Surface segregation of rigid polyarylene ether amidoxime on polyurethane nanofiber into hierarchical membranes as substrate of flexible SERS nanosensor for sulfamethoxazole detection.

Electrospun polymeric nanofibrous membranes are emerging as the promising substrates for preparation of flexible SERS nanosensors due to their intrinsic nanoscale surface roughness, easy scalability as well as rich surface reactivity. Although the nanofiber membranes prepared from high performance thermoplastics exhibit good mechanical stability, the SERS nanosensors based on these substrates normally have lower signal-to-noise ratio because of the interference from background Raman signals of aromatic moieties. Herein, we synthesized an optically transparent polyurethane (PU) and rigid polyarylene ether amidoxime (PEA), which were electrospun into core-shell nanofibers membranes with a "beads-on-web" morphology. Furthermore, the PU-PEA membranes were coated with ultra-thin silver layer and thermally annealed to prepare the flexible SERS nanosensor without any background noises. In addition, the Raman enhancement of SERS nanosensor can be readily improved by tuning of PU-PEA composition, silver thickness as well as thermal annealing temperature. Finally, the optimized SERS nanosensor enables label-free detection of sulfamethoxazole as low as 0.1 nM with a good reproducibility and detection performance in real water sample. Meanwhile, the optimized SERS nanosensor shows long term anti-biofouling capacity. Thanks to its facile fabrication, competitive analytical performance and resistance to biofouling, the current work basically open new way for design of flexible SERS nanosensors for biomedical applications.

Sub-micron microparticles with tunable fluorescence emission obtained via co-self-assembly of amidoximed polymeric ligands and lanthanide ions.

Lanthanide coordinating polymeric microparticles have witnessed increasing research interests during the past decades due to their versatile morphology and tunable fluorescent properties. Herein, we have synthesized an amidoximed block copolymer containing aromatic backbone and pendent amidoxime as well as carboxyl groups, which has been employed as the ligand to sensitize the intrinsic fluorescence emission of lanthanide ions of Tb3+ and Eu3+. Furthermore, the lanthanide coordinating polymeric microparticles showing tunable green and red emission fluorescence have been prepared via the emulsion confinement co-self-assembly of amidoximed polymeric ligands with Tb3+ and Eu3+. It is found that both the fluorescence emission and sizes of obtained fluorescent microparticles can be easily modulated in a wide range by tuning concentration of polymers and lanthanide ions, as well as emulsion evaporation temperature. Thanks to their tunable sizes (250-900 nm), fluorescence emission as well as presence of surface active functional groups, the present fluorescent microparticles would find potential applications in in-vitro detection, optical encoding and devices.

Scalable fabrication of silver covered polyurethane nanofibers as flexible SERS nanosensors for aflatoxin detection.

Flexible surface enhanced Raman spectroscopy (SERS) nanosensors, constructed by integration of plasmonic nanostructures with polymeric substrates, have received increasing research interests for recent decades. When compared to abundant works on optimization of the plasmonic nanostructures, the research involving the influence of polymeric substrates on analytical performance of resultant flexible SESR nanosensors is unexpectedly limited. Herein, the ultra-thin silver layer has been deposited on the electrospun polyurethane (ePU) nanofibrous membranes via vacuum evaporation to prepare the flexible SRES nanosensors. Interestingly, we find that the molecular weight and polydispersion index of synthesized PU play important roles in regulating the fine morphology of electrospun nanofibers, which in turns determine the Raman enhancement of resultant flexible SERS nanosensors. Specifically, the optimized SERS nanosensor, obtained by evaporating 10 nm silver layer on top of nanofibers derived from electrospinning of PU with a weight-average molecular weight of 140,354 and polydispersion index of 1.26, enables label-free detection of the carcinogen of aflatoxin down to 0.1 nM. Thanks to its scalable fabrication and good sensitivity, the current work opens new way for design of cost-effective flexible SERS nanosensors for environmental monitoring and food security applications.