Dynamics of chain molecules. Intramolecular diffusion controlled reactions for a pair of terminal reactive groups

The first order intramolecular rate constant for the reaction between the terminal groups of flexible macromolecules is calculated in the partial draining case, following the theory formulated by Wilemski and Fixman for diffusion controlled reactions. Substantial differences with respect to the nondraining and free-draining limits are evidenced, and it is shown that the rate constant in the partial-draining case has relevant contributions from all the modes of the bead-spring chain. The effects of chain flexibility and hydrodynamic interaction in macromolecules of increasing molecular weight are examined. The effective diffusion constant of the end groups increases with both the flexibility and the length of the chain. Numerical results for polystyrene (PS) and polydimethylsiloxane (PDMS) are presented and employed to calculate the relative quantum yield for fluorescence quenching. For highly flexible chains, like PDMS, quenching effects are expected in a range of molecular weight well above the limit of validity of the bead-spring model. On the contrary, for more rigid polymers, like PS, the quenching can be observed only at molecular weights lower than this limit. The calculated behavior is compared with some experimental results recently obtained by the authors.     

APPLICATIONS OF ELECTRONIC ENERGY TRANSFER IN SOLUTION*,†

Abstract— lntermolecular transfer of electronic energy is a powerful tool for obtaining information about excited molecules in solution. Proper application of excitation transfer requires giving careful attention to the spectroscopic properties of the donor and acceptor and accounting for all possible donor-acceptor interactions of consequence. Water presents no particular difficulties so that electronic energy transfer methods can be applied to the photochemistry of biologically important molecules in aqueous solvents.     

Time-reversal invariance and thermodynamics of electromagnetic fields in materials with memory

Summary In this work we consider thermal and electric conduction in rigid materials with memory. The implications due to the invariance of the entropy production under time-reversal are examined in detail. Some interesting conditions on the relaxation functions of the heat flux, the electric current and the internal energy density are discussed.

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Sunto In questo lavoro gli Autori studiano la conduzione termica ed elettrica in un materiale rigido con memoria. Vengono esaminate in dettaglio le conseguenze, dovute alla invarianza della produzione entropica per inversione temporale, sulle funzioni di rilassamento per il flusso di calore, la densità di corrente elettrica e la densità di energia interna.

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This work was supported by the ? Gruppo Nazionale per la Fisica Matematica ? of C.N.R.

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Entrata in Redazione il I^o ottobre 1973.     

PHOTOOXIDATIVE AND SPECTRAL STUDIES ON CYTOCHROME c. CONFORMATIONAL CHANGES INDUCED BY BINDING OF CARDIOLIPIN

Abstract— Binding of cardiolipin to ferrocytochrome c , to form a 4:1 molar complex, results in an approximately sixfold increase of the tryptophan fluorescence emission. Furthermore, appreciable perturbations of the circular dichroism spectrum occur in the Soret and in the far-ultraviolet regions. The irradiation of the ferrocytochrome–cardiolipin complex at pH 8·8 with visible light leads to the photooxidative modification of histidine-18, tyrosine-48 and methionine-80. Comparison of the above findings with those concerning unbound ferrocytochrome c suggests that the interaction between cardiolipin and ferrocytochrome c provokes a perturbation of the protein conformation, which possibly involves the disruption of the hydrogen bonds linking the aromatic rings of tryptophan-59 and tyrosine-48 with one propionic side chain of the heme.     

Eigenstate localization in an asymmetric coupled quantum well pair

Optical pumping of a type-I/type-II coupled asymmetric quantum well pair induces a spatially separated two dimensional charge carriers plasma in the well’s wide and narrow parts. Treating the two coupled wells as a single system we find that the eigenstate probability distribution localizes exclusively either in the wide or the narrow parts of the well pair. The energy of the narrow-well localized state determines the minimal excitation energy for optically pumped charge carriers separation. In a previously used design [Guliamov et al., PRB 64 035314 (2001)] this narrow well transition energy was measured to correspond to a wavelength of 646 nm. We propose modifications to the design suggested earlier with the purpose of pushing up the energy required for the optical pumping of the two-dimensional plasma into the green and blue regions of the visible spectrum.     

Propositional interval neighborhood logics: Expressiveness, decidability, and undecidable extensions

In this paper, we investigate the expressiveness of the variety of propositional interval neighborhood logics (PNL), we establish their decidability on linearly ordered domains and some important subclasses, and we prove the undecidability of a number of extensions of PNL with additional modalities over interval relations. All together, we show that PNL form a quite expressive and nearly maximal decidable fragment of Halpern–Shoham’s interval logic HS.     

Oxidative damage to DNA: counterion-assisted addition of water to ionized DNA

Oxidative damage to DNA, implicated in mutagenesis, aging, and cancer, follows electron loss that generates a radical cation that migrates to a guanine, where it may react with water to form 8-oxo-7,8-dihydroguanine (8-OxoG). Molecular dynamics and ab initio quantum simulations on a B-DNA tetradecamer reveal activated reaction pathways that depend on the local counterion arrangement. The lowest activation barrier, 0.73 eV, is found for a reaction that starts from a configuration where a Na(+) resides in the major groove near the N7 atoms of adjacent guanines, and evolves through a transition state where a bond between a water oxygen atom and a carbon atom forms concurrently with displacement of a proton toward a neighboring water molecule. Subsequently, a bonded complex of a hydronium ion and the nearest backbone phosphate group forms. This counterion-assisted proton shuttle mechanism is supported by experiments exploiting selective substitution of backbone phosphates by methylphosphonates.     

A Re(CO)5 fragment bonded to a polyhedral oligomeric hydroxysilsesquioxane as a model which gives further evidence to the existence of an unexpected Re(CO)5 surface species

Reaction of Re(CO)5O3SCF3 with (c-C6H11)7Si8O12O-Li+ at 273 K under a CO atmosphere affords the [Re(CO)5OR] (R = (c-C6H11)7Si8O12) derivative (1). 1 is the first example of a rhenium pentacarbonyl bearing an OR ligand (R = alkyl, aryl, or silyl) stable enough to be characterized, and it represents also the first molecular model of the surface [Re(CO)5OSi] species formed by reductive carbonylation of silica-supported [Re(CO)3OH]4. At room temperature, 1 loses one carbonyl ligand and dimerizes to afford {Re(CO)4[(mu-O)O12Si8(c-C6H11)7]}2 (2), which has been characterized by X-ray diffraction and is the first reported example of a rhenium tetracarbonyl mu-oxo-bridged dimer of the type [Re(CO)4(mu-OR)]2.