Polymerization behaviors of racemic and chiral amphiphilic monomers in organized bilayer membranes of lamellar liquid crystalline phase

A racemic amphiphilic monomer, n‐dodecyl glyceryl itaconate (DGI), forms bilayer membranes in water in the presence of small amount of ionic cosurfactant and shows iridescent color. A chiral DGI, S‐DGI, also shows an iridescent property, but with a rather red shift in the color, which can be ascribed to the increased packing density of the monomer in the bilayer membranes. Chrial DGI has a more compact packing density than racemic one owing to closer distance between the monomer molecules; the conversion rate, however, is slower than that of racemic one when H₂O₂ is used as an initiator. When the initiator is changed to an amphiphilic one, 4‐(2‐hydroxyethoxy) phenyl‐(2‐hydroxy‐2‐propyl) ketone (Irgacure 2959), the chiral DGI shows even a little faster conversion rate than that of racemic one. The NMR chemical shift results of protons in benzene ring show that the molecules of Irgacure 2959 insert into the bilayer membranes. The molecular weights of the corresponding polymers prove that the initiation by H₂O₂ is restricted compared to that by Irgacure 2959. It is concluded that the decelerated polymerization behavior of chiral DGI initiated by H₂O₂ is a result of limited diffusion of the initiator into the lamellar bilayer structures. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 4891–4900, 2007     

Effects of the H-bond donor structure on the properties of supramolecular side chain liquid crystalline polymers based on poly(3-carboxypropylmethylsiloxane-co-dimethylsiloxane)s and stilbazoles

Supramolecular side chain liquid crystalline polymers (SCLCPs) based on poly(3-carboxypropylmethylsiloxane-co-dimethylsiloxane) (PSIX, X=100, 76, 60, 41 or 23, denoting the mole percentage of 3-carboxypropylmethylsiloxane unit in the polymer) and stilbazole derivatives have been obtained through intermolecular hydrogen bonding (H-bonding) interactions between the carboxylic acid and the pyridyl moieties. The formation of H-bonding and self-assembly results in the formation of new mesogenic units, in which H-bonds function as molecular connectors. FTIR shows the existence of H-bonding in the complexes. The polymeric complexes behave as single component liquid crystalline polymers and exhibit stable and enantiotropic mesophases. The liquid crystalline properties of the supramolecular SCLCPs were studied using differential scanning calorimetry, polarizing optical microscopy and X-ray diffraction, and were found to exhibit smectic A phases with focal-conic textures. The thermal stability of the SCLCP increases on increasing the carboxylic acid content in the polysiloxane and the concentration of the stilbazole derivative in the complex. However, the thermal stability decreases on increasing the chain length of the stilbazole derivative. The crystal phase was not formed even on cooling to the glass transition temperature of the polymeric complex.     

Gap-Free Set Partitions

A set partition is called “gap-free” if its block sizes form an interval. In other words, there is at least one block of each size between the smallest and largest block sizes. Let B(n) and G(n), respectively, denote the number of partitions and the number of gap-free partitions of the set [n]. We prove that      

Biogenetically inspired approach to the Strychnos alkaloids. Concise syntheses of (+/-)-akuammicine and (+/-)-strychnine

A linear synthesis of the indole alkaloid (+/-)-akuammicine (2) was completed by a novel sequence of reactions requiring only 10 steps from commercially available starting materials. The approach features a tandem vinylogous Mannich addition and an intramolecular hetero Diels-Alder reaction to rapidly assemble the pentacyclic heteroyohimboid derivative 8 from the readily available hydrocarboline 6. Oxidation of the E ring of 8 gave the lactone 9 that was converted into deformylgeissoschizine (11). The subsequent elaboration of 11 into 2 was effected by a biomimetically patterned transformation that involved sequential oxidation and base-induced skeletal reorganization. A variation of these tactics was then applied to the synthesis of the C(18) hydroxylated akuammicine derivative 36. Because 36 had previously been converted into strychnine (1) in four steps, its preparation constitutes a concise, formal synthesis of this complex alkaloid.     

An Algorithm for Non-Linear Network Programming: Implementation,Results and Comparisons

This paper evaluates an algorithm for solving network flow optimization problems with quadratic cost functions. Strategies for fast implementation are discussed and the results of extensive numerical tests are given. The performance of the algorithm measured by CPU time is compared with that of the convex simplex method specialized for quadratic network programming. Performance of the two methods is analysed with respect to network size and density, and other parameters of interest. The algorithm is shown to perform significantly better on the majority of problems. We also show how the algorithm may be used to solve non-linear convex network optimization problems by the use of sequential quadratic programming.     

The maximum degree in a random tree and related problems

Meir and Moon studied the distribution of the maximum degree for simply generated families of trees. We have sharper results for the special case of labelled trees. © 1994 John Wiley & Sons, Inc.     

Adsorption and photocatalytic degradation of methylene blue using high surface area titanate nanotubes (TNT) synthesized via hydrothermal method

Removal of methylene blue (MB) via adsorption and photocatalysis using titanate nanotubes (TNTs) with different surface areas were investigated and compared to commercial titanium dioxide (TiO₂) P25 Degussa nanoparticles. The TNTs with surface area ranging from 20 m²/g to 200 m²/g were synthesized via hydrothermal method with different reaction times. TEM imaging confirmed the tubular structure of TNT while XRD spectra indicated all TNTs exhibited anatase crystallinity. Batch adsorption rate showed linearity with surface properties of TNTs, where materials with higher surface area showed higher adsorption rate. The highest MB adsorption (70%) was achieved by TNT24 in 60 min whereas commercial TiO₂ exhibited the lowest adsorption of only 10% after 240 min. Adsorption isotherm studies indicated that adsorption using TNT is better fitted into Langmuir adsorption isotherm than Freundlich isotherm model. Furthermore, TNT24 was able to perform up to 90% removal of MB within 120 min, demonstrating performance that is 2-fold better compared to commercial TiO₂. The high surface area and surface Bronsted acidity are the main reasons for the improvement in MB removal performance exhibited by TNT24. The improvement in surface acidity enhanced the adsorption properties of all the nanotubes prepared in this study.     

First observation of the P-wave spin-singlet bottomonium states hb(1P) and hb(2P)

We report the first observations of the spin-singlet bottomonium states h(b)(1P) and h(b)(2P). The states are produced in the reaction e(+)e(-)→h(b)(nP)π(+)π(-) using a 121.4 fb(-1) data sample collected at energies near the Υ(5S) resonance with the Belle detector at the KEKB asymmetric-energy e(+)e(-) collider. We determine M[h(b)(1P)]=(9898.2(-1.0-1.1)(+1.1+1.0)) MeV/c(2) and M[h(b)(2P)]=(10,259.8±0.6(-1.0)(+1.4)) MeV/c(2), which correspond to P-wave hyperfine splittings ΔM(HF)=(+1.7±1.5) and (+0.5(-1.2)(+1.6)) MeV/c(2), respectively. The significances of the h(b)(1P) and h(b)(2P) are 5.5σ and 11.2σ, respectively. We find that the production of the h(b)(1P) and h(b)(2P) is not suppressed relative to the production of the Υ(1S), Υ(2S), and Υ(3S).     

Electronically Excited States in Model Complexes of Noble Metal Clusters with Carbon Nanodots

Russian Physics Journal - Theoretical calculations of excited states in the complexes of gold and silver three-atom nanoclusters with carbon quantum nanodots are performed using the M062X...