Liquid metal-based synthesis of high performance monolayer SnS piezoelectric nanogenerators.

The predicted strong piezoelectricity for monolayers of group IV monochalcogenides, together with their inherent flexibility, makes them likely candidates for developing flexible nanogenerators. Within this group, SnS is a potential choice for such nanogenerators due to its favourable semiconducting properties. To date, access to large-area and highly crystalline monolayer SnS has been challenging due to the presence of strong inter-layer interactions by the lone-pair electrons of S. Here we report single crystal across-the-plane and large-area monolayer SnS synthesis using a liquid metal-based technique. The characterisations confirm the formation of atomically thin SnS with a remarkable carrier mobility of ~35 cm2 V-1 s-1 and piezoelectric coefficient of ~26 pm V-1. Piezoelectric nanogenerators fabricated using the SnS monolayers demonstrate a peak output voltage of ~150 mV at 0.7% strain. The stable and flexible monolayer SnS can be implemented into a variety of systems for efficient energy harvesting.

Antibacterial Liquid Metals: Biofilm Treatment via Magnetic Activation.

Antibiotic resistance has made the treatment of biofilm-related infections challenging. As such, the quest for next-generation antimicrobial technologies must focus on targeted therapies to which pathogenic bacteria cannot develop resistance. Stimuli-responsive therapies represent an alternative technological focus due to their capability of delivering targeted treatment. This study provides a proof-of-concept investigation into the use of magneto-responsive gallium-based liquid metal (LM) droplets as antibacterial materials, which can physically damage, disintegrate, and kill pathogens within a mature biofilm. Once exposed to a low-intensity rotating magnetic field, the LM droplets become physically actuated and transform their shape, developing sharp edges. When placed in contact with a bacterial biofilm, the movement of the particles resulting from the magnetic field, coupled with the presence of nanosharp edges, physically ruptures the bacterial cells and the dense biofilm matrix is broken down. The antibacterial efficacy of the magnetically activated LM particles was assessed against both Gram-positive and Gram-negative bacterial biofilms. After 90 min over 99% of both bacterial species became nonviable, and the destruction of the biofilms was observed. These results will impact the design of next-generation, LM-based biofilm treatments.

Publisher Correction: Room temperature CO2 reduction to solid carbon species on liquid metals featuring atomically thin ceria interfaces.

The original version of this Article contained errors in the author affiliations. Affiliation 1 incorrectly read 'School of Chemical Engineering, University of New South Wales (UNSW), Sydney, NSW 2031, Australia' and affiliation 4 incorrectly read 'School of Engineering, RMIT University, Melbourne, VIC 3001, Australia.' This has now been corrected in both the PDF and HTML versions of the Article.

Room temperature CO2 reduction to solid carbon species on liquid metals featuring atomically thin ceria interfaces.

Negative carbon emission technologies are critical for ensuring a future stable climate. However, the gaseous state of CO2 does render the indefinite storage of this greenhouse gas challenging. Herein, we created a liquid metal electrocatalyst that contains metallic elemental cerium nanoparticles, which facilitates the electrochemical reduction of CO2 to layered solid carbonaceous species, at a low onset potential of -310 mV vs CO2/C. We exploited the formation of a cerium oxide catalyst at the liquid metal/electrolyte interface, which together with cerium nanoparticles, promoted the room temperature reduction of CO2. Due to the inhibition of van der Waals adhesion at the liquid interface, the electrode was remarkably resistant to deactivation via coking caused by solid carbonaceous species. The as-produced solid carbonaceous materials could be utilised for the fabrication of high-performance capacitor electrodes. Overall, this liquid metal enabled electrocatalytic process at room temperature may result in a viable negative emission technology.

Exfoliation Behavior of van der Waals Strings: Case Study of Bi2S3.

The family of crystals constituting covalently bound strings, held together by van der Waals forces, can be exfoliated into smaller entities, similar to crystals made of van der Waals sheets. Depending on the anisotropy of such crystals, as well as the spacing between their strings in each direction, van der Waals sheets or ribbons can be obtained after the exfoliation process. In this work, we demonstrate that ultrathin nanoribbons of bismuth sulfide (Bi2S3) can be synthesized via a high-power sonication process. The thickness and width of these ribbons are governed by the van der Waals spacings around the strings within the parent crystal. The lengths of the nanoribbons are initially limited by the dimensions of the starting bulk particles. Interestingly, these nanoribbons change stoichiometry and composition and are elongated when the duration of agitation increases because of Ostwald ripening. An application of the exfoliated van der Waals strings is presented for optical biosensing using photoluminescence of Bi2S3 nanoribbons, reaching detection limits of less than 10 nM L-1 in response to bovine serum albumin. The concept of exfoliating van der Waals strings could be extended to a large class of crystals for creating bodies ranging from sheets to strings, with optoelectronic properties different from that of their bulk counterparts.

Wafer-Scale Synthesis of Semiconducting SnO Monolayers from Interfacial Oxide Layers of Metallic Liquid Tin.

Atomically thin semiconductors are one of the fastest growing categories in materials science due to their promise to enable high-performance electronic and optical devices. Furthermore, a host of intriguing phenomena have been reported to occur when a semiconductor is confined within two dimensions. However, the synthesis of large area atomically thin materials remains as a significant technological challenge. Here we report a method that allows harvesting monolayer of semiconducting stannous oxide nanosheets (SnO) from the interfacial oxide layer of liquid tin. The method takes advantage of van der Waals forces occurring between the interfacial oxide layer and a suitable substrate that is brought into contact with the molten metal. Due to the liquid state of the metallic precursor, the surface oxide sheet can be delaminated with ease and on a large scale. The SnO monolayer is determined to feature p-type semiconducting behavior with a bandgap of ∼4.2 eV. Field effect transistors based on monolayer SnO are demonstrated. The synthetic technique is facile, scalable and holds promise for creating atomically thin semiconductors at wafer scale.

Surface Water Dependent Properties of Sulfur-Rich Molybdenum Sulfides: Electrolyteless Gas Phase Water Splitting.

Sulfur-rich molybdenum sulfides are an emerging class of inorganic coordination polymers that are predominantly utilized for their superior catalytic properties. Here we investigate surface water dependent properties of sulfur-rich MoSx (x = 32/3) and its interaction with water vapor. We report that MoSx is a highly hygroscopic semiconductor, which can reversibly bind up to 0.9 H2O molecule per Mo. The presence of surface water is found to have a profound influence on the semiconductor's properties, modulating the material's photoluminescence by over 1 order of magnitude, in transition from dry to moist ambient. Furthermore, the conductivity of a MoSx-based moisture sensor is modulated in excess of 2 orders of magnitude for 30% increase in humidity. As the core application, we utilize the discovered properties of MoSx to develop an electrolyteless water splitting photocatalyst that relies entirely on the hygroscopic nature of MoSx as the water source. The catalyst is formulated as an ink that can be coated onto insulating substrates, such as glass, leading to efficient hydrogen and oxygen evolution from water vapor. The concept has the potential to be widely adopted for future solar fuel production.

Excitation dependent bidirectional electron transfer in phthalocyanine-functionalised MoS2 nanosheets.

Two-dimensional (2D) transition metal chalcogenides such as 2D MoS2 are considered prime candidate materials for the design of next generation optoelectronics. Functionalisation of these materials is considered to be a key step in tailoring their properties towards specific applications and unlocking their full potential. Here we present a van der Waals functionalisation strategy for creating MoS2 nanosheets decorated with free base phthalocyanine chromophores. The semiconducting sheets are found to intimately interact with these optoelectronically active chromophores, resulting in an electronic heterostructure that exhibits enhanced optoelectronic properties and exploitable charge transfer. We show that by utilising laterally confined MoS2 nanosheets, the conduction band of the semiconductor could be positioned between the chromophore's S1 and S2 states. Consequently, bidirectional photoinduced electron transfer processes are observed, with excitation of the functionalised nanosheet's semiconductor transition resulting in electron transfer to the phthalocyanine's LUMO, and excitation of the chromophore's S2 state leading to electron injection into the MoS2 conduction band. However, charge transfer from the dye's S1 transition to the MoS2 nanosheet is found to be thermodynamically unfavourable, resulting in intense radiative recombination. These findings may enable controlling and tuning the charge carrier density of semiconducting nanosheets via optical means through the exploitation of photoinduced electron transfer. Furthermore this work provides access to 2D semiconductor-hybrids with tailored absorption profiles and photoluminescence.

Enhanced quantum efficiency from a mosaic of two dimensional MoS2 formed onto aminosilane functionalised substrates.

Developing scalable methods of growing two dimensional molybdenum disulphide (2D MoS2) with strong optical properties, on any desired substrates, is a necessary step towards industrial uptake of this material for optical applications. In this study, Si/SiO2 substrates were functionalised using self-assembled monolayers of three different aminosilanes with various numbers of amine groups and molecular lengths as underlayers for enhancing the adherence of the molybdenum precursor. The tetrahedral [MoS4](2-) anion groups from the molybdenum precursor were bonded on these silanised Si/SiO2 substrates afterwards. The substrates were then treated with a combined thermolysis and sulphurisation step. The results showed that silanisation of the substrates using the longest chains and the largest number of amine groups provided a good foundation to grow quasi 2D MoS2 made from adjacent flakes in a mosaic formation. Microscopy and spectroscopy investigations revealed that these quasi 2D MoS2 formed using this long chain aminosilane resulted in flakes with lateral dimensions in micron and submicron ranges composed of adjoining MoS2 pieces of 20 to 60 nm in lateral dimensions, dominantly made of 3 to 5 MoS2 fundamental layers. The obtained quasi 2D MoS2 shows a high internal quantum efficiency of 2.6% associated with the quantum confinement effect and high stoichiometry of the adjoining nanoflakes that form the structure of the sheets. The synthesis technique in this study is reliable and facile and offers a procedure to form large, scalable and patternable quasi 2D MoS2 sheets on various substrates with enhanced optical properties for practical applications.

Influence of case definition on incidence and outcome of acute coronary syndromes.

OBJECTIVE: Acute coronary syndromes (ACS) are common, but their incidence and outcome might depend greatly on how data are collected. We compared case ascertainment rates for ACS and myocardial infarction (MI) in a single institution using several different strategies. METHODS: The Hull and East Yorkshire Hospitals serve a population of ∼560 000. Patients admitted with ACS to cardiology or general medical wards were identified prospectively by trained nurses during 2005. Patients with a death or discharge code of MI were also identified by the hospital information department and, independently, from Myocardial Infarction National Audit Project (MINAP) records. The hospital laboratory identified all patients with an elevated serum troponin-T (TnT) by contemporary criteria (>0.03 µg/L in 2005). RESULTS: The prospective survey identified 1731 admissions (1439 patients) with ACS, including 764 admissions (704 patients) with MIs. The hospital information department reported only 552 admissions (544 patients) with MI and only 206 admissions (203 patients) were reported to the MINAP. Using all 3 strategies, 934 admissions (873 patients) for MI were identified, for which TnT was >1 µg/L in 443, 0.04-1.0 µg/L in 435, ≤0.03 µg/L in 19 and not recorded in 37. A further 823 patients had TnT >0.03 µg/L, but did not have ACS ascertained by any survey method. Of the 873 patients with MI, 146 (16.7%) died during admission and 218 (25.0%) by 1 year, but ranging from 9% for patients enrolled in the MINAP to 27% for those identified by the hospital information department. CONCLUSIONS: MINAP and hospital statistics grossly underestimated the incidence of MI managed by our hospital. The 1-year mortality was highly dependent on the method of ascertainment.

Two-step synthesis of luminescent MoS(2)-ZnS hybrid quantum dots.

A surfactant assisted technique has been used to promote the exfoliation of molybdenum disulphide (MoS2) in a water-ethanol mixture, to avoid the use of harsh organic solvents, whilst still producing sufficient concentration of MoS2 in suspension. The exfoliated flakes are converted into MoS2 quantum dots (QDs), through a hydrothermal procedure. Alternatively, when the flakes are processed with precursors for zinc sulphide (ZnS) synthesis, a simultaneous break-down and composite growth is achieved. The products are separated by centrifugation, into large ZnS spheres (200-300 nm) and small MoS2-ZnS hybrid QD materials (<100 nm), of which, the latter show favorable optical properties. Two concurrent photoluminescent (PL) peaks are seen at 380 and 450 nm, which are assigned to MoS2 and ZnS components of QDs, respectively. The PL emission from MoS2-ZnS QDs is of high energy and is more intense than the bare MoS2 flakes or QDs, with a quantum yield as high as 1.96%. The emission wavelength is independent from the excitation wavelength and does not change over time. Due to such properties, the developed hybrid QDs are potentially suitable for imaging and sensing applications.

Tunable photoluminescence across the entire visible spectrum from carbon dots excited by white light.

Although reports have shown shifts in carbon dot emission wavelengths resulting from varying the excitation wavelength, this excitation-dependent emission does not constitute true tuning, as the shifted peaks have much weaker intensity than their dominant emission, and this is often undesired in real world applications. We report for the first time the synthesis and photoluminescence properties of carbon dots whose peak fluorescence emission wavelengths are tunable across the entire visible spectrum by simple adjustment of the reagents and synthesis conditions, and these carbon dots are excited by white light. Detailed material characterization has revealed that this tunable emission results from changes in the carbon dots' chemical composition, dictated by dehydrogenation reactions occurring during carbonization. These significantly alter the nucleation and growth process, resulting in dots with either more oxygen-containing or nitrogen-containing groups that ultimately determine their photoluminescence properties, which is in stark contrast to previous observations of carbon dot excitation-dependent fluorescence. This new ability to synthesize broadband excitable carbon dots with tunable peak emissions opens up many new possibilities, particularly in multimodal sensing, in which multiple analytes and processes could be monitored simultaneously by associating a particular carbon dot emission wavelength to a specific chemical process without the need for tuning the excitation source.

The effects of initiation or continuation of statin therapy on cholesterol level and all-cause mortality after the diagnosis of left ventricular systolic dysfunction.

BACKGROUND: Statins (3-hydroxy-3-methyl-glutaryl coenzyme A reductase inhibitors) are known to reduce mortality and cardiac events in patients with coronary artery disease who have not progressed to left ventricular systolic dysfunction (LVSD) and/or heart failure (HF). This study investigated the effect of changes in statin therapy and cholesterol level on mortality in patients with LVSD. METHODS: Data from consecutive patients with LVSD enrolled in a single local hospital HF management program were analyzed. Patients were grouped according to changes in statin treatment within 4 months after their initial visit: groups NS (no statin), IS (initiation of statin), CS (continuation of statin), and SS (statin stopped). RESULTS: Nine hundred patients were followed for a median of 36 (28-43) months (range, 16-66 months). The 2-year mortality was 16.7%. Groups IS and CS had lower 2-year mortality than groups NS and SS (11.0% and 11.9% vs 22.0% and 34.8%, respectively; P < .001). This was independent of age, sex, severity of LVSD, HF medications, New York Heart Association functional class, and baseline cholesterol. The effect was mainly observed in patients with coronary artery disease. In 734 patients who had completed 1-year follow-up on stable HF treatment, neither baseline cholesterol nor change over 1 year predicted outcome. CONCLUSION: Initiation and maintenance of treatment with statins is associated with better survival in patients with LVSD. This could not be explained by other measured variables.