Surface-enhanced Raman scattering (SERS) spectroscopy can be used for the determination and quantification of biologically representative atomic ions. In this work, the detection and quantification of chloride is demonstrated by monitoring the vibrational changes occurring at a specific interface (a Cl-sensitive dye) supported on a silver-coated silica microbead. The engineered particles play a key role in the detection, as they offer a stable substrate to support the dye, with a dense collection of SERS hot spots. These results open a new avenue toward the generation of microsensors for fast ultradetection and quantification of relevant ions inside living organisms such as cells. Additionally, the use of discrete particles rather than rough films, or other conventional SERS supports, will also enable a safe remote interrogation of highly toxic sources in environmental problems or biological fluids.
Colloidal nanoparticles are often stabilized by high surface charges. These create an electrical potential that may strongly affect the concentration of dissolved ions, which presents a formidable problem for the use of nanoparticles in ion-sensing applications. This effect is investigated systematically with organic fluorophore-gold nanoparticle hybrids, which have a chloride-sensitive fluorophore attached at varying distances from their surface. The distance-dependent fluorescence response is quantitatively assessed using fluorescence spectroscopy.
A total synthesis of the proposed structures of fulicineroside and its aglycone fulicinerine is reported. The tetrasubstituted dibenzofuran substructure was accessible either through a Pd-mediated ortho-metalation or by an Ir-catalyzed meta-borylation. The synthesis of the β,β,α-linked trisaccharide consisting of D-olivose, L-rhodinose, and L-rhamnose was challenged by the unprecedented β-linked rhodinose. A Pd-catalyzed β-selective glycosylation of a 4-epi-rhodinose and a subsequent Mitsunobu inversion provided selectively the β-linked L-rhodinose-L-rhamnose disaccharide. Comparison with the reported data for the natural product and the aglycone suggests a misassignment of the structure of the natural product.
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