Permeability- and Surface-Energy-Tunable Polyurethane Acrylate Molds for Capillary Force Lithography

A permeability- and surface-energy-controllable polyurethane acrylate (PUA) mold, a “capillary-force material (CFM)” mold, is introduced for capillary-force lithography (CFL). In CFL, the surface energy and gas permeability of the mold are crucial. However, the modulation of these two main factors at a time is difficult. Here, we introduce new CFM molds in which the surface energy and permeability can be modified by controlling the degree of cross-linking of the CFM. As the degree of cross-linking of the CFM mold increases, the surface energy and air permeability decrease. The high average functionality of the mold material makes it possible to produce patterns relatively finely and rapidly due to the high rate of capillary rise and stiffness, and the low functionality allows for patterns to form on a curved surface with conformal contact. CFMs with different functionality and controllable-interfacial properties will extend the capabilities of capillary force lithography to overcome the geometric limitations of patterning on a scale below 100 nm and micro- and nanopatterning on the curved region

pH-Responsive Charge-Conversional Poly(ethylene imine)–Poly(l‑lysine)–Poly(l‑glutamic acid) with Self-Assembly and Endosome Buffering Ability for Gene Delivery Systems

Poly­(ethylene imine)–poly­(l-lysine)–poly­(l-glutamic acid) (PKE) polymers with various glutamic acid portions were synthesized by ring opening polymerization of l-lysine N-carboxyanhydride (NCA) and l-glutamic acid NCA from poly­(ethylene imine) 1.8 kDa (PEI1.8k) as a macroinitiator. It was found that their glutamic acid residues could buffer endosomal pH. PK5E9 polymer could form nanoparticles by self-assembly and nanosized polyplexes, possessing pH-responsive charge-conversion properties. PK5E9 or its polyplex nanoparticles showed polyhedral structures with bumpy surfaces. Its cytotoxicity was marginal at both pH 7.4 and 6.0, and its transfection efficiency was highly increased at pH 6.0. The improved transfection efficiency in acidic conditions was thought to be induced by elevated cellular uptake of the polyplexes via charge-conversion from negative to positive charges. Its transfection was also found to be mediated by endosomal escape through endosome buffering by bafilomycin A1-treated transfection. In conclusion, PK5E9 polymer with self-assembly and endosome buffering ability was found to possess potentials for efficient gene delivery systems in acidic conditions via charge conversion, which may be applied for tumor microenvironment-targeting

Analysis of Preload-Dependent Reversible Mechanical Interlocking Using Beetle-Inspired Wing Locking Device

We report an analysis of preload-dependent reversible interlocking between regularly arrayed, high aspect ratio (AR) polymer micro- and nanofibers. Such a reversible interlocking is inspired from the wing-locking device of a beetle where densely populated microhairs (termed microtrichia) on the cuticular surface form numerous hair-to-hair contacts to maximize lateral shear adhesion. To mimic this, we fabricate various high AR, vertical micro- and nanopillars on a flexible substrate and investigate the shear locking force with different preloads (0.1–10 N/cm²). A simple theoretical model is developed based on the competition between van der Waals (VdW) attraction and deflection forces of pillars, which can explain the preload-dependent maximum deflection, tilting angle, and total shear adhesion force

Photothermally Triggered Cytosolic Drug Delivery <i>via</i> Endosome Disruption Using a Functionalized Reduced Graphene Oxide

Graphene oxide has unique physiochemical properties, showing great potential in biomedical applications. In the present work, functionalized reduced graphene oxide (PEG-BPEI-rGO) has been developed as a nanotemplate for photothermally triggered cytosolic drug delivery by inducing endosomal disruption and subsequent drug release. PEG-BPEI-rGO has the ability to load a greater amount of doxorubicin (DOX) than unreduced PEG-BPEI-GO <i>via</i> π–π and hydrophobic interactions, showing high water stability. Loaded DOX could be efficiently released by glutathione (GSH) and the photothermal effect of irradiated near IR (NIR) in test tubes as well as in cells. Importantly, PEG-BPEI-rGO/DOX complex was found to escape from endosomes after cellular uptake by photothermally induced endosomal disruption and the proton sponge effect, followed by GSH-induced DOX release into the cytosol. Finally, it was concluded that a greater cancer cell death efficacy was observed in PEG-BPEI-rGO/DOX complex-treated cells with NIR irradiation than those with no irradiation. This study demonstrated the development of the potential of a PEG-BPEI-rGO nanocarrier by photothermally triggered cytosolic drug delivery <i>via</i> endosomal disruption

VEGF siRNA Delivery System Using Arginine-Grafted Bioreducible Poly(disulfide amine)

Small interfering RNAs (siRNAs) are able to silence their target genes when they are successfully delivered intact into the cytoplasm. Delivery systems that enhance siRNA localization to the cytoplasm can facilitate gene silencing by siRNA therapeutics. We describe an arginine-conjugated poly(cystaminebisacrylamide-diaminohexane) (poly(CBA-DAH-R)), a bioreducible cationic polymer, as an siRNA carrier for therapeutic gene silencing for cancer. After intracellular uptake of the siRNA/poly(CBA-DAH-R) polyplexes, the reductive environment of the cytoplasm cleaves the disulfide linkages in the polymeric backbone, resulting in decomplexing of the siRNA/poly(CBA-DAH-R) polyplexes and release of siRNA molecules throughout the cytoplasm. The siRNA/poly(CBA-DAH-R) polyplexes, which demonstrate increased membrane permeability with arginine modification, have a similar level of cellular uptake as siRNA/bPEI polyplexes. The VEGF siRNA/poly(CBA-DAH-R) polyplexes, however, inhibit VEGF expression to a greater degree than VEGF siRNA/bPEI in various human cancer cell lines. The improved RNAi activity demonstrated by the VEGF siRNA/poly(CBA-DAH-R) polyplexes is due to enhanced intracellular delivery and effective localization to the cytoplasm of the VEGF siRNAs. These results demonstrate that the VEGF siRNA/poly(CBA-DAH-R) polyplex delivery system may useful for siRNA-based approaches for cancer therapy

Agmatine-Containing Bioreducible Polymer for Gene Delivery Systems and Its Dual Degradation Behavior

Agmatine-containing bioreducible polymer, poly­(cystaminebis­(acrylamide)-agmatine) (poly­(CBA-AG)) was synthesized for gene delivery systems. It could form 200–300 nm sized and positively charged polyplexes with pDNA, which could release pDNA in reducing the environment due to the internal disulfide bonds cleavage. Poly­(CBA-AG) also showed a spontaneous degradation behavior in aqueous condition in contrast to the backbone polymer, poly­(cystaminebis­(acrylamide)-diaminobutane) (poly­(CBA-DAB)) lacking guanidine moieties, probably due to the self-catalyzed hydrolysis of internal amide bonds by guanidine moieties. The cytotoxicity of poly­(CBA-AG) was cell-dependent but minimal. Poly­(CBA-AG) exhibited highly enhanced transfection efficiency in comparison with poly­(CBA-DAB) and even higher transfection efficiency than PEI25k. However, cellular uptake efficiency of the polyplexes did not show positive correlation with the transfection efficiency. Confocal microscopy observation revealed that pDNA delivered by poly­(CBA-AG) was strongly accumulated in cell nuclei. These results suggested that high transfection efficiency of poly­(CBA-AG) may be derived from the efficient pDNA localization in cell nuclei by guanidine moieties and that the polyplexes dissociation via self-catalyzed hydrolysis as well as disulfide bonds cleavage in cytosol also may facilitate the transfection process. Finally, poly­(CBA-AG)/pJDK-apoptin polyplex showed a high anticancer activity induced by apoptosis, demonstrating a potential of poly­(CBA-AG) as a gene carrier for cancer gene therapy

Fabrication of Antireflection and Antifogging Polymer Sheet by Partial Photopolymerization and Dry Etching

We present a simple method to fabricate a polymer optical sheet with antireflection and antifogging properties. The method consists of two consecutive steps: photocross-linking of UV-curable polyurethane acrylate (PUA) resin and reactive ion etching (RIE). During photopolymerization, the cured PUA film is divided into two domains of randomly distributed macromers and oligomers due to a relatively short exposure time of 20 s at ambient conditions. Using the macromer domain as an etch-mask, dry etching was subsequently carried out to remove the oligomer domain, leaving behind a nanoturf surface with tunable roughness. UV−vis spectroscopy measurements demonstrate that transmittance of a nanoturf surface is enhanced up to 92.5% as compared to a flat PUA surface (89.5%). In addition, measurements of contact angle (CA) reveal that the etched surface shows superhydrophilicity with a CA as small as 5°. To seek potential applications, I−V characteristics of a thin film organic solar cell were measured under various testing conditions. It is shown that the efficiency can be increased to 2.9% when a nanoturf film with the surface roughness of 34.73 nm is attached to indium tin oxide (ITO) glass. More importantly, the performance is maintained even in the presence of water owing to superhydrophilic nature of the film

Geometry-Controllable Graphene Layers and Their Application for Supercapacitors

A facile and ultrafast method for geometry controllable and vertically transformative 3D graphene architectures is demonstrated. The 2D stacked graphene layers produced by exfoliation of graphite were transformed, e.g., from horizontal to vertical, by applying electric charge (−2 V with 1–3 μAh/cm²). The three-dimensionally transformed graphene layers have maximized surface area as well as high specific capacitance, 410 F g^–1 in LiClO₄/PC electrolyte, which is 4.4 times higher than that of planar (stacked) graphene layers. Furthermore, they can remarkably exhibit 87% of retained capacitance as the scan rate is increased from 100 to 1000 mV s^–1, unlike planar graphene, which displays 61% retention under the same conditions

Data_Sheet_1_Layered Double Hydroxide Nanomaterials Encapsulating Angelica gigas Nakai Extract for Potential Anticancer Nanomedicine.DOC

<p>We prepared hybrids consisting of Angelica gigas Nakai (AGN) root or flower extract and layered double hydroxide (LDH) for potential anticancer nanomedicine, as decursin species (DS) in AGN are known to have anticancer activity. Dimethylsulfoxide solvent was determined hybridization reaction media, as it has affinity to both AGN and LDH moiety. In order to develop inter-particle spaces in LDH, a reversible dehydration-rehydration, so-called reconstruction route, was applied in AGN-LDH hybridization. Quantitative analyses on AGN-LDH hybrids indicated that the content of DS was two times more concentrated in the hybrids than in extract itself. Using X-ray diffraction, FT-IR spectroscopy, scanning electron microscopy, and zeta-potential measurement, we found that AGN extract moiety was incorporated into inter-particle spaces of LDH nanoparticles during the reconstruction reaction. Time-dependent DS release from hybrids at pH 7.4 (physiological condition) and pH 4.5 (lysosomal condition) exhibited a pH-dependent release of extract-incorporated LDH hybrids. An anticancer activity test using HeLa, A549, and HEK293T cells showed that the AGN-LDH hybrid, regardless of extract type, showed enhanced anticancer activity compared with extract alone at an equivalent amount of DS, suggesting a nanomedicine effect of AGN-LDH hybrids.</p