Enzymatic Degradation of Star Poly(ε-Caprolactone) with Different Central Units.

Four-arm star poly(ε-caprolactone) with a central poly(ethylene glycol) PEG unit bridged with 2,2-bis(methyl) propionic acid, (PCL)2-b-PEG-b-(PCL)2, and six-arm star PCL homopolymer with a central dipentaerythritol units were hydrolysed using a lipase from Pseudomonas cepacia and the Thermobifida cellulosilytica cutinase Thc_Cut1. For comparative analysis, Y-shaped copolymers containing methylated PEG bridged with bisMPA, MePEG-(PCL)2, and linear triblock copolymers PCL-b-PEG-b-PCL were also subjected to enzymatic hydrolysis. The hydrophilic nature of the polymers was determined using contact angle analysis, showing that a higher PEG content exhibited a lower contact angle and higher surface wettability. Enzymatic hydrolysis was monitored by % mass loss, scanning electron microscopy (SEM), and differential scanning calorimetry (DSC). A higher rate of mass loss was found for lipase catalysed hydrolysis of those polymers with the highest PEG content, leading to significant surface erosion and increase in crystallinity within the first two days. Liquid chromatography (LC) and size exclusion chromatography (SEC) of samples incubated with the cutinase showed a significant decrease in molecular weight, increase in dispersity, and release of ε-CL monomer units after 6 h of incubation.

A versatile method for functionalization and grafting of 2-hydroxyethyl cellulose (HEC) via Click chemistry.

This article describes a versatile method for the modification of 2-hydroxyethyl cellulose (HEC) involving azide-alkyne cycloaddition reaction to impart neutral (ester) and ionic (carboxylic acid and 1(ry) amine) functionalities. The synthetic approach involved, first the introduction of the azide functionality to HEC and then followed by its cycloaddition reaction with several alkyne terminated compounds: namely ethyl propiolate, 5-hexynoic acid and propargyl amine. Sequential Click reactions were also demonstrated to be feasible by the successful synthesis of polydimethylsiloxane (PDMS) grafted HEC containing neutral (ester) and ionic (carboxylic acid and 1(ry) amine) functionalities. The Click chemistry was then further utilized similarly to graft poly(lactic acid) (PLA) and poly(ethylene glycol) (PEG) segments to HEC to access its hydrophobic and hydrophilic analogs, respectively. AFM analysis revealed that while HEC itself formed uniform oval features, the PLA grafted HEC exhibited a brushlike architecture. The formation of these brushlike structures suggested that the HEC backbone exhibits an extended conformation with the side chains stretched out. The resulting polymeric materials were characterized by solution and solid state (13)C NMR and FTIR spectroscopy.

Individually addressable recessed gold microelectrode arrays with monolayers of thio-cyclodextrin nanocavities.

Four, individually addressable 30 microm diameter, e-beam deposited, gold microelectrodes recessed by 6 microm were suitably spaced on a single substrate to avoid diffusional overlap between each microelectrode. The single substrate device was functionalised with thiolated alpha-, beta-, and gamma-cyclodextrin nanocavities without spacer groups to ensure close proximity of the cavities to the electrode surface. The microelectrodes were assessed in two stages. The e-beam deposited micron sized electrodes were characterized using models for recessed and inlaid microdisk electrodes. Subsequently, each individually addressable, atomically flat, micro-patterned gold electrode with thiolated CD ensembles was treated as a nanoporous electrode assembly. Theoretical and experimental results were compared using cyclic voltammetry. Atomic force microscopy was also used to characterise the modified microelectrodes. Comparisons were made with thiolated CDs deposited on macroelectrodes. This is the first report of the behaviour of immobilized CD nanocavities ensembles on atomically flat gold microelectrodes.