Preparation and polymerization of thyroxine methacrylate monomers

Thyroxine methyl ester amides of mono-, di-, and tri-glycyl methacrylates have been prepared. Water-soluble polymers formed from thyroxine methacrylate monomers by free-radical copolymerization with acrylamide had molecular weights of (2–4) × 10⁴ (by viscometry). A fluorescent polymer was prepared by copolymerization with a fluorescein methacrylate monomer. Similarly, a polymeric thyroxine material was prepared with amine functionality by copolymerization with N-3-aminopropylmethacrylamide. These polymers may have interesting biological and immunochemical properties.     

Polymeric thiols as enzyme activators of serum creatine phosphokinase

Several hydrophilic polymeric thiols were prepared from aminoactivated polymeric supports by reaction with N-acetylhomocysteinethiolactone. Supports include agaroses, cellulose, Glycophase™ controlled-pore glass, and Matrex™ acrylic beads. Thiol content in these polymers was 3–72 μmol SH/g dry polymer. Several were effective solid-phase activators of the sulfhydryl-dependent enzyme creatine phosphokinase at concentrations comparable to that of monomeric thiol required for enzyme activation. The kinetic activation curves for the polymeric and the monomeric (thioglucose) activators were similar, suggesting unhindered interaction of the enzyme with the polymeric activator.     

Light‐Responsive Biomaterials: Development and Applications

Novel biomaterials are beneficial to the growing fields of drug delivery, cell biology, micro‐devices, and tissue engineering. With recent advances in chemistry and materials science, light is becoming an attractive option as a method to control biomaterial behavior and properties. In this Feature Article, we explore some of the early and recent advances in the design of light‐responsive biomaterials. Particular attention is paid to macromolecular assemblies for drug delivery, multi‐component surface patterning for advanced cell assays, and polymer networks that undergo chemical or shape changes upon light exposure. We conclude with some remarks about future directions of the field.

     

On the Tutte–Krushkal–Renardy polynomial for cell complexes

Recently V. Krushkal and D. Renardy generalized the Tutte polynomial from graphs to cell complexes. We show that evaluating this polynomial at the origin gives the number of cellular spanning trees in the sense of A. Duval, C. Klivans, and J. Martin. Moreover, after a slight modification, the Tutte–Krushkal–Renardy polynomial evaluated at the origin gives a weighted count of cellular spanning trees, and therefore its free term can be calculated by the cellular matrix-tree theorem of Duval et al. In the case of cell decompositions of a sphere, this modified polynomial satisfies the same duality identity as the original polynomial. We find that evaluating the Tutte–Krushkal–Renardy along a certain line gives the Bott polynomial. Finally we prove skein relations for the Tutte–Krushkal–Renardy polynomial.     

A three-way array model for resolving multicomponent fluorescent mixtures

Fluorescence lifetime provides a third independent dimension of information for the resolution of total luminescence spectra of multicomponent mixtures. The incorporation of this parameter into the Excitation-Emission Matrix (EEM) by the phase-modulation technique results in a three-dimensional Excitation-Emission-Frequency Array (EEFA). Multicomponent analysis based on the three-dimensional EEFA brings a qualitative change for the resolved spectra, i.e., individual spectra can be uniquely resolved, which is impossible with any two-dimensional analysis. In this paper, we present a method for analyzing the EEFA. We show mathematically that with the three-dimensional analysis of the EEFA individual spectra and lifetimes can be obtained. Our algorithm is developed in mathematical detail and demonstrated by its application to a two-component mixture.     

Flexible Rolled Thick‐Film Miniaturized Flow‐Cell for Minimally Invasive Amperometric Sensing

We describe here a miniaturized flexible thick‐film electrochemical biosensor flow detector, suitable for insertion into the lacrimal canaliculus towards minimally invasive amperometric monitoring of biomarkers in the tear fluid. Our focus here is on the microfabrication and in‐vitro testing of the new laterally rolled screen‐printed sensor. The new device responds rapidly and sensitively to dynamic changes in the levels of norepinephrine and glucose (the later in connection to glucose‐oxidase containing ink). Coverage of the enzyme electrode with an electropolymerized polytyramine minimizes contributions from the common electroactive interferences ascorbic and uric acids. Such attractive performance indicates great promise for minimally invasive monitoring of health biomarkers in the tear fluid, or in alternative usage such as capillary microelectrophoresis, ultralow volume sampling, or in‐flow (tubular) systems for batch processing of blood or culture media.     

Magnetic tuning of the electrochemical reactivity through controlled surface orientation of catalytic nanowires

Nanowires have received considerable attention owing to their broad potential applications. We report here on the application of nanowires for magnetic control of the electrochemical reactivity and demonstrate how one can modulate the electrocatalytic activity by orienting catalytic nanowires at different angles. Unlike early "on/off" magnetic switching studies based on functionalized magnetic spheres, the present magnetoswitchable protocol relies on modulating the electrochemical reactivity without removing the magnetic material from the surface. Such behavior is attributed to the reversible blocking of the redox processes and to changes in the tortuosity-dependent flux rate. The nanowire-based magnetoswitchable protocol may be extremely useful for adjusting the electrochemical reactivity, such as for tuning the power output of fuel cells (rather than switching the power on/off).