title: Silica nanoparticles functionalized with polyamidoamine (PAMAM) dendrimers as platforms for photoluminescence (PL) sensing of copper and cyanide ions.
abstract: Functionalized nanoparticles for photoluminescence (PL) applications are a promising technology for biomedical imaging and as sensors for small molecules. This work presents a new method to modify silica nanoparticles (SNP) using the bifunctional linker 1,1'-carbonyldiimidazole (CDI) with a series of polyamidoamine (PAMAM) dendrimer molecules followed by grafting of fluorescein isothiocyanate (FITC) or rhodamine B isothiocyanate (RITC) to create platforms for photoluminescence (PL) sensors. A dendrimer size and charge-variable response to only copper(II) ions confirmed the prediction of a selective turn-off sensor via proximity quenching. Both dye density and Cu(2+) quenching efficiency peaked with SNP-dendrimer generation 4 (64 terminal amines). In addition, changing the terminal dendrimer arms to carboxylic acid end groups increased the copper quenching suggesting that more metal ion binding sites were created in close proximity to the dyes. Of the small anions tested for a turn-off sensor, only cyanide ion fully restored the PL when reaching a 2:1 CN(-):Cu(2+) ratio, while EDTA was not as effective at the same ratio. Therefore, dendrimer size and surface charge on the nanoparticles controlled the dye loading and copper quenching efficiency, while creating multiple binding sites for cyanide over other metal binding anions.
authors.affiliation: Department of Chemistry, University of San Francisco, San Francisco, CA 94117, United States.
authors.forename: Kateryna
authors.initials: K
authors.lastname: Gerrans
authors.affiliation: Department of Chemistry, University of San Francisco, San Francisco, CA 94117, United States.
authors.forename: Alicia
authors.initials: A
authors.lastname: Luhrs
authors.affiliation: Department of Chemistry, University of San Francisco, San Francisco, CA 94117, United States.
authors.forename: Clara
authors.initials: C
authors.lastname: Feider
authors.affiliation: Department of Chemistry, University of San Francisco, San Francisco, CA 94117, United States. Electronic address: margeruml@usfca.edu.
authors.forename: Lawrence D
authors.initials: LD
authors.lastname: Margerum
mesh_terms: D003300:Copper / Q000032:analysis*; D003486:Cyanides / Q000032:analysis*; D050091:Dendrimers / Q000737:chemistry*; D007477:Ions / Q000032:analysis; D049449:Luminescence; D053758:Nanoparticles / Q000737:chemistry*; D055668:Photochemical Processes; D011073:Polyamines / Q000737:chemistry*; D012822:Silicon Dioxide / Q000737:chemistry*
chemical_list: D003486:Cyanides; D050091:Dendrimers; D007477:Ions; C531249:Poly(amidoamine); D011073:Polyamines; D012822:Silicon Dioxide; D003300:Copper
keywords: Copper(II); Cyanide; Nanoparticle optical sensor; Photoluminescence; Polyamidoamine (PAMAM) dendrimers; Quenching; Silica nanoparticles; Surface charge