The threat of biological and chemical terror acts remains a growing worldwide concern. There is therefore a need to develop appropriate technology for the detection of chemical and biological warfare agents, with early identification intended for use by first responders. Here, we disclose the developed autonomous air sampling and detection system for evaluation of the presence of chemical and biological warfare agents that can be harmful to the population. The current device utilizes the designed mist generator-assisted air collection system (338 l min − 1 ) and biosensing chip technologies, such as electrochemical measurement, Au nanoparticle-based localized surface plasmon resonance, and rapid microfluidic chip PCR for detection of minute concentrations lower than the mean lethal dose (LD 50 ) of nerve gases (sarin and VX), toxic proteins (BTX/A/Hc and ricin), and pathogens (anthrax simulant). An operation time of only 5-15 min is needed for the collection and detection; sample preparation is already integrated into the system without the need for direct human intervention. In addition to the system's sensitivity and ease of use, its portability makes it highly beneficial for first responders, which could aid in immediate risk assessment and mitigation of on-site events.
The synthesis methods, physicochemical and structural characteristics, and catalytic reactivity of new macrocyclic proton chelators, N,N',N''-tris(p-tolyl)azacalix[3](2,6)(4-pyrrolidinopyridine) and N,N',N''-tris(p-tolyl)azacalix[3](2,6)(4-piperidinopyridine), are studied. The introduction of pyrrolidino and piperidino groups into the pyridine unit enables the enhancement of the synergistic proton affinity of the cavity of the macrotricycle giving a high basicity (pK(BH+) = 28.1 and 27.1 in CD(3)CN), resulting in a catalytic activity for the Michael addition of nitromethane with α,β-unsaturated carbonyl compounds.
Aminopyridine oligomers exhibited long-lived emission at 77 K, which could be assigned to the delayed fluorescence. The macrocyclic structure predominantly dictated the emission behaviors. Their emission behaviors were elucidated from time-dependent density functional theory calculations.
The molecular design, characteristics, and catalytic activity of macrocyclic amino compounds, azacalix[3](2,6)pyridine derivatives, were studied. The introduction of an electron-donating group on the pyridine moiety and bridging amino phenyl group enabled the enhancement of the basicity of azacalix[3](2,6)pyridine up to pK(BH(+)) = 29.5 in CD(3)CN. These derivatives were shown to be efficient catalysts for 1,4-addition reactions of nitroalkanes or primary alcohols to α,β-unsaturated carbonyl compounds and 1,2-addition reactions of nitroalkanes to aromatic aldehydes.
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