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.     

Glass-specific behavior in the damping of acousticlike vibrations

High frequency sound is observed in lithium diborate glass, Li2O-2B2O3, using Brillouin scattering of light and x rays. The sound attenuation exhibits a nontrivial dependence on the wave vector, with a remarkably rapid increase towards a Ioffe-Regel crossover as the frequency approaches the boson peak from below. An analysis of literature results reveals that the boson-peak frequency is closely related with a Ioffe-Regel limit for sound in many glasses. We conjecture that this relation, specific to glassy materials, might be rather common among them.     

Mode-locked all-fiber ring laser based on broad bandwidth in-fiber acousto-optic modulator

Active mode-locking of long-cavity all-fiber ring laser based on broad bandwidth in-fiber acousto-optic modulator (AOM) is reported. The proposed AOM combines the advantages of intermodal coupling induced by standing flexural acoustic waves in a double-ended tapered fiber. We focus our attention on the effects of large tapered transitions to improve the bandwidth modulation. Our approach permits the implementation of broad modulation bandwidth (13 nm), high modulation depth (50 %), and low optical loss (1.1 dB) in an 80-μm configuration. The effects of the AOM in the laser performance are also investigated. Transform-limit optical pulses of 25 ps temporal width and 2.7 W peak power were obtained at 2.46 MHz repetition rate.     

Superfluid-insulator transition in a periodically driven optical lattice

We demonstrate that the transition from a superfluid to a Mott insulator in the Bose-Hubbard model can be induced by an oscillating force through an effective renormalization of the tunneling matrix element. The mechanism involves adiabatic following of Floquet states, and can be tested experimentally with Bose-Einstein condensates in periodically driven optical lattices. Its extension from small to very large systems yields nontrivial information on the condensate dynamics.     

Shakeup excitation during optical tunnel ionization

Shakeup of a two-electron system is investigated in the strong infrared laser field limit, both theoretically and experimentally. During tunnel ionization the electron shakes up a second electron to an excited bound state. Theoretically, a complete analytical theory of shakeup in intense laser fields is developed. We predict that shakeup produces one excited sigma(u) D(+)(2) state in approximately 10(5) ionization events. Shakeup is measured experimentally by using the molecular clock provided by the internuclear motion. The number of measured events is found to be in excellent agreement with theory.     

Tunable gold nanoparticles shape and size in reductive and structuring media containing protic ionic liquids

Herein, a facile method was developed for preparing high concentration of monodispersed gold nanoparticles (NPs) at room temperature from gold(III) chloride by using different media based on N,N-dimethylformamide or water solutions containing a protic ionic liquid (PIL), namely, the octylammonium formate or the bis(2-ethyl-hexyl)ammonium formate, based on which both PILs were used as redox-active structuring media. The formation of gold NPs in these systems was then characterized using UV–visible spectroscopy, transmission electron microscopy, and dynamic light scattering. From these investigations, it appears that the structure and aggregation pathway of PILs in selected solvents affect strongly the formation, growth, the shape, and the size of gold NPs. In fact, by using this approach, the shape-/ size-controlled gold NPs (branched and spherical) can be generated under mild condition. This approach suggests also a wealth of potential for these designer nanomaterials within the biomedical, materials, and catalysis communities by using designer and safer media based on PILs.     

High-power laser with Nd:YAG single-crystal fiber grown by the micro-pulling-down technique

We present optical characterization and laser results achieved with single-crystal fibers directly grown by the micro-pulling-down technique. We investigate the spectroscopic and optical quality of the fiber, and we present the first laser results. We achieved a cw laser power of 10 W at 1064 nm for an incident pump power of 60 W at 808 nm and 360 kW peak power for 12 ns pulses at 1 kHz in the Q-switched regime. It is, to the best of our knowledge, the highest laser power ever achieved with directly grown single-crystal fibers.     

Time-dependent density functional theory molecular dynamics simulation of doubly charged uracil in gas phase

We use time-dependent density functional theory and Born-Oppenheimer molecular dynamics methods to investigate the fragmentation of doubly ionized uracil in gas phase. Different initial electronic excited states of the dication are obtained by removing electrons from different inner-shell orbitals of the neutral species. We show that shape-equivalent orbitals lead to very different fragmentation patterns revealing the importance of the intramolecular chemical environment. The results are in good agreement with ionion coincidence measurements of uracil collision with 100 keV protons.     

The rectum of Oxaea flavescens (Andrenidae) has a specialized structure among bees

The rectum of the bee Oxaea flavescens contains six hollow rectal papillae, in contrast to rectal pads found in others Hymenoptera. The rectal epithelium is formed by cubical cells with structural specializations for fluid transport, such as apical plasma membrane invaginations, endocytic vesicles, scalariform junctions, wide extracellular space and double-membrane vesicles. Globular-shaped cells form the rectal papillae with surface plasma membrane invaginations that vary from small depressions to very large sinuses. The cell-cell contact is narrow, exhibiting extensive regions with scalariform junction, while cytoplasmic free ribosome-like material is prominent. These ultrastructural features are discussed in relation to their role in excretion in this bee.     

The algebra of differential operators on the circle and W KP (q)

Radul has recently introduced a map from the Lie algebra of differential operators on the circle of W _n . In this Letter, we extend this map to W _KP ^(q) , a recently introduced one-parameter deformation of W_KP - the second Hamiltonian structure of the KP hierarchy. We use this to give a short proof that W is the algebra of additional symmetries of the KP equation.