Stability of benzoporphyrin photosensitizers in water/ethanol mixtures: pKa determination and self‐aggregation processes

Benzoporphyrin monoacid derivatives, here named B3A and B3B, are promising new drugs for photodynamic therapy. Although both isomers show interesting characteristics as photosensitizing compounds, they have some distinct physicochemical properties such as the tendency to self‐aggregate in water‐rich media. Because pH drives the presence of each species, the pK_a of these compounds assumes strategic importance. However, traditional micro‐titration methods and UV–Vis absorption techniques fail to give reliable pK_a values due to the characteristics of this highly complex system, such as the precipitation of hydrophobic species, close pK_a values, and high absorption band superposition. In the present work, chemometric tools are employed to evaluate pK_a, and the kinetic tendency of monomers to undergo self‐aggregation is investigated. In solvent mixtures at low water percentage in ethanol, both B3A and B3B are stabilized in a monomeric state. However, in mixtures with a high water content, self‐aggregation takes place, mainly under a mild pH acid condition (3 < pH < 6), in which the prevalent protolytic species of both isomers is the neutral charged form, compounds with carboxylic and porphyrin free‐base groups. It is demonstrated that both isomers can undergo aggregation following a self‐catalytic mechanism, which is 2000 times slower to B3A than B3B. For B3A, the aggregation is manifested by a decrease in the monomer band with the aggregation band probably superposed to that of the monomer. For B3B, together with the decrease in the monomer band, a new band related to self‐aggregates is observed. Copyright © 2010 John Wiley & Sons, Ltd.     

Electric field gradient in Mg and Zn detected by β-emitters,8Li and12x0392;x0392;x0392;

The quadrupole coupling constants of⁸Li and¹²B in hcp Mg and Zn are determined by use of a newly developed nuclear quadrupole resonance technique (NNQR) as ¦eqQ(⁸Li in Mg)/h¦=3.0±0.3 kHz, ¦eqQ(⁸Li in Zn)/h¦=33.5±2 kHz, and ¦eqQ(¹²B in Mg)/h¦=47.0±0.1 kHz. Correspondingly, the electric field gradients at room temperature are deduced: ¦q(⁸Li in Mg)¦=(3.81±0.39)×10¹⁸, ¦q(⁸Li in Zn)¦=(4.25±0.27)×10¹⁹, and ¦q(¹²B in Mg)¦=(1.47±0.03)×10²⁰, all in V/m². The experiments are compared with the results of first-principles super-cell band structure calculations which can treat local lattice relaxations around the impurity nuclei. The calculations show that the most favorable location of these light interstitials in hcp Mg is not the octahedral-like sites which have the biggest interstitial volume, but the basal trigonal sites with a local lattice expansion of as big as 30%. Calculated electric field gradients at the impurity nuclei reproduce the experimental values fairly well.     

The role of mammalian autophagy in protein metabolism

Autophagy is in principle a non-selective degradation system within cells, which is conserved in all eukaryotic cells. Autophagy is usually suppressed at low levels but can be upregulated during periods of nutrient starvation, which facilitates cell survival. In addition to this fundamental role, basal autophagy was recently revealed to be important for constitutive turnover of intracellular proteins and organelles. Autophagy has been considered to be involved also in presentation of endogenous antigens, degradation of invasive bacteria, tumor suppression, cell death and development. This review will discuss the biological significance of autophagy, particularly focusing on its implications in protein metabolism in mammals.     

Quantum-Statistics Behavior of the Exciton-Biexciton System In GaAs/AlAs Type-II Superlattices

We have investigated the quantum-statistics behavior of the exciton-biexciton system from the photoluminescence properties in (GaAs) m /(AlAs) m type-II superlattices with m = 12 and 13 monolayers, where the lowest-energy type-II exciton consists of the n = 1 X electron of AlAs and n = 1 o heavy hole of GaAs. The long exciton lifetime of the order of w s due to the indirect transition nature enables us to obtain precisely the density relation between the exciton and biexciton from the line-shape analysis of time-resolved photoluminescence spectra. In a relatively low exciton-density region, the biexciton density obeys a well-known square law. At an exciton density around 1 2 10 10 cm m 2 , the biexciton density suddenly increases with a threshold-like nature. This behavior, which is realized at a bath temperature up to 8 K under an excitation power of the order of 100 mW/cm 2 , results from the characteristics of Bose-Einstein statistics of the exciton-biexciton system.     

High-Efficiency ZnCdSe/ZnSSe/ZnMgSSe Green Light-Emitting Diodes

Green light-emitting diodes (LEDs) were fabricated employing a ZnCdSe/ZnSSe triple quantum-well (TQW) active region surrounded by ZnMgSSe cladding layers grown on an n-type (100) GaAs substrate by molecular beam epitaxy (MBE). A 3.5 mW pure green emission was observed for the surface-emitting LED device at a peak wavelength of 513.3 nm (2.415 eV) with a spectral half-width of 11.7 nm (55 meV) under a 20 mA (4.6 V) direct current at room temperature (25°C). These correspond to an external quantum efficiency of 7.2%, a power conversion efficiency of 3.8%, a luminous current efficiency of 66 lm/A, and a luminous efficiency of 14 lm/W.     

Effect of 90 deg ferroelastic twin walls on lattice dynamics of nanocrystalline tetragonal ferroelectric perovskites

A combined transmission electron microscopy (TEM) and Raman spectroscopy study has been performed on nanocrystalline Ba_0.9Sr_0.1TiO₃ (BST) crystals and tubes. TEM investigations revealed the existence of 90 deg ferroelastic twins in the materials. Raman spectra showed an obvious shoulder (∼750 cm^-1) from the broad band at ∼720 cm^-1 that nominally represents the quasimode of E(LO₄) and A₁(LO₃). The intensity of this shoulder increases with the twin population in the nanocrystalline materials, suggesting a correlation between the lattice dynamical characteristics and the long-range ferroelastic strain of the twin wall. The ferroelastic strain is mainly constrained along the c-axis of the BST unit cell, and the effect of this constraint is more pronounced in nanocrystalline materials than in bulks due to a significant wall volume ratio in twinned nano-materials. A₁ phonons showing collective ion dynamics along the c-direction could be then hardened by the strain, while E symmetry exhibiting vibrations perpendicular to the c-axis would be less affected. The theoretically predicted giant LO–TO coupling in tetragonal ferroelectric perovskites [18] suggests that the hardening of the softest A₁(TO₁) mode in A₁ symmetry is accompanied by that of the hardest A₁(LO₃) phonon. Consequently, the shoulder could be ascribed to the ferroelastic strain induced hardening of the quasimode with a considerable contribution from the A₁(LO₃) phonon. PACS 61.72.Ff; 63.22.+m; 77.80.Bh; 77.80.Dj     

Front shock behavior of stable curved detonation waves in rectangular-cross-section curved channels

The propagation of curved detonation waves of gaseous explosives stabilized in rectangular-cross-section curved channels is investigated. Three types of stoichiometric test gases, C₂H₄ + 3O₂, 2H₂ + O₂, and 2C₂H₂ + 5O₂ + 7Ar, are evaluated. The ratio of the inner radius of the curved channel (r_i) to the normal detonation cell width (λ) is an important factor in stabilizing curved detonation waves. The lower boundary of stabilization is around r_i/λ = 23, regardless of the test gas. The stabilized curved detonation waves eventually attain a specific curved shape as they propagate through the curved channels. The specific curved shapes of stabilized curved detonation waves are approximately formulated, and the normal detonation velocity (D_n)?curvature (κ) relations are evaluated. The D_n nondimensionalized by the Chapman–Jouguet (CJ) detonation velocity (D_CJ) is a function of the κ nondimensionalized by λ. The D_n/D_CJ?λκ relation does not depend on the type of test gas. The propagation behavior of the stabilized curved detonation waves is controlled by the D_n/D_CJ?λκ relation. Due to this propagation characteristic, the fully-developed, stabilized curved detonation waves propagate through the curved channels while maintaining a specific curved shape with a constant angular velocity. Self-similarity is seen in the front shock shapes of the stabilized curved detonation waves with the same r_i/λ, regardless of the curved channel and test gas.     

Distinguishability and Disturbance in the Quantum Key Distribution Protocol Using the Mean Multi-Kings’ Problem

We introduce a quantum key distribution protocol using mean multi-kings’ problem. Using this protocol, a sender can share a bit sequence as a secret key with receivers. We consider a relation between information gain by an eavesdropper and disturbance contained in legitimate users’ information. In BB84 protocol, such relation is known as the so-called information disturbance theorem. We focus on a setting that the sender and two receivers try to share bit sequences and the eavesdropper tries to extract information by interacting legitimate users’ systems and an ancilla system. We derive trade-off inequalities between distinguishability of quantum states corresponding to the bit sequence for the eavesdropper and error probability of the bit sequence shared with the legitimate users. Our inequalities show that eavesdropper’s extracting information regarding the secret keys inevitably induces disturbing the states and increasing the error probability.