Hydrolyzable poly(ester-urethane) networks from L-lysine diisocyanate and D,L-lactide/ϵ-caprolactone homo- and copolyester triols

Bioabsorbable poly(ester-urethane) networks were synthesized from ethyl 2,6-diisocyanatohexanoate (L -lysine diisocyanate) (LDI) and a series of polyester triols. LDI was synthesized by refluxing L-lysine monohydrochloride with ethanol to form the ester, which was subsequently refluxed with 1,1,1,3,3,3-hexamethyldisilazane to yield a silazane-protected intermediate. This product was then phosgenated using triphosgene. Polyester triols were synthesized from D,L-lactide, ?-caprolactone, or comonomer mixtures thereof, using glycerol as initiator and stannous octoate as catalyst. Polyurethane networks were cured using [NCO]/[OH] = 1.05 and stannous octoate (0.05 wt %) for 24 h at room temperature and pressure and 24 h at 50°C and 0.1 mm Hg. LDI-based polyurethane networks were totally amorphous and possessed very low sol contents. Networks based on poly (D,L-lactide) triols were rigid (T_g ∽ 60°C) with ultimate tensile strengths of ～ 40–70 MPa, tensile moduli of ～ 1.2–2.0 GPa, and ultimate elongations of ～ 4–10%. Networks based on ?-caprolactone triols were low-modulus elastomers with tensile strengths and moduli of ～ 1–4 MPa and ～ 3–6 GPa, respectively, and ultimate elongations of ～ 50–300%. Networks based on copolymers displayed physical properties consistent with monomer composition and were tougher than the networks based on the homopolymers. Tensile strengths for the copolymers were ～ 3–25 MPa with ultimate elongations up to 600%. Hydrolytic degradation under simulated physiological conditions showed that D ,L -lactide homopolymer networks were the most resistant to degradation, undergoing virtually no change in mass or physical properties for 60 days. ?-Caprolactone-based networks were resistant to degradation for 40 days, and high-lactide copolymer-based networks suffered substantial losses in physical properties after only 3 days. © 1994 John Wiley & Sons, Inc.     

7-azasteroid analogues—I

Although 7-methoxy- and 6,7-dimethoxy-2-methyl-4-vinyl-isocarbostyrils could not be isolated and characterised, they have been generated in situ and shown to undergo cyclo-addition reactions with typical dienophiles. The enol acetate of 2-methyl-4-acetylisocarbostyril has also been trapped as its adduct with maleic anhydride and with p-benzoquinone.     

Supramolecular structures of coronene and alkane acids at the Au(111)-solution interface: a scanning tunneling microscopy study

Scanning tunneling microscopy (STM) is utilized to study the solution-solid interface formed between Au(111) and solutions of coronene in hexanoic, heptanoic, and octanoic acids. In all three cases adsorbed coronene is observed and lays flat on the metal surface. Heptanoic and hexanoic acid solutions produce a hexagonal symmetry monolayer. For the heptanoic and hexanoic cases, dipole-image dipole interactions and H bonding stabilize a surface structure in which 12 acid molecules surround each coronene and produce a coronene spacing of 1.45 nm. In the case of octanoic acid as solvent, the incorporation of the solvent into the monolayer is not as strongly favored. The coronene spacing can range from close-packed (1.2 nm) with no solvent presumed present in the monolayer, to 1.50 nm with up to 12 solvent molecules surrounding each coronene. The close-packed regions have hexagonal symmetry, as do those with the largest (1.5 nm) spacing. Heptanoic acid solutions give the clearest STM images and are associated with the most stable two-component monolayer. The present paper demonstrates that non-covalent interactions at the solution-metal interface can lead to complex multicomponent monolayer structures.     

Student enrichment in mathematics: a case study with first year university students

ABSTRACT

This paper presents an enrichment case study to showcase a possible avenue for attending to the needs of academically strong mathematics students. We report on a group of university students who were presented with the opportunity of exploring a specific first year mathematics topic deeper, using an inquiry-based learning approach as part of an enrichment programme. Following the intervention, students completed a questionnaire and a few were interviewed to establish their experiences of the enrichment programme. We discuss the successes and pitfalls of the intervention and report on the impact it had on the participants.     

Tranexamic Acid Cream Protects Ultraviolet B-induced Photoaging in Balb/c Mice Skin by Increasing Mitochondrial Markers: Changes Lead to Improvement of Histological Appearance

Tranexamic acid (TSA) is widely used as an antiaging treatment for reducing melasma and wrinkles. There are various mechanisms for wrinkle formation, and one of them is due to damage of the mitochondria. Research on mitochondria in the skin is very limited, so we are interested to see the changes that occur after application of TSA cream. We explored the effect of TSA on mitochondrial protein levels (PGC1α, Tom20, COX IV), which had affected to skin histological structure. Thirty male, 6-week-old, Balb/C mice were divided into five groups (negative control, positive control, TSA 3%, TSA 4% and TSA 5%). After 10 days of acclimatization, four groups of mice were exposed to UVB light, of which three groups were given TSA cream for 10 weeks. The skin tissue was excised for protein and histological studies. H&E staining was performed for evaluating histological changes in epidermal thickness and dermal elastosis. TSA treatment on the mice skin increased mitochondrial marker levels and epidermal thickness while decreasing dermal elastosis for all the treatment groups. Topical application of TSA significantly increased mitochondrial biogenesis which may cause alteration in epidermal thickness and reduced dermal elastosis in the histology of mice skin.     

Chaos in the dynamics generated by sequences of maps, with applications to chaotic advection in flows with aperiodic time dependence

In this paper we develop analytical techniques for proving the existence of chaotic dynamics in systems where the dynamics is generated by infinite sequences of maps. These are generalizations of the Conley-Moser conditions that are used to show that a (single) map has an invariant Cantor set on which it is topologically conjugate to a subshift on the space of symbol sequences. The motivation for developing these methods is to apply them to the study of chaotic advection in fluid flows arising from velocity fields with aperiodic time dependence, and we show how dynamics generated by infinite sequences of maps arises naturally in that setting. Our methods do not require the existence of a homoclinic orbit in order to conclude the existence of chaotic dynamics. This is important for the class of fluid mechanical examples considered since one cannot readily identify a homoclinic orbit from the structure of the equations.¶We study three specific fluid mechanical examples: the Aref blinking vortex flow, Samelson's tidal advection model, and Min's rollup-merge map that models kinematics in the mixing layer. Each of these flows is modelled as a type of "blinking flow", which mathematically has the form of a linked twist map, or an infinite sequence of linked twist maps. We show that the nature of these blinking flows is such that it is possible to have a variety of "patches" of chaos in the flow corresponding to different length and time scales.     

Residence-time distributions for chaotic flows in pipes

In this paper we derive two rigorous properties of residence-time distributions for flows in pipes and mixers motivated by computational results of Khakhar et al. [Chem. Eng. Sci. 42, 2909 (1987)], using some concepts from ergodic theory. First, a curious similarity between the isoresidence-time plots and Poincare maps of the flow observed in Khakhar et al. is resolved. It is shown that in long pipes and mixers, Poincare maps can serve as a useful guide in the analysis of isoresidence-time plots, but the two are not equivalent. In particular, for long devices isoresidence-time sets are composed of orbits of the Poincare map, but each isoresidence-time set can be comprised of many orbits. Second, we explain the origin of multimodal residence-time distributions for nondiffusive motion of particles in pipes and mixers. It is shown that chaotic regions in the Poincare map contribute peaks to the appropriately defined and rescaled axial distribution functions. (c) 1999 American Institute of Physics.     

Synthesis of main‐chain poly(carbazole)s via CuAAC

The synthesis and characterization of a novel family of main‐chain carbazole‐containing polymers using copper‐catalyzed azide‐alkyne cycloaddition chemistry is reported. The reactions were performed under mild conditions using readily available copper catalysts and ligands, which afforded polymeric products with M_ws up to 18 kDa. Using a range of techniques, the polymers were found to exhibit a glass transition temperature (T_g) of 85 °C, high thermal stability (T_d = 274 °C), and high photoluminescent quantum efficiency (?_f = 0.29; λ_em = 448 nm), which underscore their potential for use in organic light‐emitting diodes or other emissive devices, particularly where efficient blue emission is of value. The approach described offers practical advantages over other synthetic methods used to prepare main‐chain carbazole‐containing polymers, especially with regard to the lack of need for rigorously inert conditions and the absence of byproducts generated during the polymerization reaction. © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011