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1.
Angew Chem Int Ed Engl ; 60(45): 24048-24053, 2021 11 02.
Article in English | MEDLINE | ID: mdl-34494708

ABSTRACT

Hydrogen sulfide (H2 S) plays a crucial signalling role in a variety of physiological systems, existing as the hydrosulfide anion (HS- ) at physiological pH. Combining the potency of halogen bonding (XB) for anion recognition in water with coumarin fluorophore incorporation in acyclic host structural design, the first XB receptors to bind and, more importantly, sense the hydrosulfide anion in pure water in a reversible chemosensing fashion are demonstrated. The XB receptors exhibit characteristic selective quenching of fluorescence upon binding to HS- . Computational DFT and molecular dynamics simulations in water corroborate the experimental anion binding observations, revealing the mode and nature of HS- recognition by the XB receptors.

2.
Chemistry ; 27(58): 14550-14559, 2021 Oct 19.
Article in English | MEDLINE | ID: mdl-34319624

ABSTRACT

Anion receptors employing two distinct sensory mechanisms are rare. Herein, we report the first examples of halogen-bonding porphyrin BODIPY [2]rotaxanes capable of both fluorescent and redox electrochemical sensing of anions. 1 H NMR, UV/visible and electrochemical studies revealed rotaxane axle triazole group coordination to the zinc(II) metalloporphyrin-containing macrocycle component, serves to preorganise the rotaxane binding cavity and dramatically enhances anion binding affinities. Mechanically bonded, integrated-axle BODIPY and macrocycle strapped metalloporphyrin motifs enable the anion recognition event to be sensed by the significant quenching of the BODIPY fluorophore and cathodic perturbations of the metalloporphyrin P/P+. redox couple.


Subject(s)
Porphyrins , Rotaxanes , Anions , Boron Compounds , Halogens , Hydrogen Bonding
3.
Environ Sci Technol ; 52(17): 10134-10143, 2018 09 04.
Article in English | MEDLINE | ID: mdl-30064212

ABSTRACT

Designs of "improved" stoves are introduced recently to benefit the solid fuel consumption of cooking activities in developing countries, but the uncertainties concerning the combustion processes and particulate emissions remain poorly characterized. To help understand this, combustion in three examples of "improved" African cookstoves was investigated in the laboratory. A typical European heating stove was included for comparison purpose. Detailed aerosol emissions were studied in real-time with an Aerosol Mass Spectrometer and Single Particle Soot Photometer, to explore interactions between black carbon (BC) and organic carbon aerosols, which were parametrized according to modified combustion efficiency (MCE), a common metric used within the atmospheric emission community. Greater than 50% of the total organic matter (OM) was found in BC-containing particles when MCE was >0.95 for dry oak and coal fuels, whereas at lower MCE, over 80% of the total OM for most of the fuels existed in particles without detectable BC. When the OM mass fraction of total particulate matter (PM1) > 0.9, the mass ratio of OM to refractory BC in BC-containing particles was about 2-3, but only ∼0.8 when OM mass fraction <0.9. These findings are not currently included in models and such information should be considered in the future emission scenarios.


Subject(s)
Air Pollutants , Aerosols , Coal , Particulate Matter , Soot
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