RESUMEN
π-Conjugated polymers such as polythiophene provide intramolecular wire effects upon analyte capture, which contribute to sensitive detection in chemical sensing. However, inherent aggregation-induced quenching causes difficulty in fluorescent chemical sensing in the solid state. Herein, we propose a solid-state fluorescent chemosensor array device made of a paper substrate (PCSAD) for the qualitative and quantitative detection of metal ions. A polythiophene derivative modified by dipicolylamine moieties (1poly), which shows optical changes upon the addition of target metal ions (i.e., Cu2+, Cd2+, Ni2+, Co2+, Pb2+, Zn2+, and Hg2+), was highly dispersed on the paper substrate using office apparatus. In this regard, morphological observation of the PCSAD after printing of 1poly suggested the contribution of the fiber structures of the paper substrate to the homogeneous dispersion of 1poly ink to suppress aggregation-induced quenching. The optical changes in the PCSAD upon the addition of metal ions was rapidly recorded using a smartphone, which was further applied to imaging analysis and pattern recognition techniques for high-throughput sensing. Indeed, the printed PCSAD embedded with 1poly achieved the accurate detection of metal ions at ppm levels contained in river water. The limit of detection of the PCSAD-based sensing system using a smartphone (48 ppb for Cu2+ ions) is comparable to that of a solution-based sensing system using a stationary spectrophotometer (16 ppb for Cu2+ ions). Therefore, the methodology based on a combination of a paper-based sensor array and a π-conjugated polymer will be a promising approach for solid-state fluorescent chemosensors.
RESUMEN
Bimetallic complexes have enabled precise control of catalysis by accumulating two discrete metal centres. In these complexes, bridging ligands are essential to combine multiple metals into one molecule. Among some bridging modes, an unsymmetric bridging mode will differentiate the electronic structures of the two metal centres. In this study, a dinuclear Rh(-i)/Rh(i) complex bridged by tridentate phosphine-phosphinine-phosphine ligands was prepared by reduction of the corresponding Rh(i) complex. Single-crystal X-ray analysis and DFT calculations suggest that the phosphinine ligands adopt an unsymmetric bridging mode wherein phosphinine accepts d-electrons from one Rh centre and, at the same time, donates lone pairs to the other Rh centre.
RESUMEN
A self-assembled chemosensor prepared using off-the-shelf materials has shown various fluorescence responses including ratiometric and simple ON-OFF switching profiles by adding different toxic metal ions. The unique fingerprint-like responses have been applied to pattern recognition of metal ions in river water for environmental analysis.
RESUMEN
Herein, we propose a novel amphiphilic polythiophene-based chemosensor functionalized with a Zn(II)-dipicolylamine side chain (1poly â Zn) for the pattern recognition of oxyanions. Optical changes in amphiphilic 1poly â Zn can be induced by the formation of a random coil from a backbone-planarized structure upon the addition of target oxyanions, which results in blueshifts in the UV-vis absorption spectra and turn-on-type fluorescence responses. Dynamic behavior in a polythiophene wire and/or among wires could be a driving force for obtaining visible color changes, while the molecular wire effect is dominant in obtaining fluorescence sensor responses. Notably, the magnitude of optical changes in 1poly â Zn has depended on differences in properties of oxyanions, such as their binding affinity, hydrophilicity, and molecular geometry. Thus, various colorimetric and fluorescence response patterns of 1poly â Zn to oxyanions were obtained, albeit using a single chemosensor. A constructed information-rich dataset was applied to pattern recognition for the simultaneous group categorization of phosphate and carboxylate groups and the prediction of similar structural oxyanions at a different order of concentrations in their mixture solutions.
