Flexible Nanowire Cluster as a Wearable Colorimetric Humidity Sensor

Wearable plasmonic devices combine the advantages of high flexibility, ultrathinness, light weight, and excellent integration with the optical benefits mediated by plasmon‐enhanced electric fields. However, two obstacles severely hinder further developments and applications of a wearable plasmonic device. One is the lack of efficient approach to obtaining devices with robust antimotion‐interference property, i.e., the devices can work independently on the morphology changes of their working structures caused by arbitrary wearing conditions. The other issue is to seek a facile and high‐throughput fabrication method to satisfy the financial requirement of industrialization. In order to overcome these two challenges, a functional flexible film of nanowire cluster is developed, which can be easily fabricated by taking the advantages of both conventional electrochemical and sputtering methods. Such flexible plasmonic films can be made into wearable devices that work independently on shape changes induced by various wearing conditions (such as bending, twisting and stretching). Furthermore, due to plasmonic advantages of color controlling and high sensitivity to environment changes, the flexible film of nanowire cluster can be used to fabricate wearable items (such as bracelet, clothes, bag, or even commercial markers), with the ability of wireless visualization for humidity sensing.     

Plasmon Enhanced Fluorescence Based on Porphyrin–Peptoid Hybridized Gold Nanoparticle Platform

A porphyrin–peptoid‐hybridized silica‐coated gold nanoparticle is developed, which is inspired by the protein–chlorophyll ensemble found in photosynthetic antenna. In the natural antenna, chlorophylls are integrated into dense assemblies that are supported by frameworks of proteins, which ensure optimal pigment arrangement for effective light harvesting. In the subject platform, porphyrins are conjugated to the peptoid helix scaffold in a structurally well‐defined alignments and subsequently immobilized on the surface of nanoparticles. This prevents intermolecular aggregation among porphyrins and allows high resolution analysis of the effect of porphyrin configuration on the optical properties of the system. Interestingly, under the influence of plasmon from the gold nanoparticle core, the fluorescence of porphyrin is enhanced up to 24‐fold at the wavelength where the plasmon resonance matches the porphyrin excitation wavelength. In addition, differences in porphyrin configuration result in spectral modification of their fluorescence emissions. Particularly, the peptoid bearing two porphyrins at a distance of 6 Å shows the most significant alteration in fluorescence. The platform can facilitate extensive studies on the relationship between porphyrin arrangement design and their photophysical interaction in antenna complexes.     

Dual‐Action Cancer Therapy with Targeted Porous Silicon Nanovectors

There is a pressing need to develop more effective therapeutics to fight cancer. An idyllic chemotherapeutic is expected to overcome drug resistance of tumors and minimize harmful side effects to healthy tissues. Antibody‐functionalized porous silicon nanoparticles loaded with a combination of chemotherapy drug and gold nanoclusters (AuNCs) are developed. These nanocarriers are observed to selectively deliver both payloads, the chemotherapy drug and AuNCs, to human B cells. The accumulation of AuNCs to target cells and subsequent exposure to an external electromagnetic field in the microwave region render them more susceptible to the codelivered drug. This approach represents a targeted two‐stage delivery nanocarrier that benefits from a dual therapeutic action that results in enhanced cytotoxicity.     

A Novel and Facile Route to Synthesize Atomic‐Layered MoS2 Film for Large‐Area Electronics

High‐quality and large‐area molybdenum disulfide (MoS₂) thin film is highly desirable for applications in large‐area electronics. However, there remains a challenge in attaining MoS₂ film of reasonable crystallinity due to the absence of appropriate choice and control of precursors, as well as choice of suitable growth substrates. Herein, a novel and facile route is reported for synthesizing few‐layered MoS₂ film with new precursors via chemical vapor deposition. Prior to growth, an aqueous solution of sodium molybdate as the molybdenum precursor is spun onto the growth substrate and dimethyl disulfide as the liquid sulfur precursor is supplied with a bubbling system during growth. To supplement the limiting effect of Mo (sodium molybdate), a supplementary Mo is supplied by dissolving molybdenum hexacarbonyl (Mo(CO)₆) in the liquid sulfur precursor delivered by the bubbler. By precisely controlling the amounts of precursors and hydrogen flow, full coverage of MoS₂ film is readily achievable in 20 min. Large‐area MoS₂ field effect transistors (FETs) fabricated with a conventional photolithography have a carrier mobility as high as 18.9 cm² V^?1 s^?1, which is the highest reported for bottom‐gated MoS₂‐FETs fabricated via photolithography with an on/off ratio of ≈10⁵ at room temperature.     

Creation of Faceted Polyhedral Microgels from Compressed Emulsions

Compressed monodisperse emulsions in confined space exhibit highly ordered structures. The influence of the volume fraction and the confinement geometry on the organized structures is investigated and the mechanism by which structural transition occurs is studied. Based on the understanding of ordering behavior of compressed emulsions, a simple and high‐throughput method to fabricate monodisperse polyhedral microgels using the emulsions as the template is developed. By controlling the geometry of the confined spaces, a variety of shapes such as hexagonal prism, Fejes Toth honeycomb prism, truncated octahedron, pyritohedron, and truncated hexagonal trapezohedron are implemented. Moreover, the edge sharpness of each shape is controllable by adjusting the drop volume fraction. This design principle can be readily extended to other shapes and materials, and therefore provides a useful means to create polyhedral microparticles for both fundamental study and practical applications.     

Photonic Reactions Leading to Fluorescence in a Polymeric System Induced by the Photothermal Effect of Magnetite Nanoparticles Using a 780 nm Multiphoton Laser

Recently, polymer‐coated magnetite (Fe₃O₄) nanoparticles (NPs) are extensively studied for applications in therapeutics or diagnostics using photothermal effect. Therefore, it is essential to understand the interactions between Fe₃O₄ NPs and polymers when optical stimuli are applied. Herein, the photonic reactions of Fe₃O₄ NPs and polymer composites upon application of a 780 nm multiphoton laser are analyzed. The photonic reactions produce unique results including fluorescence from conformationally changed polymer and low‐temperature phase transformation of Fe₃O₄ NPs. Typically, π‐conjugated chains are formed, inducing fluorescence through a series of main and side‐chain cleavage reactions of polymers with the aliphatic chain. In addition, fluorescence is detected in the cellular system by photonic reactions between Fe₃O₄ NPs and biomolecules. After multiphoton laser irradiation, light emission is detected near the intracellular Fe₃O₄ NPs, and a stronger intensity is observed in large‐sized NPs.     

High Figure of Merit (FOM) of Bragg Modes in Au‐Coated Nanodisk Arrays for Plasmonic Sensing

Gold‐coated nanodisk arrays of nearly micron periodicity are reported that have high figure of merit (FOM) and sensitivity necessary for plasmonic refractometric sensing, with the added benefit of suitability for surface‐enhanced Raman scattering (SERS), large‐scale microfabrication using standard photolithographic techniques and a simple instrumental setup. Gold nanodisk arrays are covered with a gold layer to excite the Bragg modes (BM), which are the propagative surface plasmons localized by the diffraction from the disk array. This generates surface‐guided modes, localized as standing waves, leading to highly confined fields confirmed by a mapping of the SERS intensity and numerical simulations with 3D finite element method. The optimal gold‐coated nanodisk arrays are applied for refractometric sensing in transmission spectroscopy with better performance than nanohole arrays and they are integrated to a 96‐well plate reader for detection of IgY proteins in the nanometer range in PBS. The potential for sensing in biofluids is assessed with IgG detection in 1:1 diluted urine. The structure exhibits a high FOM of up to 46, exceeding the FOM of structures supporting surface plasmon polaritons and comparable to more complex nanostructures, demonstrating that subwavelength features are not necessary for high‐performance plasmonic sensing.     

Metallic Conductive Nanowires Elaborated by PVD Metal Deposition on Suspended DNA Bundles

Metallic conductive nanowires (NWs) with DNA bundle core are achieved, thanks to an original process relying on double‐stranded DNA alignment and physical vapor deposition (PVD) metallization steps involving a silicon substrate. First, bundles of DNA are suspended with a repeatable process between 2 µm high parallel electrodes with separating gaps ranging from 800 nm to 2 µm. The process consists in the drop deposition of a DNA lambda‐phage solution on the electrodes followed by a naturally evaporation step. The deposition process is controlled by the DNA concentration within the buffer solution, the drop volume, and the electrode hydrophobicity. The suspended bundles are finally metallized with various thicknesses of titanium and gold by a PVD e‐beam evaporation process. The achieved NWs have a width ranging from a few nanometers up to 100 nm. The electrical behavior of the achieved 60 and 80 nm width metallic NWs is shown to be Ohmic and their intrinsic resistance is estimated according to different geometrical models of the NW section area. For the 80 nm width NWs, a resistance of about few ohms is established, opening exploration fields for applications in microelectronics.     

Differential Electrochemical Conductance Imaging at the Nanoscale

Electron transfer in proteins is essential in crucial biological processes. Although the fundamental aspects of biological electron transfer are well characterized, currently there are no experimental tools to determine the atomic‐scale electronic pathways in redox proteins, and thus to fully understand their outstanding efficiency and environmental adaptability. This knowledge is also required to design and optimize biomolecular electronic devices. In order to measure the local conductance of an electrode surface immersed in an electrolyte, this study builds upon the current–potential spectroscopic capacity of electrochemical scanning tunneling microscopy, by adding an alternating current modulation technique. With this setup, spatially resolved, differential electrochemical conductance images under bipotentiostatic control are recorded. Differential electrochemical conductance imaging allows visualizing the reversible oxidation of an iron electrode in borate buffer and individual azurin proteins immobilized on atomically flat gold surfaces. In particular, this method reveals submolecular regions with high conductance within the protein. The direct observation of nanoscale conduction pathways in redox proteins and complexes enables important advances in biochemistry and bionanotechnology.     

Writing with Fluid: Structuring Hydrogels with Micrometer Precision by AFM in Combination with Nanofluidics

Hydrogels have many applications in biomedical surface modification and tissue engineering. However, the structuring of hydrogels after their formation represents still a major challenge, in particular due to their softness. Here, a novel approach is presented that is based on the combination of atomic force microscopy (AFM) and nanofluidics, also referred to as FluidFM technology. Its applicability is demonstrated for supramolecular hydrogel films that are prepared from low‐molecular weight hydrogelators, such as derivates of 1,3,5‐benzene tricarboxamides (BTAs). BTA films can be dissolved selectively by ejecting alkaline solution through the aperture of a hollow AFM‐cantilever connected to a nanofluidic controller. The AFM‐based force control is essential in preventing mechanical destruction of the hydrogels. The resulting “chemical writing” process is studied in detail and the influence of various parameters, such as applied pressure and time, is validated. It is demonstrated that the achievable structuring precision is primarily limited by diffusion and the aperture dimensions. Recently, various additive techniques have been presented to pattern hydrogels. The here‐presented subtractive approach can not only be applied to structure hydrogels from the large class of reversibly formed gels with superior resolution but would also allow for the selective loading of the hydrogels with active substances or nanoparticles.