Time-resolved fluorescence studies on covalently linked porphyrin�nitroarene complexes. Conformational control of photoinduced electron transfer reactions

Time-resolved fluorescence studies were carried out on a series of free-base and zinc(II) derivatives of meso-tetraphenylporphyrins covalently linked to either 1,3-dinitrobenzene (DNB) or 1,3,5-trinitrobenzene (TNB) acceptor units. These acceptor units were linked at different sites (at the ortho, meta or para positions of one of the phenyl groups of meso-tetraphenylporphyrin) to the donor porphyrins such that the resulting isomeric intramolecular donor-acceptor complexes exhibit different centre-to-centre (ctc) distances and relative orientations. Biexponential fluorescence decay profiles observed for several of these covalently linked complexes were rationalized in terms of the presence of ''closed'' and ''extended'' conformers. Detailed analyses of the fluorescence decay data have provided a comprehensive understanding of the photoinduced electron transfer (PET) reactions occurring in systems containing zinc(II) porphyrin donors. It is observed that although DNB-linked zinc(II) complexes follow the trends predicted for the efficiency of PET with respect to donor-acceptor distance, the TNB-linked zinc(II) porphyrins exhibit a behaviour which is dictated by steric effects. Similarly, although the thermodynamic criteria predict a greater efficiency of charge separation in TNB-linked complexes compared with DNB-linked complexes, the reverse trend observed has been attributed to orientational effects. In the complexes containing free-base porphyrin donors, PET is expected to be less efficient from a thermodynamic viewpoint. In a few of these cases, fluorescence quenching seems to occur by parallel mechanisms other than PET.

A model for heat transfer in a honey bee swarm

A swarm is a temporary structure formed when several thousand honey bees leave their hive and settle on some object such as the branch of a tree. They remain in this position until a suitable site for a new home is located by the scout bees. A continuum model based on heat conduction and heat generation is used to predict temperature profiles in swarms. Since internal convection is neglected, the model is applicable only at low values of the ambient temperature T-a. Guided by the experimental observations of Heinrich (1981a-c, J. Exp. Biol. 91, 25-55; Science 212, 565-566; Sci. Am. 244, 147-160), the analysis is carried out mainly for non-spherical swarms. The effective thermal conductivity is estimated using the data of Heinrich (1981a, J. Exp. Biol. 91, 25-55) for dead bees. For T-a = 5 and 9 degrees C, results based on a modified version of the heat generation function due to Southwick (1991, The Behaviour and Physiology of Bees, PP 28-47. C.A.B. International, London) are in reasonable agreement with measurements. Results obtained with the heat generation function of Myerscough (1993, J. Theor. Biol. 162, 381-393) are qualitatively similar to those obtained with Southwick's function, but the error is more in the former case. The results suggest that the bees near the periphery generate more heat than those near the core, in accord with the conjecture of Heinrich (1981c, Sci. Am. 244, 147-160). On the other hand, for T-a = 5 degrees C, the heat generation function of Omholt and Lonvik (1986, J. Theor. Biol. 120, 447-456) leads to a trivial steady state where the entire swarm is at the ambient temperature. Therefore an acceptable heat generation function must result in a steady state which is both non-trivial and stable with respect to small perturbations. Omholt and Lonvik's function satisfies the first requirement, but not the second. For T-a = 15 degrees C, there is a considerable difference between predicted and measured values, probably due to the neglect of internal convection in the model.

Lectin binding to complex carbohydrate at the interface: a study by resonance energy transfer

The binding affinity of the oligosaccharide moiety of a neutral glycosphingolipid, asialoGM1, towards Ricinus communis agglutinin (RCAI) was determined for the first time by fluorescence resonance energy transfer (RET). The asialoGM1 was incorporated into a phospholipid (DMPC) vesicle doped with dansylated DPPE and then titrated with an increasing amount of the galactose specific RCAI. The efficiency of RET was determined by a saturable increase in the quenching of 'donor' fluorescence, i.e. the 'trp' residue of RCAI, due to the energy transfer from the 'acceptor' dansyl group on the surface of the vesicle. The apparent binding constant was found to be in the range of 10(5)-10(6) M-1 at 27 degrees C.

A transfer matrix approach for evaluation of the response of a multi-layer infinite plate to a two-dimensional pressure excitation

A 6 X 6 transfer matrix is presented to evaluate the response of a multi-layer infinite plate to a given two-dimensional pressure excitation on one of its faces or, alternatively, to evaluate the acoustic pressure distribution excited by the normal velocity components of the radiating surfaces. It is shown that the present transfer matrix is a general case embodying the transfer matrices of normal excitation and one-dimensional pressure excitation due to an oblique incident wave. It is also shown that the present transfer matrix obeys the necessary checks to categorize the physically symmetric multi-layer plate as dynamically symmetric. Expressions are derived to obtain the wave propagation parameters, such as the transmission, absorption and reflection coefficients, in terms of the elements of the transfer matrix presented. Numerical results for transmission loss and reflection coefficients of a two-layer configuration are presented to illustrate the effect of angles of incidence, layer characteristics and ambient media.

Mixed convection heat transfer from the bottom tip of a cylinder spinning about a vertical axis in a saturated porous medium

The present work is a numerical study of heat transfer characteristics from the bottom tip of a cylinder spinning about a vertical axis in an infinitely saturated porous medium. The problem is axisymmetric. The non-dimensionalized governing equations are solved using the SIMPLER algorithm on a staggered grid. The influence of rotational Reynolds numbers and Darcy numbers on the heat transfer for a Grashof number of 104 and Prandtl number of 7.0 is studied. It is found that for very high Darcy numbers, over a wide range of rotational Reynolds numbers, the heat transfer takes place mainly due to conduction. The convective heat transfer takes place for lower Darcy numbers and for higher rotational Reynolds numbers. Moreover, there is a rapid increase in the overall Nusselt number below a certain Darcy number with increase in the rotational Reynolds numbers. The effect of the Darcy number and the rotational Reynolds number on the heat transfer and fluid flow in the porous medium is depicted in the form of streamline and isotherm plots. The variation of the overall Nusselt number with respect to the Darcy number for various rotational Reynolds numbers is plotted. The variation of the local Nusselt number with respect to the radial coordinate at the heated tip of the vertical cylinder is plotted for various Darcy and rotational Reynolds numbers.

Characterization of lysozyme crystals with unusually low solvent content

Studies on the low-humidity (88%) forms of tetragonal and monoclinic lysozyme, resulting from water-mediated transformations, have provided a wealth of information on the variability in protein hydration, its structural consequences and the water structure associated with proteins, in addition to facilitating the delineation of the rigid and the flexible regions in the protein molecule and the invariant features in its hydration shell. Surprisingly, monoclinic lysozyme continues to diffract even when the environmental humidity is drastically reduced, thus permitting the structural study of the enzyme at different levels of hydration. As part of a study in this direction, three very low humidity forms, two of them occuring at a nominal relative humidity of 38% and the other at 5% relative humidity, have been characterized. These have unprecedented low solvent contents of 16.9, 17.6 and 9.4%, respectively, as determined by the Matthews method.

Molecular interpretation of the linear relationship between the entropy and the enthalpy of activation of charge transfer reactions in polar liquids

The well-known linear relationship (T?S# =??H# +?, where 1 >? > 0,? > 0) between the entropy (?S#) and the enthalpy (?H#) of activation for reactions in polar liquids is investigated by using a molecular theory. An explicit derivation of this linear relation from first principles is presented for an outersphere charge transfer reaction. The derivation offers microscopic interpretation for the quantities? and?. It has also been possible to make connection with and justify the arguments of Bell put forward many years ago.

Natural Convection Heat Transfer From an Isothermal Vertical Surface to a Stable Thermally Stratified Fluid

Natural convection from an isothermal vertical surface to a thermally stratified fluid is studied numerically. A wide range of stratification levels is considered. It is shown that at high levels of ambient thermal stratification, a portion at the top of the plate absorbs heat, while a horizontal plume forms around a location where the plate temperature equals the ambient temperature. The plume is shown to be inherently unsteady, and its transient nature is investigated in detail. The effect of the temperature defect in striating the plume is discussed. Average Nusselt number data are presented for Pr = 6.0 and 0.7.

Piperidinium tetrathiotungstate as sulfur transfer reagent: synthesis of cyclic disulfides

Piperidinium tetrathiotungstate has been found to react with a number of 1,n-dihalo compounds to afford the corresponding cyclic disulfides in good yields, under mild reaction conditions. This new methodology has been used as a key step in the synthesis of (+/-)-lipoic acid (35) and asparagusic acid (37).

Synthesis of epoxy-terminated polymers by radical polymerization using alpha-(t-butylperoxymethyl)styrene as chain transfer agent

Epoxy-terminated polystyrene has been synthesized by radical polymerization using alpha-(t-butylperoxymethyl) styrene (TPMS) as the chain transfer agent. The chain transfer constants were found to be 0.66 and 0.80 at 60 and 70 degrees C, respectively. The presence of epoxy end groups was confirmed by functional group modification of epoxide to aldehyde by treatment with BF3.Et(2)O. Thermal stability of TPMS was followed by differential scanning calorimetry and iodimetry. Thermal decomposition of TPMS in toluene follows first order kinetics with an activation energy of 23 kcal/mol. (C) 1996 John Wiley & Sons, Inc.

Role of Water in the Enzymatic Catalysis: Study of ATP plus AMP -> 2ADP Conversion by Adenylate Kinase

The catalytic conversion ATP + AMP -> 2ADP by the enzyme adenylate kinase (ADK) involves the binding of one ATP. molecule to the LID domain and one AMP molecule to the NMP domain. The latter is followed by a. phosphate transfer and then the release of two ADP molecules. We have computed a novel two-dimensional configurational free energy surface (2DCFES), with one reaction coordinate each for the LID and the NMP domain motions, while considering explicit water interactions. Our computed 2DCFES clearly reveals the existence of a stable half-open half-closed (HOHC) intermediate stale of the enzyme. Cycling of the enzyme through the HOHC state reduces the conformational free energy barrier for. the reaction by about 20 kJ/mol. We find that the stability of the HOHC state (missed in all earlier studies with implicit solvent model) is largely because of the increase of specific interactions of the polar amino acid side chains with water, particularly with the arginine and the histidine residues. Free energy surface of the LID domain is rather rugged, which can conveniently slow down LID's conformational motion, thus facilitating a new substrate capture after the product release in the catalytic cycle.

Effect of wall emissivities on radiation heat transfer in glass tank forehearths

In an earlier work, we had proposed a two-band, non-grey radiative transfer model for heat transfer in forehearths with simultaneous optically thick and thin approximations for molten glass interiors and at boundaries. Here using the same model, the radiative interaction of the top-crown and bottom-refractory walls with interior layers of shallow molten glass is studied by varying the wall emissivities. The forehearth exit temperature profiles for higher wall emissivities (0.9) show better conditioning of the glass for white flint glasses (optically thin).

The effect of surface mass transfer on buoyancy induced flow in a variable porosity medium adjacent to a vertical heated plate

The effect of surface mass transfer on buoyancy induced flow in a variable porosity medium adjacent to a heated vertical plate is studied for high Rayleigh numbers. Similarity solutions are obtained within the frame work of boundary layer theory for a power law variation in surface temperature,T Wpropx lambda and surface injectionv Wpropx(lambda–1/2). The analysis incorporates the expression connecting porosity and permeability and also the expression connecting porosity and effective thermal diffusivity. The influence of thermal dispersion on the flow and heat transfer characteristics are also analysed in detail. The results of the present analysis document the fact that variable porosity enhances heat transfer rate and the magnitude of velocity near the wall. The governing equations are solved using an implicit finite difference scheme for both the Darcy flow model and Forchheimer flow model, the latter analysis being confined to an isothermal surface and an impermeable vertical plate. The influence of the intertial terms in the Forchheimer model is to decrease the heat transfer and flow rates and the influence of thermal dispersion is to increase the heat transfer rate.

Theory of electron transfer processes via chemisorbed intermediates: Part II. Current-potential characteristics

Current-potential characteristics are obtained numerically for a lone-adsorbate-mediated anodic charge transfer at the electrode-solution interface. An increase in the overpotential leads to the appearance of maxima in the anodic current-potential plots instead of the extended activationless region (i.e. a saturation current at large positive overpotentials) predicted by the direct heterogeneous outer-sphere anodic charge transfer process. A detailed analysis of the dependence of current-potential profiles and other kinetic parameters on various system parameters is also presented.