Role of Metal Lattice Expansion and Molecular pi-Conjugation for the Magnetic Hardening at Cu-Organics Interfaces

Magnetic hardening and generation of room-temperature ferromagnetism at the interface between originally nonmagnetic transition metals and π-conjugated organics is understood to be promoted by interplay between interfacial charge transfer and relaxation-induced distortion of the metal lattice. The relative importance of the two contributions for magnetic hardening of the metal remains unquantified. Here, we disentangle their role via density functional theory simulation of several models of interfaces between Cu and polymers of different steric hindrance, π-conjugation, and electron-accepting properties: polyethylene, polyacetylene, polyethylene terephthalate, and polyurethane. In the absence of charge transfer, expansion and compression of the Cu face-centered cubic lattice is computed to lead to magnetic hardening and softening, respectively. Contrary to expectations based on the extent of π-conjugation on the organic and resulting charge transfer, the computed magnetic hardening is largest for Cu interfaced with polyethylene and smallest for the Cu–polyacetylene systems as a result of a differently favorable rehybridization leading to different enhancement of exchange interactions and density of states at the Fermi level. It thus transpires that neither the presence of molecular π-conjugation nor substantial charge transfer may be strictly needed for magnetic hardening of Cu–substrates, widening the range of organics of potential interest for enhancement of emergent magnetism at metal–organic interfaces

Binding mechanism of the model charged dye carboxyfluorescein to hyaluronan/polylysine multilayers

Biopolymer-based multilayers become more and more attractive due to the vast span of biological application they can be used for, e.g., implant coatings, cell culture supports, scaffolds. Multilayers have demonstrated superior capability to store enormous amounts of small charged molecules, such as drugs, and release them in a controlled manner; however, the binding mechanism for drug loading into the multilayers is still poorly understood. Here we focus on this mechanism using model hyaluronan/polylysine (HA/PLL) multilayers and a model charged dye, carboxyfluorescein (CF). We found that CF reaches a concentration of 13 mM in the multilayers that by far exceeds its solubility in water. The high loading is not related to the aggregation of CF in the multilayers. In the multilayers, CF molecules bind to free amino groups of PLL; however, intermolecular CF–CF interactions also play a role and (i) endow the binding with a cooperative nature and (ii) result in polyadsorption of CF molecules, as proven by fitting of the adsorption isotherm using the BET model. Analysis of CF mobility in the multilayers by fluorescence recovery after photobleaching has revealed that CF diffusion in the multilayers is likely a result of both jumping of CF molecules from one amino group to another and movement, together with a PLL chain being bound to it. We believe that this study may help in the design of tailor-made multilayers that act as advanced drug delivery platfor

Multifunctional ZnO-Co3O4 @ polymer hybrid nanocoatings with controlled adsorption, photocatalytic and anti-microbial functions for polluted water systems

Triple action pollutant responsive multi-layer hybrid nanocoatings of architecture PEI(PAA/ZnO-Co3O4)n were constructed through ZnO-Co3O4 binary oxide co-precipitation followed by its inclusion in multi-layer polymeric thin films using Layer-by-Layer (LbL) deposition. Characterization of the designed architecture was carried out via FTIR, XRD, UV-Vis, and Raman spectroscopic studies to evaluate the chemical nature, bonding, and crystallographic behavior of ZnO-Co3O4. Peaks of ZnO-Co3O4 were recorded at 586.38, 486.08, and 443.64 cm-1 while pronounced shifting of ZnO characteristic E2 (high) peak ~ 450 cm-1 and appearance of modes around 495, 530, 630, and 719 cm-1 indexed via Raman studies validated Co3O4 impregnation into ZnO structure. XRD patterns of ZnO-Co3O4 compared to their previously reported pristine structures also justified the formation of binary oxide as unit composite. SEM micrographs confirmed homogenous multi-layered depositions while EDX analysis confirmed their uniform elemental distribution in the unit structure. Sequential multi-layer buildup up to 48 layer pairs was monitored using ellipsometry with maximum film thickness ~ 89 nm and by UV-Vis at 376 nm. The prepared thin films exhibited significant photodegradation of methylene blue ~ 91% and Cu (II) adsorption capacity ~ 89% within first 90 min of contact, along with prominent bactericidal efficiency against E. coli within 24 h of reaction time. FAAS, ICP-OES, and UV-Vis spectroscopy analyses make these multifunctional hybrid nanocoatings promising for industrial wastewater as well as drinking water purification setups. Furthermore, protuberant recycling and regenerative capacity make these hybrid nanocoatings an eco-friendly system for hydro-remediation

Polymer-decorated anisotropic silica nanotubes with combined shape and surface properties for guest delivery

We report on amphiphilic diblock copolymer-decorated anisotropic silica nanotubes with well-defined dual functions of shape and surface properties in one nanocontainer. Amphiphilic poly(lactic acid)block-poly(ethylene glycol) (PLA-b-PEG) diblock copolymers are covalently grafted to the surface of mesoporous silica nanotubes via silane chemistry and esterification. The released percentage of probe molecules from the resultant silica-g-(PLA-b-PEG) hybrid nanocontainer is around 40% over a release time of 48 h, in contrast to 90% from bare silica nanotubes prior to surface modification. The diblock copolymer-decorated anisotropic nanocontainers with large aspect ratio lead to enhanced viability of NIH 3T3 fibroblast cells. A theoretical model based on the free energy cost for cell membranes to encapsulate nanocontainers is utilized to understand the cytotoxicity. This work demonstrates that the release dynamics of the active molecules and the interaction of hybrid nanocontainers with cell membranes can be regulated by the synergistic effect of nanocontainer shape and surface properties. (C) 2016 Elsevier Ltd. All rights reserved.</p