Multifunctional Gadolinium‐Doped Mesoporous TiO2 Nanobeads: Photoluminescence,Enhanced Spin Relaxation,and Reactive Oxygen Species Photogeneration,Beneficial for Cancer Diagnosis and Treatment

Materials with controllable multifunctional abilities for optical imaging (OI) and magnetic resonant imaging (MRI) that also can be used in photodynamic therapy are very interesting for future applications. Mesoporous TiO₂ sub‐micrometer particles are doped with gadolinium to improve photoluminescence functionality and spin relaxation for MRI, with the added benefit of enhanced generation of reactive oxygen species (ROS). The Gd‐doped TiO₂ exhibits red emission at 637 nm that is beneficial for OI and significantly improves MRI relaxation times, with a beneficial decrease in spin–lattice and spin–spin relaxation times. Density functional theory calculations show that Gd³⁺ ions introduce impurity energy levels inside the bandgap of anatase TiO₂, and also create dipoles that are beneficial for charge separation and decreased electron–hole recombination in the doped lattice. The Gd‐doped TiO₂ nanobeads (NBs) show enhanced ability for ROS monitored via ^?OH radical photogeneration, in comparison with undoped TiO₂ nanobeads and TiO₂ P25, for Gd‐doping up to 10%. Cellular internalization and biocompatibility of TiO₂@x Gd NBs are tested in vitro on MG‐63 human osteosarcoma cells, showing full biocompatibility. After photoactivation of the particles, anticancer trace by means of ROS photogeneration is observed just after 3 min irradiation.     

Rational Design and Synthesis of Extremely Efficient Macroporous CoSe2–CNT Composite Microspheres for Hydrogen Evolution Reaction

Uniquely structured CoSe₂–carbon nanotube (CNT) composite microspheres with optimized morphology for the hydrogen‐evolution reaction (HER) are prepared by spray pyrolysis and subsequent selenization. The ultrafine CoSe₂ nanocrystals uniformly decorate the entire macroporous CNT backbone in CoSe₂–CNT composite microspheres. The macroporous CNT backbone strongly improves the electrocatalytic activity of CoSe₂ by improving the electrical conductivity and minimizing the growth of CoSe₂ nanocrystals during the synthesis process. In addition, the macroporous structure resulting from the CNT backbone improves the electrocatalytic activity of the CoSe₂–CNT microspheres by increasing the removal rate of generated H₂ and minimizing the polarization of the electrode during HER. The CoSe₂–CNT composite microspheres demonstrate excellent catalytic activity for HER in an acidic medium (10 mA cm^?2 at an overpotential of ≈174 mV). The bare CoSe₂ powders exhibit moderate HER activity, with an overpotential of 226 mV at 10 mA cm^?2. The Tafel slopes for the CoSe₂–CNT composite and bare CoSe₂ powders are 37.8 and 58.9 mV dec^?1, respectively. The CoSe₂–CNT composite microspheres have a slightly larger Tafel slope than that of commercial carbon‐supported platinum nanoparticles, which is 30.2 mV dec^–1.     

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.     

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.     

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.     

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.