RESUMO
Measurements have been made of the modulated light-induced changes in conductivity and the associated relaxation times of bacteriorhodopsin in a variety of strong electrolytes, both unbuffered and buffered. The effects of pH and temperature variation have been studied as well as the effect of adding valinomycin. Two relaxation times can be distinguished: a fast lifetime associated with protonation-deprotonation, and a slow lifetime associated with ion binding. The ion-binding effects appear to be cation specific.
Assuntos
Bacteriorodopsinas/efeitos da radiação , Condutividade Elétrica , Halobacterium/efeitos da radiação , Concentração de Íons de Hidrogênio , Cinética , Luz , Valinomicina/farmacologiaRESUMO
A strong band at 412 nm has been observed in the photoacoustic spectrum of partially dried purple membrane, peaking sharply at a modulation frequency of about 70 Hz. This may be explained in terms of a disorder-order transition.
RESUMO
In an attempt to understand the chemistry of the light-induced staining of children's teeth by tetracycline, we studied the photo-chemical behavior of tetracycline adsorbed on hydroxyapatite, as a simple model of enamel. Tetracycline was strongly bound by hydroxyapatite to give a pale yellow material which, under ultraviolet light, showed a bright yellow fluorescence (lambda max 525 nm). On exposure of this material to the radiation from a medium-pressure mercury lamp, the fluorescence gradually disappeared, and a red-purple product was formed. Photo-acoustic spectroscopy was employed to follow the disappearance of tetracycline and the concomitant formation of the red-purple product, the spectrum of which (lambda max 530 nm) led to the conclusion that it was 4 alpha, 12 alpha-anhydro-4-oxo-4-dedimethylaminotetracycline (AODTC). This assignment was supported by the observation that 1 mole of oxygen was absorbed per mole of adsorbed tetracycline converted to the red-purple product. It is suggested that the formation of AODTC on hydroxyapatite probably takes place by a mechanism of photo-oxidation similar to that already proposed for solutions of tetracycline, and that the formation of AODTC in children's teeth is responsible for the light-induced staining caused by tetracycline.
Assuntos
Cor , Hidroxiapatitas , Luz/efeitos adversos , Tetraciclina/efeitos adversos , Descoloração de Dente/induzido quimicamente , Criança , Durapatita , Humanos , Modelos Químicos , Oxirredução , Fotoquímica , Tetraciclina/efeitos da radiaçãoRESUMO
Small light-induced changes in the conductivity of light-adapted purple membrane suspended in strong electrolyte solutions were detected. The method used involved modulated light and a phase sensitive detector and it allowed us to detect accurately changes as small as 0.0001% in the conductivity of the suspension. The light-induced conductivity changes turned out to be composed of at least two different event: a small fast increase in conductivity (tau approximately 2 ms) followed by a slower and larger decrease in this parameter (tau = 70 ms-80 ms). The effects of pH and temperature on these changes were studied. Both events reached maximal values around neutral pH and approached zero at both high and low pH's. Heating the suspension decreased the photoconductivity change and Arrhenius plots of the data showed breaks around 31 degrees C. It is suggested that the conductivity changes reflect changes in the surface charge of the membrane and can be used to follow the kinetics of the conformational changes occurring in the system.
Assuntos
Bacteriorodopsinas , Carotenoides , Condutividade Elétrica , Halobacterium , Concentração de Íons de Hidrogênio , Luz , Temperatura , TermodinâmicaRESUMO
The visible chromophore of bacteriorhodopsin, BR(570), undergoes progressive bleaching when subjected to 60CO gamma-irradiation. The low G-value for bleaching confirms that the site of the chromophore is highly protected. Positive and negative circular dichroic (CD) bands associated with the chromosphone undergo concomitant decrease in a manner which is consistent with two independent chromophores rather than exciton coupling between neighbouring chromophoric site.
Assuntos
Bacteriorodopsinas/efeitos da radiação , Carotenoides/efeitos da radiação , Halobacterium/efeitos da radiação , Dicroísmo Circular , Radioisótopos de Cobalto , Raios gama , Método de Monte CarloRESUMO
E.s.r. spectra have been obtained of gamma-irradiated dry purine and pyrimidine powders. Relative radical yields have been calculated and dose-response curves obtained. Relative recombination rates and recombination rates and formation rates of the radicals have been derived from the dose-response curves. The effect of crystalline structure on the dose-response curves is discussed.
Assuntos
Raios gama , Purinas/efeitos da radiação , Pirimidinas/efeitos da radiação , Radiação Ionizante , Relação Dose-Resposta à Radiação , Espectroscopia de Ressonância de Spin Eletrônica , Radicais LivresRESUMO
The effect of adding triazolopyrazines to a p-benzoquinone-proline system and a p-benzoquinone-histamine system was studied by observing the kinetics of the spectral changes and analyzing the results using digital simulation methods. Below 35 degrees, the major effect was that the triazolopyrazine competed with the electron donors for the acceptors to form complexes. Above 35 degrees, there was predominantly a chemical interaction between the triazolopyrazine and the acceptors. A separate experiment showed that the triazolopyrazine interacted with p-benzoquinone to form a complex initially but that a chemical interaction took place later.
Assuntos
Pirazinas , Quinonas/análise , Triazóis , Quelantes , Fenômenos Químicos , Química , Histamina , Cinética , Prolina , Espectrofotometria , Termodinâmica , Fatores de TempoRESUMO
Aqueous suspensions of bacteriorhodopsin in purple membrane fragments from Halobacterium halobium have bben subjected to microsecond flash photometry utilizing both unpolarized and polarized light. Depletion of the ground state chromophore centered at 570 nm is accompanied by the formation of transients absorbing maximally at 410 nm and 660 nm with rise times of about 0.4 and 6 ms, respectively. Decay of both transients and reformation of the ground state chromophore occurs with identical first-order kinetics with a half life of about 6 ms. All three chromophores are polarized with dichroic ratios which remain constant throughout the transient lifetimes, indicating that Brownian rotation of the chromophore within the membrane is considerably restricted. Whereas agents which induce permeability of membranes to protons (2,4-dinitrophenol, carbonylcyanide-m-chlorophenylhydrazone) and non-specific univalent cations (gramicidin) or inhibit ATPase (ouabain) had no influence, the K+-specific ionophore valinomycin in the presence of K+ inhibited and quenched the formation of the 660 nm transient with concomitant increase in lifetime of the 410 nm transient and delay in recovery of the 570 nm chromophore. High concentrations of Na+ produced an effect similar to that of valinomycin. The relationship of these data to the mechanism of the proton pump in the intact bacterium is discussed, with the conclusion that the 410 nm transient performs a key role.
Assuntos
Bacteriorodopsinas/metabolismo , Carotenoides/metabolismo , Halobacterium/metabolismo , Membrana Celular/efeitos dos fármacos , Membrana Celular/metabolismo , Halobacterium/efeitos dos fármacos , Cinética , Fotólise , Espectrofotometria , Temperatura , Fatores de Tempo , Valinomicina/farmacologiaRESUMO
Comparative ultraviolet (UV) spectral measurements of direct and scattered sunlight, between 300 and 400 nm, reaching the Dead Sea and Beersheba were made. It was found that the sunlight reaching Beersheba is at least twice as high in UV content as that reaching the Dead Sea. The UV content of the sunlight reaching the Dead Sea in the erythemal band (290 to 330 nm) is particularly low. The implications for heliotherapy are discussed.