The interplay o light and heat in bleaching rhodopsin

Rhodopsin, the pigment of the retinal rods, can be bleached either by light or by high temperature. Earlier work had shown that when white light is used the bleaching rate does not depend on temperature, and so must be independent of the internal energy of the molecule. On the other hand thermal bleaching in the dark has a high temperature dependence from which one can calculate that the reaction has an apparent activation energy of 44 kg. cal. per mole. It has now been shown that the bleaching rate of rhodopsin becomes temperature-dependent in red light, indicating that light and heat cooperate in activating the molecule. Apparently thermal energy is needed for bleaching at long wave lengths where the quanta are not sufficiently energy-rich to bring about bleaching by themselves. The temperature dependence appears at 590 mµ. This is the longest wave length at which bleaching by light proceeds without thermal activation, and corresponds to a quantum energy of 48.5 kg. cal. per mole. This value of the minimum energy to bleach rhodopsin by light alone is in agreement with the activation energy of thermal bleaching in the dark. At wave lengths between 590 and 750 mµ, the longest wave length at which the bleaching rate was fast enough to study, the sum of the quantum energy and of the activation energy calculated from the temperature coefficients remains between 44 and 48.5 kg. cal. This result shows that in red light the energy deficit of the quanta can be made up by a contribution of thermal energy from the internal degrees of freedom of the rhodopsin molecule. The absorption spectrum of rhodopsin, which is not markedly temperature-dependent at shorter wave lengths, also becomes temperature-dependent in red light of wave lengths longer than about 570 to 590 mµ. The temperature dependence of the bleaching rate is at least partly accounted for by the temperature coefficient of absorption. There is some evidence that the temperature coefficient of bleaching is somewhat greater than the temperature coefficient of absorption at wave lengths longer than 590 mmicro;. This means that the thermal energy of the molecule is a more critical factor in bleaching than in absorption. It shows that some of the molecules which absorb energy-deficient quanta of red light are unable to supply the thermal component of the activation energy needed for bleaching, so bringing about a fall in the quantum efficiency. The experiments show that there is a gradual transition between the activation of rhodopsin by light and the activation by internal energy. It is suggested that energy can move freely between the prosthetic group and the protein moiety of the molecule. In this way a part of the large amount of energy in the internal degrees of freedom of rhodopsin could become available to assist in thermal activation. Assuming that the minimum energy required for bleaching is 48.5 kg. cal., an equation familiar in the study of unimolecular reaction has been used to estimate the number of internal degrees of freedom, n, involved in supplying the thermal component of the activation energy when rhodopsin is bleached in red light. It was found that n increases from 2 at 590 mµ to a minimum value of 15 at 750 mµ. One wonders what value n has at 1050 mµ, where vision still persists, and where rhodopsin molecules may supply some 16 kg. cal. of thermal energy per mole in order to make up for the energy deficit of the quanta.     

THE EFFECT OF SOME BEVERAGES ON THE PERCEPTION OF SUCCEEDING BASIC TASTES

The objective of this study was to investigate the effect beverages have on subsequently perceived basic tastes. Two types of milk, Cola and water were used to rinse the mouth prior to conducting a Time Intensity study with basic taste solutions. From this some effects of the prior beverage onto the TI parameters was found. Especially Cola showed an effect on the intensity of the subsequently tasted sweet taste, and whole milk showed a stronger effect than skim milk. The effects showed both in size and timing of the basic taste intensities.     

Characterization of the threshold response of initiation of blood clotting to stimulus patch size

This article demonstrates that the threshold response of initiation of blood clotting to the size of a patch of stimulus is a robust phenomenon under a wide range of conditions and follows a simple scaling relationship based on the Damk?hler number. Human blood and plasma were exposed to surfaces patterned with patches presenting clotting stimuli using microfluidics. Perturbations of the complex network of hemostasis, including temperature, variations in the concentration of stimulus (tissue factor), and the absence or inhibition of individual components of the network (factor IIa, factor V, factor VIII, and thrombomodulin), did not affect the existence of this response. A scaling relationship between the threshold patch size and the timescale of reaction for clotting was supported in numerical simulations, a simple chemical model system, and experiments with human blood plasma. These results may be useful for understanding the spatiotemporal dynamics of other autocatalytic systems and emphasize the relevance of clustering of proteins and lipids in the regulation of signaling processes.     

Behavioural responses of wheat stem sawflies to wheat volatiles

1 Adult wheat stem sawflies Cephus cinctus, pests of cultivated cereals that also infests wild grasses, migrate into wheat fields where they oviposit in elongating, succulent stems.
2 Volatiles released by wheat plants at susceptible stages were analyzed to determine potential semiochemical compounds. Seven major compounds were identified and quantified.
3 A Y-tube bioassay was developed to evaluate upwind orientation of adult sawflies in response to an airstream that passed over elongated wheat plants. The bioassay was also conducted with synthetic volatile compounds. The compounds were tested using a range of concentrations spanning those identified in the airstream passing over wheat plants.
4 A significant number of adult females were attracted to wheat plants when given a choice of either purified air or the air passing over plants.
5 A significant number of female C. cinctus were attracted to ( Z )-3-hexenyl acetate, β-ocimene, and ( Z )-3-hexen-1-ol, but were repelled by 6-methyl-5-hepten-2-one. Females did not respond to ( E )-2-hexenal, or ( E )-2-hexenyl acetate. The behavioural responses were concentration dependent; the highest tested concentration of ( Z )-3-hexenyl acetate was repellent to females of this species.
6 Adult males did not discriminate between air passing over wheat plants and air from a purified airstream. Males did not respond to any tested synthetic compound at any concentration.
7 The present study demonstrates for the first time that adult females of wheat stem sawfly display innate behaviours in response to synthetic volatiles. These results provide a basis for the potential development of resistant wheat varieties and for the development of semiochemically-based pest management.     

Identifying structural features on 1,1-diphenyl-hexahydro-oxazolo[3,4-a]pyrazin-3-ones critical for Neuropeptide S antagonist activity

A series of 7-substituted 1,1-diphenyl-hexahydro-oxazolo[3,4-a]pyrazin-3-ones were synthesized and tested for Neuropeptide S (NPS) antagonist activity. A concise synthetic route was developed, which features a DMAP catalyzed carbamate formation. 4-Fluorobenzyl urea (1c) and benzyl urea (1d) were identified as the most potent antagonists among the compounds examined. Structure-activity relationships (SARs) demonstrate that a 7-position urea functionality is required for potent antagonist activity and alkylation of the urea nitrogen (1e) or replacement with carbon or oxygen (5a) results in reduced potency. In addition, compounds with alpha-methyl substitution (1b) or elongated alkyl chains (1h and 1j) had reduced potency, indicating a limited tolerance for 7-position substituents.