Spatial and temporal diffusion-control of dynamic multi-domain self-assembled gels

The dynamic assembly of a pH-responsive low-molecular-weight gelator (LMWG) within the pre-formed matrix of a second LMWG has been achieved via diffusion of an acid from a reservoir cut into the gel. Self-assembly of the acid-triggered LMWG as it converts from micellar aggregates at basic pH into gel nanofibers at lower pH values can be both spatially and temporally controlled. The pH-responsive LMWG has an impact on the stiffness of the pre-formed gel in the domains in which it assembles. When low acid concentrations are used, LMWG assembly is transient – after the initial proton diffusion phase, the pH rises and disassembly occurs as the system equilibrates. Re-application of additional acid as ‘fuel’ can then re-assemble the LMWG network. Using glucono-δ-lactone (which slowly hydrolyses to gluconic acid) instead of HCl gives slower, more spatially-restricted assembly, and creates longer-lasting pH gradients within the gel. The presence of an agarose polymer gel network improves the mechanical strength of the gels and appears to slightly enhance the rate of proton diffusion. More sophisticated reservoir shapes can be cut into these more mechanically robust gels, enabling the creation of diffusion waves with different geometries, and hence different patterns of LMWG activation. Multiple reservoirs can be used to create overlapping proton diffusion waves, hence achieving differentiated pH patterns in the gel. Using acid diffusion in this way within gels is an intriguing and powerful way of dynamic patterning. The ability to temporally-evolve spatially-resolved patterns using biocompatible weak acids, and the change in rheological performance of the triggered domains, suggest potential future applications of this strategy in tissue engineering.

The assembly of a pH-sensitive LMWG within a pre-formed network of a second LMWG can be achieved by diffusing acids from pre-cut reservoirs, giving rise to patterned gels in which the rheological properties evolve with spatial and temporal control.     

Structured replacement policies for a Markov-modulated shock model

We establish the optimality of structured replacement policies for a periodically inspected system that fails silently whenever the cumulative number of shocks, or the magnitude of a single shock it has received, exceeds a corresponding threshold. Shocks arrive according to a Markov-modulated Poisson process which represents the (controllable or uncontrollable) environment.     

Nondurable K-Theory Equivalence and Bousfield Localization*

In this paper we consider what happens when Adams self maps are modified by adding certain unstable maps. The unstable maps which are added are trivial after a single suspension. We can choose the modification so that the maps are still K-theory equivalences but the loops on the map are no longer K-theory equivalences. As a corollary we note that the maps are K-theory equivalences but not v ₁-periodic equivalences. Another consequence is the behavior of the cobar spectral sequences for generalized homology theories. Tamaki shows that in certain cases a cobar-type spectral sequence for generalized homology theories is well behaved. The maps we construct give an example where despite the connectivity of the spaces the cobar spectral sequence is still poorly behaved. Finally we use our maps to construct spaces whose Bousfield class is distinct from the cofiber of the Adams map but which becomes the same after one suspension.     

Thermogravimetric analysis of layered double hydroxides with chloramphenicol and salicylate in the interlayer space

The thermal behavior of the new inorganic-organic nanohybrid materials obtained by intercalation of chloramphenicol and salicylate into layered double hydroxides (LDHs) by direct synthesis method, anion exchange reaction and the reconstruction method was evaluated by dynamic thermogravimetric analysis in air, at heating rates of 5°C min⁻¹. The XRD patterns of the samples are characteristic for those of well crystallized solids with layered double hydroxide structures. The FTIR spectroscopy results show the presence of the organic compound within the network structure of the synthesized LDHs. The kinetic parameters (reaction order (n) apparent activation energy (E _a) and pre-exponential factor (lnA) were calculated by the Coats-Redfern method. The compensation effects were determined.     

Highly regioselective palladium-catalyzed methoxycarbonylation of styrene using chiral ferrocene- and biphosphole-based ligands

The methoxycarbonylation of styrene has been studied using Pd(OAc)₂/L/acid catalytic systems with L being chiral ferrocene- and biphosphole-based ligands. Good activities are obtained in mild conditions. Chemoselectivities and regioselectivities (up to 98% in favour of the branched isomer) are excellent but enantioselectivities remain moderate (ee up to 17%).     

Synthesis of N-benzyl-des-D-ring lamellarin K via an acyl-Claisen/Paal-Knorr approach

Lamellarin K is a complex pyrrole natural product and member of the lamellarin family – a group of natural products known for their potent biological activities, such as, antiproliferative activity and inhibition of P-gp mediated drug efflux pumps. We herein describe the synthesis of the N-benzyl-des-D ring analogue of lamellarin K using a route that centres on an acyl-Claisen reaction to eventually prepare a highly-functionalised 1-aryl-4-methyl-1,4-diketone. Paal-Knorr pyrrole formation using this diketone undergoes auto-oxidation to give a fully-substituted 5-formyl pyrrole which was converted into the natural lactone B ring. Antiproliferative testing of the N-benzyl-des-D ring analogue gave an IC₅₀ of 2.63 μM against the MDA-MB-231 breast cancer cell line.