Hole-burning kinetics in biomolecules and polymers

1990 ◽  
Vol 68 (9) ◽  
pp. 1023-1026 ◽  
Author(s):  
Takashi Kushida ◽  
Atusi Kurita ◽  
Yasuo Kanematsu ◽  
Yoshikatsu Touyama
Keyword(s):  
Absorption Spectrum ◽  
Ground State ◽  
Low Temperatures ◽  
Laser Light ◽  
Protein A ◽  
Hole Burning ◽  
Absorption Bands ◽  
Broad Distribution ◽  
Doped Polymer ◽  
Electronic Ground

Various characteristics of the change in the absorption spectrum induced by monochromatic laser-light irradiation were compared for a chromophore in a protein, a dye-doped polymer, and a dye-intercalated DNA. It was found that persistent spectral holes are burned in the absorption spectrum of Zn-substituted myoglobin (ZnMb) and of methylene blue intercalated into DNA as easily as of rhodamine 640 in polyvinyl alcohol when the lowest optical absorption bands are illuminated with laser light at low temperatures. In both ZnMb and dye-doped polymer, the hole depth has been found to grow almost logarithmically with burning time. This is explained well by a dispersive burning-kinetics model. A heat-cycle experiment using ZnMb has revealed that the conformational barrier height in the electronic ground state has a broad distribution. We conclude that the hole-burning characteristics are very similar among the systems examined.

The A2Πi–X2Πi absorption spectrum of BrO

1981 ◽  
Vol 59 (12) ◽  
pp. 1908-1916 ◽  
Author(s):  
M. Barnett ◽  
E. A. Cohen ◽  
D. A. Ramsay
Keyword(s):  
Absorption Spectrum ◽  
Absorption Spectra ◽  
Ground State ◽  
Flash Photolysis ◽  
Absorption Bands ◽  
Long Wavelength ◽  
Numbering Scheme ◽  
Ozonized Oxygen ◽  
Good Agreement

Absorption spectra of isotopically enriched 81Br16O and of normal BrO have been obtained by the flash photolysis of mixtures of bromine and ozonized oxygen. Rotational analyses are given for the 7–0, 12–0, 18–0, 19–0, 20–0, 21–0, 7–1, and 20–1 A2Π3/2–X2Π3/2 sub-bands of 81Br16O. The value for [Formula: see text] is found to be 722.1 ± 1.1 cm−1 in good agreement with the value calculated from microwave constants. Several additional bands have been found at the long wavelength end of the spectrum, necessitating a revision of the vibrational numbering scheme for both the emission and absorption bands. "Hot" bands up to ν″ = 6 have been observed in the absorption spectrum for the 2Π3/2 component of the ground state but no bands have yet been identified from the 2Π1/2 component.

A spectroscopic study of the solvent dependent processes of the anils of benzaldehyde and salicylaldehyde

1982 ◽  
Vol 60 (13) ◽  
pp. 1727-1737 ◽  
Author(s):  
Jerry W. Lewis ◽  
Camille Sandorfy
Keyword(s):  
Hydrogen Bond ◽  
Ground State ◽  
Spectral Characteristics ◽  
Infrared And Raman Spectra ◽  
Absorption Data ◽  
Absorption Bands ◽  
Visible Absorption ◽  
Raman Spectral ◽  
Dependent Processes ◽  
Electronic Ground

The ultraviolet–visible, infrared, and Raman spectral characteristics of some anils of benzaldehyde and salicylaldehyde in several solvents have been investigated. The ultraviolet–visible absorption data indicate that in solvents with a proton donating ability less than or equal to trifluoroethanol a single equilibrium exists in solutions of N-(2-hydroxybenzylidene)aniline, whereas in solvents with a proton donating ability equal to or greater than hexafluoroisopropanol more than one equilibrium occurs. The infrared spectra of this compound dissolved in trifluoroethanol do not show new absorption bands in the 1700–1500 cm−1 region; however, new absorption bands in this region do appear when hexafluoroisopropanol is employed as solvent. From these data it is inferred that the first equilibrium involves the breaking of the chelate hydrogen bond and the second equilibrium involves actual protonation of N-(2-hydroxybenzylidene)aniline in the electronic ground state. A comparison of the infrared and Raman spectra of the title compounds is also made and alternate assignments for several observed bands in the 1700–1500 cm−1 region are proposed.

ABSORPTION SPECTRA OF C3 AND C3H2 FROM THE FLASH PHOTOLYSIS OF DIAZOPROPYNE

1967 ◽  
Vol 45 (12) ◽  
pp. 4103-4111 ◽  
Author(s):  
A. J. Merer
Keyword(s):  
Absorption Spectrum ◽  
Free Radical ◽  
Ground State ◽  
Time Delays ◽  
Flash Photolysis ◽  
State Level ◽  
Vibrational Structure ◽  
Absorption Bands ◽  
Text Component ◽  
Ground State Level

The flash photolysis of diazopropyne (HC2∙CHN2) provides a particularly strong absorption spectrum of the free C3 radical. About 40 μs after the photolysis flash, the appearance of the [Formula: see text] (4 050 Å) system of C3 is similar to that obtained in the flash photolysis of diazomethane by Gausset, Herzberg, Lagerqvist, and Rosen, though much more intense. The intensity of the spectrum has permitted a study of the l-type doubling effect in the ground-state level 6ν2, of which the [Formula: see text] component has been found to lie at 458.2 cm−1. At shorter time delays [Formula: see text] the spectrum is complicated by bands arising from the levels ν1″ (1 224.5 cm−1) and 2ν1″ (2 436.0 cm−1).Below 3 700 Å the C3 spectrum is overlapped by absorption bands belonging to a new free radical, which has been identified from the intensity alternation in the rotational structure as the HCCCH radical. The vibrational structure of this system is exceptionally complex, and analysis has not been possible. The bands extend to about 3 100 Å, but are predissociated below 3 450 Å.

The ultraviolet absorption spectrum of the F 2 CN radical

1967 ◽  
Vol 300 (1462) ◽  
pp. 405-414 ◽  
Keyword(s):  
Molecular Structure ◽  
Absorption Spectrum ◽  
Ground State ◽  
Flash Photolysis ◽  
Ultraviolet Absorption ◽  
Ultraviolet Absorption Spectrum ◽  
Rotational Analysis ◽  
Absorption Bands ◽  
New System

A new system of absorption bands near 3600 Å has been observed during the flash photolysis of CF 3 NCF 2 and is ascribed to the free F 2 CN radical. The rotational analysis of the 0–0 band leads to the ground state molecular structure r CF = 1.310 Å (assumed), r CN = 1.265 ± 0.02 Å, FCF angle = 113.5 + 1°. The bands are shown to be type A bands arising from the transition 2 A 1 ← 2 B 2 , and the spectrum is compared with those of the iso-electronic molecules NO 3 and F 2 BO.

Forbidden absorption bands of O2 in the argon continuum region

1969 ◽  
Vol 47 (17) ◽  
pp. 1805-1811 ◽  
Author(s):  
M. Ogawa ◽  
K. R. Yamawaki
Keyword(s):  
Absorption Spectrum ◽  
Ground State ◽  
Electronic States ◽  
Absorption Bands ◽  
Rotational Constants ◽  
Continuum Region

The absorption spectrum of O2 has been photographed in the argon continuum region with a 3-m vacuum spectrograph at a dispersion of 1.42 Å/mm. Based on the known rotational constants of the ground state, the rotational constants of the upper states have been determined for Tanaka progession (I), β–X3Σg−, progression (II), α1Σu+–X3Σ−, and those of a new band at 1144.6 Å. In a brief discussion of the upper electronic states, it is suggested that both the β state and the upper states of the 1144.6 Å band are 3Σu+ states and their electron configurations are (πg2p)(3pπ) and (πg2p)(4pπ), respectively, and also the α state is (πg2p)(3pπ)1Σu+.

THE ABSORPTION SPECTRUM OF 35Cl2 FROM 4780 TO 6000 Å

1963 ◽  
Vol 41 (7) ◽  
pp. 1174-1192 ◽  
Author(s):  
A. E. Douglas ◽  
Chr. Kn. Møller ◽  
B. P. Stoicheff
Keyword(s):  
Absorption Spectrum ◽  
High Resolution ◽  
Ground State ◽  
Dissociation Limit ◽  
Complex Spectrum ◽  
Absorption Bands ◽  
Isotopic Species ◽  
Concave Grating

The discrete absorption bands of gaseous chlorine which lie between 6000 Å and the dissociation limit, near 4780 Å, have been photographed at high resolution with a 10-meter concave-grating spectrograph. This complex spectrum has been simplified by the use of the separated isotopic species 35Cl2 and by cooling the cell. An analysis of all the strong bands has been achieved. The principal constants of the ground state are Be = 0.24407, α = 0.00153, ωe = 559.71, ωexe = 2.70, [Formula: see text], and re = 1.9878 Å.

Magnetic hyperfine interactions in the electronic spectra of diatomic molecules I. The rotational structure of absorption bands of gaseous BiO

1967 ◽  
Vol 300 (1463) ◽  
pp. 469-486 ◽  
Keyword(s):  
Absorption Spectrum ◽  
Ground State ◽  
Electronic Spectra ◽  
Hyperfine Interactions ◽  
Magnetic Hyperfine ◽  
Doppler Width ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Absorption Bands ◽  
Single Level

The absorption spectrum of gaseous BiO has been photographed at a resolution of about 300000. The ground state X 1 , is the Ω = 1/2 component of a 2 π state in which the spin-orbit coupling must be very large, ~ 1 eV. The doubling in X 1 is large, and for v = 0, ∆ v cd ~ 0.187 ( J + 1/2). Structure of 16 bands has been analysed: the bands arise from transitions from X 1 to four states, A 2 π 1/2 , B ( 4 Ʃ - ) Ω = 1/2, C ( 2 ∆ 3/2 ) Ω = 3/2 and D ( 2 π 1/2 ) Ω = 1/2. They show a number of unusual features, not least of which is the fact that, with the exception of D ─ X 1 , the lines in the regions analysed, 251/2 ≼ J ≼ 90 1/2, have a half-width, ∆ v 1/2 ~ 0.25 cm -1 , apparently independent of J , and far larger than the Doppler width. It is shown that this effect arises from unresolved nuclear magnetic hyperfine doubling of the levels in the ground state. The rotational levels in the single level of state D to be observed are predissociated both at high and at low J , but for intermediate values comparatively sharp lines are observed, by a partial cancellation of the h. f. s. between states D and X 1 . The case b designation of state B is 4 Ʃ - , but the structure of the bands show that the transition is better described as Ω = 1/2 — Ω = 1/2, in which the perpendicular transition moment is somewhat larger than the parallel one.

scholarly journals XIII. The absorption spectra of the vapours of benzene and its homolognes, at different temperatures and pressures, and of solutions of benzene

1908 ◽  
Vol 208 (427-440) ◽  
pp. 475-528 ◽  
Keyword(s):  
Molecular Weight ◽  
Absorption Spectrum ◽  
Emission Spectrum ◽  
Low Temperatures ◽  
Molecular Absorption ◽  
Absorption Bands ◽  
Royal Dublin Society ◽  
Different Temperatures ◽  
Complete Investigation ◽  
Narrow Bands

The absorption spectrum of benzene in a state of vapour and in solution was photographed by W. A. Miller (‘ Phil. Trans.,’ 1862, vol. 152, II., pp. 861-887). It was also photographed by me in 1880 (‘ J. Chem. Soc.,’ 1881, vol. 39, p. 153; 1882, vol. 41 ; 1885, vol. 47, pp. 685-757), with the instrument and by the method described in the ‘ Scientific Proceedings of the Royal Dublin Society ’ in 1881 (vol. iii., p. 93, New Series) and ‘ J. Society of Arts,’ 1885. For these investigations a molecular weight in milligrammes was employed to test the molecular absorption of the hydrocarbon, but the quantity of vapour was too large even at low temperatures, and the temperature, as since ascertained, was in other experiments too high to admit of the numerous absorption bands being observed, although a series of bands had been photographed from very dilute solutions of benzene in alcohol. The continuous rays which accompany the lines in the emission spectrum of the strongly condensed spark of cadmium were found to afford the best source of light in the region of short wavelengths. J. Pauer, in 1897 (‘ Wiedemann’s Annalen,’ vol. 61, p. 363), also used the cadmium spectrum precisely in the same manner for a more complete investigation of benzene and its homologues, but his experiments were not quantitative, although he compared the same substances in the states of vapour, of liquid, and in solution at a temperature of 20° C. He accurately measured 29 different narrow bands characteristic of the spectrum of the vapour of benzene. More recently this work has been repeated by Wilhelm Friederichs (‘ Zeitschrift f. Wissenschaftl. Photographie,’ 1905, vol. 3, p. 154) and by Leonard Grebe ( loc. cit ., 1905, p . 363).

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