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Protein nanoparticles are a promising approach for nanotherapeutics, as proteins combine versatile chemical and biological function with controlled biodegradability. In this work, the development of an adaptable synthesis method is presented for synthetic protein nanoparticles (SPNPs) based on reactive electrojetting. In contrast to past work with electrohydrodynamic cojetting using inert polymers, the jetting solutions are comprised of proteins and chemically activated macromers, designed to react with each other during the processing step, to form insoluble nanogel particles. SPNPs made from a variety of different proteins, such as transferrin, insulin, or hemoglobin, are stable and uniform under physiological conditions and maintain monodisperse sizes of around 200 nm. SPNPs comprised of transferrin and a disulfide containing macromer are stimuli‐responsive, and serve as markers of oxidative stress within HeLa cells. Beyond isotropic SPNPs, bicompartmental nanoparticles containing human serum albumin and transferrin in two distinct hemispheres are prepared via reactive electrojetting. This novel platform provides access to a novel class of versatile protein particles with nanoscale architectures that i) can be made from a variety of proteins and macromers, ii) have tunable biological responses, and iii) can be multicompartmental, a prerequisite for controlled release of multiple drugs. [ABSTRACT FROM AUTHOR]

Linearly arranged metal atoms that are embedded in discrete molecules have fascinated scientists across various disciplines for decades; this is attributed to their potential use in microelectronic devices on a submicroscopic scale. Luminescent oligonuclear Group 11 metal complexes are of particular interest for applications in molecular light-emitting devices. Herein, we describe the synthesis and characterization of a rare, homoleptic, and neutral linearly arranged tetranuclear CuI complex that is helically bent, thus representing a molecular coil in the solid state. This tetracuprous arrangement dimerizes into a unique octanuclear assembly bearing a linear array of six CuI centers with two additional bridging cuprous ions that constitute a central pseudo-rhombic CuI4 cluster. The crystal structure determinations of both complexes reveal close d10⋅⋅⋅d10 contacts between all cuprous ions that are adjacent to each other. The dynamic behavior in solution, DFT calculations, and the luminescence properties of these remarkable complexes are also discussed. [ABSTRACT FROM AUTHOR]

Shape memory polymer (SMP) foams have been developed for use in neurovascular occlusion applications. These materials are predominantly polyurethanes that are known for their biocompatibility and tunable properties. However, these polymers inherently lack X-ray visibility, which is a significant challenge for their use as implantable materials. Herein, low density, highly porous shape memory polyurethane foams were developed with tungsten nanoparticles dispersed into the foam matrix, at increasing concentrations, to serve as a radiopaque agent. Utilizing X-ray fluoroscopy sufficient visibility of the foams at small geometries was observed. Thermal characterization of the foams indicated altered thermal response and delayed foam actuation with increasing nanoparticle loading (because of restricted network mobility). Mechanical testing indicated decreased toughness and strength for higher loading because of disruption of the SMP matrix. Overall, filler addition imparted x-ray visibility to the SMP foams and allowed for tuned control of the transition temperature and actuation kinetics for the material. Copyright © 2015 John Wiley & Sons, Ltd. [ABSTRACT FROM AUTHOR]

An array of films composed of a third‐generation hyperbranched fluoropolymer crosslinked with poly(ethylene glycol) is generated and tested as an anti‐icing coating. Through variation of the hydrophilic:hydrophobic component ratios and drop‐casting solvent, significant reductions in the water melting transition temperatures (−5 and −27 °C for free and bound water, respectively) are achieved. The novel application of this system displays the expansion and diversity of a well‐established coating that demonstrates unique water confinement and sequestration behaviors with the ability to reorganize at the surface. [ABSTRACT FROM AUTHOR]

ABSTRACT Three microparticle additives, tungsten (W), zirconium oxide (ZrO2) , and barium sulfate (BaSO4) were selected to enhance the radio-opacity in shape memory polymer (SMP) foam biomaterials. The addition of filler causes no significant alterations of glass transition temperatures, density of the materials increases, pore diameter decreases, and total volume recovery decreases from approximately 70 times in unfilled foams to 20 times (4% W and 10% ZrO2). The addition of W increases time to recovery; ZrO2 causes little variation in time to shape recovery; BaSO4 increases the time to recovery. On a 2.00 mean X-ray density (mean X.D.) scale, a GDC coil standard has a mean X.D. of 0.62 ; 4% W enhances the mean X.D. to 1.89, 10% ZrO2 to 1.39 and 4% BaSO4 to 0.74. Radio-opacity enhancing additives could be used to produce SMP foams with controlled shape memory kinetics, low density , and enhanced X-ray opacity for medical materials. © 2015 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015, 132, 42054. [ABSTRACT FROM AUTHOR]

The reported diblock brush terpolymer displays the fundamental advantages of high macromolecular and regiochemical control in simultaneous top ‐ down/bottom ‐ up construction of advanced positive ‐ tone photoresist materials. By selective partition the substrate adhesion, surface ‐ active migration, and chemically ‐ reactive deblocking functional compositions into the cylindrical polymer brush architectures, large ‐ areas of vertical alignment of the polymers within thin films are realized. The bottom ‐ up premeditated system enables effective top ‐ down lithography to produce near ‐ molecular pixel resolution (2–3 molecules) at low operation dosage. [ABSTRACT FROM AUTHOR]

Previously developed shape-memory polymer foams display fast actuation in water due to plasticization of the polymer network. The actuation presents itself as a depression in the glass-transition temperature when moving from dry to aqueous conditions; this effect limits the working time of the foam to 10 min when used in a transcatheter embolic device. Reproducible foams are developed by altering the chemical backbone, which can achieve working times of greater than 20 min. This is accomplished by incorporating isophorone diisocyanate into the foam, resulting in increased hydrophobicity, glass transitions, and actuation time. This delayed actuation, when compared with previous systems, allows for more optimal working time in clinical applications. [ABSTRACT FROM AUTHOR]

A facile polymerization of an allyl-functionalized N-carboxyanhydride (NCA) monomer is utilized to construct an A-B-A-type triblock structure containing β-sheet-rich oligomeric peptide segments tethered by a poly(ethylene oxide) chain, which are capable of dispersing and gelating single-walled carbon nanotubes (SWCNTs) noncovalently in organic solvents, resulting in significant enhancement of the mechanical properties of polypeptide-based organogels. [ABSTRACT FROM AUTHOR]

Protein nanoparticles are an attractive class of materials for nanomedicine applications due to the intrinsic biocompatibility, biodegradability, and intrinsic functionality of their constituent proteins. Despite the clinical success of select protein nanoparticles, this class of nanocarriers remains understudied and underdeveloped compared to lipid and polymer nanoparticles due to challenges related to formulation optimization, large design space, and their structural complexity. In this work, a modular strategy for protein nanoparticle preparation based on the concept of photoreactive jetting is introduced. The process relies on continuous ultraviolet irradiation during electrohydrodynamic (EHD) jetting of protein solutions that contain a homobifunctional photocrosslinker. Protein nanoparticles exhibit nanogel‐like architectures comprised of proteins that are linked via synthetic moieties. Compared to conventional protein nanoparticles, this method reduces nanoparticle processing times to minutes, rather than hours to days. The inclusion of an emissive structural motif as the molecular scaffold of the photocrosslinker is used to study the supramolecular architecture of the stable nanoparticles via time‐resolved fluorescence spectroscopy. [ABSTRACT FROM AUTHOR]