Porous polyurethane film fabricated via the breath figure approach for sustained drug release

The breath figure (BF) method is an effective process for fabricating porous polymeric films. In this study, we fabricated porous polymer films from thermoplastic polyurethane (PU) through static BF with CHCl₃ as a solvent under 55–80% relative humidity. The porous PU films were prepared within various pore structures and sizes, which were adjustable, depending on the fabrication conditions. The humidity and exposure time were examined as variable parameters affecting the surface morphology, wettability, and cytotoxicity. Atorvastatin calcium, a hyperlipidemic agent, was loaded into the porous films during the casting process, and the drug-loading and drug-releasing behaviors of the porous PU membranes were evaluated. Approximately 60–80% of the drug was released in 14 days. The films exhibited sustained drug-release performances because of the hydrophobicity and nonbiodegradable nature of PU for perivascular drug administration. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2019 , 136, 47658.     

Layer-by-layer self-assembly of multifunctional enzymatic UF membranes

In order to eliminate membrane fouling and to ensure enzymatic hydrolysis of urea, multifunctional biocatalytic membranes were prepared by using urease (URE) and trypsin (TRY) enzymes on the sulfonated polysulfone (SPSf) ultrafiltration membrane via layer-by-layer (LbL) self-assembly method. The membrane architecture consisted of multilayer assembly with TRY and URE enzymes as the outer layer and inner sandwiched layer, respectively. Polyethyleneimine (PEI) and alginate (ALG) were used as cationic and anionic polyelectrolytes. Sulfonation and PEI deposition were successfully accomplished as confirmed by attenuated total reflectance Fourier transform infrared spectroscopy, differential scanning calorimetry (DSC) and scanning electron microscopy analysis, contact angle measurements, staining with toluidine blue and Congo red dyes and dead-end filtration experiments. A characteristic value of SPSf membrane with a high water permeability (1000 L/m².h.bar) and 95% bovine serum albumin (BSA) rejection was observed. In static conditions, URE activities of SPSf2-PEI-URE membrane were not affected by BSA fouling, while TRY immobilizations with increased concentrations (SPSf2-PEI-URE-PEI-ALG-TRY) significantly lowered the activity of URE. In dynamic conditions, each deposited layer exhibited individual resistance to flow that can be considered as irreversible fouling and caused 90% of flux decline for the SPSf2-PEI-URE-PEI-ALG-TRY membrane assembly. The recovery of the initial flux for the multilayered membrane at the end of six fouling and washing cycles was observed 85%. Moreover, at the end of 5 cycles, 78% of the URE initial activity of the multilayered membrane was preserved. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48750.     

Investigation on carbon nanotube oxide for anhydrous proton exchange membranes application

The widespread participation of polymers in the membrane preparation has been considering to be critical for the development of proton exchange membranes (PEMs). For the polymers without functional groups to conduct protons, the introduction of proton conduction carriers with the formation of composite membranes is an effective strategy to prepare PEMs with the outstanding proton conductivity. However, there remains a potential risk of the components leaking from composite membranes due to the lack of the interaction force. Here, the composite of carbon nanotube oxide (OCNT) assembling with cadmium telluride (CdTe) and 1-butyl-3-methylimidazolium hexafluorophosphate (bmimPF₆) was introduced into the system of phosphoric acid (PA) doping poly(vinylidene fluoride) (PVDF) with the formation of PVDF/OCNT-CdTe-bmimPF₆/85%PA membranes. PA molecules are anchored by the inorganics of OCNT-CdTe-bmimPF₆ and are stabilized in membranes. The high and stable proton conductivity values at the elevated temperature are obtained comparing the reported PVDF/bmimPF₆/PA membranes. Specifically, the proton conductivity value reached 1.28 × 10⁻¹ S/cm at 160 °C and the value is stable 1.70 × 10⁻² S/cm at 120 °C lasting for 350 h. The fine stability in components could make the membranes extricate from the predicament of proton conductivity decline exceeding 120 °C under anhydrous conditions in PVDF/bmimPF₆/PA membranes. © 2019 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2020 , 137, 48833.     

Aggregation Behavior,Antibacterial Activity and Biocompatibility of Catanionic Assemblies Based on Amino Acid-Derived Surfactants

The surface activity, aggregates morphology, size and charge characteristics of binary catanionic mixtures containing a cationic amino acid-derived surfactant N(π), N(τ)-bis(methyl)-L-Histidine tetradecyl amide (DMHNHC₁₄) and an anionic surfactant (the lysine-based surfactant N^α-lauroyl-N^εacetyl lysine (C₁₂C₃L) or sodium myristate) were investigated for the first time. The cationic surfactant has an acid proton which shows a strong pK_a shift irrespective of aggregation. The resulting catanionic mixtures exhibited high surface activity and low critical aggregation concentration as compared with the pure constituents. Catanionic vesicles based on DMHNHC₁₄/sodium myristate showed a monodisperse population of medium-size aggregates and good storage stability. According to Small-Angle X-Ray Scattering (SAXS), the characteristics of the bilayers did not depend strongly on the system composition for the positively charged vesicles. Negatively charged vesicles (cationic surfactant:myristate ratio below 1:2) had similar bilayer composition but tended to aggregate. The DMHNHC₁₄-rich vesicles exhibited good antibacterial activity against Gram-positive bacteria and their bactericidal effectivity declined with the decrease of the cationic surfactant content in the mixtures. The hemolytic activity and cytotoxicity of these catanionic formulations against non-tumoral (3T3, HaCaT) and tumoral (HeLa, A431) cell lines also improved by increasing the ratio of cationic surfactant in the mixture. These results indicate that the biological activity of these systems is mainly governed by the cationic charge density, which can be modulated by changing the cationic/anionic surfactant ratio in the mixtures. Remarkably, the incorporation of cholesterol in those catanionic vesicles reduces their cytotoxicity and increases the safety of future biomedical applications of these systems.     

Emerging Plasmonic Assemblies Triggered by DNA for Biomedical Applications

Plasmonic gold nanocrystal represents plasmonic metal nanomaterials, and has a variety of unique and beneficial properties, such as optical signal enhancement, catalytic activity, and photothermal properties tuned by local temperature, which are useful in physical, chemical, and biological applications. In addition, the inherent properties of predictable programmability, sequence specificity, and structural plasticity provide DNA nanostructures with precise controllability, spatial addressability, and targeting recognition, serving as ideal ligands to link or position building blocks during the self-assembly process. Self-assembly is a common technique for the organization of prefabricated and discrete nanoparticle blocks for the construction of extremely sophisticated nanocomposites. To this end, the integration of DNA nanotechnology with Au nanomaterials, followed by assembly of DNA-functionalized Au nanomaterials can form novel functional Au nanomaterials that are difficult to obtain through conventional methods. Here, recent progress in DNA-assembled Au nanostructures of various shapes is summarized, and their functions are discussed. The fabrication strategies that employ DNA for the self-assembly of Au nanostructures, including dimers, tetramers, satellites, nanochains, and other nanostructures with more complex geometric configurations are first described. Then, the characteristic optical properties and applications of biosensing, bioimaging, drug delivery, and therapy are discussed. Finally, the remaining challenges and prospects are elucidated.     

Covalent Linkage and Macrocylization Preserve and Enhance Synergistic Interactions in Catalytic Amyloids

The self-assembly of short peptides into catalytic amyloid-like nanomaterials has proven to be a powerful tool in both understanding the evolution of early proteins and identifying new catalysts for practically useful chemical reactions. Here we demonstrate that both parallel and antiparallel arrangements of β-sheets can accommodate metal ions in catalytically productive coordination environments. Moreover, synergistic relationships, identified in catalytic amyloid mixtures, can be captured in macrocyclic and sheet-loop-sheet species, that offer faster rates of assembly and provide more complex asymmetric arrangements of functional groups, thus paving the way for future designs of amyloid-like catalytic proteins. Our findings show how initial catalytic activity in amyloid assemblies can be propagated and improved in more-complex molecules, providing another link in a complex evolutionary chain between short, potentially abiotically produced peptides and modern-day enzymes.     

Renoprotective Angiographic Polymersomes

Computed tomography (CT) angiography is powerful for the diagnosis of vascular diseases. Unfortunately, this method usually requires a high dosage of iodinated contrast agents, which can lead to severe elevation of reactive oxygen species (ROS) levels within kidneys. This causes oxidative stress, apoptosis, and hence contrast-induced nephropathy (CIN), a leading cause of iatrogenic renal failure, especially for patients with renal insufficiency. Herein, a route is shown to circumvent such problems with the usage of rationally designed renoprotective angiographic polymersomes (RAPs) as blood pool CT contrast agents. RAPs are biodegradable nanoparticles prepared via self-assembly of poly(ethylene oxide)-block-poly(triiodobenzoic chloride-conjugated polylysine-stat-phenylboronic acid pinacol ester-conjugated polylysine) (PEO₄₅-b-P[(Lys-IBC)₄₅-stat-(Lys-PAPE)₁₅]). The key to the efficiency of such nanoparticles as renoprotective contrast agents arises from the rationally chosen repeat units: Lys-IBC exhibits a concentration-dependent X-ray attenuation capability and Lys-PAPE introduces an ROS-scavenging ability to the polymersome. The study shows that RAPs can reduce the risk of CIN in mice with kidney injury. Additionally, a 5-fold increase in angiographic live time is observed using RAPs, compared to commonly used iodinated small molecule contrast agents. In summary, a new strategy is proposed for the design of a renoprotective angiographic contrast agent that is capable of reducing the risk of CIN.     

Reversible Control of Gelatin Hydrogel Stiffness by Using DNA Crosslinkers**

Biomaterials with dynamically tunable properties are critical for a range of applications in regenerative medicine and basic biology. In this work, we show the reversible control of gelatin methacrylate (GelMA) hydrogel stiffness through the use of DNA crosslinkers. We replaced some of the inter-GelMA crosslinks with double-stranded DNA, allowing for their removal through toehold-mediated strand displacement. The crosslinks could be restored by adding fresh dsDNA with complementary handles to those on the hydrogel. The elastic modulus (G’) of the hydrogels could be tuned between 500 and 1000 Pa, reversibly, over two cycles without degradation of performance. By functionalizing the gels with a second DNA strand, it was possible to control the crosslink density and a model ligand in an orthogonal fashion with two different displacement strands. Our results demonstrate the potential for DNA to reversibly control both stiffness and ligand presentation in a protein-based hydrogel, and will be useful for teasing apart the spatiotemporal behavior of encapsulated cells.     

Superconducting Quantum Metamaterials from High Pressure Melt Infiltration of Metals into Block Copolymer Double Gyroid Derived Ceramic Templates

Mesoscale order can lead to emergent properties including phononic bandgaps or topologically protected states. Block copolymers offer a route to mesoscale periodic architectures, but their use as structure directing agents for metallic materials has not been fully realized. A versatile approach to mesostructured metals via bulk block copolymer self-assembly derived ceramic templates, is demonstrated. Molten indium is infiltrated into mesoporous, double gyroidal silicon nitride templates under high pressure to yield bulk, 3D periodic nanocomposites as free-standing monoliths which exhibit emergent quantum-scale phenomena. Vortices are artificially introduced when double gyroidal indium metal behaves as a type II superconductor, with evidence of strong pinning centers arrayed on the order of the double gyroid lattice size. Sample behavior is reproducible over months, showing high stability. High pressure infiltration of bulk block copolymer self-assembly based ceramic templates is an enabling tool for studying high-quality metals with previously inaccessible architectures, and paves the way for the emerging field of block-copolymer derived quantum metamaterials.     

A Dynamic Combinatorial Approach for Identifying Side Groups that Stabilize DNA-Templated Supramolecular Self-Assemblies

DNA-templated self-assembly is an emerging strategy for generating functional supramolecular systems, which requires the identification of potent multi-point binding ligands. In this line, we recently showed that bis-functionalized guanidinium compounds can interact with ssDNA and generate a supramolecular complex through the recognition of the phosphodiester backbone of DNA. In order to probe the importance of secondary interactions and to identify side groups that stabilize these DNA-templated self-assemblies, we report herein the implementation of a dynamic combinatorial approach. We used an in situ fragment assembly process based on reductive amination and tested various side groups, including amino acids. The results reveal that aromatic and cationic side groups participate in secondary supramolecular interactions that stabilize the complexes formed with ssDNA.