Photothermal Nanomaterials: A Powerful Light-to-Heat Converter.

All forms of energy follow the law of conservation of energy, by which they can be neither created nor destroyed. Light-to-heat conversion as a traditional yet constantly evolving means of converting light into thermal energy has been of enduring appeal to researchers and the public. With the continuous development of advanced nanotechnologies, a variety of photothermal nanomaterials have been endowed with excellent light harvesting and photothermal conversion capabilities for exploring fascinating and prospective applications. Herein we review the latest progresses on photothermal nanomaterials, with a focus on their underlying mechanisms as powerful light-to-heat converters. We present an extensive catalogue of nanostructured photothermal materials, including metallic/semiconductor structures, carbon materials, organic polymers, and two-dimensional materials. The proper material selection and rational structural design for improving the photothermal performance are then discussed. We also provide a representative overview of the latest techniques for probing photothermally generated heat at the nanoscale. We finally review the recent significant developments of photothermal applications and give a brief outlook on the current challenges and future directions of photothermal nanomaterials.

Orientation-Dependent Soft Plasmonics of Gold Nanobipyramid Plasmene Nanosheets.

In parallel to the burgeoning field of soft electronics, soft plasmonics focuses on the design and fabrication of plasmonic structures supported on elastomers and to understand how their properties respond to mechanical deformations. Here, we report on a partial ligand-stripping strategy to fabricate elastomer-supported gold nanobipyramid (NBP) plasmene nanosheets. Unlike spherelike building blocks, NBP-building blocks display complex orientation-dependent plasmonic responses to external strains. By collecting polarized plasmonic resonance spectra in conjunction with electrostatic eigenmode modeling, we reveal simultaneous changes in interparticle spacing and spatial orientations of NBP building blocks under mechanical strains. Such changes are directly related to initial NBP packing orders. Further analysis of strain sensitivities for various NBP plasmenes indicated that plasmonic spectra of ∼45° oriented samples are mostly susceptible to strain at acute polarized angles. The results presented may enable novel applications in future soft optoelectronic devices in sensing, encryption, and data storage.

Aqueous Dispersion of Aramid Nanofibers Achieved by Using Tannic Acid for Ultrahigh Strength Films.

Polymer nanofibers have established a robust foundation and possess immense potential in various emerging fields such as sensors and biotechnology. In this study, aqueous dispersions of aramid nanofibers (ANFs) were successfully prepared by using tannic acid (TA). Morphological analysis revealed that TA effectively prevented self-aggregation of ANFs, and preserved the nanofiber structure during TA-assisted solvent exchange. Subsequently, the ANF and TA/ANF films were fabricated using casting and vacuum-assisted filtration techniques. Notably, the tensile strength of the casting TA/ANF film reached 393.8 MPa, exhibiting a remarkable improvement of 41.3% compared to that of the pure ANF film. These exceptional mechanical properties can be attributed to the well-dispersed nanostructures, hydrogen-bonding interactions, zigzag structures, and fiber-bridging effects. Furthermore, the TA/ANF film demonstrated superior ultraviolet (UV) shielding capabilities, visible transparency properties, and excellent resistance to chemical reagents. The above-mentioned interesting findings demonstrate its potential as a nanofiber-reinforced material for poly(vinyl alcohol) (PVA) composites.

Synthesis of flower-like MnO2 nanostructure with freshly prepared Cu particles and electrochemical performance in supercapacitors.

Four types of flowerlike manganese dioxide in nano scale was synthesized via a liquid phase method in KMnO4-H2SO4 solution and Cu particles, wherein the effect of Cu particles was investigated in detail. The obtained manganese dioxide powder was characterized by XRD, SEM and TEM, and the supercapacity properties of MnO2 electrode materials were measured. The results showed that doping carbon black can benefit to better dispersion of copper particles, resulting in generated smaller size of Cu particles, and the morphology of MnO2 nanoparticles was dominated by that of Cu particles. The study of MnO2 synthesis by different sources of Cu particles showed that the size of MnO2 particles decreased significantly with freshly prepared fine copper powder compared with using commercial Cu powder, and the size of MnO2 particles can be further reduced to 120 nm by prepared Cu particles with smaller size. Therefore, it was suggested that the copper particles served as not only the reductant and but also the nuclei centre for the growth of MnO2 particles in synthesis process MnO2, and that is the reason how copper particles worked on the growth of flower-like MnO2 and electrochemical property. In the part of investigation for electrochemical property, the calculated results of b values indicated that the electrode materials have pseudo capacitance property, and the highest specific capacitance of 197.2 F g-1 at 2 mV s-1 and 148 F/g at 1 A/g were obtained for MCE electrode materials (MnO2 was synthesized with freshly prepared copper particles, where carbon black was used and dispersed in ethanol before preparation of Cu particles). The values of charge transfer resistance in all types of MnO2 materials electrodes were smaller than 0.08 Ω. The cycling retention of MCE material electrode is still kept as 93.8% after 1000 cycles.

Cell Sheet-Like Soft Nanoreactor Arrays.

Tissues, which consist of groups of closely packed cell arrays, are essentially sheet-like biosynthesis plants. In tissues, individual cells are discrete microreactors working under highly viscous and confined environments. Herein, soft polystyrene-encased nanoframe (PEN) reactor arrays, as analogous nanoscale "sheet-like chemosynthesis plants", for the controlled synthesis of novel nanocrystals, are reported. Although the soft polystyrene (PS) is only 3 nm thick, it is elastic, robust, and permeable to aqueous solutes, while significantly slowing down their diffusion. PEN-associated palladium (Pd) crystallization follows a diffusion-controlled zero-order kinetics rather than a reaction-controlled first-order kinetics in bulk solution. Each individual PEN reactor has a volume in the zeptoliter range, which offers a unique confined environment, enabling a directional inward crystallization, in contrast to the conventional outward nucleation/growth that occurs in an unconfined bulk solution. This strategy makes it possible to generate a set of mono-, bi-, and trimetallic, and even semiconductor nanocrystals with tunable interior structures, which are difficult to achieve with normal systems based on bulk solutions.

Omnidirectional Hydrogen Generation Based on a Flexible Black Gold Nanotube Array.

Solar-driven hydrogen generation is emerging as an economical and sustainable means of producing renewable energy. However, current photocatalysts for hydrogen generation are mostly powder-based or rigid-substrate-supported, which suffer from limitations, such as difficulties in catalyst regeneration or poor omnidirectional light-harvesting. Here, we report a two-dimensional (2D) flexible photocatalyst based on elastomer-supported black gold nanotube (GNT) arrays with conformal CdS coating and Pt decoration. The highly porous GNT arrays display a strong light-trapping effect, leading to near-complete absorption over almost the entire range of the solar spectrum. In addition, they offer high surface-to-volume ratios promoting efficient photocatalytic reactions. These structural features result in high H2 generation efficiencies. Importantly, our elastomer-supported photocatalyst displays comparable photocatalytic activity even when being mechanically deformed, including bending, stretching, and twisting. We further designed a three-dimensional (3D) tree-like flexible photocatalytic system to mimic Nature's photosynthesis, which demonstrated omnidirectional H2 generation. We believe our strategy represents a promising route in designing next-generation solar-to-fuel systems that rival natural plants.

A soft and ultrasensitive force sensing diaphragm for probing cardiac organoids instantaneously and wirelessly.

Time-lapse mechanical properties of stem cell derived cardiac organoids are important biological cues for understanding contraction dynamics of human heart tissues, cardiovascular functions and diseases. However, it remains difficult to directly, instantaneously and accurately characterize such mechanical properties in real-time and in situ because cardiac organoids are topologically complex, three-dimensional soft tissues suspended in biological media, which creates a mismatch in mechanics and topology with state-of-the-art force sensors that are typically rigid, planar and bulky. Here, we present a soft resistive force-sensing diaphragm based on ultrasensitive resistive nanocracked platinum film, which can be integrated into an all-soft culture well via an oxygen plasma-enabled bonding process. We show that a reliable organoid-diaphragm contact can be established by an 'Atomic Force Microscope-like' engaging process. This allows for instantaneous detection of the organoids' minute contractile forces and beating patterns during electrical stimulation, resuscitation, drug dosing, tissue culture, and disease modelling.

Seagrass-inspired design of soft photocatalytic sheets based on hydrogel-integrated free-standing 2D nanoassemblies of multifunctional nanohexagons.

Natural leaves are virtually two-dimensional (2D) flexible photocatalytic system. In particular, seagrass can efficiently harvest low-intensity sunlight to drive photochemical reactions continuously in an aqueous solution. To mimic this process, we present a novel 2D hydrogel-integrated photocatalytic sheet based on free-standing nanoassemblies of multifunctional nanohexagons (mNHs). The mNHs building blocks is made of plasmonic gold nanohexagons (NHs) decorated with Pd nanoparticles in the corners and CdS nanoparticles throughout their exposed surfaces. The mNHs can self-assemble into free-standing 2D nanoassemblies and be integrated with thin hydrogel films, which can catalyze chemical reactions under visible light illumination. Hydrogels are translucent, porous, and soft, allowing for continuous photochemical conversion in an aqueous environment. Using methylene blue (MB) as a model system, we demonstrate a soft seagrass-like photodegradation design, which offers high efficiency, continuous operation without the need of catalyst regeneration, and omnidirectional light-harvesting capability under low-intensity sunlight irradiation, defying their rigid substrate-supported random aggregates and solution-based discrete counterparts.

Self-assembled Janus plasmene nanosheets as flexible 2D photocatalysts.

A leaf is a free-standing photocatalytic system that can effectively harvest solar energy and convert CO2 and H2O into carbohydrates in a continuous manner without the need for regeneration or tedious product extraction steps. Despite encouraging advances achieved in designing artificial photocatalysts, most of them function in bulk solution or on rigid surfaces. Here, we report on a 2D flexible photocatalytic system based on close packed Janus plasmene nanosheets. One side of the Janus nanosheets is hydrophilic with catalytically active palladium, while the opposite side is hydrophobic with plasmonic nanocrystals. Such a unique design ensures a stable nanostructure on a flexible polymer substrate, preventing dissolution/degradation of plasmonic photocatalysts during chemical conversion in aqueous solutions. Using catalytic reduction of 4-nitrophenol as a model reaction, we demonstrated efficient plasmon-enhanced photochemical conversion on our flexible Janus plasmene. The photocatalytic efficiency could be tuned by adjusting the palladium thickness or types of constituent building blocks or their orientations, indicating the potential for tailor-made catalyst design for desired reactions. Furthermore, the flexible Janus plasmene nanosheets were designed into a small 3D printed artificial tree, which could continuously convert 30 mL of chemicals in 45 minutes.

Plasmene nanosheets as optical skin strain sensors.

Skin-like optoelectronic sensors can have a wide range of technical applications ranging from wearable/implantable biodiagnostics, human-machine interfaces, and soft robotics to artificial intelligence. The previous focus has been on electrical signal transduction, whether resistive, capacitive, or piezoelectric. Here, we report on "optical skin" strain sensors based on elastomer-supported, highly ordered, and closely packed plasmonic nanocrystal arrays (plasmene). Using gold nanocubes (AuNCs) as a model system, we find that the types of polymeric ligands, interparticle spacing, and AuNC sizes play vital roles in strain-induced plasmonic responses. In particular, brush-forming polystyrene (PS) is a "good" ligand for forming elastic plasmenes which display strain-induced blue shift of high-energy plasmonic peaks with high reversibility upon strain release. Further experimental and simulation studies reveal the transition from isotropic uniform plasmon coupling at a non-strained state to anisotropic plasmon coupling at strained states, due to the AuNC alignment perpendicular to the straining direction. The two-term plasmonic ruler model may predict the primary high-energy peak location. Using the relative shift of the averaged high-energy peak to the coupling peak before straining, a plasmene nanosheet may be used as a strain sensor with the sensitivity depending on its internal structures, such as the constituent AuNC size or inter-particle spacing.

Flexible Piezoelectric Pressure Tactile Sensor Based on Electrospun BaTiO3/Poly(vinylidene fluoride) Nanocomposite Membrane.

Poly(vinylidene fluoride) (PVDF)-based piezoelectric materials are promising candidates for sensors, transducers, and actuators, due to several distinctive characteristics such as good flexibility, easy processability, and high mechanical resistance. In the present work, PVDF-based nanocomposites loaded with BaTiO3 nanoparticles (NPs) of various weight fractions were prepared by the electrospinning technique and used for the fabrication of a flexible piezoelectric pressure tactile sensor (PPTS). The addition (5, 10, and 20 wt %) of piezoelectric BaTiO3 NPs improves the piezoelectric performance, especially the ß phase crystals of PVDF/BaTiO3 (10 wt %) nanocomposites that can reach 91.0%. In addition, the mechanical strength of PVDF/BaTiO3 nanocomposites is up to 26.7 MPa, which is an increase of 66% compared to neat PVDF. It should be emphasized that the elongation at break continuously increases from 71% to 153% with increasing BaTiO3 NPs. More importantly, the PPTS (piezoelectric pressure tactile sensor) with the combination of electrospun PVDF/BaTiO3 nanocomposite membranes and polydimethylsiloxane (PDMS) displays excellent flexibility and linear response to external mechanical force. The flexible PPTS devices capable of detecting different music sounds have potential uses in wide fields, such as voice recognition, speech therapy, and ultrasound imaging.

Self-assembly and characterization of 2D plasmene nanosheets.

Freestanding plasmonic nanoparticle (NP) superlattice sheets are novel 2D nanomaterials with tailorable properties that enable their use for broad applications in sensing, anticounterfeit measures, ionic gating, nanophotonics and flat lenses. We recently developed a robust, yet general, two-step drying-mediated approach to produce freestanding monolayer, plasmonic NP superlattice sheets, which are typically held together by holey grids with minimal solid support. Within these superlattices, NP building blocks are closely packed and have strong plasmonic coupling interactions; hence, we termed such freestanding materials 'plasmene nanosheets'. Using the desired NP building blocks as starting material, we describe the detailed fabrication protocol, including NP surface functionalization by thiolated polystyrene and the self-assembly of NPs at the air-water interface. We also discuss various characterization approaches for checking the quality and optical properties of the as-obtained plasmene nanosheets: optical microscopy, spectrophotometry, transmission/scanning electron microscopy (TEM/SEM) and atomic force microscopy (AFM). With regard to different constituent building blocks, the key experimental parameters, including NP concentration and volume, are summarized to guide the successful fabrication of specific types of plasmene nanosheets. This protocol, from initial NP synthesis to the final fabrication and characterization, takes ~33.5 h.

2D Freestanding Janus Gold Nanocrystal Superlattices.

2D freestanding nanocrystal superlattices represent a new class of advanced metamaterials in that they can integrate mechanical flexibility with novel optical, electrical, plasmonic, and magnetic properties into one multifunctional system. The freestanding 2D superlattices reported to date are typically constructed from symmetrical constituent building blocks, which have identical structural and functional properties on both sides. Here, a general ligand symmetry-breaking strategy is reported to grow 2D Janus gold nanocrystal superlattice sheets with nanocube morphology on one side yet with nanostar on the opposite side. Such asymmetric metallic structures lead to distinct wetting and optical properties as well as surface-enhanced Raman scattering (SERS) effects. In particular, the SERS enhancement of the nanocube side is about 20-fold of that of the nanostar side, likely due to the combined "hot spot + lightening-rod" effects. This is nearly 700-fold of SERS enhancement as compared with the symmetric nanocube superlattices without Janus structures.

Covalent-Cross-Linked Plasmene Nanosheets.

Thiol-polystyrene (SH-PS)-capped plasmonic nanoparticles can be fabricated into free-standing, one-nanoparticle-thick superlattice sheets (termed plasmene) based on physical entanglement between ligands, which, however, suffer from irreversible dissociation in organic solvents. To address this issue, we introduce coumarin-based photo-cross-linkable moieties to the SH-PS ligands to stabilize gold nanoparticles. Once cross-linked, the obtained plasmene nanosheets consisting of chemically locked nanoparticles can well maintain structural integrity in organic solvents. Particularly, arising from ligand-swelling-induced enlargement of the interparticle spacing, these plasmene nanosheets show significant optical responses to various solvents in a specific as well as reversible manner, which may offer an excellent material for solvent sensing and dynamic plasmonic display.

2D Binary Plasmonic Nanoassemblies with Semiconductor n/p-Doping-Like Properties.

The electronic, optical, thermal, and magnetic properties of an extrinsic bulk semiconductor can be finely tuned by adjusting its dopant concentration. Here, it is demonstrated that such a doping concept can be extended to plasmonic nanomaterials. Using two-dimensional (2D) assemblies of Au@Ag and Au nanocubes (NCs) as a model system, detailed experimental and theoretical studies are carried out, which reveal collective semiconductor n/p-doping-like plasmonic properties. A threshold doping concentration of Au@Ag NCs is observed, below which p-doping dominates and above which n-doping prevails. Furthermore, Au@Ag NC dopants can be converted into corresponding Au seed "voids" dopants by selectively removing Ag without changing the overall structural integrity. The results show that the plasmonic doping concept may serve as a general design principle guiding synthesis and assembly of plasmonic metamaterials for programmable optoelectronic devices.

Preparation, Characterization, and Electrochromic Properties of Nanocellulose-Based Polyaniline Nanocomposite Films.

On the basis of nanocellulose obtained by acidic swelling and ultrasonication, rodlike nanocellulose/polyaniline nanocomposites with a core-shell structure have been prepared via in situ polymerization. Compared to pure polyaniline, the nanocomposites show superior film-forming properties, and the prepared nanocomposite films demonstrate excellent electrochemical and electrochromic properties in electrolyte solution. Nanocomposite films, especially the one prepared with 40% polyaniline coated nanocomposite, exhibited faster response time (1.5 s for bleaching and 1.0 s for coloring), higher optical contrast (62.9%), higher coloration efficiency (206.2 cm2/C), and more remarkable switching stability (over 500 cycles). These novel nanocellulose-based nanorod network films are promising novel electrochromic materials with excellent properties.

Hypoxia-reoxygenation-induced apoptosis in cultured neonatal rat cardiomyocyets and the protective effect of prostaglandin E.

The aim of the present study was to investigate the effect of prostaglandin (PG) E1 on hypoxia/re-oxygenation (H/R) apoptosis and the expression of bcl-2 and bax in cultured neonatal rat cardiomyocytes. The H/R model was made using the first generation of cultured neonatal rat cardiomyocytes. Hypoxia/re-oxygenation apoptosis was studied by electron microscopy and agarose gel electrophoresis. The percentage of apoptotic cells was measured by terminal deoxyribonucleotidyl transferase-mediated dUTP-digoxigenin nick end-labeling (TUNEL). The expression of bcl-2 and bax was detected by in situ hybridization and immunohistochemical staining. Most cells of the H/R group tested by electron microscopy showed cytoplasmic concentration, nuclear chromatin condensation and margination. Prostaglandin E1 (5, 15 and 45 microg/L) relieved the injury. The results of DNA electrophoresis in the H/R group showed a typical DNA ladder and the DNA ladder decreased gradually corresponding with increasing doses of PGE1. The TUNEL staining showed that the total number of apoptotic cells in the H/R group was much more than that in the PGE1 (45 microg/L) group. The results of in situ hybridization and immunohistochemical staining showed that the bcl-2 content in the H/R group was lower than that in the control group; bax content showed the reverse. Compared with the H/R group, bcl-2 content was significantly higher in the PGE1 (5, 15 and 45 microg/L) groups. However, bax content in the PGE1 (5, 15 and 45 microg/L) groups was significantly lower than that in the H/R group. 6. In conclusion, H/R injury can induce cardiomyocyte apoptosis. Prostaglandin E1 obviously has anti-apoptotic effects on cardiomyocytes and the mechanisms probably involve the inhibition of bax expression and increased expression of bcl-2.

Effect of G(alphaq/11) protein and ATP-sensitive potassium channels on prostaglandin E(1) preconditioning in rat hearts.

AIM: To investigate the effect of G(alphaq/11) signaling pathway and ATP-sensitive potassium channels (K(ATP) channels) on prostaglandin E1 (PGE1) induced early and delay-preconditioning protection in rat hearts. METHODS: Two series of experiments were performed in Wistar rat hearts. In the first series of experiment, all rats were pretreated with PGE1 40 min or 23 h 20 min before the experiment. Ischemia-reperfusion injury was induced by 30 min coronary artery occlusion followed by 90 min reperfusion. Hemodynamics, infarct size, and scores of ventricular arrhythmias were measured. The expression of G(alphaq/11) protein in the heart was measured by Western blot analysis in the second series. RESULTS: Preconditioning with PGE1 (25 microg/kg) markedly reduced infarct size, left ventricular end-diastolic pressure, and scores of ventricular arrhythmia. The effect of PGE1 was significantly attenuated by glibenclamide (1 mg/kg, ip), a nonselective K(ATP) channel inhibitor. PGE1 caused a significant increase in the expression of G(alphaq/11) protein. CONCLUSION: Activations of G(alphaq/11) signal pathway and K(ATP) channel played significant roles in the cardioprotection of PGE1 preconditioning in rat heart and might be an important mechanism of signal transduction pathway during the PGE1 preconditioning.