Light-Assisted Fabrication of Hierarchical Azopolymer Structures Using the Breath Figure Method and AAO Templates.

Hierarchical polymer structures have garnered widespread application across various fields owing to their distinct surface properties and expansive surface areas. Conventional hierarchical polymer structures, however, often lack postfabrication scalability and spatial selectivity. In this study, we propose a novel strategy to prepare light-assisted hierarchical polymer structures using azopolymers (PAzo), the breath figure method, and anodic aluminum oxide (AAO) templates. Initially, the breath figure PAzo films are prepared by dripping a PAzo chloroform solution onto glass substrates in a high-humidity environment. The AAO templates are then placed on the breath figure PAzo film. Upon ultraviolet (UV) light exposure, the azobenzene groups in the azopolymers undergo trans-cis photoisomerization. This process causes the glass transition temperature (Tg) of the PAzo to become lower than room temperature, allowing the azopolymer to enter the nanopores of the AAO templates. The hierarchical azopolymer structures are then formed by using a sodium hydroxide solution to remove the templates. Furthermore, exploring the effects of PAzo concentration and UV light exposure duration on the film morphology reveals optimized conditions for hierarchical structure formation. Additionally, the water contact angles of these polymer structures are measured. The hierarchical PAzo structures exhibit higher hydrophobicity compared with the flat PAzo films and the PAzo breath figure films. Finally, patterned breath figure films can be prepared using designed photomasks, demonstrating the method's capability for spatial selectivity.

Photo-Healable Fabrics: Achieving Structural Control via Photochemical Solid-Liquid Transitions of Polystyrene/Azobenzene-Containing Polymer Blends.

While polymer fabrics are integral to a wide range of applications, their vulnerability to mechanical damage limits their sustainability and practicality. Addressing this challenge, our study introduces a versatile strategy to develop photohealable fabrics, utilizing a composite of polystyrene (PS) and an azobenzene-containing polymer (PAzo). This combination leverages the structural stability of PS to compensate for the mechanical weaknesses of PAzo, forming the fiber structures. Key to our approach is the reversible trans-cis photoisomerization of azobenzene groups within the PAzo under UV light exposure, enabling controlled morphological alterations in the PS/PAzo blend fibers. The transition of PAzo sections from a solid to a liquid state at a low glass transition temperature (Tg ∼ 13.7 °C) is followed by solidification under visible light, thus stabilizing the altered fiber structures. In this study, we explore various PS/PAzo blend ratios to optimize surface roughness and mechanical properties. Additionally, we demonstrate the capability of these fibers for photoinduced self-healing. When damaged fabrics are clamped and subjected to UV irradiation for 20 min and pressed for 24 h, the mobility of the cis-form PAzo sections facilitates healing while retaining the overall fabric structure. This innovative approach not only addresses the critical issue of durability in polymer fabrics but also offers a sustainable and practical solution, paving the way for its application in smart clothing and advanced fabric-based materials.

Boosting Ion Conductivities: Light-Modulated Azobenzene-Based Ionic Liquids in Vertical Nanochannels.

Exploring stimuli-responsive ion-conductive materials is a challenging task, but it has gained increasing attention because of their enormous potential applications in actuators, sensors, and smart electronics. Here, we demonstrate a distinctive photoresponsive ion-conductive device that utilizes azobenzene-based ionic liquids ([AzoCnMIM][Br], where n = 2, 6, and 10), confined in nanochannels of anodic aluminum oxide (AAO) templates for photoisomerization. The structure of [AzoCnMIM][Br] comprises photoresponsive and hydrophobic azobenzene moieties, hydrophilic imidazolium cations, and negatively charged bromide ions. Therefore, [AzoCnMIM][Br] can form micelles and exhibit photoresponsive ion conductivities. The nanochannels of AAO templates exhibit a confinement effect on the formation of azobenzene-based ionic liquid micelles due to the pore size, thereby preventing the formation of larger micelles that could lead to a decrease in conductivity. Consequently, the ion conductivities of the azobenzene-based ionic liquids are higher in the nanochannels of the AAO templates. The effects of the length of carbon chains on the azobezene-based ionic liquids and the pore size of the AAO templates have also been investigated. Additionally, through irradiation with UV/vis light, [AzoCnMIM][Br] can undergo reversible isomerization, thereby reversibly changing the sizes of the micelles and subsequently altering the ion conductivities.

Smart Temperature-Gating and Ion Conductivity Control of Grafted Anodic Aluminum Oxide Membranes.

Over the past few decades, stimuli-responsive materials have been widely applied to porous surfaces. Permeability and conductivity control of ions confined in nanochannels modified with stimuli-responsive materials, however, have been less investigated. In this work, the permeability and conductivity control of ions confined in nanochannels of anodic aluminum oxide (AAO) templates modified with thermo-responsive poly(N-isopropylacrylamide) (PNIPAM) brushes are demonstrated. By surface-initiated atom transfer radical polymerization (SI-ATRP), PNIPAM brushes are successfully grafted onto the hexagonally packed cylindrical nanopores of AAO templates. The surface hydrophilicities of the membranes can be reversibly altered because of the lower critical solution temperature (LCST) behavior of the PNIPAM polymer brushes. From electrochemical impedance spectroscopy (EIS) analysis, the temperature-gating behaviors of the AAO-g-PNIPAM membranes exhibit larger impedance changes than those of the pure AAO membranes at higher temperatures because of the aggregation of the grafted PNIPAM chains. The reversible surface properties caused by the extended and collapsed states of the polymer chains are also demonstrated by dye release tests. The smart thermo-gated and ion-controlled nanoporous membranes are suitable for future smart membrane applications.

Muscle atrophy-related myotube-derived exosomal microRNA in neuronal dysfunction: Targeting both coding and long noncoding RNAs.

In mammals, microRNAs can be actively secreted from cells to blood. miR-29b-3p has been shown to play a pivotal role in muscle atrophy, but its role in intercellular communication is largely unknown. Here, we showed that miR-29b-3p was upregulated in normal and premature aging mouse muscle and plasma. miR-29b-3p was also upregulated in the blood of aging individuals, and circulating levels of miR-29b-3p were negatively correlated with relative appendicular skeletal muscle. Consistently, miR-29b-3p was observed in exosomes isolated from long-term differentiated atrophic C2C12 cells. When C2C12-derived miR-29b-3p-containing exosomes were uptaken by neuronal SH-SY5Y cells, increased miR-29b-3p levels in recipient cells were observed. Moreover, miR-29b-3p overexpression led to downregulation of neuronal-related genes and inhibition of neuronal differentiation. Interestingly, we identified HIF1α-AS2 as a novel c-FOS targeting lncRNA that is induced by miR-29b-3p through down-modulation of c-FOS and is required for miR-29b-3p-mediated neuronal differentiation inhibition. Our results suggest that atrophy-associated circulating miR-29b-3p may mediate distal communication between muscle cells and neurons.

Two-channel autofluorescence analysis for oral cancer.

We created a two-channel autofluorescence test to detect oral cancer. The wavelengths 375 and 460 nm, with filters of 479 and 525 nm, were designed to excite and detect reduced-form nicotinamide adenine dinucleotide (NADH) and flavin adenine dinucleotide (FAD) autofluorescence. Patients with oral cancer or with precancerous lesions, and a control group with healthy oral mucosae, were enrolled. The lesion in the autofluorescent image was the region of interest. The average intensity and heterogeneity of the NADH and FAD were calculated. The redox ratio [(NADH)/(NADH + FAD)] was also computed. A quadratic discriminant analysis (QDA) was used to compute boundaries based on sensitivity and specificity. We analyzed 49 oral cancer lesions, 34 precancerous lesions, and 77 healthy oral mucosae. A boundary (sensitivity: 0.974 and specificity: 0.898) between the oral cancer lesions and healthy oral mucosae was validated. Oral cancer and precancerous lesions were also differentiated from healthy oral mucosae (sensitivity: 0.919 and specificity: 0.755). The two-channel autofluorescence detection device and analyses of the intensity and heterogeneity of NADH, and of FAD, and the redox ratio combined with a QDA classifier can differentiate oral cancer and precancerous lesions from healthy oral mucosae.

Enhanced vibrational spectroscopy, intracellular refractive indexing for label-free biosensing and bioimaging by multiband plasmonic-antenna array.

In this study, we report a multiband plasmonic-antenna array that bridges optical biosensing and intracellular bioimaging without requiring a labeling process or coupler. First, a compact plasmonic-antenna array is designed exhibiting a bandwidth of several octaves for use in both multi-band plasmonic resonance-enhanced vibrational spectroscopy and refractive index probing. Second, a single-element plasmonic antenna can be used as a multifunctional sensing pixel that enables mapping the distribution of targets in thin films and biological specimens by enhancing the signals of vibrational signatures and sensing the refractive index contrast. Finally, using the fabricated plasmonic-antenna array yielded reliable intracellular observation was demonstrated from the vibrational signatures and intracellular refractive index contrast requiring neither labeling nor a coupler. These unique features enable the plasmonic-antenna array to function in a label-free manner, facilitating bio-sensing and imaging development.