Polymerizations and mechanistic studies have been performed to understand the kinetic pathways for the\ud polymerization of the monomer oligo(ethylene oxide)\ud monomethyl ether acrylate (OEOA) in aqueous media.\ud Typically, the medium consisted of 18 wt % OEOA in\ud water, in the presence of Cu catalysts coordinated by tris[2(dimethylamino)ethyl]amine (Me6TREN). Well-controlled\ud polymerization of OEOA can be achieved in the presence of\ud halide anions and Cu wire with≲600 ppm of soluble CuII\ud species, rather than previously reported ca. 10 000 ppm of CuII and Cu0 particles formed by predisproportionation of CuI prior to monomer and initiator addition. The mechanistic studies conclude that even though disproportionation is thermodynamically favored in aqueous media, the SARA ATRP, not SET-LRP,\ud mechanism holds in these reactions. This is because alkyl halides are much more rapidly activated by CuI than by Cu0\ud (contribution of Cu0 to activation is <1%). Because of the high activity of CuI species toward alkyl halide activation,\ud [CuI/Me6TREN] in solution is very low (<5μM) and classical ATRP equilibrium between CuI and CuII species is maintained.\ud Although in aqueous media disproportionation of CuI/Me6TREN is thermodynamically favored over comproportionation, unexpectedly, in the presence of alkyl halides, i.e., during polymerization, disproportionation is kinetically minimized.\ud Disproportionation is slow because its rate is proportional to [CuI/Me6TREN]2 and [CuI/Me6TREN] is very small. Thus, during polymerization, comproportionation is 104 times faster than disproportionation, and the final thermodynamic equilibrium between disproportionation and comproportionation could be reached only after polymerization is completed. Activation of alkyl\ud halides by CuI/Me6TREN in aqueous media occurs 8 orders of magnitude faster than disproportionation

Advanced drug delivery systems (DDS) present indubitable benefits for drug administration. Over the past three decades, new approaches have been suggested for the development of novel carriers for drug delivery. In this review, we describe general concepts and emerging research in this field based on multidisciplinary approaches aimed at creating personalized treatment for a broad range of highly prevalent diseases (e.g., cancer and diabetes). This review is composed of two parts. The first part provides an overview on currently available drug delivery technologies including a brief history on the development of these systems and some of the research strategies applied. The second part provides information about the most advanced drug delivery devices using stimuli-responsive polymers. Their synthesis using controlled-living radical polymerization strategy is described. In a near future it is predictable the appearance of new effective tailor-made DDS, resulting from knowledge of different interdisciplinary sciences, in a perspective of creating personalized medical solutions.

Surface biopotentials collected from the human epidermis contain important information about human physiology, such as muscular, heart, and brain activities. However, commercially available wearable biomonitoring devices are generally composed of rigid hardware incompatible with the mechanical compliance of soft human tissues. Thin‐film stretchable e‐skin circuits that can interface the human skin represent an excellent alternative for long‐term wearable biomonitoring. Here, a series of soft and stretchable electrodes are evaluated for their applicability in biopotential sensing. This includes conductive composites made of polydimethylsiloxane (PDMS) as a base substrate and conductive particles, i.e., carbon (cPDMS), silver (AgPDMS), anisotropic z‐axis conductors made with silver‐coated nickel particles (zPDMS), as well as a combination of a conductive tough hydrogel with PDMS, and finally ultrathin tattoo‐like adhesive poly(vinyl alcohol)‐coated films with stretchable biphasic Ag‐EGaIn electrodes. These electrodes are compared between themselves and against the gold‐standard Ag/AgCl and stainless steel electrodes, in order to assess relative performance in signal‐to‐noise ratio (SNR) during electrocardiography, and electrode‐skin impedance for a range of frequencies. Results show a direct relation between conformity of the electrode–skin interface and the SNR value. An all‐integrated biomonitoring patch with embedded processing and communication electronics, hydrogel electrodes, and a multilayer liquid metal circuit is presented for electromyography.

A novel technique that permits, for the first time, fabrication of stretchable traces with linewidths as low as 20 µm and line‐spacing of 30 µm, based on simple coating and printing techniques, performed entirely at ambient condition, is demonstrated. By relying on existing inkjet printing technique, the proposed sinter‐free method is a step toward scalable fabrication of high‐resolution stretchable circuits, with application in logic gates, transparent conductors, and solar panels. This is accomplished by coating a layer of poly(vinyl alcohol) (PVA) over an elastic substrate, inkjet printing a circuit with silver nanoparticle (AgNP) ink, and then coating the printed circuit with a thin film of eutectic gallium‐indium‐tin (Galinstan) alloy. The Galinstan coating selectively wets to the printed AgNPs, resulting in highly conductive (6.65 × 106 S m−1) circuits that can withstand over 100% of strain with a modest gauge factor of ≈2.7. The process does not need thermal sintering, thanks to the Galinstan fusion with AgNPs, thus being compatible with heat‐sensitive substrates. The PVA coating has a critical role as a hydrophilic surface that absorbs the water‐based ink but resists wetting of the Galinstan. This method is demonstrated over a variety of substrates, including ultrasoft polyurethanes, ultra‐stretchable styrene–ethylene/butylynestyrene, and polyimide.

2-(Diisopropylamino)ethyl methacrylate was polymerized by Atom Transfer Radical Polymerization using sodium dithionite as a reducing agent and supplemental activator with a Cu(ii)Br2/Me6TREN catalytic system.