Multichannel detection and differentiation of explosives with a quantum dot array

The sensing and differentiation of explosive molecules is key for both security and environmental monitoring. Single fluorophores are a widely used tool for explosives detection, but a fluorescent array is a more powerful tool for detecting and differentiating such molecules. By combining array elements into a single multichannel platform, faster results can be obtained from smaller amounts of sample. Here, five explosives are detected and differentiated using quantum dots as luminescent probes in a multichannel platform: 2,4-dinitrotoluene (DNT), 2,4,6-trinitrotoluene (TNT), tetryl (2,4,6-trinitrophenylmethylnitramine), cyclotrimethylenetrinitramine (RDX), and pentaerythritol tetranitrate (PETN). The sharp, variable emissions of the quantum dots, from a single excitation wavelength, make them ideal for such a system. Each color quantum dot is functionalized with a different surface receptor via a facile ligation process. These receptors undergo nonspecific interactions with the explosives, inducing variable fluorescence quenching of the quantum dots. Pattern analysis of the fluorescence quenching data allows for explosive detection and identification with limits-of-detection in the ppb range

Fluorinated models of the iron-only hydrogenase: An electrochemical study of the influence of an electron-withdrawing bridge on the proton reduction overpotential and catalyst stability

AbstractHere we report the synthesis, electrochemistry and electrocatalytic activity of Fe2(CO)6(μ-SC6F5)2 (1) where the highly fluorinated bridge is electron-withdrawing, resulting in decreased electron-density at the iron–iron bond. Additionally we discuss the related substituted complexes Fe2(CO)5(PPh3)(μ-SC6F5)2 (2) and Fe2(CO)4(μ-Ph2PCH2PPh2)(μ-SC6F5)2 (3). As none of the complexes could be protonated in their neutral form it was found that proton reduction catalysis in the presence of strong acid (HBF4) took place at the potential of the first reduction of complex 1 and 3, following an EC mechanism. Complex 2 was unstable in the presence of strong acid. For 1 the potential at which proton reduction took place represented a relatively mild reduction potential (−1.15V vs. Fc/Fc+ in acetonitrile) that was comparable to examples of similar complexes in the literature. Complex 1 generated a small concentration of a highly catalytic species after electrochemical reduction, which we attribute to cleavage of the Fe–Fe bond and formation of a mono-nuclear iron species or to Fe–S bond breakage generating a vacant coordination site. The contributions to the catalytic currents were simulated using DigiSim, where it was found that the rate limiting step for 3 was the elimination of H2. It was also found that the highly catalytic species generated after reduction of 1 was more basic than 1− and also that protonation of this species was faster

Phase control during the synthesis of nickel sulfide nanoparticles from dithiocarbamate precursors

Square-planar nickel bis(dithiocarbamate) complexes, [Ni(S2CNR2)2], have been prepared and utilised as single source precursors to nanoparticulate nickel sulfides. While they are stable in the solid-state to around 300 °C, heating in oleylamine at 230 °C, 5 mM solutions afford pure α-NiS, where the outcome is independent of the substituents. DFT calculations show an electronic effect rather than steric hindrance influences the resulting particle size. Decomposition of the iso-butyl derivative, [Ni(S2CNiBu2)2], has been studied in detail. There is a temperature-dependence of the phase of the nickel sulfide formed. At low temperatures (150 °C), pure α-NiS is formed. Upon raising the temperature, increasing amounts of β-NiS are produced and at 280 °C this is formed in pure form. A range of concentrations (from 5–50 mM) was also investigated at 180 °C and while in all cases pure α-NiS was formed, particle sizes varied significantly. Thus at low concentrations average particle sizes were ca. 100 nm, but at higher concentrations they increased to ca. 150 nm. The addition of two equivalents of tetra-iso-butyl thiuram disulfide, (iBu2NCS2)2, to the decomposition mixture was found to influence the material formed. At 230 °C and above, α-NiS was generated, in contrast to the results found without added thiuram disulfide, suggesting that addition of (iBu2NCS2)2 stabilises the metastable α-NiS phase. At low temperatures (150–180 °C) and concentrations (5 mM), mixtures of α-NiS and Ni3S4, result. A growing proportion of Ni3S4 is noted upon increasing precursor concentration to 10 mM. At 20 mM a metastable phase of nickel sulfide, NiS2 is formed and as the concentration is increased, α-NiS appears alongside NiS2. Reasons for these variations are discussed

Copper-doped CdSe/ZnS quantum dots : controllable photoactivated copper(I) cation storage and release vectors for catalysis

The first photoactivated doped quantum dot vector for metal-ion release has been developed. A facile method for doping copper(I) cations within ZnS quantum dot shells was achieved through the use of metal-dithiocarbamates, with Cu(+) ions elucidated by X-ray photoelectron spectroscopy. Photoexcitation of the quantum dots has been shown to release Cu(+) ions, which was employed as an effective catalyst for the Huisgen [3+2] cycloaddition reaction. The relationship between the extent of doping, catalytic activity, and the fluorescence quenching was also explored

Co2 capture and electrochemical conversion using superbasic [p-66614]-[124triz]

The ionic liquid trihexyltetradecylphosphonium 1,2,4- triazolide, [P66614][124Triz], has been shown to chemisorb CO2 through equimolar binding of the carbon dioxide with the 1,2,4-triazolide anion. This leads to a possible new, low energy pathway for the electrochemical reduction of carbon dioxide to formate and syngas at low overpotentials, utilizing this reactive ionic liquid media. Herein, an electrochemical investigation of water and carbon dioxide addition to the [P66614][124Triz] on gold and platinum working electrodes is reported. Electrolysis measurements have been performed using CO2 saturated [P66614][124Triz] based solutions at -0.9 V and -1.9 V on gold and platinum electrodes. The effects of the electrode material on the formation of formate and syngas using these solutions are presented and discussed18338940

Combined EXAFS, XRD, DRIFTS, and DFT Study of Nano Copper-Based Catalysts for CO2 Hydrogenation

Highly monodispersed CuO nanoparticles (NPs) were synthesized via continuous hydrothermal flow synthesis (CHFS) and then tested as catalysts for CO2 hydrogenation. The catalytic behavior of unsupported 11 nm sized nanoparticles from the same batch was characterized by diffuse reflectance infrared fourier transform spectroscopy (DRIFTS), extended X-ray absorption fine structure (EXAFS), X-ray diffraction (XRD), and catalytic testing, under CO2/H2 in the temperature range 25–500 °C in consistent experimental conditions. This was done to highlight the relationship among structural evolution, surface products, and reaction yields; the experimental results were compared with modeling predictions based on density functional theory (DFT) simulations of the CuO system. In situ DRIFTS revealed the formation of surface formate species at temperatures as low as 70 °C. DFT calculations of CO2 hydrogenation on the CuO surface suggested that hydrogenation reduced the CuO surface to Cu2O, which facilitated the formation of formate. In situ EXAFS supported a strong correlation between the Cu2O phase fraction and the formate peak intensity, with the maxima corresponding to where Cu2O was the only detectable phase at 170 °C, before the onset of reduction to Cu at 190 °C. The concurrent phase and crystallite size evolution were monitored by in situ XRD, which suggested that the CuO NPs were stable in size before the onset of reduction, with smaller Cu2O crystallites being observed from 130 °C. Further reduction to Cu from 190 °C was followed by a rapid decrease of surface formate and the detection of adsorbed CO from 250 °C; these results are in agreement with heterogeneous catalytic tests where surface CO was observed over the same temperature range. Furthermore, CH4 was detected in correspondence with the decomposition of formate and formation of the Cu phase, with a maximum conversion rate of 2.8% measured at 470 °C (on completely reduced copper), supporting the indication of independent reaction pathways for the conversion of CO2 to CH4 and CO that was suggested by catalytic tests. The resulting Cu NPs had a final crystallite size of ca. 44 nm at 500 °C and retained a significantly active surface

Insight into nature of iron sulfide surfaces during the electrochemical hydrogen evolution and CO2 reduction reactions

Greigite and other iron sulfides are potential cheap, earth-abundant electrocatalysts for the hydrogen evolution reaction (HER), yet little is known about the underlying surface chemistry. Structural and chemical changes to a greigite (Fe3S4) modified electrode were determined at −0.6 V vs. SHE at pH 7, under conditions of the HER. In situ X-ray Absorption Spectroscopy (XAS) was employed at the Fe K-edge to show that iron-sulfur linkages were replaced by iron-oxygen units under these conditions. The resulting material was determined as 60% greigite and 40% iron hydroxide (goethite) with a proposed core-shell structure. A large increase in pH at the electrode surface (to pH 12) is caused by the generation of OH− as a product of the HER. Under these conditions iron sulfide materials are thermodynamically unstable with respect to the hydroxide. In situ IR spectroscopy of the solution near the electrode interface confirmed changes in the phosphate ion speciation consistent with a change in pH from 7 to 12 when −0.6 V vs. SHE is applied. Saturation of the solution with CO2 resulted in inhibition of the hydroxide formation, potentially due to surface adsorption of HCO3−. This study shows that the true nature of the greigite electrode under conditions of the HER is a core-shell greigite-hydroxide material and emphasises the importance of in situ investigation of the catalyst under operation in order to develop true and accurate mechanistic models

Resolution of LPS-induced airway inflammation and goblet cell hyperplasia is independent of IL-18

BACKGROUND: The resolution of inflammatory responses in the lung has not been described in detail and the role of specific cytokines influencing the resolution process is largely unknown. METHODS: The present study was designed to describe the resolution of inflammation from 3 h through 90 d following an acute injury by a single intratracheal instillation of F344/N rats with LPS. We documented the inflammatory cell types and cytokines found in the bronchoalveolar lavage fluid (BALF), and epithelial changes in the axial airway and investigated whether IL-18 may play a role in the resolution process by reducing its levels with anti-IL-18 antibodies. RESULTS: Three major stages of inflammation and resolution were observed in the BALF during the resolution. The first stage was characterized by PMNs that increased over 3 h to 1 d and decreased to background levels by d 6–8. The second stage of inflammation was characterized by macrophage influx reaching maximum numbers at d 6 and decreasing to background levels by d 40. A third stage of inflammation was observed for lymphocytes which were elevated over d 3–6. Interestingly, IL-18 and IL-9 levels in the BALF showed a cyclic pattern with peak levels at d 4, 8, and 16 while decreasing to background levels at d 1–2, 6, and 12. Depletion of IL-18 caused decreased PMN numbers at d 2, but no changes in inflammatory cell number or type at later time points. CONCLUSION: These data suggest that IL-18 plays a role in enhancing the LPS-induced neutrophilic inflammation of the lung, but does not affect the resolution of inflammation

Replacing the services sector and three-sector theory: urbanization and control as economic sectors

Developed during the Second World War, ‘three-sector theory’ popularized the notion of the ‘services’ sector. It has quietly underpinned understandings of economic structure ever since. The limitations and influence of this basic breakdown have led to many critiques and extensions, but no replacements. Inspired by Henri Lefebvre’s The Urban Revolution (1968), we develop a four-sector model that replaces services with sectors focused on urbanization and control. We argue that this model is a better reflection of material economic life, and a more useful way of approaching the 21st-century economy. It also offers scholars of urbanization and regional development a creative new way of seeing urbanization