Embedded Au Nanoparticles-Based Ratiometric Electrochemical Sensing Strategy for Sensitive and Reliable Detection of Copper Ions.

The ratiometric method allows the measurement of ratio changes between two signals, which can reduce the detection signal fluctuations caused by distinct background conditions and greatly improve the reproducibility and reliability of detection. However, in contrast with the emerging dual excitation or dual emission dyes applied in ratiometric luminescence measurement, only a few internal reference probes have been exploited for ratiometric electrochemical detection. In this paper, a gold nanoparticles@carbonized resin nanospheres composite with thermally reduced graphene oxide as scaffold (AuNPs@CRS-TrGNO) has been fabricated, and the AuNPs embedded in the CRS were first used as an internal reference probe for ratiometric electrochemical detection. The detachment and aggregation of AuNPs is suppressed by embedding in the CRS, so its redox signal is very stable, which provides feasibility for ratiometric detection. Moreover, the embedment of AuNPs, carbonization of resin spheres, and hybridization with TrGNO all have played positive roles in improving the charge transfer rate, which leads to excellent electrochemical performance of the composite. Based on these characteristics of the AuNPs@CRS-TrGNO, a new ratiometric electrochemical detection platform was constructed, and copper ions (Cu2+) in simulated seawater were successfully detected. This ratiometric method has the advantages of simple design and convenient operation, and obviously it improves the reproducibility and reliability of the electrochemical sensor.

Mechanistic and Kinetic Investigations on the Ozonolysis of Biomass Burning Products: Guaiacol, Syringol and Creosol.

The lignin pyrolysis products generated by biomass combustion make an essential contribution to the formation of secondary organic aerosols (SOAs). The ozone-initiated oxidation of guaiacol, syringol and creosol, major constituents of biomass burning, were investigated theoretically by using the density functional theory (DFT) method at the MPWB1K/6-311+G(3df,2p)//MPWB1K/6-31+G(d,p) level. Six primary addition reaction pathways and further decomposition routes with corresponding thermodynamic values were proposed. The Criegee intermediates can be excited by small molecules, such as NOx, H2O in the atmosphere, and would further proceed via self-decomposition or isomerization. The most predominant product for ozonation of guaiacol is the monomethyl muconate (P1). At 295 K and atmospheric pressure, the rate constant is 1.10 × 10-19 cm3 molecule-1 s-1, which is lies a factor of 4 smaller than the previous experimental study. The branching ratios of the six channels are calculated based on corresponding rate coefficient. The present work mainly provides a more comprehensive and detailed theoretical research on the ozonation of methoxyphenol, which aspires to offer novel insights and reference for future experimental and theoretical work and control techniques of SOAs caused by lignin pyrolysis products.