Vibrational frequencies,infrared absorption intensities and energy differences between rotational isomers of propyl halides

Infrared absorption intensities of fundamental bands of propyl halides n-C₃ H₇ Cl, n-C₃H₇ Br and n-C₃H₇I were measured in the pure liquid state. In order to obtain L matrix data necessary for the intensity computation, normal frequencies of the rotational isomers were calculated, and LSFF force constants were determined by the least squares method so as to attain the best fit between the observed and calculated frequencies. By applying the absolute intensity method, energy differences between the rotational isomers were evaluated, which are in quite good agreement with values obtained by the temperature variation method.     

A geometric method in nonlinear programming

A differential geometric approach to the constrained function maximization problem is presented. The continuous analogue of the Newton-Raphson method due to Branin for solving a system of nonlinear equations is extended to the case where the system is under-determined. The method is combined with the continuous analogue of the gradient-projection method to obtain a constrained maximization method with enforced constraint restoration. Detailed analysis of the global behavior of both methods is provided. It is shown that the conjugate-gradient algorithm can take advantage of the sparse structure of the problem in the computation of a vector field, which constitutes the main computational task in the methods.This is part of a paper issued as Stanford University, Computer Science Department Report No. STAN-CS-77-643 (Ref. 45), which was presented at the Gatlinburg VII Conference, Asilomar, California, 1977. This work was supported in part by NSF Grant No. NAT BUR OF ECON RES/PO No. 4369 and by Department of Energy Contract No. EY-76-C-02-0016.The main part of this work was presented at the Japan-France Seminar on Functional Analysis and Numerical Analysis, Tokyo, Japan, 1976. The paper was prepared in part while the author was a visitor at the Department of Mathematics, North Carolina State University, Raleigh, North Carolina, 1976–77, and was completed while he was a visitor at the Computer Science Department, Stanford University, Stanford, California, 1977. He acknowledges the hospitality and stimulating environment provided by Professor G. H. Golub, Stanford University, and Professors N. J. Rose and C. D. Meyer, North Carolina State University.     

Polarization dependence of the optical absorption of single-walled carbon nanotubes

Anisotropic optical absorption properties of single-walled carbon nanotubes (SWNTs) are determined from a vertically aligned SWNT film for 0.5-6 eV. Absorption peaks at 4.5 and 5.25 eV are found to exhibit remarkable polarization dependence and have relevance to optical properties of graphite. A method for determining a nematic order parameter for an aligned SWNT film based on the collinear absorption peak at 4.5 eV is presented, followed by the determination of the optical absorption cross section.     

Long-lived charge-separated state leading to DNA damage through hole transfer

The hole transfer causes the long-lived charge-separated state in DNA during the photosensitized one-electron oxidation of DNA. The combination of the transient absorption measurement and DNA damage quantification by HPLC clearly demonstrated that the yield of the DNA damage correlates well with the lifetime of the charge-separated state.     

Near-infrared emissions with widely different widths in two kinds of Er-doped oxide glasses with high refractive indices and low phonon energies

Er³⁺-doped alkali-barium-bismuth-tellurite (LKBBT) and alkali-barium-bismuth-gallate (LKBBG) glasses with high refractive indices and low phonon energies have been designed, fabricated, characterized and compared. Intense 1.53 μm emissions with widely different widths in the two kinds of glasses were observed and recorded under 980 nm diode laser excitation. The full-widths at half-maximum of the 1.53 μm emission bands in LKBBT and LKBBG glasses are 58 and 40 nm, and the lifetimes of them were measured to be 3.21 and 3.97 ms, respectively. The quantum efficiencies for the ⁴I_13/2 level in both glasses are almost 100%. The 1.53 μm broad and narrow emissions with high spontaneous emission probabilities and large emission cross-sections indicate that Er³⁺-doped LKBBT and LKBBG glasses are suitable materials in developing broadband optical amplifier and infrared laser, respectively.     

Solubilization of C60 by micellization with a thermoresponsive block copolymer in water: Characterization,singlet oxygen generation,and DNA photocleavage

Water‐soluble diblock copolymer, poly(N‐isopropylacrylamide)‐block‐poly(N‐vinyl‐2‐pyrroridone) (PNIPAM_m‐b‐PNVP_n), was found to associate with fullerene (C₆₀), and thus C₆₀ can be solubilized in water. The 63C₆₀/PNIPAM_m‐b‐PNVP_n micelle formed a core‐shell micelle‐like aggregate comprising a C₆₀/PNVP hydrophobic core and a thermoresponsive PNIPAM shell. The C₆₀‐containing polymer micelle formation and its thermoresponsive behavior were characterized using light scattering and ¹H NMR techniques. The hydrodynamic radius (R_h) of the C₆₀‐bound polymer micelle increased with increasing temperature, which was ascribed to the hydrophobic association between dehydrated PNIPAM shells above lower critical solution temperature (LCST). ¹H NMR data suggest that the motion of the PNIPAM block is restricted above LCST due to the dehydration of the PNIPAM shell in water. The generation of singlet oxygen by photosensitization by the C₆₀‐bound polymer micelle was confirmed from photooxidation of 9,10‐anthracenedipropionic acid. Furthermore, DNA was found to be cleaved by visible light irradiation in the presence of the C₆₀‐bound polymer micelle. Therefore, there may be a hope for a pharmaceutical application of the C₆₀‐bound polymer micelle to cancer photodynamic therapy. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011.