CHARGE TRANSFER ACROSS PIGMENTED BILAYER LIPID MEMBRANE AND ITS INTERFACES

Abstract— The technique of forming bilayer lipid membranes (BLM) has made it possible to study photoreactions of pigments in an environment that is much closer to those in photosynthetic and visual membranes. A pigmented BLM system with Mg²⁺-porphyrins as membrane-bound pigments and with ferricyanide and ferrocyanide as the aqueous electron acceptor and donor, respectively, was used to illustrate the photoelectric effects due to coupled interfacial charge transfer reactions.
The steady-state continuous photoresponse was studied by means of the voltage clamp method and a null current method. The independence of the pigment conductance channel and the ionic conductance channel was demonstrated. A tunable voltage clamp method was used to study the transient pulsed photoresponses. Such a measurement permits us to characterize the photosystem in terms of an equivalent circuit model which contains a novel chemical capacitance. Molecular interpretation of this equivalent circuit model was given.
A microscopic model based on the Gouy–Chapman theory and chemical kinetics calculation leads to an equivalent circuit which is also equivalent to the previous one. Generalization of this microscopic model further leads to a physical mechanism of the generation of the early receptor potential (ERP) in visual membranes. Relevance of pigmented BLM research to photosynthesis and other disciplines was also discussed.     

Mass-spectrometric studies on alkylated 6-thiopurines

6-Thiopurine and its N- or C-alkyl derivatives all form an [M – 1]-ion upon fragmentation. In the 7-alkyl derivatives, this ion represents the major component of the spectrum. This is ascribed to formation of a five-membered thiazoline-like ring. Similar ring formation stabilises the [M – 1]-ion in the 7-methyl derivatives of hypoxanthine, adenine and 6-selenopurine.     

Palladium salicylaldimine complexes containing boronate esters

Reactions of salicylaldehydes with boronate ester derivatives of aniline have been examined. Addition of these Schiff base ligands to palladium acetate or Na₂PdCl₄ afforded novel boron-containing trans-bis(N-arylsalicylaldiminato) palladium complexes.Condensation of salicylaldehyde (2-HOC₆H₄C(O)H) with H₂NC₆H₄Bpin (pin=1,2-O₂C₂Me₄) afforded the boron-containing Schiff bases, 2-HOC₆H₄C(H)=NC₆H₄Bpin (1–3a). Similar reactivity with 2-hydroxy-5-nitrobenzaldehyde and 2-hydroxy-1-naphthaldehyde gave the corresponding Schiff bases (1-3b) and (1-3c), respectively. Reaction of Schiff bases (2) and (3) with palladium acetate or Na₂PdCl₄ afforded complexes of the type PdL₂ (4,5), where L=deprotonated Schiff base. The molecular structure of the nitro-salicylaldehyde 4-Bpin palladium complex (5b) was characterized by an X-ray diffraction study. All new palladium compounds have been characterized fully and tested for their antifungal activity against Aspergillus niger and Aspergillus flavus.     

Characterization of a β-glucanase produced by Rhizopus microsporus var. microsporus, and its potential for application in the brewing industry

Background  

In the barley malting process, partial hydrolysis of β-glucans begins with seed germination. However, the endogenous 1,3-1,4-β-glucanases are heat inactivated, and the remaining high molecular weight β-glucans may cause severe problems such as increased brewer mash viscosity and turbidity. Increased viscosity impairs pumping and filtration, resulting in lower efficiency, reduced yields of extracts, and lower filtration rates, as well as the appearance of gelatinous precipitates in the finished beer. Therefore, the use of exogenous β-glucanases to reduce the β-glucans already present in the malt barley is highly desirable.     

Folding Free Energy Determination of an RNA Three-Way Junction Using Fluctuation Theorems

Nonequilibrium work relations and fluctuation theorems permit us to extract equilibrium information from nonequilibrium measurements. They find application in single-molecule pulling experiments where molecular free energies can be determined from irreversible work measurements by using unidirectional (e.g., Jarzynski’s equality) and bidirectional (e.g., Crooks fluctuation theorem and Bennet’s acceptance ratio (BAR)) methods. However, irreversibility and the finite number of pulls limit their applicability: the higher the dissipation, the larger the number of pulls necessary to estimate ΔG within a few kBT. Here, we revisit pulling experiments on an RNA three-way junction (3WJ) that exhibits significant dissipation and work-distribution long tails upon mechanical unfolding. While bidirectional methods are more predictive, unidirectional methods are strongly biased. We also consider a cyclic protocol that combines the forward and reverse work values to increase the statistics of the measurements. For a fixed total experimental time, faster pulling rates permit us to efficiently sample rare events and reduce the bias, compensating for the increased dissipation. This analysis provides a more stringent test of the fluctuation theorem in the large irreversibility regime.     

A Volatility Estimator of Stock Market Indices Based on the Intrinsic Entropy Model

Grasping the historical volatility of stock market indices and accurately estimating are two of the major focuses of those involved in the financial securities industry and derivative instruments pricing. This paper presents the results of employing the intrinsic entropy model as a substitute for estimating the volatility of stock market indices. Diverging from the widely used volatility models that take into account only the elements related to the traded prices, namely the open, high, low, and close prices of a trading day (OHLC), the intrinsic entropy model takes into account the traded volumes during the considered time frame as well. We adjust the intraday intrinsic entropy model that we introduced earlier for exchange-traded securities in order to connect daily OHLC prices with the ratio of the corresponding daily volume to the overall volume traded in the considered period. The intrinsic entropy model conceptualizes this ratio as entropic probability or market credence assigned to the corresponding price level. The intrinsic entropy is computed using historical daily data for traded market indices (S&P 500, Dow 30, NYSE Composite, NASDAQ Composite, Nikkei 225, and Hang Seng Index). We compare the results produced by the intrinsic entropy model with the volatility estimates obtained for the same data sets using widely employed industry volatility estimators. The intrinsic entropy model proves to consistently deliver reliable estimates for various time frames while showing peculiarly high values for the coefficient of variation, with the estimates falling in a significantly lower interval range compared with those provided by the other advanced volatility estimators.     

Spectral theory and L∞-time decay estimates for Klein–Gordon equations on two half axes with transmission: The tunnel effect

Consider two copies N₁, N₂ of the interval [0, ∞]. Consider Klein-Gordon equations with (different) constant coefficients on ? × N_j ( = time × space). Assume the coincidence of the values of the solution at the boundary points of the N_j for all times and a transmission condition relating its first (one-sided) space derivatives at these points. Under a symmetry condition, we extend the spatial part of the equation and the transmission conditions to a self-adjoint operator (by Friedrichs extension) and reformulate our problem in terms of an abstract wave equation in a suitable Hilbert space. We derive an expansion of the solution in generalized eigenfunctions of this self-adjoint extension and show, that the L^∞-norms (in space) of the solution and its first k space derivatives at the time t decay for t → ∞ at least as const. t^¼, if the initial conditions satisfy a compatibility condition of order k derived in this paper. The loss of decay rate in comparison with the full line case (const. t^?½, cf. [28]) is caused by the tunnel effect. Further we show that an abstract wave equation in a Hilbert space with a Friedrichs extension as spatial part can always be derived from a stationarity principle for an associated action-type functional. This yields a physical legitimation of our model by the principle of stationary action and moreover a criterion for the physical interpretability of all models created by the linear interaction concept [4, 6, 8, 10], in particular for the coupling of media of different dimension (alternative to [13, 16] for similar models).     

Identified particle production in p+p, d+Au and Au+Au collisions at RHIC

Measurements of identified particle production with the PHENIX experiment at RHIC have reached a mature state, where a multitude of nuclear systems at different colliding energies have been studied. The discovery configurations of $\sqrt {s_{NN} } = 130$ and 200 GeV Au+Au collisions have now been supplemented by additional Au+Au and Cu+Cu configurations at various energies, along with baseline p+p and d+Au runs at $\sqrt {s_{NN} } = 130$ GeV. In this work we present a systematic study of the Cronin effect in d+Au collisions and recent results from p+p collisions. We then proceed to make a critical comparison of pion, kaon and proton production in heavy ion and baseline systems, and discuss the observed nuclear effects on hadron production.