Three-Dimensional Dendritic Au-Ag Substrate for On-Site SERS Detection of Trace Molecules in Liquid Phase.

The development of a facile surface-enhanced Raman scattering (SERS) sensor for the on-site detection of trace molecules in liquid phase is a compelling need. In this paper, a three-dimensional (3D) dendritic Au-Ag nanostructure was constructed by a two-step electro displacement reaction in a capillary tube for the on-site liquid phase detection of trace molecules. The multiplasmon resonance mechanism of the dendritic Au-Ag structure was simulated using the finite-difference time domain (FDTD) method. It was confirmed that the highly branched 3D structure promoted the formation of high-density "hot spots" and interacted with the gold nanoparticles at the dendrite tip, gap, and surface to maximize the spatial electric field, which allowed for high signal intensification to be observed. More importantly, the unique structure of the capillary made it possible to achieve the on-site detection of trace molecules in liquids. Using Rhodamine 6G (R6G) solution as a model molecule, the 3D dendritic Au-Ag substrate exhibited a high detection sensitivity (10-13 mol/L). Furthermore, the developed sensor was applied to the detection of antibacterial agents, ciprofloxacin (CIP), with clear Raman characteristic peaks observed even at concentrations as low as 10-9 mol/L. The results demonstrated that the 3D dendritic Au-Ag sensor could successfully realize the rapid on-site SERS detection of trace molecules in liquids, providing a promising platform for ultrasensitive and on-site liquid sample analysis.

Aggregation-induced emission luminogens for highly effective microwave dynamic therapy.

Aggregation-induced emission luminogens (AIEgens) exhibit efficient cytotoxic reactive oxygen species (ROS) generation capability and unique light-up features in the aggregated state, which have been well explored in image-guided photodynamic therapy (PDT). However, the limited penetration depth of light in tissue severely hinders AIEgens as a candidate for primary or adjunctive therapy for clinical applications. Coincidentally, microwaves (MWs) show a distinct advantage for deeper penetration depth in tissues than light. Herein, for the first time, we report AIEgen-mediated microwave dynamic therapy (MWDT) for cancer treatment. We found that two AIEgens (TPEPy-I and TPEPy-PF6) served as a new type of microwave (MW) sensitizers to produce ROS, including singlet oxygen (1O2), resulting in efficient destructions of cancer cells. The results of 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and live/dead assays reveal that the two AIEgens when activated by MW irradiation can effectively kill cancer cells with average IC-50 values of 2.73 and 3.22 µM, respectively. Overall, the ability of the two AIEgens to be activated by MW not only overcomes the limitations of conventional PDT, but also helps to improve existing MW ablation therapy by reducing the MW dose required to achieve the same therapeutic outcome, thus reducing the occurrence of side-effects of MW radiation.

Radiolabeling strategies and pharmacokinetic studies for metal based nanotheranostics.

Radiolabeled metal-based nanoparticles (MNPs) have drawn considerable attention in the fields of nuclear medicine and molecular imaging, drug delivery, and radiation therapy, given the fact that they can be potentially used as diagnostic imaging and/or therapeutic agents, or even as theranostic combinations. Here, we present a systematic review on recent advances in the design and synthesis of MNPs with major focuses on their radiolabeling strategies and the determinants of their in vivo pharmacokinetics, and together how their intended applications would be impacted. For clarification, we categorize all reported radiolabeling strategies for MNPs into indirect and direct approaches. While indirect labeling simply refers to the use of bifunctional chelators or prosthetic groups conjugated to MNPs for post-synthesis labeling with radionuclides, we found that many practical direct labeling methodologies have been developed to incorporate radionuclides into the MNP core without using extra reagents, including chemisorption, radiochemical doping, hadronic bombardment, encapsulation, and isotope or cation exchange. From the perspective of practical use, a few relevant examples are presented and discussed in terms of their pros and cons. We further reviewed the determinants of in vivo pharmacokinetic parameters of MNPs, including factors influencing their in vivo absorption, distribution, metabolism, and elimination, and discussed the challenges and opportunities in the development of radiolabeled MNPs for in vivo biomedical applications. Taken together, we believe the cumulative advancement summarized in this review would provide a general guidance in the field for design and synthesis of radiolabeled MNPs towards practical realization of their much desired theranostic capabilities. This article is categorized under: Nanotechnology Approaches to Biology > Nanoscale Systems in Biology Diagnostic Tools > Diagnostic Nanodevices Therapeutic Approaches and Drug Discovery > Nanomedicine for Oncologic Disease.

Graphene oxide-highly anisotropic noble metal hybrid systems for intensified surface enhanced Raman scattering and direct capture and sensitive discrimination in PCBs monitoring.

Graphene oxide (GO)-anisotropic noble metal hybrid systems were developed as highly sensitive and reproducible surface enhanced Raman scattering (SERS) platform, in which ultrathin GO was embedded between two metallic layers of flower-like Ag nanoparticles (AgNFs) and gold nanostars (AuNSts). Due to multi-dimensional plasmonic coupling effect, the well-designed AgNFs-GO-AuNSts sandwich structures possessed ultrahigh sensitivity with the detection limit of R6G as low as 1.0 × 10-13 M and high enhancement factor of 2.59 × 107. Additionally, the GO interlayer could function as protective shell to suppress the oxidation of bottom silver layer and efficiently position the target analytes within hot spots. These features endow the substrate with high stability and excellent reproducibility (Signal variations < 7%). Particularly, the GO sandwiched substrate can be explored for the direct capture and sensitive detection of polychlorinated biphenyls (PCBs) without any organic modifier as molecule harvester. This minimum detected concentration was estimated as low as 3.4 × 10-6 M. The detection method based on GO mediated sandwich substrate avoids complicated surface modification manipulations and improves the substrate cleanness. Moreover, the resultant sandwich substrates can be used to recognize fingerprint peaks of different PCBs in their complex mixture, revealing great potential applications in SERS-based simultaneous detection of multiple pollutants with low affinity.

Fabrication and Emission Performance of Nanostructured Re-W Matrix Impregnated Cathodes.

In this study, rhenium-tungsten mixed particles with different content of rhenium have been prepared by spray-drying method followed by hydrogen reduction. Using such particles, the cathodes have been prepared by powder metallurgy followed by impregnating BaO, CaO, and Al2O3 with 4:1:1 molar ratio. After proper activation, electron emission test is performed in standard parallel-plate diode configuration. The emission results reveal that the Re-W matrix cathode containing 75% rhenium has the highest direct current emission density of 11.67 A/cm2 at 1000 °C. The work function of Re-W matrices has been investigated by density functional theory method in the frame of the generalized gradient approximation (GGA). The theoretical calculation results indicate that the work function of the matrix has limited contribution to the emission current density of Re-W matrix dispenser cathode. The in situ AES, SEM, and XRD were applied and the results reveal that the superior emission property of the 75Re cathode is owing to a plenty of nanoparticles and higher free barium concentration on the cathode surface, which is attributed to the Re3W single phase in 75Re matrix.

Theranostic Nanoseeds for Efficacious Internal Radiation Therapy of Unresectable Solid Tumors.

Malignant tumors are considered "unresectable" if they are adhere to vital structures or the surgery would cause irreversible damages to the patients. Though a variety of cytotoxic drugs and radiation therapies are currently available in clinical practice to treat such tumor masses, these therapeutic modalities are always associated with substantial side effects. Here, we report an injectable nanoparticle-based internal radiation source that potentially offers more efficacious treatment of unresectable solid tumors without significant adverse side effects. Using a highly efficient incorporation procedure, palladium-103, a brachytherapy radioisotope in clinical practice, was coated to monodispersed hollow gold nanoparticles with a diameter about 120 nm, to form (103)Pd@Au nanoseeds. The therapeutic efficacy of (103)Pd@Au nanoseeds were assessed when intratumorally injected into a prostate cancer xenograft model. Five weeks after a single-dose treatment, a significant tumor burden reduction (>80%) was observed without noticeable side effects on the liver, spleen and other organs. Impressively, >95% nanoseeds were retained inside the tumors as monitored by Single Photon Emission Computed Tomography (SPECT) with the gamma emissions of (103)Pd. These findings show that this nanoseed-based brachytherapy has the potential to provide a theranostic solution to unresectable solid tumors.

Au/Pd core-shell nanoparticles with varied hollow Au cores for enhanced formic acid oxidation.

A facile method has been developed to synthesize Au/Pd core-shell nanoparticles via galvanic replacement of Cu by Pd on hollow Au nanospheres. The unique nanoparticles were characterized by X-ray diffraction, X-ray photoelectron spectroscopy, transmission electron microscopy, ultraviolet-visible spectroscopy, and electrochemical measurements. When the concentration of the Au solution was decreased, grain size of the polycrystalline hollow Au nanospheres was reduced, and the structures became highly porous. After the Pd shell formed on these Au nanospheres, the morphology and structure of the Au/Pd nanoparticles varied and hence significantly affected the catalytic properties. The Au/Pd nanoparticles synthesized with reduced Au concentrations showed higher formic acid oxidation activity (0.93 mA cm-2 at 0.3 V) than the commercial Pd black (0.85 mA cm-2 at 0.3 V), suggesting a promising candidate as fuel cell catalysts. In addition, the Au/Pd nanoparticles displayed lower CO-stripping potential, improved stability, and higher durability compared to the Pd black due to their unique core-shell structures tuned by Au core morphologies.

Synthesis of highly active and stable Au-PtCu core-shell nanoparticles for oxygen reduction reaction.

Au-PtCu core-shell nanoparticles were successfully synthesized via galvanic replacement of Cu by Pt on hollow Au nano-spheres. Characterizations of the nanoparticles were conducted by X-ray diffraction (XRD), transmission electron microscopy (TEM), and electrochemical measurements. Results indicate 2-2.5 times higher specific activity and mass activity of the Au-PtCu catalysts than commercial Pt black and Pt/C in oxygen reduction reaction (ORR), measured in a rotating disk electrode system. Besides, thinner PtCu coating (25 nm thick, deposition time of 20 min) on the hollow Au nano-spheres demonstrated a pronounced CO oxidation peak shift (by 0.13 V) and long-term durability probably due to the unique core-shell structure and strong electronic coupling between the Au core and the PtCu shell.

Plasmonic properties of polycrystalline hollow Au nanoparticles: a surface roughness effect.

Hollow Au nanoparticles with a 25 nm polycrystalline shell and a 50 nm hollow core were produced in large amounts by using electrochemically evolved hydrogen nanobubbles as templates and reducing agents for electroless deposition from a Na3Au(SO3)2 electrolyte. The surface roughness of these nanoparticles can be tuned by adding NaSO3 into the electrolyte. Different surface roughnesses can be readily obtained for sub-100 nm particles with the same size. As surface roughness increases, surface plasmon resonance (SPR) peaks shift to longer wavelengths. Particles with an 8 nm roughness have a SPR peak centered at 750 nm, which is particularly attractive for in vivo diagnostic and therapeutic applications. A three-dimensional finite difference time domain (FDTD) simulation confirms that the red-shifts of SPR peaks are mainly caused by their surface roughness, and the hollow nature of these particles plays only a minor role. This unique plasmonic property of hollow Au nanoparticles opens up the possibility to maintain the desirable optical properties after loading other substances into the hollow core to form multifunctional core-shell nanoparticles.

Trapping Iron Oxide into Hollow Gold Nanoparticles.

Synthesis of the core/shell-structured Fe3O4/Au nanoparticles by trapping Fe3O4 inside hollow Au nanoparticles is described. The produced composite nanoparticles are strongly magnetic with their surface plasmon resonance peaks in the near infrared region (wavelength from 700 to 800 nm), combining desirable magnetic and plasmonic properties into one nanoparticle. They are particularly suitable for in vivo diagnostic and therapeutic applications. The intact Au surface provides convenient anchorage sites for attachment of targeting molecules, and the particles can be activated by both near infrared lights and magnetic fields. As more and more hollow nanoparticles become available, this synthetic method would find general applications in the fabrication of core-shell multifunctional nanostructures.

Capturing electrochemically evolved nanobubbles by electroless deposition. A facile route to the synthesis of hollow nanoparticles.

Gas evolution during electrochemical deposition has long been regarded as undesired and deliberately suppressed. Here, we show a new role of electrochemically evolved hydrogen bubbles, serving as both templates and reducing agent to form hollow Au nanoparticles via electroless deposition. Hollow gold nanoparticles with a complete nanocrystalline shell and a 50 nm hollow core were fabricated. By controlling the shell thickness, particle size can be varied from 100 to 150 nm. The process is very simple, scalable, and with a high throughput. Using this method, more complicated hollow nanostructures such as double nanoshells ("nanomatryoshka") can also be synthesized. These hollow nanoparticles possess desirable plasmonic properties and can potentially be used as nanocontainers to store and deliver gaseous materials. In addition, the process can be used for fundamental studies of nanobubble formation mechanism.

The fabrication of short metallic nanotubes by templated electrodeposition.

Template-based electrochemical synthesis has widely been used to produce metal nanowires and nanorods. Commercially available filtration membranes, such as anodic aluminum oxide (AAO) and polycarbonate track etch membranes, have commonly been utilized as hard templates for this purpose. In this process, a thick metal film is usually sputtered or vacuum evaporated onto one side of the membrane to block the pores and serve as the working electrode for the subsequent electrodeposition. Here, we show that during the deposition of the metal electrode for AAO membranes, the electrode metal diffuses into the pores and is deposited on the pore walls which leads to preferential electrodeposition of metal on the walls and therefore forms metal tubes. This phenomenon has been utilized to fabricate short nanotubes by carefully controlling the electrodeposition conditions. The process is a straightforward method for any electroplatable materials to form nanoscale tubular structures. The effects of working electrodes and electrodeposition conditions on the formation of tubular structures are discussed in detail. A new mechanism based on this simple fact is proposed to explain the formation of Ni tubes by Ni-Cu co-deposition. Also, we demonstrate how to distinguish magnetic nanotubes from nanorods by a simple magnetic measurement.