Identifying the intermediate species in an electrocatalytic reaction can provide a great opportunity to understand the reaction mechanism and fabricate a better catalyst. However, the direct observation of intermediate species at a single crystal surface is a daunting challenge for spectroscopic techniques. In this work, electrochemical shell-isolated nanoparticle-enhanced Raman spectroscopy (EC-SHINERS) is utilized to in situ monitor the electrooxidation processes at atomically flat Au(hkl) single crystal electrode surfaces. We systematically explored the effects of crystallographic orientation, pH value, and anion on electrochemical behavior of intermediate (AuOH/AuO) species. The experimental results are well correlated with our periodic density functional theory calculations and corroborate the long-standing speculation based on theoretical calculations in previous electrochemical studies. The presented in situ electrochemical SHINERS technique offers a unique way for a real-time investigation of an electrocatalytic reaction pathway at various well-defined noble metal surfaces.

Iron−platinum alloy nanoparticles (FePt NPs) are extremely promising candidates for the next generation of contrast agents for magnetic resonance (MR) diagnostic imaging and MR-guided interventions, including hyperthermic ablation of solid cancers. FePt has high Curie temperature, saturation magnetic moment, magneto-crystalline anisotropy, and chemical stability. We describe the synthesis and characterization of a family of biocompatible FePt NPs suitable for biomedical applications, showing and discussing that FePt NPs can exhibit low cytotoxicity. The importance of engineering the interface of strongly magnetic NPs using a coating allowing free aqueous permeation is demonstrated to be an essential parameter in the design of new generations of diagnostic and therapeutic MRI contrast agents. We report effective cell internalization of FePt NPs and demonstrate that they can be used for cellular imaging and in vivo MRI applications. This opens the way for several future applications of FePt NPs, including regenerative medicine and stem cell therapy in addition to enhanced MR diagnostic imaging.

Scattering-type scanning near-field microscopy (s-SNOM) at terahertz (THz) frequencies could become a highly valuable tool for studying a variety of phenomena of both fundamental and applied interest, including mobile carrier excitations or phase transitions in 2D materials or exotic conductors. Applications, however, are strongly challenged by the limited signal-to-noise ratio. One major reason is that standard atomic force microscope (AFM) tips -which have made s-SNOM a highly practical and rapidly emerging tool -provide weak scattering efficiencies at THz frequencies. Here we report a combined experimental and theoretical study of commercial and custom-made AFM tips of different apex diameter and length, in order to understand signal formation in THz s-SNOM and to provide insights for tip optimization. Contrary to common beliefs, we find that AFM tips with large (micrometer-scale) apex diameter can enhance s-SNOM signals by more than one order of magnitude, while still offering a spatial resolution of about 100 nm at a wavelength of λ = 119 µm. On the other hand, exploiting the increase of s-SNOM signals with tip length, we succeeded in sub-15 nm (<λ/8000) resolved THz imaging employing a tungsten tip with 6 nm apex radius. We explain our findings and provide novel insights into s-SNOM via rigorous numerical modeling of the near-field scattering process. Our findings will be of critical importance for pushing THz nanoscopy to its ultimate limits regarding sensitivity and spatial resolution. TOC graphics

Incorporating two-dimensional (2D) graphene sheets into a 3D graphene structure provides porous structures to bind enzyme but with low enzyme affinity and unstable structure because of removal of the surficial functional group and the flexibility of graphene sheets. To address this issue, we herein constructed a 3D porous Ti3C2T x MXene–graphene (MG) hybrid film through a facile mixing–drying process. Ti3C2T x MXene nanosheets (MNS) with hydrophilic groups on the rigid flakes endowed the MG hybrid film with open porous structure and a highly hydrophilic miroenvironment. By simply controlling the content of Ti3C2T x MNS and graphene sheets, the sizes of the internal pores were accordingly tunable. The 3D porous hybrid film, fabricated from Ti3C2T x MNS and graphene sheets (weight ratios of 1:2 abd 1:3), supplied more open structure to facilitate the glucose oxidase (GOx) entering the internal pores, which probably enhanced the stable immobilization and retaining of the GOx in the film. As a result, the as-proposed biosensor exhibited prominent electrochemical catalytic capability toward glucose biosensing, which was finally applied for glucose assay in sera. The preparation of the size-controlled 3D porous hybrid film provided a method for effectively binding enzymes/protein further to develop elegant biosensors.