A Smart Photothermal Nanosystem with an Intrinsic Temperature-Control Mechanism for Thermostatic Treatment of Bacterial Infections.

Photothermal therapy (PTT) has attracted extensive attention in disease treatments. However, conventional photothermal systems do not possess a temperature-control mechanism, which poses a serious risk to healthy tissues and/or organs due to inevitable thermal damage. Herein, a smart photothermal nanosystem with an intrinsic temperature-control mechanism for thermostatic treatment of bacterial infections is reported. The smart photothermal nanosystem is constructed by loading a thermochromic material into a hollow-structured silica nanocarrier, in which the thermochromic material is composed of naturally occurring phase-change materials (PCMs), a proton-responsive spirolactone, and a proton source. The resulting nanosystem shows strong near-infrared (NIR) absorption and efficient photothermal conversion in solid PCMs but becomes NIR-transparent when PCMs are melted upon NIR irradiation. Such an attractive feature can precisely regulate the photothermal equilibrium temperature to the melting point of PCMs, regardless of the variation in external experimental parameters. In contrast to conventional PTT with severe thermal damage, the reported smart photothermal nanosystem provides an internal protection mechanism on healthy tissues and/or organs, which remarkably accelerates the recovery of bacteria-infected wounds. The smart photothermal nanosystem is a versatile PTT platform, holding great promise in the safe and efficient treatment of bacterial infections and multimodality synergistic therapy.

Bridging D-A type photosensitizers with the azo group to boost intersystem crossing for efficient photodynamic therapy.

Photodynamic therapy (PDT) has attracted much attention in disease treatments. However, the exploration of a novel method for the construction of outstanding photosensitizers (PSs) with stimuli-responsiveness remains challenging. In this study, we, for the first time, report a novel and effective strategy to boost reactive oxygen species (ROS) generation by bridging donor-acceptor (D-A) type PSs with the azo group. In contrast to the counterpart without azo-bridging, the azo-bridged PSs exhibit remarkably enhanced ROS generation via both type-I and type-II photochemical reactions. Theoretical calculations suggest that azo-bridging leads to a prominent reduction in ΔE ST, thereby enabling enhanced ROS generation via efficient intersystem crossing (ISC). The resulting azo-bridged PS (denoted as Azo-TPA-Th(+)) exhibits a particularly strong bactericidal effect against clinically relevant drug-resistant bacteria, with the killing efficiency up to 99.999999% upon white light irradiation. Since azo-bridging generates an azobenzene structure, Azo-TPA-Th(+) can undergo trans-to-cis isomerization upon UV irradiation to form emissive aggregates by shutting down the ISC channel. By virtue of the fluorescence turn-on property of unbound Azo-TPA-Th(+), we propose a straightforward method to directly discern the effective photodynamic bactericidal dose without performing the tedious plate-counting assay. This study opens a brand-new avenue for the design of advanced PSs with both strong ROS generation and stimuli-responsiveness, holding great potential in high-quality PDT with rapid prediction of the therapeutic outcome.

Polarity-Sensitive Fluorescent Probe for Reflecting the Packing Degree of Bacterial Membrane Lipids.

The maintenance of an intact membrane structure is of great importance for bacteria to execute various biological functions. However, chemical probes for monitoring the dynamic changes of bacterial membranes are barely reported. Herein, we, for the first time, report a novel polarity-sensitive probe for reflecting the packing degree of bacterial membrane lipids. Specifically, we synthesize a membrane-targeting fluorescent probe (TICT-lipid) that possesses both twist intramolecular charge transfer and aggregation-induced emission properties. TICT-lipid exhibits sensitive responses to the minute difference in the packing degree of membrane lipids, facilitating rapid differentiation of Gram-negative and Gram-positive bacteria. Interestingly, in the presence of membrane-disrupting antibiotics, the localization of TICT-lipid shifts from the outer membrane to the cell membrane by outputting blue-shifted and enhanced emission, making the mechanism of action of antibiotics clearly visible. TICT-lipid is a polarity-sensitive fluorescent probe, holding great promise in the study of membrane-related bacterial processes and antibiotic screening.

A Sensitive and Reliable Organic Fluorescent Nanothermometer for Noninvasive Temperature Sensing.

Sensing temperature at the subcellular level is of great importance for the understanding of miscellaneous biological processes. However, the development of sensitive and reliable organic fluorescent nanothermometers remains challenging. In this study, we report the fabrication of a novel organic fluorescent nanothermometer and study its application in temperature sensing. First of all, we synthesize a dual-responsive organic luminogen that can respond to the molecular state of aggregation and environmental polarity. Next, natural saturated fatty acids with sharp melting points as well as reversible and rapid phase transition are employed as the encapsulation matrix to correlate external heat information with the fluorescence properties of the luminogen. To apply the composite materials for biological application, we formulate them into colloidally dispersed nanoparticles by a technique that combines in situ surface polymerization and nanoprecipitation. As anticipated, the resultant zwitterionic nanothermometer exhibits sensitive, reversible, reliable, and multiparametric responses to temperature variation within a narrow range around the physiological temperature (i.e., 37 °C). Taking spectral position, fluorescence intensity, and fluorescence lifetime as the correlation parameters, the maximum relative thermal sensitivities are determined to be 2.15% °C-1, 17.06% °C-1, and 17.72% °C-1, respectively, which are much higher than most fluorescent nanothermometers. Furthermore, we achieve the multimodal temperature sensing of bacterial biofilms using these three complementary fluorescence parameters. Besides, we also fabricate a cationic form of the nanothermometer to facilitate efficient cellular uptake, holding great promise for studying thermal behaviors in biological systems.

Two-Dimensional Gold Quantum Dots with Tunable Bandgaps.

Metallic gold nanoparticles (Au NPs) with multilayer Au atoms are useful for plasmonic, chemical, medical, and metamaterial application. In this article, we report the opening of the bandgap in substrate-supported two-dimensional (2D) gold quantum dots (Au QDs) with monolayer Au atoms. Calculations based on density functional theory suggest that 2D Au QDs are energetically favorable over 3D Au clusters when coated on hexagonal boron nitride (BN) surfaces. Experimentally, we find that BN nanotubes (BNNTs) can be used to stabilize 2D Au QDs on their cylindrical surfaces as well as Au atoms, dimers, and trimers. The electrically insulating and optically transparent BNNTs enable the detection of the optical bandgaps of the Au QDs in the visible spectrum. We further demonstrate that the size and shapes of 2D Au QDs could be atomically trimmed and restructured by electron beam irradiation. Our results may stimulate further exploration of energetically stable, metal-based 2D semiconductors, with properties tunable atom by atom.

New Flexible Channels for Room Temperature Tunneling Field Effect Transistors.

Tunneling field effect transistors (TFETs) have been proposed to overcome the fundamental issues of Si based transistors, such as short channel effect, finite leakage current, and high contact resistance. Unfortunately, most if not all TFETs are operational only at cryogenic temperatures. Here we report that iron (Fe) quantum dots functionalized boron nitride nanotubes (QDs-BNNTs) can be used as the flexible tunneling channels of TFETs at room temperatures. The electrical insulating BNNTs are used as the one-dimensional (1D) substrates to confine the uniform formation of Fe QDs on their surface as the flexible tunneling channel. Consistent semiconductor-like transport behaviors under various bending conditions are detected by scanning tunneling spectroscopy in a transmission electron microscopy system (in-situ STM-TEM). As suggested by computer simulation, the uniform distribution of Fe QDs enable an averaging effect on the possible electron tunneling pathways, which is responsible for the consistent transport properties that are not sensitive to bending.

Evolution of Irradiation-Induced Vacancy Defects in Boron Nitride Nanotubes.

Irradiation-induced vacancy defects in multiwalled (MW) boron nitride nanotubes (BNNTs) are investigated via in situ high-resolution transmission electron microscope operated at 80 kV, with a homogeneous distribution of electron beam intensity. During the irradiation triangle-shaped vacancy defects are gradually generated in MW BNNTs under a mediate electron current density (30 A cm(-2)), by knocking the B atoms out. The vacancy defects grow along a well-defined direction within a wall at the early stage as a result of the curvature induced lattice strain, and then develop wall by wall. The orientation or the growth direction of the vacancy defects can be used to identify the chirality of an individual wall. With increasing electron current density, the shape of the irradiation-induced vacancy defects changes from regular triangle to irregular polygon.

A Simple and Universal Technique To Extract One- and Two-Dimensional Nanomaterials from Contaminated Water.

We demonstrate a universal approach to extract one- and two-dimensional nanomaterials from contaminated water, which is based on a microscopic oil-water interface trapping mechanism. Results indicate that carbon nanotubes, graphene, boron nitride nanotubes, boron nitride nanosheets, and zinc oxide nanowires can be successfully extracted from contaminated water at a successful rate of nearly 100%. The effects of surfactants, particle shape, and type of organic extraction fluids are evaluated. The proposed extraction mechanism is also supported by in situ monitoring of the extraction process. We believe that this extraction approach will prove important for the purification of water contaminated by nanoparticles and will support the widespread adoption of nanomaterial applications.

Switching Behaviors of Graphene-Boron Nitride Nanotube Heterojunctions.

High electron mobility of graphene has enabled their application in high-frequency analogue devices but their gapless nature has hindered their use in digital switches. In contrast, the structural analogous, h-BN sheets and BN nanotubes (BNNTs) are wide band gap insulators. Here we show that the growth of electrically insulating BNNTs on graphene can enable the use of graphene as effective digital switches. These graphene-BNNT heterojunctions were characterized at room temperature by four-probe scanning tunneling microscopy (4-probe STM) under real-time monitoring of scanning electron microscopy (SEM). A switching ratio as high as 10(5) at a turn-on voltage as low as 0.5 V were recorded. Simulation by density functional theory (DFT) suggests that mismatch of the density of states (DOS) is responsible for these novel switching behaviors.

Formation of nanodiamonds at near-ambient conditions via microplasma dissociation of ethanol vapour.

Clusters of diamond-phase carbon, known as nanodiamonds, exhibit novel mechanical, optical and biological properties that have elicited interest for a wide range of technological applications. Although diamond is predicted to be more stable than graphite at the nanoscale, extreme environments are typically used to produce nanodiamonds. Here we show that nanodiamonds can be stably formed in the gas phase at atmospheric pressure and neutral gas temperatures <100 °C by dissociation of ethanol vapour in a novel microplasma process. Addition of hydrogen gas to the process allows in flight purification by selective etching of the non-diamond carbon and stabilization of the nanodiamonds. The nanodiamond particles are predominantly between 2 and 5 nm in diameter, and exhibit cubic diamond, n-diamond and lonsdaleite crystal structures, similar to nanodiamonds recovered from meteoritic residues. These results may help explain the origin of nanodiamonds in the cosmos, and offer a simple and inexpensive route for the production of high-purity nanodiamonds.

Room-temperature tunneling behavior of boron nitride nanotubes functionalized with gold quantum dots.

One-dimensional arrays of gold quantum dots (QDs) on insulating boron nitride nanotubes (BNNTs) can form conduction channels of tunneling field-effect transistors. We demonstrate that tunneling currents can be modulated at room temperature by tuning the lengths of QD-BNNTs and the gate potentials. Our discovery will inspire the creative use of nanostructured metals and insulators for future electronic devices.