Bis-squaramide receptors L1–L4 bearing a dansyl moiety were considered as fluorescent probes for ... more Bis-squaramide receptors L1–L4 bearing a dansyl moiety were considered as fluorescent probes for non steroidal antinflamatory drugs naproxene and ketoprofen.
Peptide-decorated nanosystems have demonstrated higher stability and improved cellular uptake as ... more Peptide-decorated nanosystems have demonstrated higher stability and improved cellular uptake as compared to bare NPs and appear highly promising in diagnostics and theranostics of cancer. Herein, we discuss the preparation and structural characterization of peptide-functionalized silica/PEG NPs, starting from peptide–block copolymers, prepared in turn by conjugation of the peptides to block copolymers before NP formation. This synthetic design allowed full control of density and composition of peptide surface coverage. Preliminary experiments support the low toxicity of the fluorescent peptide–NPs and their ability of cell internalization.
The synthesis of a new RuII complex, in which the metal is coordinated by two 1,10-phenanthroline... more The synthesis of a new RuII complex, in which the metal is coordinated by two 1,10-phenanthroline ligands and a 2,2′-bipyridyl unit linked, via methylene bridges in its 4 and 4′ positions, to two 1,4,7,10-tetraazacyclododecane (cyclen) macrocycles ([Ru(phen)2L]2+) is reported. Protonation and ZnII binding by [Ru(phen)2L]2+ have been analyzed by potentiometric titration, evidencing the formation of mixed hetero-binuclear and hetero-trinuclear ZnII/RuII complexes. These complexes were tested as bis-phenol A (BPA) binders. Only the dizinc complex with [Ru(phen)2L]2+ is able to bind BPA in aqueous solution, affording a remarkably stable {Zn2[Ru(phen)2L]BPA(H−2)}4+ adduct at neutral pH, in which BPA is bound in its doubly deprotonated form to the two ZnII ions. BPA binding was found to quench the luminescence emission of the RuII(phen)2bipy core. Although the quenching effect is modest, this study demonstrates that appropriately designed dizinc complexes can be used for binding and optic...
Photochemical & Photobiological Sciences, 2019
Small PEGylated silica nanoparticles are synthesized in the presence of high concentrations of or... more Small PEGylated silica nanoparticles are synthesized in the presence of high concentrations of organic solvents. This method allows for the efficient incorporation of dyes with poor solubility in water, yielding bright silica nanoparticles.
Understanding polarity gradients inside nanomaterials is essential to capture their potential as ... more Understanding polarity gradients inside nanomaterials is essential to capture their potential as nanoreactors, catalysts or in drug delivery applications. We propose here a method to obtain detailed, quantitative information on heterogeneous polarity in multicompartment nanostructures. The method is based on a 2-steps procedure, (i) deconvolution of complex emission spectra of two solvatochromic probes followed by (ii) spectrally resolved analysis of FRET between the same solvatochromic dyes. While the first step yields a list of polarities probed in the nanomaterial suspension, the second step correlates the polarities in space. Colocalization of polarities falling within few nanometer radius is obtained via FRET, a process called here nanopolarity mapping. Here, Prodan and Nile Red are tested to map the polarity of a water-dispersable, multicompartment nanostructure, named PluS nanoparticle (NPs). PluS NPs are uniform core-shell nanoparticles with silica cores (diameter ~10 nm) an...
Journal of the American Chemical Society, Dec 14, 2016
The impact of nanotechnology on analytical science is hardly overlooked. In the search for ever-i... more The impact of nanotechnology on analytical science is hardly overlooked. In the search for ever-increasing sensitivity in biomedical sensors, nanoparticles have been playing a unique role as, for instance, ultrabright labels, and unravelling the intimate mechanisms which govern their functioning is mandatory for the design of ultrasentitive devices. Herein, we investigated the mechanism of electrogenerated chemiluminescence (ECL) in a family of core-shell silica-PEG nanoparticles (DDSNs), variously doped with a Ru(bpy)3(2+) triethoxysilane derivative, and displaying homogeneous morphological, hydrodynamic, and photophysical properties. ECL experiments, performed in the presence of 2-(dibutylamino)ethanol (DBAE) as coreactant, showed two parallel mechanisms of ECL generation: one mechanism (I) which involves exclusively the radicals deriving from the coreactant oxidation and a second one (II) involving also the direct anodic oxidation of the Ru(II) moieties. The latter mechanism incl...
Monitoring Prostate Cancer (PCa) biomarkers is an efficient way to diagnosis this disease early, ... more Monitoring Prostate Cancer (PCa) biomarkers is an efficient way to diagnosis this disease early, since it improves the therapeutic success rate and suppresses PCa patient mortality: for this reason a powerful analytical technique such as electrochemiluminescence (ECL) is already used for this application, but its widespread usability is still hampered by the high cost of commercial ECL equipment. We describe an innovative approach for the selective and sensitive detection of the PCa biomarker sarcosine, obtained by a synergistic ECL-supramolecular approach, in which the free base form of sarcosine acts as co-reagent in a Ru(bpy)32+-ECL process. We used magnetic micro-beads decorated with a supramolecular tetraphosphonate cavitand (Tiiii) for the selective capture of sarcosine hydrochloride in a complex matrix like urine. Sarcosine determination was then obtained with ECL measurements thanks to the complexation properties of Tiiii, with a protocol involving simple pH changes – to dri...
Pyrazino-fused tetrarylporphyrins, Dyes and Pigments (2013), doi: 10.1016/ j.dyepig.2013.04.024. ... more Pyrazino-fused tetrarylporphyrins, Dyes and Pigments (2013), doi: 10.1016/ j.dyepig.2013.04.024. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Dye-doped near infrared-emitting silica nanoparticles (DD-NIRsiNPs) represent a valuable tool in ... more Dye-doped near infrared-emitting silica nanoparticles (DD-NIRsiNPs) represent a valuable tool in bioimaging, because they provide sufficient brightness, resistance to photobleaching and consist of hydrophilic non-toxic materials.
... Luca Prodi*a, Fabrizio Bollettaa, Marco Montaltia, Nelsi Zaccheronia, Alessandro Casnati*b, F... more ... Luca Prodi*a, Fabrizio Bollettaa, Marco Montaltia, Nelsi Zaccheronia, Alessandro Casnati*b, Francesco Sansoneb and Rocco Ungarob. a ... 1, GD Andreetti, F. Ugozzoli, A. Pochini and R. Ungaro, in Inclusion Compounds, ed. JL Atwood, JED Davies and DD MacNicol, Oxford ...
Electrochemiluminescence (ECL) starting from being a laboratory curiosity has become a powerful d... more Electrochemiluminescence (ECL) starting from being a laboratory curiosity has become a powerful diagnostic technique. i In the perspective of be used in ECL-based biological assays a luminophore must meet several requirements: his ECL signal must be intense ...
Bis-squaramide receptors L1–L4 bearing a dansyl moiety were considered as fluorescent probes for ... more Bis-squaramide receptors L1–L4 bearing a dansyl moiety were considered as fluorescent probes for non steroidal antinflamatory drugs naproxene and ketoprofen.
Peptide-decorated nanosystems have demonstrated higher stability and improved cellular uptake as ... more Peptide-decorated nanosystems have demonstrated higher stability and improved cellular uptake as compared to bare NPs and appear highly promising in diagnostics and theranostics of cancer. Herein, we discuss the preparation and structural characterization of peptide-functionalized silica/PEG NPs, starting from peptide–block copolymers, prepared in turn by conjugation of the peptides to block copolymers before NP formation. This synthetic design allowed full control of density and composition of peptide surface coverage. Preliminary experiments support the low toxicity of the fluorescent peptide–NPs and their ability of cell internalization.
The synthesis of a new RuII complex, in which the metal is coordinated by two 1,10-phenanthroline... more The synthesis of a new RuII complex, in which the metal is coordinated by two 1,10-phenanthroline ligands and a 2,2′-bipyridyl unit linked, via methylene bridges in its 4 and 4′ positions, to two 1,4,7,10-tetraazacyclododecane (cyclen) macrocycles ([Ru(phen)2L]2+) is reported. Protonation and ZnII binding by [Ru(phen)2L]2+ have been analyzed by potentiometric titration, evidencing the formation of mixed hetero-binuclear and hetero-trinuclear ZnII/RuII complexes. These complexes were tested as bis-phenol A (BPA) binders. Only the dizinc complex with [Ru(phen)2L]2+ is able to bind BPA in aqueous solution, affording a remarkably stable {Zn2[Ru(phen)2L]BPA(H−2)}4+ adduct at neutral pH, in which BPA is bound in its doubly deprotonated form to the two ZnII ions. BPA binding was found to quench the luminescence emission of the RuII(phen)2bipy core. Although the quenching effect is modest, this study demonstrates that appropriately designed dizinc complexes can be used for binding and optic...
Photochemical & Photobiological Sciences, 2019
Small PEGylated silica nanoparticles are synthesized in the presence of high concentrations of or... more Small PEGylated silica nanoparticles are synthesized in the presence of high concentrations of organic solvents. This method allows for the efficient incorporation of dyes with poor solubility in water, yielding bright silica nanoparticles.
Understanding polarity gradients inside nanomaterials is essential to capture their potential as ... more Understanding polarity gradients inside nanomaterials is essential to capture their potential as nanoreactors, catalysts or in drug delivery applications. We propose here a method to obtain detailed, quantitative information on heterogeneous polarity in multicompartment nanostructures. The method is based on a 2-steps procedure, (i) deconvolution of complex emission spectra of two solvatochromic probes followed by (ii) spectrally resolved analysis of FRET between the same solvatochromic dyes. While the first step yields a list of polarities probed in the nanomaterial suspension, the second step correlates the polarities in space. Colocalization of polarities falling within few nanometer radius is obtained via FRET, a process called here nanopolarity mapping. Here, Prodan and Nile Red are tested to map the polarity of a water-dispersable, multicompartment nanostructure, named PluS nanoparticle (NPs). PluS NPs are uniform core-shell nanoparticles with silica cores (diameter ~10 nm) an...
Journal of the American Chemical Society, Dec 14, 2016
The impact of nanotechnology on analytical science is hardly overlooked. In the search for ever-i... more The impact of nanotechnology on analytical science is hardly overlooked. In the search for ever-increasing sensitivity in biomedical sensors, nanoparticles have been playing a unique role as, for instance, ultrabright labels, and unravelling the intimate mechanisms which govern their functioning is mandatory for the design of ultrasentitive devices. Herein, we investigated the mechanism of electrogenerated chemiluminescence (ECL) in a family of core-shell silica-PEG nanoparticles (DDSNs), variously doped with a Ru(bpy)3(2+) triethoxysilane derivative, and displaying homogeneous morphological, hydrodynamic, and photophysical properties. ECL experiments, performed in the presence of 2-(dibutylamino)ethanol (DBAE) as coreactant, showed two parallel mechanisms of ECL generation: one mechanism (I) which involves exclusively the radicals deriving from the coreactant oxidation and a second one (II) involving also the direct anodic oxidation of the Ru(II) moieties. The latter mechanism incl...
Monitoring Prostate Cancer (PCa) biomarkers is an efficient way to diagnosis this disease early, ... more Monitoring Prostate Cancer (PCa) biomarkers is an efficient way to diagnosis this disease early, since it improves the therapeutic success rate and suppresses PCa patient mortality: for this reason a powerful analytical technique such as electrochemiluminescence (ECL) is already used for this application, but its widespread usability is still hampered by the high cost of commercial ECL equipment. We describe an innovative approach for the selective and sensitive detection of the PCa biomarker sarcosine, obtained by a synergistic ECL-supramolecular approach, in which the free base form of sarcosine acts as co-reagent in a Ru(bpy)32+-ECL process. We used magnetic micro-beads decorated with a supramolecular tetraphosphonate cavitand (Tiiii) for the selective capture of sarcosine hydrochloride in a complex matrix like urine. Sarcosine determination was then obtained with ECL measurements thanks to the complexation properties of Tiiii, with a protocol involving simple pH changes – to dri...
Pyrazino-fused tetrarylporphyrins, Dyes and Pigments (2013), doi: 10.1016/ j.dyepig.2013.04.024. ... more Pyrazino-fused tetrarylporphyrins, Dyes and Pigments (2013), doi: 10.1016/ j.dyepig.2013.04.024. This is a PDF file of an unedited manuscript that has been accepted for publication. As a service to our customers we are providing this early version of the manuscript. The manuscript will undergo copyediting, typesetting, and review of the resulting proof before it is published in its final form. Please note that during the production process errors may be discovered which could affect the content, and all legal disclaimers that apply to the journal pertain.
Dye-doped near infrared-emitting silica nanoparticles (DD-NIRsiNPs) represent a valuable tool in ... more Dye-doped near infrared-emitting silica nanoparticles (DD-NIRsiNPs) represent a valuable tool in bioimaging, because they provide sufficient brightness, resistance to photobleaching and consist of hydrophilic non-toxic materials.
... Luca Prodi*a, Fabrizio Bollettaa, Marco Montaltia, Nelsi Zaccheronia, Alessandro Casnati*b, F... more ... Luca Prodi*a, Fabrizio Bollettaa, Marco Montaltia, Nelsi Zaccheronia, Alessandro Casnati*b, Francesco Sansoneb and Rocco Ungarob. a ... 1, GD Andreetti, F. Ugozzoli, A. Pochini and R. Ungaro, in Inclusion Compounds, ed. JL Atwood, JED Davies and DD MacNicol, Oxford ...
Electrochemiluminescence (ECL) starting from being a laboratory curiosity has become a powerful d... more Electrochemiluminescence (ECL) starting from being a laboratory curiosity has become a powerful diagnostic technique. i In the perspective of be used in ECL-based biological assays a luminophore must meet several requirements: his ECL signal must be intense ...
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