Plasmonic Annular Nanotrenches with 1 nm Nanogaps for Detection of SARS-CoV-2 Using SERS-Based Immunoassay.

This study represents the synthesis of a novel class of nanoparticles denoted as annular Au nanotrenches (AANTs). AANTs are engineered to possess embedded, narrow circular nanogaps with dimensions of approximately 1 nm, facilitating near-field focusing for detection of severe acute respiratory syndrome coronavirus 2 (SARS-CoV-2) via a surface-enhanced Raman scattering (SERS)-based immunoassay. Notably, AANTs exhibited an exceedingly low limit of detection (LOD) of 1 fg/mL for SARS-CoV-2 spike glycoproteins, surpassing the commercially available enzyme-linked immunosorbent assay (ELISA) by 6 orders of magnitude (1 ng/mL from ELISA). To assess the real-world applicability, a study was conducted on 50 clinical samples using an SERS-based immunoassay with AANTs. The results revealed a sensitivity of 96% and a selectivity of 100%, demonstrating the significantly enhanced sensing capabilities of the proposed approach in comparison to ELISA and commercial lateral flow assay kits.

Ready-to-Use Free-Standing Super-Powder Made with Complex Nanoparticles for SERS.

This study presents a straightforward and efficient synthetic approach for producing high-yield, ready-to-use, free-standing super-powder. The synthesis protocol demonstrates versatility, enabling the creation of assemblies from various nanoparticle morphologies and compositions without the need for specific substrates. Au nanorings are employed as building blocks for fabricating the super-powder, which can be used in surface-enhanced Raman spectroscopy (SERS). The distinctive aspect ratio of the ring nanoframes allows the formation of densely packed columnar assemblies on the substrate, aligning the exposed gaps perpendicular to the laser beam. This arrangement significantly enhances the charge separation among nanorings, leading to a highly focused near-field that is applicable to SERS analysis. The SERS detection feasibility of this powder in both pre- and post-contamination conditions is demonstrated. Using a wide range of building blocks, encompassing various shapes (for instance, rods, hexagons, cubes, cuboctahedrons, elongated dodecahedrons, triangular rings, double-rings, elongated dodecahedra frames, cuboctahedra frames, and double-walled frames), the generalizability of the process for synthesizing super-powders with diverse morphologies is substantiated.

Combinatorial Effect of Tricomponent Dual-Rim Nanoring Building Blocks: Label-Free SERS Detection of Biomolecules.

Detecting weakly adsorbing molecules via label-free surface-enhanced Raman scattering (SERS) has presented a significant challenge. To address this issue, we propose a novel approach for creating tricomponent SERS substrates using dual-rim nanorings (DRNs) made of Au, Ag, and CuO, each possessing distinct functionalities. Our method involves depositing different metals on Pt nanoring skeletons to obtain each nanoring with varying surface compositions while maintaining a similar size and shape. Next, the mixture of these nanorings is transferred into a monolayer assembly with homogeneous intermixing on a solid substrate. The surface of the CuO DRNs has dangling bonds (Cu2+) that facilitate the strong adsorption of carboxylates through the formation of chelating bonds, while the combination of Au and Ag DRNs significantly enhances the SERS signal intensity through a strong coupling effect. Notably, the tricomponent assemblies enable the successful SERS-based analysis of biomolecules such as amino acids, proteins, nucleobases, and nucleotides.

Step-by-Step Nanoscale Top-Down Blocking and Etching Lead to Nanohexapods with Cartesian Geometry.

In this research, we designed a stepwise synthetic method for Au@Pt hexapods where six elongated Au pods are arranged in a pairwise perpendicular fashion, sharing a common point (the central origin in a Cartesian-coordinate-like hexapod shape), featured with tip-selectively decorated Pt square nanoplates. Au@Pt hexapods were successfully synthesized by applying three distinctive chemical reactions in a stepwise manner. The Pt adatoms formed discontinuous thin nanoplates that selectively covered six concave facets of a Au truncated octahedron and served as etching masks in the succeeding etching process, which prevented underlying Au atoms from being oxidized. The subsequent isotropic etching proceeded radially, starting from the bare Au surface, carving the central nanocrystal in a concave manner. By controlling the etching conditions, Au@Pt hexapods were successfully fabricated, wherein the core Au domain is connected to six protruding arms, which hold Pt nanoplates at the ends. Due to their morphology, Au@Pt hexapods feature distinctive optical properties in the near-infrared region, as a proof of concept, allowing for surface-enhanced Raman spectroscopy (SERS)-based monitoring of in situ CO electrooxidation. We further extended our synthetic library by tailoring the size of the Pt nanoplates and neck widths of Au branches, demonstrating the validity of selective blocking and etching-based colloidal synthesis.

Octahedron in a Cubic Nanoframe: Strong Near-Field Focusing and Surface-Enhanced Raman Scattering.

Here, we describe the synthesis of a plasmonic particle-in-a-frame architecture in which a solid Au octahedron is enclosed by a Au cubic nanoframe. The octahedra are positioned inside and surrounded by outer Au cubic nanoframes, creating intra-nanogaps within a single entity. Six sharp vertexes in the Au octahedra point toward the open (100) facets of the cubic nanoframes. This allows not only efficient interactions with the surroundings but also tip-enhanced electromagnetic near-field focusing at the sharp tips of the octahedra, combined with intraparticle coupling. The solid core-frame shell structure enhances near-field focusing, giving rise to a heightened concentration of "hot spots". This effect enables highly sensitive detection of 2-naphthalenethiol and thiram, indicating these substrates for use in surface-enhanced Raman spectroscopy-related applications.

Three-Dimensional Au Octahedral Nanoheptamers: Single-Particle and Bulk Near-Field Focusing for Surface-Enhanced Raman Scattering.

Herein, we present a synthetic approach to fabricate Au nanoheptamers composed of six individual Au nanospheres interconnected through thin metal bridges arranged in an octahedral configuration. The resulting structures envelop central Au nanospheres, producing Au nanosphere heptamers with an open architectural arrangement. Importantly, the initial Pt coating of the Au nanospheres is a crucial step for protecting the inner Au nanospheres during multiple reactions. As-synthesized Au nanoheptamers exhibit multiple hot spots formed by nanogaps between nanospheres, resulting in strong electromagnetic near-fields. Additionally, we conducted surface-enhanced Raman-scattering-based detection of a chemical warfare agent simulant in the gas phase and achieved a limit of detection of 100 ppb, which is 3 orders lower than that achieved using Au nanospheres and Au nanohexamers. This pseudocore-shell nanostructure represents a significant advancement in the realm of complex nanoparticle synthesis, moving the field one step closer to sophisticated nanoparticle engineering.

Plasmonic Dodecahedral-Walled Elongated Nanoframes for Surface-Enhanced Raman Spectroscopy.

Here, elongated pseudohollow nanoframes composed of four rectangular plates enclosing the sides and two open-frame ends with four ridges pointing at the tips for near-field focusing are reported. The side facets act as light-collecting domains and transfer the collected light to the sharp tips for near-field focusing. The nanoframes are hollow inside, allowing the gaseous analyte to penetrate through the entire architecture and enabling efficient detection of gaseous analytes when combined with Raman spectroscopy. The resulting nanostructures are named Au dodecahedral-walled nanoframes. Synthesis of the nanoframes involves shape transformation of Au nanorods with round tips to produce Au-elongated dodecahedra, followed by facet-selective Pt growth, etching of the inner Au, and regrowth steps. The close-packed assembly of Au dodecahedral-walled nanoframes exhibits an attomolar limit of detection toward benzenethiol. This significant enhancement in SERS is attributed to the presence of a flat solid terrace for a large surface area, sharp edges and vertices for strong electromagnetic near-field collection, and open frames for effective analyte transport and capture. Moreover, nanoframes are applied to detect chemical warfare agents, specifically mustard gas simulants, and 20 times higher sensitivity is achieved compared to their solid counterparts.

Au Octahedral Nanosponges: 3D Plasmonic Nanolenses for Near-Field Focusing.

Here, we report the synthesis of three-dimensional plasmonic nanolenses for strong near-field focusing. The nanolens exhibits a distinctive structural arrangement composed of nanoporous sponge-like networks within their interior. We denote these novel nanoparticles as "Au octahedral nanosponges" (Au Oh NSs). Employing a carefully planned multistep synthetic approach with Au octahedra serving as sacrificial templates, we successfully synthesized Au Oh NSs in solution. The porous domains resembling sponges contributed to enhanced scattering and absorption of incident light within metal ligaments. This optical energy was subsequently transferred to the nanospheres at the vertex, where near-field focusing was maximized. We named this observed enhancement a "lightning-sphere effect". Using single particle-by-particle surface-enhanced Raman scattering (SERS), we optimized the morphological dimensions of the spheres and porous domains to achieve the most effective near-field focusing. In the context of bulk SERS measurements targeting weakly adsorbing analytes (2-chloroethyl phenyl sulfide) in the gas phase, we achieved a low detection limit of 10 ppb. For nonadsorbing species (dimethyl methyl phosphonate), utilization of hybrid SERS substrates consisting of Au Oh NSs and metal-organic frameworks as gas-adsorbing intermediate layers was highly effective for successful SERS detection.

Bimetallic alloy Ag@Au nanorings with hollow dual-rims focus near-field on circular intra-nanogaps.

Here, we report a highly sensitive and reliable surface enhanced Raman scattering (SERS)-based immunoassay using bimetallic alloy Ag@Au hollow dual-rim nanorings (DRNs) where two hollow nanorings with different diameters are concentrically overlapped and connected by thin metal ligaments, forming circular hot-zones in the intra-nanogaps between the inner and outer rims. Pt DRNs were first prepared, and then Ag was deposited on the surface of the Pt skeleton, followed by Au coating, resulting in alloy Ag@Au hollow DRNs. The chemical stability of Au and the high optical properties of Ag are incorporated into a single entity, Ag@Au hollow DRNs, enabling strong single-particle SERS activity and biocompatibility through surface modification with thiol-containing functionalities. When Ag@Au hollow DRNs were utilized as nanoprobes for detecting human chorionic gonadotropin (HCG) hormone through a SERS-based immunoassay, a very low limit of detection of 10 pM with high reliability was achieved, strongly indicating their advantage as ultrasensitive SERS nanoprobes.

Multi-Layered PtAu Nanoframes and Their Light-Enhanced Electrocatalytic Activity via Plasmonic Hot Spots.

Here, the rational design of complex PtAu double nanoframes (DNFs) for plasmon-enhanced electrocatalytic activity toward the methanol oxidation reaction (MOR) is reported. The synthetic strategy for the DNFs consists of on-demand multiple synthetic chemical toolkits, including well-faceted Au growth, rim-on selective Pt deposition, and selective Au etching steps. DNFs are synthesized by utilizing Au truncated octahedrons (TOh) as a starting template. The outer octahedral (Oh) nanoframes (NFs) nest the inner TOh NFs, eventually forming DNFs with a tunable intra-nanogap distance. Residual Au adatoms on Pt skeletons act as light entrappers and produce plasmonic hot spots between inner and outer frames through localized surface plasmon resonance (LSPR) coupling, which promotes enhanced electrocatalytic activity for the MOR. Importantly, the correlation between the gap-induced hot carriers and electrocatalytic activity is evaluated. The highest catalytic activity is achieved when the gap is the narrowest. To further harness their light-trapping capability, hierarchically structured triple NFs (TNFs) are synthesized, wherein three NFs are entangled in a single entity with a high density of hot regions, exhibiting superior electrocatalytic activity toward the MOR with a sixfold larger current density under light irradiation compared to the dark conditions.

Postoperative Contralateral Hematoma in Patient with Acute Traumatic Brain Injury.

OBJECTIVE: Head injury is a leading cause of death and disability in subjects who suffer a traumatic accident. Contralateral hematomas after surgery for traumatic brain injury are rare. However, an unrecognized, these hematomas can cause devastating results. We presented our experience of these patients and discussed diagnosis and management. METHODS: This study included 12 traumatic patients with acute traumatic brain injury who developed delayed contralateral hematoma after evacuation of an acute hematoma. Clinical and radiographic data was obtained through review of medical records and radiographs retrospectively. RESULTS: Ten males and two females were included in the study. Ten (83.3%) patients had severe head injury (Glasgow Coma Scale [GCS] score <8). Intraoperative brain swelling during removal of the traumatic subdural hematoma was noted in 10 (83.3%) patients. A skull fracture on the side contralateral to the acute hematoma was noted on computed tomography (CT) scans of nine (75%) patients. Three (33.3%) patients with severe head injury (GCS <8) died. Only (10%) one patient with a severe head injury had less severe disability. CONCLUSION: A postoperative CT scan is essential in patients with acute traumatic brain injury and a contralateral skull fracture or a low GCS score. Our results indicated that it is very important to evaluate this rare but potentially devastating complication.

Neural Axis Metastasis from Metachronous Pulmonary Basaloid Carcinoma Developed after Chemotherapy & Radiation Therapy of Uterine Cervical Carcinoma.

Multiple primary or secondary malignancies after anticancer therapy were recently reported to be increasing in frequency. The authors describe a case of metachronous metastatic pulmonary basaloid carcinoma to the central nervous system that was discovered after chemotherapy and radiation therapy for cervical uterine carcinoma. Two different types of cancer developed within some interval. There's the possibility that a secondary pulmonary neoplasm developed after the chemotherapy and radiotherapy conducted as cervical cancer treatment.

Serpentine Cavernous Aneurysm Presented with Visual Symptoms Improved by Endovascular Coil Trapping.

This report describes a case of a serpentine fusiform aneurysm of the internal carotid artery in a patient who presented with visual disturbances. The serpentine aneurysm was treated successfully by coil trapping and occlusion of the parent artery, accompanied by balloon dilation. Nine months post-operatively, the patient's visual acuity had improved considerably.

Hollow polydimethylsiloxane beads with a porous structure for cell encapsulation.

Based on a water-in-oil-in-water emulsion system, porous and hollow polydimethylsiloxane (PDMS) beads containing cells using a simple fluidic device with three flow channels are fabricated. Poly(ethylene glycol) (PEG) in the PDMS oil phase is served as a porogen for pore development. The feasibility of the porous PDMS beads prepared with different PEG concentrations (10, 20, and 30 wt%) for cell encapsulation in terms of pore size, protein diffusion, and cell proliferation inside the PDMS beads is evaluated. The PDMS beads prepared with PEG 30 wt% are exhibited a highly porous structure and facilitated fast diffusion of protein from the core domain to the outer phase, eventually leading to enhanced cell proliferation. The results clearly indicate that hollow PDMS beads with a porous structure could provide a favorable microenvironment for cell survival due to the large porous structure.

Uniform tricalcium phosphate beads with an open porous structure for tissue engineering.

Uniform tricalcium phosphate (TCP) porous beads with micro and macro pore sizes were fabricated using a simple fluidic device. For micro-porous TCP beads, an aqueous gelatin mixture containing TCP powder was introduced as the discontinuous phase into the fluidic device, where a toluene phase served as the continuous phase. The resulting aqueous TCP droplets were instantly frozen at -20°C and freeze-dried, followed by calcination at 1200°C. An oil-in-water-in-oil (O/W/O) emulsion templating method was employed to fabricate macro-porous TCP beads. An oil-in-water (O/W) emulsion was introduced into the fluidic device as the discontinuous phase with all other experimental conditions the same as for the micro-porous TCP beads. Uniform macro-porous TCP beads with a highly porous structure were finally obtained after freeze-drying and calcination. Large pore size and good interconnectivity of the macro-porous TCP beads were confirmed by scanning electron microscopy and porosimetry. In addition, penetration of host tissue into the macro-pores of the TCP beads was demonstrated by subcutaneously implanting the two types of porous TCP beads into mice and histologically analyzing stained sections at 1-4 weeks post implantation. The macro-porous TCP beads with a highly open porous structure could potentially be used as an injectable material for bone tissue engineering.

A facile method for the preparation of monodisperse beads with uniform pore sizes for cell culture.

This paper describes a facile method for the preparation of porous gelatin beads with uniform pore sizes using a simple fluidic device and their application as supporting materials for cell culture. An aqueous gelatin droplet containing many uniform toluene droplets, produced in the fluidic device, is dropped into liquid nitrogen for instant freezing and the small toluene droplets evolve into pores in the gelatin beads after removal of toluene and then freeze-drying. The porous gelatin beads exhibit a uniform pore size and monodisperse diameter as well as large open pores at the surface. Fluorescence microscopy images of fibroblast-loaded gelatin beads confirm the attachment and proliferation of the cells throughout the porous gelatin beads.

Dibromido(dimethyl sulfoxide-kappaO)(1,10-phenanthroline-kappa(2)N,N')copper(II).

The solvent effect on the molecular structures of copper(II) complexes produced from the reaction between CuBr(2) and 1,10-phenanthroline is evident. The monomeric title compound, [CuBr(2)(C(12)H(8)N(2))(C(2)H(6)OS)], which consists of discrete units, is produced from this reaction in dimethyl sulfoxide (DMSO), whereas a polymeric copper(II) compound is known to be produced from the same reaction in the poor coordinating solvent ethanol. The geometry around the copper(II) ion in the title compound is best described as trigonal-bipyramidal distorted square-based pyramidal, with a tau value of 0.37. The two phenanthroline N atoms, the DMSO O atom and one of the Br atoms occupy the four basal positions, while the second Br atom occupies the axial position. The magnetic susceptibility data also indicate that the title compound is monomeric, but there is still a weak antiferromagnetic interaction between paramagnetic copper(II) centers via the intermolecular 'Cu-Br...Br-Cu' contact pathway.

Tris(1,10-phenanthroline)copper(II) di-mu-iodo-bis(diiodomercurate) dimethyl sulfoxide monohydrate.

In the cationic complex present in the title compound, [Cu(C12H8N2)3][Hg2I6].C2H6OS.H2O, the copper(II) center adopts a highly distorted octahedral geometry, ligated by the six N atoms of three 1,10-phenanthroline ligands. The structure includes an iodide-bridged dimeric mercurate anion for neutrality and uncoordinated dimethyl sulfoxide and water molecules.