Photodissociation of isomeric dichloroethylenes in the ultraviolet: Effect of the second chlorine atom substitution on the dynamics

We report the Cl-*(P-2(1/2)) production dynamics in the near-UV dissociation of three isomers (cis-, gem-, and trans-) of dichloroethylene using the conventional resonance enhanced multiphoton ionization technique. Substantial amounts of Cl-* are produced in the wavelength range 222-304 nm. The Cl-* quantum yield (phi(*)) i maximum at 304 nm for all the isomers and phi(*)(cis) is markedly higher than phi(*)(gem) and phi(*)(trans) except at 222 nm. Existence of both direct and indirect dissociation pathways at these wavelengths complicates the Cl* production dynamics. The higher value of phi(*)(cis) originates from a large contribution from direct dissociation via the (n, sigma(*)) state.

Thermodynamic and structural studies of cavity formation in proteins suggest that loss of packing interactions rather than the hydrophobic effect dominates the observed energetics

The hydrophobic effect is widely believed to be an important determinant of protein stability. However, it is difficult to obtain unambiguous experimental estimates of the contribution of the hydrophobic driving force to the overall free energy of folding. Thermodynamic and structural studies of large to small substitutions in proteins are the most direct method of measuring this contribution. We have substituted the buried residue Phe8 in RNase S with alanine, methionine, and norleucine, Binding thermodynamics and structures were characterized by titration calorimetry and crystallography, respectively. The crystal structures of the RNase S F8A, F8M, and F8Nle mutants indicate that the protein tolerates the changes without any main chain adjustments, The correlation of structural and thermodynamic parameters associated with large to small substitutions was analyzed for nine mutants of RNase S as well as 32 additional cavity-containing mutants of T4 lysozyme, human lysozyme, and barnase. Such substitutions were typically found to result in negligible changes in Delta C-p and positive values of both Delta Delta H degrees and aas of folding. Enthalpic effects were dominant, and the sign of Delta Delta S is the opposite of that expected from the hydrophobic effect. Values of Delta Delta G degrees and Delta Delta H degrees correlated better with changes in packing parameters such as residue depth or occluded surface than with the change in accessible surface area upon folding. These results suggest that the loss of packing interactions rather than the hydrophobic effect is a dominant contributor to the observed energetics for large to small substitutions. Hence, estimates of the magnitude of the hydrophobic driving force derived from earlier mutational studies are likely to be significantly in excess of the actual value.

Experimental Verification of the Lateral Periodicity of Axially Periodic Incoherent Fields Using the Lau Effect

General' objects, which are specially prepared to possess restricted spatial frequency spectra, have been used in the conventional Lau experiment to obtain experimental proof for the existence of lateral periodicity arising from axial periodicity, for a subclass of axially periodic wavefields in an incoherent situation.

The Waldmeier effect and the flux transport solar dynamo

We confirm that the evidence for the Waldmeier effect WE1 (the anticorrelation between rise times of sunspot cycles and their strengths) and the related effect WE2 (the correlation between rise rates of cycles and their strengths) is found in different kinds of sunspot data. We explore whether these effects can be explained theoretically on the basis of the flux transport dynamo models of sunspot cycles. Two sources of irregularities of sunspot cycles are included in our model: fluctuations in the poloidal field generation process and fluctuations in the meridional circulation. We find WE2 to be a robust result which is produced in different kinds of theoretical models for different sources of irregularities. The Waldmeier effect WE1, on the other hand, arises from fluctuations in the meridional circulation and is found only in the theoretical models with reasonably high turbulent diffusivity which ensures that the diffusion time is not more than a few years.

The 'neighbour effect' and its role in shaping the positional pattern of seed development in fruits: An illustration from the pods of Erythrina suberosa

Plants exhibit certain intra-fruit positional patterns in the development of seeds. These patterns have been generally interpreted to be a consequence of resource and fertilization gradients. However, such positional patterns might also be shaped by the 'neighbour effect', wherein formation and development of a seed at any position might positively or negatively influence those of other seeds in the neighbourhood. In this article, we examine the role of such neighbour effect in shaping the positional pattern of seeds in the pods of Erythrina suberosa. The results suggest the existence of a positive neighbour effect leading to a higher frequency of seeds in contiguous positions.

On the isotope effect in some cuprate superconductors

The combined mechanism involving phonon and lochon (local charged boson) induced pairing of fermions developed earlier for cuprate superconductors is used to study the variation of the oxygen isotope effect (alpha(0)) in these systems. The recently observed results for some cuprates are in agreement with the calculated trend in which (alpha(0)) tends to larger value when the critical temperature (T-c) is reduced by appropriate doping. These results support the combined phononic and electronic (lochonic) mechanism for cuprates with the latter dominating in the higher T-c regions.

Temperature dependence of the levitation effect - Implications for separation of multicomponent mixtures

Sufficiently long molecular dynamics simulations have been carried out on spherical monatomic sorbates in NaY zeolite, interacting via simple Lennard-Jones potentials, to investigate the dependence of the levitation effect on the temperature. Simulations carried out in the range 100-300 K suggest that the anomalous peak in the diffusion coefficient (observed when the levitation parameter, gamma, is near unity) decreases in intensity with increase in temperature. The rate of cage-to-cage migrations also exhibits a similar trend. The activation energy obtained from Arrhenius plots is found to exhibit a minimum when the diffusion coefficient is a maximum, corresponding to the gamma approximate to 1 sorbate diameter. In the linear or normal regime, the activation energy increases with increase in sorbate diameter until it shows a sharp decrease in the anomalous regime. Locations and energies of the adsorption sites and their dependence on the sorbate size gives interesting insight into the nature of the underlying potential-energy surface and further explain the observed trend in the activation energy with sorbate size. Cage residence times, tau(c), show little or no change with temperature for the sorbate with diameter corresponding to gamma approximate to 1, whereas there is a significant decrease in tau(c) with increase in temperature for sorbates in the linear regime. The implications of the present study for the separation of mixtures of sorbates are discussed.

The dynamo effect - a dynamic renormalisation group approach

The dynamo effect is used to describe the generation of magnetic fields in astrophysical objects. However, no rigorous derivation of the dynamo equation is available. We justify the form of the equation using an Operator Product Expansion (OPE) of the relevant fields. We also calculate the coefficients of the OPE series using a dynamic renormalisation group approach and discuss the time evolution of the initial conditions on the initial seed magnetic field.

The bystander effect in optically trapped red blood cells due to Plasmodium falciparum infection

In a previous study of the properties of red blood cells (RBC) trapped in an optical tweezers trap, an increase in the spectrum of Brownian fluctuations for RBCs from a Plasmodium falciparum culture (due to increased rigidity) compared with normal RBCs was measured. A bystander effect was observed, whereby RBCs actually hosting the parasite had an effect on the physical properties of remaining non-hosting RBCs. The distribution of corner frequency (f(c)) in the power spectrum of single RBCs held in an optical tweezers trap was studied. Two tests were done to confirm the bystander effect. In the first, RBCs from an infected culture were separated into hosting and non-hosting RBCs. In the second, all RBCs were removed from the infected culture, and normal RBCs were incubated in the spent medium. The trapping environment was the same for all measurements so only changes in the properties of RBCs were measured. In the first experiment, a similar and statistically significant increase was measured both for hosting and non-hosting RBCs. In the second experiment, normal RBCs incubated in spent medium started to become rigid after a few hours and showed complete changes (comparable with RBCs from the infected culture) after 24 h. These experiments provide direct evidence of medium-induced changes in the properties of RBCs in an infected culture, regardless of whether the RBCs actually host the parasite.

Fluctuations in the alpha-effect and grand solar minima

The parameters of a special type of alpha-effect known in dynamo theory as the Babcock-Leighton mechanism are estimated using the data of sunspot catalogs. The estimates support the presence of the Babcock-Leighton alpha-effect on the Sun. Fluctuations of the alpha-effect are also estimated. The fluctuation amplitude appreciably exceeds themean value, and the characteristic time for the fluctuations is comparable to the period of the solar rotation. Fluctuations with the parameters found are included in a numericalmodel for the solar dynamo. Computations show irregular changes in the amplitudes of the magnetic cycles on time scales of centuries and millennia. The calculated statistical characteristics of the grand solar minima and maxima agree with the data on solar activity over the Holocene.

A pseudobinary approach to study interdiffusion and the Kirkendall effect in multicomponent systems

Interdiffusion studies become increasingly difficult to perform with the increasing number of elements in a system. It is rather easy to calculate the interdiffusion coefficients for all the compositions in the interdiffusion zone in a binary system. The intrinsic diffusion coefficients can be calculated for the composition of Kirkendall marker plane in a binary system. In a ternary system, however, the interdiffusion coefficients can only be calculated for the composition where composition profiles from two different diffusion couples intersect. Intrinsic diffusion coefficients are possible to calculate when the Kirkendall markers are also present at that composition, which is a condition that is generally difficult to satisfy. In a quaternary system, the composition profiles for three different diffusion couples must intersect at one particular composition to calculate the diffusion parameters, which is a condition that is almost impossible to satisfy. To avoid these complications in a multicomponent system, the average interdiffusion coefficients are calculated. I propose a method of calculating the intrinsic diffusion coefficients and the variation in the interdiffusion coefficients for multicomponent systems. This method can be used for a single diffusion couple in a multicomponent pseudobinary system. The compositions of the end members of a diffusion couple should be selected such that only two elements diffuse into the interdiffusion zone. A few hypothetical diffusion couples are considered in order to validate and explain our method. Various sources of error in the calculations are also discussed.