Multichannel selective femtosecond coherent control based on symmetry properties

We present and implement a new scheme for extended multichannel selective femtosecond coherent control based on symmetry properties of the excitation channels. Here, an atomic nonresonant two-photon absorption channel is coherently incorporated in a resonance-mediated (2+1) three-photon absorption channel. By proper pulse shaping, utilizing the invariance of the two-photon absorption to specific phase transformations of the pulse, the three-photon absorption is tuned independently over an order-of-magnitude yield range for any possible two-photon absorption yield. Noticeable is a set of "two-photon dark pulses" inducing widely tunable three-photon absorption.     

Direct calculation of solid-liquid interfacial free energy for molecular systems: TIP4P ice-water interface

By extending the cleaving method to molecular systems, we perform direct calculations of the ice Ih-water interfacial free energy for the TIP4P model. The values for the basal, prism, and {112[over]0} faces are 23.3+/-0.8 mJ m{-2}, 23.6+/-1.0 mJ m{-2}, and 24.7+/-0.8 mJ m{-2}, respectively. The closeness of these values implies a minimal role of thermodynamic factors in the anisotropic growth of ice crystals. These results are about 20% lower than the best experimental estimates. However, the Turnbull coefficient is about 50% higher than for real water, indicating a possible limitation of the TIP4P model in describing freezing.     

Defect-free surface states in modulated photonic lattices

We predict that interfaces of periodically curved waveguide arrays can support a novel type of surface states which exist in a certain region of modulation parameters associated with the band flattening. Such linear surface states appear in truncated but otherwise perfect (defect-free) lattices as a direct consequence of the periodic modulation of the lattice potential. We show that the existence of these modes in different band gaps can be flexibly controlled by selecting the modulation profile, with no restrictions on Bloch-wave symmetries characteristic of Shockley states.     

Near-infrared luminescence of RbPb2Cl5:Bi crystals

A wideband near-IR (NIR) luminescence centered at 1080 nm was found in a RbPb(2)Cl(5):Bi single crystal grown by the Bridgman technique. Absorption, luminescence, and excitation of luminescence spectra were investigated at room and cryogenic temperatures. The luminescence was proposed to be due to the (3)P(1)-->(3)P(0) transition in Bi(+) ion.     

Preliminary Assessment of the Anti-inflammatory Activity of New Structural Honokiol Analogs with a 4′-O-(2-Fluoroethyl) Moiety and the Potential of Their 18F-Labeled Derivatives for Neuroinflammation Imaging

Neolignans honokiol and 4′-O-methylhonokiol (MH) and their derivatives have pronounced anti-inflammatory activity, as evidenced by numerous pharmacological studies. Literature data suggested that cyclooxygenase type 2 (COX-2) may be a target for these compounds in vitro and in vivo. Recent studies of [¹¹C]MPbP (4′-[¹¹C]methoxy-5-propyl-1,1′-biphenyl-2-ol) biodistribution in LPS (lipopolysaccharide)-treated rats have confirmed the high potential of MH derivatives for imaging neuroinflammation. Here, we report the synthesis of four structural analogs of honokiol, of which 4′-(2-fluoroethoxy)-2-hydroxy-5-propyl-1, 1′-biphenyl (F-IV) was selected for labeling with fluorine-18 (T_1/2 = 109.8 min) due to its high anti-inflammatory activity confirmed by enzyme immunoassays (EIA) and neuromorphological studies. The high inhibitory potency of F-IV to COX-2 and its moderate lipophilicity and chemical stability are favorable factors for the preliminary evaluation of the radioligand [¹⁸F]F-IV in a rodent model of neuroinflammation. [¹⁸F]F-IV was prepared with good radiochemical yield and high molar activity and radiochemical purity by ¹⁸F-fluoroethylation of the precursor with Boc-protecting group (15) with [¹⁸F]2-fluoro-1-bromoethane ([¹⁸F]FEB). Ex vivo biodistribution studies revealed a small to moderate increase in radioligand uptake in the brain and peripheral organs of LPS-induced rats compared to control animals. Pretreatment with celecoxib resulted in significant blocking of radioactivity uptake in the brain (pons and medulla), heart, lungs, and kidneys, indicating that [¹⁸F]F-IV is likely to specifically bind to COX-2 in a rat model of neuroinflammation. However, in comparison with [¹¹C]MPbP, the new radioligand showed decreased brain uptake in LPS rats and high retention in the blood pool, which apparently could be explained by its high plasma protein binding. We believe that the structure of [¹⁸F]F-IV can be optimized by replacing the substituents in the biphenyl core to eliminate these disadvantages and develop new radioligands for imaging activated microglia.     

Rational Design 2-Hydroxypropylphosphonium Salts as Cancer Cell Mitochondria-Targeted Vectors: Synthesis,Structure, and Biological Properties

It has been shown for a wide range of epoxy compounds that their interaction with triphenylphosphonium triflate occurs with a high chemoselectivity and leads to the formation of (2-hydroxypropyl)triphenylphosphonium triflates 3 substituted in the 3-position with an alkoxy, alkylcarboxyl group, or halogen, which were isolated in a high yield. Using the methodology for the disclosure of epichlorohydrin with alcohols in the presence of boron trifluoride etherate, followed by the substitution of iodine for chlorine and treatment with triphenylphosphine, 2-hydroxypropyltriphenylphosphonium iodides 4 were also obtained. The molecular and supramolecular structure of the obtained phosphonium salts was established, and their high antitumor activity was revealed in relation to duodenal adenocarcinoma. The formation of liposomal systems based on phosphonium salt 3 and L-α-phosphatidylcholine (PC) was employed for improving the bioavailability and reducing the toxicity. They were produced by the thin film rehydration method and exhibited cytotoxic properties. This rational design of phosphonium salts 3 and 4 has promising potential of new vectors for targeted delivery into mitochondria of tumor cells.     

A monte carlo lattice study of living polymers in a confined geometry

We investigate the changes in the average chain length of a solution of semi-flexible living polymers between two hard repulsive walls as the width of the slit, D, is varied. Two different Monte Carlo models, that of the ‘slithering snake’ and of the ‘independent monomer states’ are employed in order to simulate a polydisperse system of chain molecules confined in a gap which is either closed (with fixed total density), or open and in contact with an external reservoir. It appears that the mean chain length L in a state of equilibrium polymerization depends essentially on the geometry constraints for sufficiently small D. We find that in the case of an open slit the mean length L(D) decreases with D → 0 for flexible chains whereas it grows if the chains are sufficiently stiff. As the width of a closed gap D is decreased, in a three-dimensional gap L(D) gradually decreases for absolutely flexible chains whereas for semi-rigid chains it goes through a minimum at D = 2 and then grows again for D = 1. In two dimensions, in a closed strip the average chain length L(D) for both flexible and rigid macromolecules goes through a sharp minimum and then grows steeply in compliance with a predicted divergence for semi-rigid polymers as D → 0. We attribute the observed discrepancies of our numeric experiments with some recent analytic predictions to the ordering effect of container walls on the polymer solution when chain stiffness and excluded volume interactions are taken into account.     

1-acetoxyvinyl phosphonates: Facile synthesis via catalytic acylation of dialkyl phosphites

A new and facile method of synthesis of 1-acetoxyvinyl phosphonates ( 2 ) has been found. Dialkyl phosphites react readily with acetic anhydride in acetonitrile solution in the presence of catalysts to produce 2 and acylphosphonates ( 1 ) as a minor product. The most efficient catalysts are metal compounds of variable valency: iron(II), iron(III), and cobalt(II) chlorides. The same compounds catalyze transformation of 1 into 2 in an acetonitrile solution of acetic anhydride.