Bio-Inspired Interlocking Structures for Enhancing Flexible Coatings Adhesion.

The flexible protective coatings and substrates frequently exhibit unstable bonding in industrial applications. For strong interfacial adhesion of heterogeneous materials and long-lasting adhesion of flexible protective coatings even in harsh corrosive environments. Inspired by the interdigitated structures in Phloeodes diabolicus elytra, a straightforward magnetic molding technique is employed to create an interlocking microarray for reinforced heterogeneous assembly. Benefiting from this bio-inspired microarrays, the interlocking polydimethylsiloxane (PDMS) coating recorded a 270% improvement in tensile adhesion and a 520% increase in shear resistance, approaching the tensile limitation of PDMS. The elastic polyurethane-polyamide (PUPI) coating equipped with interlocking structures demonstrated a robust adhesion strength exceeding 10.8 MPa and is nearly unaffected by the corrosion immersion. In sharp contrast, its unmodified counterpart exhibited low initial adhesion and maintain ≈20% of its adhesion strength after 30 d of immersion. PUPI coating integrated with microarrays exhibits superior resistance to corrosion (30 d, |Z|0.01HZ ≈1010  Ω cm2 , Rct ≈108  Ω cm2 ), cavitation and long-term adhesion retention. These interlocking designs can also be adapted to curved surfaces by 3D printing and enhances heterogeneous assembly of non-bonded materials like polyvinylidene fluoride (PTFE) and PDMS. This bio-inspired interlocking structures offers a solution for durably bonding incompatible interfaces across varied engineering applications.

Regio- and Diastereoselective Hydrophosphination and Hydroamidation of gem-Difluorocyclopropenes.

In this study, concise, efficient, and modular hydrophosphinylation and hydroamidation of gem-difluorocyclopropenes were disclosed in a mild and transition-metal-free pattern. Through this approach, phosphorus, and nitrogen-containing gem-difluorocyclopropanes were produced in moderate to good yields with excellent regio- and diastereoselectivity. Readily available gem-difluorocyclopropenes and nucleophilic reagents, along with inexpensive inorganic bases, were employed. Multiple synthetic applications, including gram-scale and derivatization reactions and modification of bioactive molecules, were subsequently elaborated.

Ultrasensitive, Multiplexed Buoyant Sensor for Monitoring Cytokines in Biofluids.

Multiplexed quantification of low-abundance protein biomarkers in complex biofluids is important for biomedical research and clinical diagnostics. However, in situ sampling without perturbing biological systems remains challenging. In this work, we report a buoyant biosensor that enables in situ monitoring of protein analytes at attomolar concentrations with a 15 min temporal resolution. The buoyant biosensor implemented with fluorescent nanolabels enabled the ultrasensitive and multiplexed detection and quantification of cytokines. Implementing the biosensor in a digital manner (i.e., counting the individual nanolabels) further improves the low detection limit. We demonstrate that the biosensor enables the detection and quantification of the time-varying concentrations of cytokines (e.g., IL-6 and TNF-α) in macrophage culture media without perturbing the live cells. The easy-to-apply biosensor with attomolar sensitivity and multiplexing capability can enable an in situ analysis of protein biomarkers in various biofluids and tissues to aid in understanding biological processes and diagnosing and treating diverse diseases.

A synergistic antibacterial platform: combining mechanical and photothermal effects based on Van-MoS2-Au nanocomposites.

Herein, we successfully developed a new multifunctional antibacterial system, which combined mechano-bactericidal (Au-nanostars) and photothermal (MoS2) mechanism. Meanwhile, the targeting molecule of vancomycin was modified on the surface of MoS2-Au nanocomposites (Van-MoS2-Au), that generally yield high efficiency in antibacterial performance due to their effective working radii. Van-MoS2-Au nanocomposites were capable of completely destroying both gram-negative (E. coli) and gram-positive (B. subtilis) bacteria under 808 NIR laser irradiation for 20 min, and nearly no bacterial growth was detected after 12 h incubation. Moreover, these nanocomposites could destruct the refractory biofilm as well, which was a much more difficult medical challenge. The new antibacterial nanomaterials might offer many biomedical applications because of the biocompatibility and strong antibacterial ability.

Bio-Integrated Wearable Systems: A Comprehensive Review.

Bio-integrated wearable systems can measure a broad range of biophysical, biochemical, and environmental signals to provide critical insights into overall health status and to quantify human performance. Recent advances in material science, chemical analysis techniques, device designs, and assembly methods form the foundations for a uniquely differentiated type of wearable technology, characterized by noninvasive, intimate integration with the soft, curved, time-dynamic surfaces of the body. This review summarizes the latest advances in this emerging field of "bio-integrated" technologies in a comprehensive manner that connects fundamental developments in chemistry, material science, and engineering with sensing technologies that have the potential for widespread deployment and societal benefit in human health care. An introduction to the chemistries and materials for the active components of these systems contextualizes essential design considerations for sensors and associated platforms that appear in following sections. The subsequent content highlights the most advanced biosensors, classified according to their ability to capture biophysical, biochemical, and environmental information. Additional sections feature schemes for electrically powering these sensors and strategies for achieving fully integrated, wireless systems. The review concludes with an overview of key remaining challenges and a summary of opportunities where advances in materials chemistry will be critically important for continued progress.

Conductively coupled flexible silicon electronic systems for chronic neural electrophysiology.

Materials and structures that enable long-term, intimate coupling of flexible electronic devices to biological systems are critically important to the development of advanced biomedical implants for biological research and for clinical medicine. By comparison with simple interfaces based on arrays of passive electrodes, the active electronics in such systems provide powerful and sometimes essential levels of functionality; they also demand long-lived, perfect biofluid barriers to prevent corrosive degradation of the active materials and electrical damage to the adjacent tissues. Recent reports describe strategies that enable relevant capabilities in flexible electronic systems, but only for capacitively coupled interfaces. Here, we introduce schemes that exploit patterns of highly doped silicon nanomembranes chemically bonded to thin, thermally grown layers of SiO2 as leakage-free, chronically stable, conductively coupled interfaces. The results can naturally support high-performance, flexible silicon electronic systems capable of amplified sensing and active matrix multiplexing in biopotential recording and in stimulation via Faradaic charge injection. Systematic in vitro studies highlight key considerations in the materials science and the electrical designs for high-fidelity, chronic operation. The results provide a versatile route to biointegrated forms of flexible electronics that can incorporate the most advanced silicon device technologies with broad applications in electrical interfaces to the brain and to other organ systems.

A Microthermal Sensor for Cryoablation Balloons.

Treatment of atrial fibrillation by cryoablation of the pulmonary vein (PV) suffers from an inability to assess probe contact, tissue thickness, and freeze completion through the wall. Unfortunately, clinical imaging cannot be used for this purpose as these techniques have resolutions similar in scale (∼1 to 2 mm) to PV thickness and therefore are unable to resolve changes within the PV during treatment. Here, a microthermal sensor based on the "3ω" technique which has been used for thin biological systems is proposed as a potential solution and tested for a cryoablation scenario. First, the sensor was modified from a linear format to a serpentine format for integration onto a flexible balloon. Next, using numerical analyses, the ability of the modified sensor on a flat substrate was studied to differentiate measurements in limiting cases of ice, water, and fat. These numerical results were then complemented by experimentation by micropatterning the serpentine sensor onto a flat substrate and onto a flexible balloon. In both formats (flat and balloon), the serpentine sensor was experimentally shown to: (1) identify tissue contact versus fluid, (2) distinguish tissue thickness in the 0.5 to 2 mm range, and (3) measure the initiation and completion of freezing as previously reported for a linear sensor. This study demonstrates proof of principle that a serpentine 3ω sensor on a balloon can monitor tissue contact, thickness, and phase change which is relevant to cryo and other focal thermal treatments of PV to treat atrial fibrillation.

Stretchable array of metal nanodisks on a 3D sinusoidal wavy elastomeric substrate for frequency tunable plasmonics.

Metal nanostructures integrated with soft, elastomeric substrates provide an unusual platform with capabilities in plasmonic frequency tuning of mechanical strain. In this paper, we have prepared a tunable optical device, dense arrays of plasmonic nanodisks on a low-modulus, and high-elongation elastomeric substrate with a three-dimensional (3D) sinusoidal wavy, and their optical characteristics have been measured and analyzed in detail. Since surface plasmon is located and propagates along metal surfaces with sub-wavelength structures, and those dispersive properties are determined by the coupling strength between the individual structures, in this study, a 3D sinusoidal curve elastomeric substrate is used to mechanically control the inter-nanodisk spacing by applying straining and creating a frequency tunable plasmonic device. Here we study the optical resonance peak shifting generated by stretching this type of flexible device, and the role that 3D sinusoidal curve surface configuration plays in determining the tunable properties. Since only the hybrid dipolar mode has been observed in experiments, the coupled dipole approximation (CDA) method is employed to simulate the optical response of these devices, and the experimental and simulation results show that these devices have high tunability to shift optical resonance peaks at near-infrared wavelengths, which will provide strong potential for new soft optical sensors and wearable plasmonic sensors.

Plasmonic Biofoam: A Versatile Optically Active Material.

Owing to their ability to confine and manipulate light at the nanoscale, plasmonic nanostructures are highly attractive for a broad range of applications. While tremendous progress has been made in the synthesis of size- and shape-controlled plasmonic nanostructures, their integration with other materials and application in solid-state is primarily through their assembly on rigid two-dimensional (2D) substrates, which limits the plasmonically active space to a few nanometers above the substrate. In this work, we demonstrate a simple method to create plasmonically active three-dimensional biofoams by integrating plasmonic nanostructures with highly porous biomaterial aerogels. We demonstrate that plasmonic biofoam is a versatile optically active platform that can be harnessed for numerous applications including (i) ultrasensitive chemical detection using surface-enhanced Raman scattering; (ii) highly efficient energy harvesting and steam generation through plasmonic photothermal heating; and (iii) optical control of enzymatic activity by triggered release of biomolecules encapsulated within the aerogel. Our results demonstrate that 3D plasmonic biofoam exhibits significantly higher sensing, photothermal, and loading efficiency compared to conventional 2D counterparts. The design principles and processing methodology of plasmonic aerogels demonstrated here can be broadly applied in the fabrication of other functional foams.

3D Printed Programmable Release Capsules.

The development of methods for achieving precise spatiotemporal control over chemical and biomolecular gradients could enable significant advances in areas such as synthetic tissue engineering, biotic-abiotic interfaces, and bionanotechnology. Living organisms guide tissue development through highly orchestrated gradients of biomolecules that direct cell growth, migration, and differentiation. While numerous methods have been developed to manipulate and implement biomolecular gradients, integrating gradients into multiplexed, three-dimensional (3D) matrices remains a critical challenge. Here we present a method to 3D print stimuli-responsive core/shell capsules for programmable release of multiplexed gradients within hydrogel matrices. These capsules are composed of an aqueous core, which can be formulated to maintain the activity of payload biomolecules, and a poly(lactic-co-glycolic) acid (PLGA, an FDA approved polymer) shell. Importantly, the shell can be loaded with plasmonic gold nanorods (AuNRs), which permits selective rupturing of the capsule when irradiated with a laser wavelength specifically determined by the lengths of the nanorods. This precise control over space, time, and selectivity allows for the ability to pattern 2D and 3D multiplexed arrays of enzyme-loaded capsules along with tunable laser-triggered rupture and release of active enzymes into a hydrogel ambient. The advantages of this 3D printing-based method include (1) highly monodisperse capsules, (2) efficient encapsulation of biomolecular payloads, (3) precise spatial patterning of capsule arrays, (4) "on the fly" programmable reconfiguration of gradients, and (5) versatility for incorporation in hierarchical architectures. Indeed, 3D printing of programmable release capsules may represent a powerful new tool to enable spatiotemporal control over biomolecular gradients.

Plasmonic nanorattles with intrinsic electromagnetic hot-spots for surface enhanced Raman scattering.

The synthesis of plasmonic nanorattles with accessible electromagnetic hotspots that facilitate highly sensitive detection of chemical analytes using surface enhanced Raman scattering (SERS) is demonstrated. Raman spectra obtained from individual nanorattles demonstrate the significantly higher SERS activity compared to solid plasmonic nanostructures.

Single nanoparticle detection using photonic crystal enhanced microscopy.

We demonstrate a label-free biosensor imaging approach that utilizes a photonic crystal (PC) surface to detect surface attachment of individual dielectric and metal nanoparticles through measurement of localized shifts in the resonant wavelength and resonant reflection magnitude from the PC. Using a microscopy-based approach to scan the PC resonant reflection properties with 0.6 µm spatial resolution, we show that metal nanoparticles attached to the biosensor surface with strong absorption at the resonant wavelength induce a highly localized reduction in reflection efficiency and are able to be detected by modulation of the resonant wavelength. Experimental demonstrations of single-nanoparticle imaging are supported by finite-difference time-domain computer simulations. The ability to image surface-adsorption of individual nanoparticles offers a route to single molecule biosensing, in which the particles can be functionalized with specific recognition molecules and utilized as tags.

Effects and mechanisms of surface topography on the antiwear properties of molluscan shells (Scapharca subcrenata) using the fluid-solid interaction method.

The surface topography (surface morphology and structure) of the left Scapharca subcrenata shell differs from that of its right shell. This phenomenon is closely related to antiwear capabilities. The objective of this study is to investigate the effects and mechanisms of surface topography on the antiwear properties of Scapharca subcrenata shells. Two models are constructed-a rib morphology model (RMM) and a coupled structure model (CSM)-to mimic the topographies of the right and left shells. The antiwear performance and mechanisms of the two models are studied using the fluid-solid interaction (FSI) method. The simulation results show that the antiwear capabilities of the CSM are superior to those of the RMM. The CSM is also more conducive to decreasing the impact velocity and energy of abrasive particles, reducing the probability of microcrack generation, extension, and desquamation. It can be deduced that in the real-world environment, Scapharca subcrenata's left shell sustains more friction than its right shell. Thus, the coupled structure of the left shell is the result of extensive evolution.

Probing distance-dependent plasmon-enhanced near-infrared fluorescence using polyelectrolyte multilayers as dielectric spacers.

Owing to their applications in biodetection and molecular bioimaging, near-infrared (NIR) fluorescent dyes are being extensively investigated. Most of the existing NIR dyes exhibit poor quantum yield, which hinders their translation to preclinical and clinical settings. Plasmonic nanostructures are known to act as tiny antennae for efficiently focusing the electromagnetic field into nanoscale volumes. The fluorescence emission from NIR dyes can be enhanced by more than thousand times by precisely placing them in proximity to gold nanorods. We have employed polyelectrolyte multilayers fabricated using layer-by-layer assembly as dielectric spacers for precisely tuning the distance between gold nanorods and NIR dyes. The aspect ratio of the gold nanorods was tuned to match the longitudinal localized surface plasmon resonance wavelength with the absorption maximum of the NIR dye to maximize the plasmonically enhanced fluorescence. The design criteria derived from this study lays the groundwork for ultrabright fluorescence bullets for in vitro and in vivo molecular bioimaging.

Contact pressure-guided wearable dual-channel bioimpedance device for continuous hemodynamic monitoring.

Wearable devices for continuous monitoring of arterial pulse waves have the potential to improve the diagnosis, prognosis, and management of cardiovascular diseases. These pulse wave signals are often affected by the contact pressure between the wearable device and the skin, limiting the accuracy and reliability of hemodynamic parameter quantification. Here, we report a continuous hemodynamic monitoring device that enables the simultaneous recording of dual-channel bioimpedance and quantification of pulse wave velocity (PWV) used to calculate blood pressure (BP). Our investigations demonstrate the effect of contact pressure on bioimpedance and PWV. The pulsatile bioimpedance magnitude reached its maximum when the contact pressure approximated the mean arterial pressure of the subject. We employed PWV to continuously quantify BP while maintaining comfortable contact pressure for prolonged wear. The mean absolute error and standard deviation of the error compared to the reference value were determined to be 0.1 ± 3.3 mmHg for systolic BP, 1.3 ± 3.7 mmHg for diastolic BP, and -0.4 ± 3.0 mmHg for mean arterial pressure when measurements were conducted in the lying down position. This research demonstrates the potential of wearable dual-bioimpedance sensors with contact pressure guidance for reliable and continuous hemodynamic monitoring.

Multifunctional analytical platform on a paper strip: separation, preconcentration, and subattomolar detection.

We report a plasmonic paper-based analytical platform with functional versatility and subattomolar (<10(-18) M) detection limit using surface-enhanced Raman scattering as a transduction method. The microfluidic paper-based analytical device (µPAD) is made with a lithography-free process by a simple cut and drop method. Complex samples are separated by a surface chemical gradient created by differential polyelectrolyte coating of the paper. The µPAD with a starlike shape is designed to enable liquid handling by lateral flow without microchannel patterning. This design generates a rapid capillary-driven flow capable of dragging liquid samples as well as gold nanorods into a single cellulose microfiber, thereby providing an extremely preconcentrated and optically active detection spot.

Hot Spot-Localized Artificial Antibodies for Label-Free Plasmonic Biosensing.

The development of biomolecular imprinting over the last decade has raised promising perspectives in replacing natural antibodies with artificial antibodies. A significant number of reports have been dedicated to imprinting of organic and inorganic nanostructures, but very few were performed on nanomaterials with a transduction function. Herein we describe a relatively fast and efficient plasmonic hot spot-localized surface imprinting of gold nanorods using reversible template immobilization and siloxane co-polymerization. The technique enables a fine control of the imprinting process at the nanometer scale and provides a nanobiosensor with high selectivity and reusability. Proof of concept is established by the detection of neutrophil gelatinase-associated lipocalin (NGAL), a biomarker for acute kidney injury, using localized surface plasmon resonance spectroscopy. The work represents a valuable step towards plasmonic nanobiosensors with synthetic antibodies for label-free and cost-efficient diagnostic assays. We expect that this novel class of surface imprinted plasmonic nanomaterials will open up new possibilities in advancing biomedical applications of plasmonic nanostructures.

Vesicle-mediated growth of tubular branches and centimeter-long microtubes from a single molecule.

The mechanism by which small molecules assemble into microscale tubular structures in aqueous solution remains poorly understood, particularly when the initial building blocks are non-amphiphilic molecules and no surfactant is used. It is here shown how a subnanometric molecule, namely p-aminothiophenol (p-ATP), prepared in normal water with a small amount of ethanol, spontaneously assembles into a new class of nanovesicle. Due to Brownian motion, these nanostructures rapidly grow into micrometric vesicles and start budding to yield macroscale tubular branches with a remarkable growth rate of ∼20 µm s⁻¹. A real-time visualization by optical microscopy reveals that tubular growth proceeds by vesicle walk and fusion on the apex (growth cone) and sides of the branches and ultimately leads to the generation of centimeter-long microtubes. This unprecedented growth mechanism is triggered by a pH-activated proton switch and maintained by hydrogen bonding. The vesicle fusion-mediated synthesis suggests that functional microtubes with biological properties can be efficiently prepared with a mixture of appropriate diaminophenyl blocks and the desired macromolecule. The reversibility, timescale, and very high yield (90%) of this synthetic approach make it a valuable model for the investigation of hierarchical and structural transition between organized assemblies with different size scales and morphologies.

Molecular linker-mediated self-assembly of gold nanoparticles: understanding and controlling the dynamics.

This study sheds light on the mechanism and dynamics of self-assembly of gold nanoparticles (AuNPs) using molecular linkers such as aminothiols. An experimental model is established that enables a fine control and prediction of both assembly rate and degree. Furthermore, we have found that under certain conditions, the increase in the molar ratio of linker/AuNPs beyond a certain threshold unexpectedly and dramatically slows down the assembly rate by charge reversal of the surface of nanoparticles. As a result, the assembly rate can be easily tuned to reach a maximum growth within seconds to several days. The decrease of the same molar ratio (linker/AuNPs) below a certain value leads to self-termination of the reaction at different phases of the assembly process, thus providing nanoparticles chains of different length. This work introduces new handles for a rational design of novel self-assembled architectures in a very time-effective manner and contributes to the understanding of the effect of the assembly morphology on the optical properties of gold nanoparticles.

Plasmonic planet-satellite analogues: hierarchical self-assembly of gold nanostructures.

In the past few years, a remarkable progress has been made in unveiling novel and unique optical properties of strongly coupled plasmonic nanostructures, known as plasmonic molecules. However, realization of such plasmonic molecules using nonlithographic approaches remains challenging largely due to the lack of facile and robust assembly methods. Previous attempts to achieve plasmonic nanoassemblies using molecular ligands were limited to dipolar assembly of nanostructures, which typically results in polydisperse linear and branched chains. Here, we demonstrate that core-satellite structures comprised of shape-controlled plasmonic nanostructures can be achieved through self-assembly using simple molecular cross-linkers. Prevention of self-conjugation and promotion of cross-conjugation among cores and satellites plays a key role in the formation of core-satellite heteroassemblies. The in-built electromagnetic hot-spots and Raman reporters of core-satellite structures make them excellent candidates for surface-enhanced Raman scattering probes.