arteries were studied by light microscopy and the contractile responses of isolated arterial rings were recorded under isometric tension. UV treatment had induced a substantial loss of smooth muscle cells (SMC) along the entire circumference of the media on days 7 and 14, whereas loss of SMC on day 1 was negligible. Contractile responses of arteries that had been exposed to UV light were significantly reduced on days, 1, 7 and 14. The susceptibility of UV-treated arteries to phenylephrine and prostaglandin F2 alpha was significantly decreased on days 1 and 7, but decreased susceptibility was not seen on day 14. Acetylcholine-induced relaxations were not altered by UV treatment. These results suggest that the long-term effect of UV light is an attenuation of smooth muscle contractility without impairment of endothelial function.     

Dissolution behavior of homologously generated surfactant molecular complexes (SMC) in aqueous media: A clue to the elucidation of the phenomenon "solubilization"

The solution behavior of homologously obtained crystalline surfactant molecular complexes (SMCs) that are generated between quaternary ammonium bromide and several additive materials has shed light on the recognition of fundamentals of solubilization. It has been revealed that the SMCs derived from long-alkyl-chain surfactants are sufficiently dissolved in water through the path of micellar dispersion above the cmc's of the complex surfactants, whereas the short-chain homologues cannot dissolve in water but dissociate the complexes, resulting in a heterogeneous phase made up of the liberated additives. The fact agrees perfectly with the familiar aspects of solubilization by surfactant; i.e., the longer the alkyl chain of the surfactant becomes, the more effective it is for solubilization. Based on these results, it has been deduced that the possibility for any pair of surfactant and solubilizate (additive) to realize solubilization simply depends on the relative importance of equilibrium of dissociation or association of the SMC species in aqueous medium.     

The First Observation of the Temperature-Dependent Phenomenon of Muon Catalyzed Fusion in Solid D–T Mixtures

A systematic study on muon catalyzed fusion (μCF) was conducted in solid deuterium and tritium (D–T) mixture. A variety of experimental conditions were investigated, i.e., tritium concentrations from 20 to 70%, temperatures from 5 to 16 K. A preliminary analysis result suggests a steep decrease in the dtμ-molecule formation rate with decreasing temperature, and also an increase in the probability for a muon reactivation after an α-sticking phenomenon. This revised version was published online in August 2006 with corrections to the Cover Date.     

Finiteness of polyhedral decompositions of cusped hyperbolic manifolds obtained by the Epstein-Penner's method

Epstein and Penner give a canonical method of decomposing a cusped hyperbolic manifold into ideal polyhedra. The decomposition depends on arbitrarily specified weights for the cusps. From the construction, it is rather obvious that there appear at most a finite number of decompositions if the given weights are slightly changed. However, since the space of weights is not compact, it is not clear whether the total number of such decompositions is finite. In this paper we prove that the number of polyhedral decompositions of a cusped hyperbolic manifold obtained by the Epstein-Penner's method is finite.