Photochemical tuning of dynamic defects for high-performance atomically dispersed catalysts.

Developing active and stable atomically dispersed catalysts is challenging because of weak non-specific interactions between catalytically active metal atoms and supports. Here we demonstrate a general method for synthesizing atomically dispersed catalysts via photochemical defect tuning for controlling oxygen-vacancy dynamics, which can induce specific metal-support interactions. The developed synthesis method offers metal-dynamically stabilized atomic catalysts, and it can be applied to reducible metal oxides, including TiO2, ZnO and CeO2, containing various catalytically active transition metals, including Pt, Ir and Cu. The optimized Pt-DSA/TiO2 shows unprecedentedly high photocatalytic hydrogen evolution activity, producing 164 mmol g-1 h-1 with a turnover frequency of 1.27 s-1. Furthermore, it generates 42.2 mmol gsub-1 of hydrogen via a non-recyclable-plastic-photoreforming process, achieving a total conversion of 98%; this offers a promising solution for mitigating plastic waste and simultaneously producing valuable energy sources.

Cation Exchange in Colloidal Transition Metal Nitride Nanocrystals.

Transition metal nitride (TMN)-based nanostructures have emerged as promising materials for diverse applications in electronics, photonics, energy storage, and catalysis due to their highly desirable physicochemical properties. However, synthesizing TMN-based nanostructures with designed compositions and morphologies poses challenges, especially in the solution phase. The cation exchange reaction (CER) stands out as a versatile postsynthetic strategy for preparing nanostructures that are otherwise inaccessible through direct synthesis. Nevertheless, exploration of the CER in TMNs lags behind that in metal chalcogenides and metal phosphides. Here, we demonstrate cation exchange in colloidal metal nitride nanocrystals, employing Cu3N nanocrystals as starting materials to synthesize Ni4N and CoN nanocrystals. By controlling the reaction conditions, Cu3N@Ni4N and Cu3N@CoN core@shell heterostructures with tunable compositions can also be obtained. The Ni4N and CoN nanocrystals are evaluated as catalysts for the electrochemical oxygen evolution reaction (OER). Remarkably, CoN nanocrystals demonstrate superior OER performance with a low overpotential of 286 mV at 10 mA·cm-2, a small Tafel slope of 89 mV·dec-1, and long-term stability. Our CER approach in colloidal TMNs offers a new strategy for preparing other metal nitride nanocrystals and their heterostructures, paving the way for prospective applications.

Optimization of micelle-encapsulated extremely small sized iron oxide nanoparticles as a T1 contrast imaging agent: biodistribution and safety profile.

BACKGROUND: Iron oxide nanoparticles (IONPs) have been cleared by the Food and Drug Administration (FDA) for various clinical applications, such as tumor-targeted imaging, hyperthermia therapy, drug delivery, and live-cell tracking. However, the application of IONPs as T1 contrast agents has been restricted due to their high r2 values and r2/r1 ratios, which limit their effectiveness in T1 contrast enhancement. Notably, IONPs with diameters smaller than 5 nm, referred to as extremely small-sized IONPs (ESIONs), have demonstrated potential in overcoming these limitations. To advance the clinical application of ESIONs as T1 contrast agents, we have refined a scale-up process for micelle encapsulation aimed at improving the hydrophilization of ESIONs, and have carried out comprehensive in vivo biodistribution and preclinical toxicity assessments. RESULTS: The optimization of the scale-up micelle-encapsulation process, specifically employing Tween60 at a concentration of 10% v/v, resulted in ESIONs that were uniformly hydrophilized, with an average size of 9.35 nm and a high purification yield. Stability tests showed that these ESIONs maintained consistent size over extended storage periods and dispersed effectively in blood and serum-mimicking environments. Relaxivity measurements indicated an r1 value of 3.43 mM- 1s- 1 and a favorable r2/r1 ratio of 5.36, suggesting their potential as T1 contrast agents. Biodistribution studies revealed that the ESIONs had extended circulation times in the bloodstream and were primarily cleared via the hepatobiliary route, with negligible renal excretion. We monitored blood clearance and organ distribution using positron emission tomography and magnetic resonance imaging (MRI). Additionally, MRI signal variations in a dose-dependent manner highlighted different behaviors at varying ESIONs concentrations, implying that optimal dosages might be specific to the intended imaging application. Preclinical safety evaluations indicated that ESIONs were tolerable in rats at doses up to 25 mg/kg. CONCLUSIONS: This study effectively optimized a scale-up process for the micelle encapsulation of ESIONs, leading to the production of hydrophilic ESIONs at gram-scale levels. These optimized ESIONs showcased properties conducive to T1 contrast imaging, such as elevated r1 relaxivity and a reduced r2/r1 ratio. Biodistribution study underscored their prolonged bloodstream presence and efficient clearance through the liver and bile, without significant renal involvement. The preclinical toxicity tests affirmed the safety of the ESIONs, supporting their potential use as T1 contrast agent with versatile clinical application.

Next-Generation Cardiac Interfacing Technologies Using Nanomaterial-Based Soft Bioelectronics.

Cardiac interfacing devices are essential components for the management of cardiovascular diseases, particularly in terms of electrophysiological monitoring and implementation of therapies. However, conventional cardiac devices are typically composed of rigid and bulky materials and thus pose significant challenges for effective long-term interfacing with the curvilinear surface of a dynamically beating heart. In this regard, the recent development of intrinsically soft bioelectronic devices using nanocomposites, which are fabricated by blending conductive nanofillers in polymeric and elastomeric matrices, has shown great promise. The intrinsically soft bioelectronics not only endure the dynamic beating motion of the heart and maintain stable performance but also enable conformal, reliable, and large-area interfacing with the target cardiac tissue, allowing for high-quality electrophysiological mapping, feedback electrical stimulations, and even mechanical assistance. Here, we explore next-generation cardiac interfacing strategies based on soft bioelectronic devices that utilize elastic conductive nanocomposites. We first discuss the conventional cardiac devices used to manage cardiovascular diseases and explain their undesired limitations. Then, we introduce intrinsically soft polymeric materials and mechanical restraint devices utilizing soft polymeric materials. After the discussion of the fabrication and functionalization of conductive nanomaterials, the introduction of intrinsically soft bioelectronics using nanocomposites and their application to cardiac monitoring and feedback therapy follow. Finally, comments on the future prospects of soft bioelectronics for cardiac interfacing technologies are discussed.

[Au9Ag6(CCR)10(DPPM)2Cl2](PPh4): a four-electron cluster with a bi-decahedral twisted metal core.

The assembly of cluster units in a distinct manner can give rise to nanoclusters exhibiting unique geometrical structures and properties. Herein, we present a one-pot synthesis and structural characterization of a AuAg alloy cluster, [Au9Ag6(CCR)10(DPPM)2Cl2](PPh4), denoted as Au9Ag6 (where HCCR is 3,5-bis(trifluoromethyl)phenylacetylene, and DPPM is bis(diphenylphosphino)methane). Single-crystal X-ray diffraction data analysis reveals that Au9Ag6 features a distinctive Au7Ag6 bi-decahedral core, formed by a twisted assembly of two Au4Ag3 decahedra sharing one vertex. The Au4Ag3 building blocks are bridged by two gold atoms on opposite sides of the bi-decahedral core. The Au9Ag6 cluster is monoanionic and it is stabilized by two chloride, two DPPM and ten alkynyl ligands. This cluster represents the first instance of a cluster of clusters built upon decahedral units.

Recent advances in synthesis and properties of silver nanoclusters.

Achieving atomic precision in nanostructured materials is essential for comprehending formation mechanisms and elucidating structure-property relationships. Within the realm of nanoscience and technology, atomically precise ligand-protected noble metal nanoclusters (NCs) have emerged as a rapidly expanding area of interest. These clusters manifest quantum confinement-induced optoelectronic, photophysical, and chemical properties, along with remarkable catalytic capabilities. Among coinage metals, silver distinguishes itself for the fabrication of stable nanoclusters, primarily due to its cost-effectiveness compared to gold. This minireview provides an overview of recent advancements since 2020 in synthetic methodologies and ligand selections toward attaining NCs boasting a minimum of two free valence electrons. Additionally, it explores strategies for fine-tuning optical properties. The discussion extends to surface reactivity, elucidating how exposure to ligands, heat, and light induces transformations in size and structure. Of paramount significance are the applications of silver NCs in catalytic reactions for energy and chemical conversion, supplemented by in-depth mechanistic insights. Furthermore, the review delineates challenges and outlines future directions in the NC field, with an eye toward the design of new functional materials and prospective applications in diverse technologies, including optoelectronics, energy conversion, and fine chemical synthesis.

Tailoring the subshell and electronic structure of an atomically precise AuAg alloy nanocluster.

Manipulating the atomic-level structure of the subshell of a nanocluster while preserving the inner and outer shell structure is challenging. We present the synthesis and molecular structure of an alkynyl-protected Au34Ag27 nanocluster, which exhibits distinct third shell atomic arrangement, electronic structure, and optical properties from those of the Au34Ag28 nanocluster.

Nanocluster Surface Microenvironment Modulates Electrocatalytic CO2 Reduction.

The catalytic activity and product selectivity of the electrochemical CO2 reduction reaction (eCO2RR) depend strongly on the local microenvironment of mass diffusion at the nanostructured catalyst and electrolyte interface. Achieving a molecular-level understanding of the electrocatalytic reaction requires the development of tunable metal-ligand interfacial structures with atomic precision, which is highly challenging. Here, the synthesis and molecular structure of a 25-atom silver nanocluster interfaced with an organic shell comprising 18 thiolate ligands are presented. The locally induced hydrophobicity by bulky alkyl functionality near the surface of the Ag25 cluster dramatically enhances the eCO2RR activity (CO Faradaic efficiency, FECO: 90.3%) with higher CO partial current density (jCO) in an H-cell compared to Ag25 cluster (FECO: 66.6%) with confined hydrophilicity, which modulates surface interactions with water and CO2. Remarkably, the hydrophobic Ag25 cluster exhibits jCO as high as -240 mA cm-2 with FECO >90% at -3.4 V cell potential in a gas-fed membrane electrode assembly device. Furthermore, this cluster demonstrates stable eCO2RR over 120 h. Operando surface-enhanced infrared absorption spectroscopy and theoretical simulations reveal how the ligands alter the neighboring water structure and *CO intermediates, impacting the intrinsic eCO2RR activity, which provides atomistic mechanistic insights into the crucial role of confined hydrophobicity.

Needle-Like Multifunctional Biphasic Microfiber for Minimally Invasive Implantable Bioelectronics.

Implantable bioelectronics has attracted significant attention in electroceuticals and clinical medicine for precise diagnosis and efficient treatment of target diseases. However, conventional rigid implantable devices face challenges such as poor tissue-device interface and unavoidable tissue damage during surgical implantation. Despite continuous efforts to utilize various soft materials to address such issues, their practical applications remain limited. Here, a needle-like stretchable microfiber composed of a phase-convertible liquid metal (LM) core and a multifunctional nanocomposite shell for minimally invasive soft bioelectronics is reported. The sharp tapered microfiber can be stiffened by freezing akin to a conventional needle to penetrate soft tissue with minimal incision. Once implanted in vivo where the LM melts, unlike conventional stiff needles, it regains soft mechanical properties, which facilitate a seamless tissue-device interface. The nanocomposite incorporating with functional nanomaterials exhibits both low impedance and the ability to detect physiological pH, providing biosensing and stimulation capabilities. The fluidic LM embedded in the nanocomposite shell enables high stretchability and strain-insensitive electrical properties. This multifunctional biphasic microfiber conforms to the surfaces of the stomach, muscle, and heart, offering a promising approach for electrophysiological recording, pH sensing, electrical stimulation, and radiofrequency ablation in vivo.

Highly Conductive and Stretchable Hydrogel Nanocomposite Using Whiskered Gold Nanosheets for Soft Bioelectronics.

The low electrical conductivity of conductive hydrogels limits their applications as soft conductors in bioelectronics. This low conductivity originates from the high water content of hydrogels, which impedes facile carrier transport between conductive fillers. This study presents a highly conductive and stretchable hydrogel nanocomposite comprising whiskered gold nanosheets. A dry network of whiskered gold nanosheets is fabricated and then incorporated into the wet hydrogel matrices. The whiskered gold nanosheets preserve their tight interconnection in hydrogels despite the high water content, providing a high-quality percolation network even under stretched states. Regardless of the type of hydrogel matrix, the gold-hydrogel nanocomposites exhibit a conductivity of ≈520 S cm-1 and a stretchability of ≈300% without requiring a dehydration process. The conductivity reaches a maximum of ≈3304 S cm-1 when the density of the dry gold network is controlled. A gold-adhesive hydrogel nanocomposite, which can achieve conformal adhesion to moving organ surfaces, is fabricated for bioelectronics demonstrations. The adhesive hydrogel electrode outperforms elastomer-based electrodes in in vivo epicardial electrogram recording, epicardial pacing, and sciatic nerve stimulation.