Plasmon‐Enhanced Spectroscopies with Shell‐Isolated Nanoparticles

Shell‐isolated nanoparticle‐enhanced Raman spectroscopy (SHINERS), due to its versatility, has been able to break the long‐term limitations of the material‐ and substrate‐specific generalities in the traditional field of surface‐enhanced Raman spectroscopy. With a shell‐isolated work principle, this method provides an opportunity to investigate successfully in surface, biological systems, energetic materials, and environmental sciences. Both the shell material and core morphology are being improved continuously to meet the requirements in diverse systems, such as the electrochemical studies at single crystal electrode surfaces, in situ monitoring of photoinduced reaction processes, practical applications in energy conversion and storage, inspections in food safety, and the surface‐enhanced fluorescence. Predictably, the concept of shell‐isolated nanoparticle‐enhancement could be expanded to the wider range for the performance of plasmon‐enhanced spectral modifications.     

Drug‐Loaded Mesoporous Tantalum Oxide Nanoparticles for Enhanced Synergetic Chemoradiotherapy with Reduced Systemic Toxicity

Combining chemotherapy and radiotherapy (chemoradiotherapy) has been widely applied in many clinical practices, showing promises in enhancing therapeutic outcomes. Nontoxic nanocarriers that not only are able to deliver chemotherapeutics into tumors, but could also act as radiosensitizers to enhance radiotherapy would thus be of great interest in the development of chemoradiotherapies. To achieve this aim, herein mesoporous tantalum oxide (mTa₂O₅) nanoparticles with polyethylene glycol (PEG) modification are fabricated. Those mTa₂O₅‐PEG nanoparticles could serve as a drug delivery vehicle to allow efficient loading of chemotherapeutics such as doxorubicin (DOX), whose release appears to be pH responsive. Meanwhile, owing to the interaction of Ta with X‐ray, mTa₂O₅‐PEG nanoparticles could offer an intrinsic radiosensitization effect to increase X‐ray‐induced DNA damages during radiotherapy. As a result, DOX‐loaded mTa₂O₅‐PEG (mTa₂O₅‐PEG/DOX) nanoparticles can offer a strong synergistic therapeutic effect during the combined chemoradiotherapy. Furthermore, in chemoradiotherapy, such mTa₂O₅‐PEG/DOX shows remarkably reduced side effects compared to free DOX, which at the same dose appears to be lethal to animals. This work thus presents a new type of mesoporous nanocarrier particularly useful for the delivery of safe and effective chemoradiotherapy.     

High‐Performance Piezoelectric Nanogenerators with Imprinted P(VDF‐TrFE)/BaTiO3 Nanocomposite Micropillars for Self‐Powered Flexible Sensors

Piezoelectric nanogenerators with large output, high sensitivity, and good flexibility have attracted extensive interest in wearable electronics and personal healthcare. In this paper, the authors propose a high‐performance flexible piezoelectric nanogenerator based on piezoelectrically enhanced nanocomposite micropillar array of polyvinylidene fluoride‐trifluoroethylene (P(VDF‐TrFE))/barium titanate (BaTiO₃) for energy harvesting and highly sensitive self‐powered sensing. By a reliable and scalable nanoimprinting process, the piezoelectrically enhanced vertically aligned P(VDF‐TrFE)/BaTiO₃ nanocomposite micropillar arrays are fabricated. The piezoelectric device exhibits enhanced voltage of 13.2 V and a current density of 0.33 µA cm^?2, which an enhancement by a factor of 7.3 relatives to the pristine P(VDF‐TrFE) bulk film. The mechanisms of high performance are mainly attributed to the enhanced piezoelectricity of the P(VDF‐TrFE)/BaTiO₃ nanocomposite materials and the improved mechanical flexibility of the micropillar array. Under mechanical impact, stable electricity is stably generated from the nanogenerator and used to drive various electronic devices to work continuously, implying its significance in the field of consumer electronic devices. Furthermore, it can be applied as self‐powered flexible sensor work in a noncontact mode for detecting air pressure and wearable sensors for detecting some human vital signs including different modes of breath and heartbeat pulse, which shows its potential applications in flexible electronics and medical sciences.     

Polypyrrole Whelk‐Like Arrays toward Robust Controlling Manipulation of Organic Droplets Underwater

Whelk‐like polypyrrole (PPy) arrays film is successfully prepared by electropolymerization of pyrrole in the presence of low‐surface‐energy tetraethylammonium perfluorooctanesulfonate (TEAPFOS) as dopant. The underwater wettability of PPy whelk‐like arrays can be successfully tuned by electrical doping/dedoping of PFOS ions. Interestingly, CCl₄ droplets with microliter‐size as a representative sample are gathered together to form a larger droplet underwater at the potential of +0.8 V (vs Ag/AgCl), because PPy is in its PFOS‐doped states. Note that CCl₄ droplet can climb uphill successfully on the inclined whelk‐like arrays PPy film under the applied potential of ?1.0 V (vs Ag/AgCl), which may be attributed to wettability gradient derived from different oxidation states of PPy induced by electrochemical potential. These results may provide a simple strategy for on‐demand manipulation of organic droplets underwater at low voltage.     

Hollow Pd/MOF Nanosphere with Double Shells as Multifunctional Catalyst for Hydrogenation Reaction

A new type of hollow nanostructure featured double metal‐organic frameworks shells with metal nanoparticles (MNPs) is designed and fabricated by the methods of ship in a bottle and bottle around the ship. The nanostructure material, hereinafter denoted as Void@HKUST‐1/Pd@ZIF‐8, is confirmed by the analyses of photograph, transmission electron microscopy, scanning electron microscopy, powder X‐ray diffraction, inductively coupled plasma, and N₂ sorption. It possesses various multifunctionally structural characteristics such as hollow cavity which can improve mass transfer, the adjacent of the inner HKUST‐1 shell to the void which enables the matrix of the shell to host and well disperse MNPs, and an outer ZIF‐8 shell which acts as protective layer against the leaching of MNPs and a sieve to guarantee molecular‐size selectivity. This makes the material eligible candidates for the heterogeneous catalyst. As a proof of concept, the liquid‐phase hydrogenation of olefins with different molecular sizes as a model reaction is employed. It demonstrates the efficient catalytic activity and size‐selectivity of Void@HKUST‐1/Pd@ZIF‐8.