Sunlight-Driven Photothermally Boosted Photocatalytic Eradication of Superbugs Using a Plasmonic Gold Nanoparticle-Decorated WO3 Nanowire-Based Heterojunction.

Superbug infections are currently one of the biggest global health problems in our society. Herein, we report the design of a plasmonic gold nanoparticle (GNP)-decorated WO3 nanowire-based heterojunction for the proficient usage of sunlight-based renewable energy to inactivate 100% superbugs via photothermally boosted photocatalytic action. Additionally, a synergistic photothermal and photocatalytic approach has been used for sunlight-driven complete eradication of carbapenem-resistant Enterobacteriaceae Escherichia coli (CRE E. coli) and methicillin-resistant Staphylococcus aureus (MRSA) superbugs. Interestingly, photocatalytic activity of methylene blue (MB) dye degradation in the presence of 670 nm near-infrared light shows that photothermally boosted photocatalytic performance is much superior to that of only a photocatalytic or photothermal process. The observed higher photocatalytic performance for the heterojunction is because the plasmonic GNP enhanced the absorption capability at 670 nm and increased the temperature of the photocatalyst surface, which reduces the activation energy of the degradation reaction. Similarly, sunlight-driven photocatalytic experiments show 100% degradation of MB after 60 min of sunlight irradiation. Moreover, sunlight-based photocatalytic inactivation of MRSA and CRE E. coli experiments show 100% inactivation after 60 min of light irradiation.

Musculoskeletal defects associated with myosin heavy chain-embryonic loss of function are mediated by the YAP signaling pathway.

Mutations in MYH3, the gene encoding the developmental myosin heavy chain-embryonic (MyHC-embryonic) skeletal muscle-specific contractile protein, cause several congenital contracture syndromes. Among these, recessive loss-of-function MYH3 mutations lead to spondylocarpotarsal synostosis (SCTS), characterized by vertebral fusions and scoliosis. We find that Myh3 germline knockout adult mice display SCTS phenotypes such as scoliosis and vertebral fusion, in addition to reduced body weight, muscle weight, myofiber size, and grip strength. Myh3 knockout mice also exhibit changes in muscle fiber type, altered satellite cell numbers and increased muscle fibrosis. A mass spectrometric analysis of embryonic skeletal muscle from Myh3 knockouts identified integrin signaling and cytoskeletal regulation as the most affected pathways. These pathways are closely connected to the mechanosensing Yes-associated protein (YAP) transcriptional regulator, which we found to be significantly activated in the skeletal muscle of Myh3 knockout mice. To test whether increased YAP signaling might underlie the musculoskeletal defects in Myh3 knockout mice, we treated these mice with CA3, a small molecule inhibitor of YAP signaling. This led to increased muscle fiber size, rescue of most muscle fiber type alterations, normalization of the satellite cell marker Pax7 levels, increased grip strength, reduced fibrosis, and decline in scoliosis in Myh3 knockout mice. Thus, increased YAP activation underlies the musculoskeletal defects seen in Myh3 knockout mice, indicating its significance as a key pathway to target in SCTS and other MYH3-related congenital syndromes.

Picomolar Detection of Lead Ions (Pb2+) by Functionally Modified Fluorescent Carbon Quantum Dots from Watermelon Juice and Their Imaging in Cancer Cells.

Water contamination due to the presence of lead is one of the leading causes of environmental and health hazards because of poor soil and groundwater waste management. Herein we report the synthesis of functionally modified luminescent carbon quantum dots (CQDs) obtained from watermelon juice as potential nanomaterials for the detection of toxic Pb2+ ions in polluted water and cancer cells. By introducing surface passivating ligands such as ethanolamine (EA) and ethylenediamine (ED) in watermelon juice, watermelon-ethanolamine (WMEA)-CQDs and watermelon-ethylenediamine (WMED)-CQDs exhibited a remarkable ~10-fold and ~6-fold increase in fluorescence intensity with respect to non-doped WM-CQDs. The relative fluorescence quantum yields of WMEA-CQDs and WMED-CQDs were found to be 8% and 7%, respectively, in an aqueous medium. Among various functionally-modified CQDs, only WMED-CQDs showed high selectivity towards Pb2+ ions with a remarkably good limit of detection (LoD) of 190 pM, which is less than that of the permissible limit (72 nM) in drinking water. The functionally altered WMED-CQDs detected Pb2+ metal ions in polluted water and in a human cervical cancer cell line (HeLa), thus advocating new vistas for eco-friendly nanomaterials for their use as diagnostic tools in the environment and biomedical research areas.

Scalable Hybrid Antibacterial Surfaces: TiO2 Nanoparticles with Black Silicon.

With the increase of drug resistance, there is a need for surface coatings that inhibit microbes without antibiotics. Nanostructured photocatalysts, like TiO2-coated nanotubes, are promising alternatives to antibiotics. Nanostructures rupture the cell wall by impaling the bacteria. Photocatalysts generate reactive oxygen species (ROS) in the presence of light, which oxidize organic matter. The combined effect of photocatalysts and nanostructures is better than the addition of individual components, as nanostructures also enhance the ROS production by trapping light. The synergetic effect is remarkably effective in reducing the growth of bacterial colonies, but scalability still remains a challenge. Conventional techniques like atomic layer deposition (ALD) are excellent for proof of concept but are not scalable to hundreds of square meters, as needed for practical applications. This report demonstrates two scalable and cost-effective techniques for synthesizing photocatalytic nanostructures: spray- and spin-coating TiO2 nanoparticles. Unlike ALD, spray- and spin-coated TiO2 nanoparticles do not reduce the roughness of a structured surface, which improves antibacterial performance by 23%. Integration of nanostructures with spray-coated TiO2 is potentially a low-cost and scalable technology for large-area antibacterial surfaces.

Ambient Light-Activated Antibacterial Material: Manganese Vanadium Oxide (Mn2V2O7).

Antimicrobial surfaces can reduce the spread of bacteria from high-touch surfaces, saving millions of lives worldwide. Antibacterial photocatalytic films, like TiO2, are widely reported but limited in practice because they need high-intensity UV light. More practical but less reported are photocatalysts that work under low-intensity visible light from an indoor lamp. Here, we demonstrate that manganese vanadium oxide (MVO) is an antibacterial photocatalyst that works under light-emitting diode (LED) lights at ∼3000 lux. MVO is an earth-abundant semiconductor with a band gap of 1.7 eV that absorbs visible light to create reactive oxygen species (ROS) in water. ROS reduces bacteria counts by 4 orders of magnitude in 8 h under 9000 lux LED light. The antibacterial effect is significant even in MVO powder and films, which are amenable to large-area fabrication. MVO is a promising candidate for next-generation antimicrobial coatings that are stable, cheap, effective, earth-abundant, and activated by indoor lights.

Designing Photocatalytic Nanostructured Antibacterial Surfaces: Why Is Black Silica Better than Black Silicon?

The efficiency of photocatalytic antibacterial surfaces is limited by the absorption of light in it. Light absorption in photocatalytic surfaces can be enhanced by structuring it, leading to increased generation of reactive oxygen species (ROS) and hence improved bactericidal efficacy. A second, more passive methodology to kill bacteria involves the use of sharp nanostructures that mechanically disrupt the bacterial membrane. Recently, these two mechanisms were combined to form photoactive nanostructured surfaces with better antibacterial efficacy. However, the design rules for fabricating the optimal photoactive nanostructured surfaces have not been articulated. Here we show that for optimal performance it is very important to account for optoelectrical properties and geometry of the photoactive coating and the underlying pillar. We show that TiO2-coated nanopillars arrays made of SiO2, a material with a low extinction coefficient, have 73% higher bactericidal efficacies than those made of Si, a material with a high extinction coefficient. The finite element method (FEM) shows that despite the higher absorption in higher aspect ratio nanopillars, their performance is not always better. The concentration of bulk ROS saturates around 5 µm. For taller pillars, the improvement in surface ROS concentration is minimal due to the diffusion bottleneck. Simulation results corroborate with the experimentally observed methylene blue degradation and bacterial count measurements and provide an explanation of the observed phenomenon. The guidelines for designing these optically activated photocatalyst nanopillars can be extended to other photocatalytic material after adjusting for their respective properties.

Synthesis of Solution-Processable Donor-Acceptor Pyranone Dyads for White Organic Light-Emitting Devices.

A series of donor-acceptor pyranones (3a-m, 4a-h) were synthesized using α-oxo-ketene- S, S-acetal as the synthon for their application as emissive materials for energy-saving organic light-emitting devices (OLEDs). Among them, five pyranones 3f, 3g, 3h, 3m, and 4e exhibited highly bright fluorescence in the solid state and weak or no emission in the solution state. Photophysical analysis of these dyes revealed that only 3f and 3m showed aggregation-induced emission behavior in a THF/water mixture (0-99%) with varying water fractions ( fw) leading to bright fluorescence covering the entire visible region, while other derivatives 3g, 3h, and 4e did not show any fluorescence signal. The computational studies of the compounds revealed that the longer wavelength absorption originates from HOMO to LUMO electronic excitation. These dyes exhibited good thermal stability with 5% weight loss temperature in the range of 218-347 °C. The potential application of the donor-acceptor pyranone dyads was demonstrated by fabrication of solution-processed OLEDs. Remarkably, OLED devices prepared using highly emissive compounds 6-(anthracen-9-yl)-4-(methylthio)-2-oxo-2 H-pyran-3-carbonitrile (3m) and 6-(4-methoxyphenyl)-4-(methylthio)-2-oxo-2 H-pyran-3-carbonitrile (3f) displayed pure white emission with CIE coordinates of (0.29, 0.31) and (0.32, 0.32), respectively. Additionally, the resultant devices exhibited external quantum efficiencies of 1.9 and 1.2% at 100 cd m-2, respectively.

Facile synthesis of mixed O, S or Se bearing hexasubstituted benzenes and their potential as Cu(ii) ion probe.

The present study offers a facile route for the synthesis of unsymmetrical hexasubstituted benzenes bearing alternate heteroatoms (O, S and Se) with the formula [1,3,5-(RSeCH2)3-2,4,6-(R'ECH2)3C6] (E = O, S or Se). The synthetic protocol involves the use of an in situ generated tris(selenonium) ion followed by treatment with another nucleophile affording the targeted species in >70% yields. The unsymmetrical hexasubstituted derivatives were characterized on the basis of physicochemical and spectroscopic data and in a representative case with single crystal X-ray study. The current work assumes great significance as the potential of these species as "turn-off" chemical sensors for Cu2+, which is a biologically and environmentally crucial metal ion, was also successfully demonstrated by 5a which bears alternate oxygen and selenium centres.

En Route Activity of Hydration Water Allied with Uranyl (UO22+) Salts Amid Complexation Reactions with an Organothio-Based (O, N, S) Donor Base.

This study provides en route activity of hydration water allied with uranyl salts amid complexation reactions with a donor species L bearing O, N, and S (phenolic, -OH; imine, -HC═N-; and thio-, -S-) donor functionalities. The UO22+/L reaction encounters a series of hydrolytic steps with hydration water released from uranyl salts during the complexation processes. Primarily, the coordinated [L(-HC=N)(OH)(-HC=N) → UO2(NO3)2/(OAc)2] species formed during the complexation process undergoes partial hydrolysis of the coordinated ligand resulting in the isolation of an aldehyde coordinated uranyl species [L(-HC=N)(OH)(-HC=O) → UO2(NO3)2/(OAc)2]. The influence of hydration water continued as the reaction further proceeded to the next stage resulting in alteration of the aldehyde coordinated uranyl species [L(-HC=N)(OH)(-HC=O) → UO2(NO3)2/(OAc)2] to an oxidized carboxy coordinated uranyl species [L(-HC=N) (OH){-C(═O)O} → (NO3)/(OAc)]2 without the use of any external oxidizing agents. These studies are of particular significance as they allow one to realize the adventitious role of hydration water released from commonly used uranyl salts during their reaction with organic donor substrates in nonaqueous medium. These results also form an experimental basis to understand the critical behavior of UO22+ ion activity (as oxidizing, reducing, or catalytic) relevant in many chemical, biological, and environmental processes.

First Dual Responsive "Turn-On" and "Ratiometric" AIEgen Probe for Selective Detection of Hydrazine Both in Solution and the Vapour Phase.

A new dual responsive "turn-on" and "ratiometric" aggregation-induced emission luminogen (AIEgen) 3-formyl-5-(piperidin-1-yl)biphenyl-4-carbonitrile 6 a (FPBC 6 a) for selective detection of hydrazine in solution as well as in vapour phase is described. At a low concentration of 2.5 µm, the probe FPBC 6 a is non-fluorescent (turn-off) but remarkably lights up (turn-on with blue emission) in the presence of hydrazine solution (0.25-25 µm). Interestingly, at higher concentrations, the nanoaggregates of FPBC 6 a (>25 µm, 99 % HEPES in DMSO) displayed ratiometric response in the presence of hydrazine with a remarkable hypsochromic shift from the green (500-550 nm) to blue regions (440-480 nm). Furthermore, a real application of FPBC 6 a was successfully demonstrated through the detection and visualization of hydrazine in live cervical cancer cells as well as using portable test strips.

White Light Induced E/Z-Photoisomerization of Diphenylamine-Tethered Fluorescent Stilbene Derivatives: Synthesis, Photophysical, and Electrochemical Investigation.

A facile synthesis and detailed photophysical investigation of E/Z-isomerization of fluorescent diphenylamine tethered stilbene derivatives (DPASs) under white light exposure have been carried out to understand the effect on fluorescence, electrochemical properties, and photostability under various activation/deactivation pathways. In solution state, in the dark, the E-isomer of DPASs (6a-d) exhibited high fluorescence quantum yields (Φfl ≈ 53% to 60% in DMSO). However, on white light exposure, 1H NMR and HPLC studies revealed that pure E-isomer of the DPAS 6a (∼9.5 mM) started converting into its Z-form by photoisomerization until it reaches to nearly equilibrium. At low concentrations (∼10 µM), the absorption band of the pure E-isomer in the range of 350-450 nm gradually decreased to adopt Z-conformation 6a' until a photostationary state was reached. The structure of the E-isomer 6a was unequivocally confirmed by X-ray diffraction analysis. The synthesized DPAS compounds 6a-d possessed positive solvatochromic properties, two photon absorption properties, and good thermal stability. The electrochemical investigations using DPASs showed reversible oxidation resulting in formation of a stable radical cation. Owing to useful photophysical, electrochemical and thermal properties, these DPAS derivatives are suitable for their application in biomedical imaging as well as in fabrication of electroluminescent materials.