Damiano Genovese

• PhD
• PostDoc Position at Karlsruhe Institute of Technology

Ion-receptor binding is a key mechanism for various biological responses that greatly inspire biomimetic approaches in technologies ranging from nanomedicine to energy storage and active membrane separation. Interaction between analytes and nanopores has been reported to either favour the transport (electrochemical studies performed in the millimol...

Mechanofluorescent polymers represent a promising class of materials exhibiting fluorescence changes in response to mechanical stimuli. One approach to fabricating these polymers involves incorporating aggregachromic dyes, whose emission properties are governed by the intermolecular distance, which can, in turn, be readily altered by microstructura...

We have investigated the effect of dye distribution on the electrochemiluminescence (ECL) intensity measured with a simplified magnetic beads-based immunoassay for two families of silica nanoparticles (NPs) doped with the...

Single- and multi-nanoporous (1–100 nm pore size) solid-state membranes (SSNMs) receive significant attention in various fields, spanning from biosensing to water purification. Their finely tunable nanopore geometry and chemistry, combined with the large selection of materials that they can be made of, such as polymers, inorganic materials (e.g., s...

Six novel bicyclic and tricyclic difluoroboron NBN and OBN heterocycles were designed here in the quest for novel luminogenic molecular architectures because of their strong application potential as active layers in optoelectronics and as responsive units in sensing. They were prepared and then characterized with spectral (UV-vis, NMR, and luminesc...

Proteins are broadly versatile biochemical materials, whose functionality is tightly related to their folding state. Native folding can be lost to yield misfolded conformations, often leading to formation of protein oligomers, aggregates, and biomolecular phase condensates. The fluorogenic hyaluronan HA-RB, a nonsulfonated glycosaminoglycan with a...

Quantification of biomarkers is an important research area due to its impact on the early treatment and diagnosis of diseases. However, the detection of these analytes with simple and accurate methods is still an open issue due to their ultralow levels. In this context, luminescence-based techniques and electrochemiluminescence (ECL), appear as pow...

Over the past two decades, the chirality‐induced spin selectivity (CISS) effect was reported in several experiments disclosing a unique connection between chirality and electron spin. Recent theoretical works highlighted time‐resolved Electron Paramagnetic Resonance (trEPR) as a powerful tool to directly detect the spin polarization resulting from...

Aggregation‐induced emission (AIE) luminogens are attractive dyes to probe polymer properties that depend on changes in chain mobility and free volume. When embedded in polymers the restriction of intramolecular motion (RIM) can lead to their photoluminescence quantum yield (PLQY) strong enhancement if local microviscosity increases (lowering of ch...

Over the past two decades, the chirality-induced spin selectivity (CISS) effect was reported in several experiments disclosing a unique connection between chirality and electron spin. Recent theoretical works have highlighted time-resolved Electron Paramagnetic Resonance (trEPR) as a powerful tool to directly detect the spin polarisation resulting...

Luminescence-based techniques are powerful tools in biological sensing and imaging, because of their sensitivity and versatility. Great attention has been given to the development of luminescent nanomaterials that have been used for many purposes like temperature sensors, lasers, solar cells, biosensors, biological probes and drug delivery. It is w...

This annual review, the 50th volume in the series, provides critical analysis for anyone wanting to keep up to date with the literature on photochemistry and its applications. This essential volume combines reviews on the latest advances in photochemical research with specific topical highlights in the field. The volume starts with periodical repor...

Nano- and microplastics are polluting the environment and their detection remains elusive. A fluorogenic hyaluronan shows high affinity toward their surfaces, turning brightly emissive, and its lifetime allows discrimination of plastics in nature.

Environmental pollution especially by micro‐ and nanoplastics is highly topical our days. The elimination of these plastics is extremely difficult, however, detecting them is also very challenging. Different detection methods are discussed in the Review by L. Prodi et al. on page 17529 ff.

The growing numbers related to plastic pollution are impressive, with ca. 70 % of produced plastic (>350 tonnes/year) being indiscriminately wasted in the environment. The most dangerous forms of plastic pollution for biota and human health are micro‐ and nano‐plastics (MNPs), which are ubiquitous and more bioavailable. Their elimination is extreme...

Luminescence quenching is a process exploited in transversal applications in science and technology and it has been studied for a long time. The luminescence quenching mechanisms are typically distinguished in dynamic (collisional) and static, which can require different quantitative treatments. This is particularly important - and finds broad and...

Nitroxides are an important class of radical trapping antioxidants whose promising biological activities are connected to their ability to scavenge peroxyl (ROO•) radicals. We have measured the rate constants of the reaction with ROO• (kinh) for a series of 2,2,6,6-tetramethyl-1-piperidinyloxy (TEMPO) derivatives as 5.1 × 10⁶, 1.1 × 10⁶, 5.4 × 10⁵,...

Electrochemiluminescence (ECL) is a leading technique in bioanalysis.[1] It is a luminescent phenomenon where the excited species are produced with an electrochemical stimulus rather than with a light excitation source. For this reason, ECL displays improved signal-to-noise ratio compared to photoluminescence, with minimized effects due to light sc...

Microplastics (MP) are micrometric plastic particles present in drinking water, food and the environment that constitute an emerging pollutant and pose a menace to human health. Novel methods for the fast detection of these new contaminants are needed. Fluorescence-based detection exploits the use of specific probes to label the MP particles. This...

Nanostructured systems constitute versatile carriers with multiple functions engineered in a nanometric space. Yet, such multimodality often requires adapting the chemistry of the nanostructure to the properties of the hosted functional molecules. Here, we show the preparation of core-shell Pluronic-organosilica "PluOS" nanoparticles with the use o...

Semisolid redox flow batteries simultaneously address the need for high energy density and design flexibility. The electrical percolating network and electrochemical stability of the flowable electrodes are key features that are required to fully exploit the chemistry of the semisolid slurries. Superconcentrated electrolytes are getting much attent...

Protein aggregation is a phenomenon widespread in all organisms, that responds to a variety of external stimuli and is involved in complex functions such as storage and recycling of protein...

Imaging Agents In their Communication on page 21858, L. Prodi et al. report the synthesis of a new family of dye‐doped silica nanoparticles and their application for efficient electrochemiluminescence imaging.

Kontrastmittel In der Zuschrift auf S. 22042 berichten L. Prodi et al. über die Synthese einer neuen Familie von farbstoffdotierten Silika‐Nanopartikeln und deren Anwendung in der effizienten Elektrochemilumineszenz‐Bildgebung.

The combination of highly sensitive techniques such as electrochemiluminescence (ECL) with nanotechnology sparked new analytical applications, in particular for immunoassay‐based detection systems. In this context, nanomaterials, particularly dye‐doped silica nanoparticles (DDSNPs) are of high interest, since they can offer several advantages in te...

Using silica nanoparticles, a 8.5‐fold higher ECL intensity was achieved with respect to a system mimicking a commercial immunosense system, benefiting from the deep knowledge acquired by combining ECL with nanostructures. Abstract The combination of highly sensitive techniques such as electrochemiluminescence (ECL) with nanotechnology sparked new...

The detection of the Cerenkov radiation (CR) is an emerging preclinical imaging technique which allows monitoring the in vivo distribution of radionuclides. Among its possible advantages, the most interesting is the simplicity and cost of the required instrumentation compared, e.g., to that required for PET scans. On the other hand, one of its main...

Hybrid nanomaterials are a subject of extensive research in nanomedicine, and their clinical application is reasonably envisaged in the near future. However, the fate of nanomaterials in biological environments poses serious limitations to their application; therefore, schemes to monitor them and gain control on their toxicity could be of great hel...

Lasing from cells has recently been subject of thorough investigation because of the potential for sensitive and fast biosensing. Yet, lasing from individual cells has been studied in high‐quality resonators, resulting in limited dependence of the lasing properties on the cellular microenvironment. Here, lasing is triggered by cells floating in a l...

Chlorin e6 (Ce6) and its derivatives are among the most important photosensitizers in photodynamic therapy. Due to their intense fluorescence, chlorins may also be used for diagnostics. However, low solubility in water and high tendency to aggregation restrict their medical use. Here we demonstrate that apo-myoglobin, by reinserting Ce6 in its heme...

The processing of advanced and functional polymers with electrospinning brings enormous potentialities to either improve or extend their properties. A representative example is the field of mechanochromic materials, potentially exploitable for imaging mechanical damages and stress/strain distribution. An effective stress-sensing material must respo...

Protein aggregation is a complex physiological process, primarily determined by stress-related factors revealing the hidden aggregation propensity of proteins that otherwise are fully soluble. Here we report a mechanism by which glycolytic glyceraldehyde-3-phosphate dehydrogenase of Arabidopsis thaliana (AtGAPC1) is primed to form insoluble aggrega...

Two synthetic routes for the preparation of the water soluble 5,10,15‐tris(4‐sulfonatophenyl)corrole are reported. The first approach explores the chlorosulfonation reaction on the phosphorus complex of 5,10,15‐tris(4‐trimethylsilylphenyl)corrole. Following this route, the P complex of the target corrole has been obtained in low yields, while the m...

Silica nanostructures are widely investigated for theranostic applications since relatively mild and easy synthetic methods allow the fabrication of multicompartment nanoparticles (NPs) and fine modulation of their properties. Here, we report the optimization of a synthetic strategy leading to brightly fluorescent silica NPs with a high loading abi...

Protein aggregation is a complex physiological process that is primarily determined by stress-related factors. Here we report a mechanism by which cytoplasmic glyceraldehyde-3-phosphate dehydrogenase of Arabidopsis thaliana (AtGAPC1) evolves into globular aggregates after S-glutathionylation of its catalytic cysteine (Cys149). Although in principle...

Abstract 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) deconv...

A nanosensor with dual‐mode fluorescence response to pH and an encoded identification signal, was developed by exploiting excitation energy transfer and tailored control of molecular organization in core–shell nanoparticles. Multiple signals were acquired in a simple single‐excitation dual‐emission channels set‐up. A nanosensor with dual‐mode fluor...

Mechanochromic polymeric systems are intensively investigated for real‐time stress detection applications. However, an effective stress‐sensing material must respond to low deformation with a detectable color change that should be quickly reversible upon force unloading. In this work, mechanochromic nanofibers made by electrospinning are used to pr...

The development of nanostructures devoted to in vivo imaging and theranostic applications is one of the frontier fields of research worldwide. In this context, silica nanoparticles (SiO2-NPs) offer unquestionable positive properties: silica is intrinsically non-toxic, several versatile and accessible synthetic methods are available and many variati...

Copper and gallium β-acrolein corroles have been obtained by reaction of corrole complexes with 3-(dimethylamino)-acrolein/phosphoryl chloride (3-DMA/POCl3) under Vilsmeier conditions. In the case of the Ga complex, up to four acroleyl substituents have been introduced at the β-peripheral positions of the corrole macrocycle. The introduction of the...

Silicon complexes of corrole have been obtained for the first time by reaction of the corrole free‐base with hexachlorodisilane. The peripheral substituents of corrole strongly influence the nature of the reaction products: ‐octaalkylcorrole has been mainly isolated as the ‐oxo dimer, while a hydroxo‐complex is obtained in the case of the 5,10,15‐t...

Dye-doped nanoparticles (NPs) are intriguing fluorescent systems in which collective properties can arise, which are ascribable to the ensemble of dyes rather than to individual ones. Collective properties can be tailored to increase brightness and introduce photophysical versatility. In this context, self-quenching has long been regarded as the ph...

Electrolytes are key components of Li/O2 batteries. Solvent-in-salt electrolytes feature an ionic liquid-like structure and good electrochemical and thermal stability that are important for battery cycling performance. Here, a voltammetric study is reported to investigate how salt concentration affects oxygen redox reaction. Solutions of lithium bi...

Bottom-up self-assembly of simple molecular compounds is a prime pathway to complex materials with interesting structures and functions. Coupled reaction systems are known to spontaneously produce highly ordered patterns, so far observed in soft matter. Here we show that similar phenomena can occur during silica-carbonate crystallization, the emerg...

Supplementary Figures

This video is an animated sequence of images recorded by fluorescence microscopy during the growth of a biomorph in the presence of the fluorescent dye acridine orange (selected frames are shown in Figure 2 of the main text). Strong fluorescence is only observed at the rim of the evolving structure, demonstrating that the pH is locally decreased. D...

The N,N'-dimethyl-3,3'-biquinoxalinium "methylbiquinoxen" dicationic platform is revealed to have even more fascinating possibilities than we originally thought in terms of its chemical versatility. In addition to its rich redox chemistry and coordination abilities, we have now unveiled an unexpected Lewis acid/base chemistry linked with a tuneable...

The synthesis, spectroscopic and optical properties of the water soluble phosphorus complex of a 2-sulfonato-10-(4-sulfonatophenyl)-5,15-dimesitylcorrole have been investigated. The compound was prepared adopting a novel strategy for the corrole sulfonation, leading to the regioselective isomer in an almost quantitative yield. The phosphorus coordi...

The molecular structure of the units that get incorporated into the nuclei of the crystalline phase and sustain their growth is a fundamental issue in the pathway from a supersaturated solution to the formation of crystals. Using a fluorescent dye we have recorded the variation of the pH value in time along a gel where CaCl2 and NaHCO3 counter-diff...

Indium tin oxide (ITO) and silicon with a thermally grown SiO2 layer (Si/SiO2) substrates have been functionalized by ferrocene bound through Sn(O)x (x=2 or 3) linkers preliminarly grafted on the surface by reaction of the terminal hydroxyl groups with tetra(tert-butoxy)tin. The two steps modification of the surface was carried out by chemical vapo...

A Pt(II) complex, bearing an oligo-ethyleneoxide pendant, is able to self-assemble in ultralong ribbons that display mechanochromism upon nanoscale mechanical stimuli, delivered through atomic force microscopy (AFM). Such observation paves the way to fine understanding and manipulation of the mechanochromic properties of such material at the nanosc...

Supramolecular weak interactions can be used for preparing functional self-assembled architectures by powerful bottom-up approaches. In particular, when closed-shell metallophilic and π-π interactions between adjacent transition-metal complexes are established, profound changes in compounds' properties are obtained and novel features often achieved...

With the aim to improve the features of surfactant solutions in terms of sustainability and biocompatibility we propose the use of the hydrogenated natural and sustainable plant-derived cardanol as an additive to commercial surfactants. In the present study we demonstrated that its addition, in amount as high as 10%, to commercial surfactants of di...

A nanostructure formed by the insertion in silica nanoparticles of a pyrene-derivatized cavitand, able to specifically recognize ecstasy in water, is presented. The absence of effects from interferents and an efficient electron transfer process occurring after complexation of ecstasy, makes this system an efficient fluorescent probe for this popula...

We report here the design of two sets of multifluorophoric silica nanoparticles, observing unprecedented efficiencies in the energy-transfer processes among the doping dyes. These nanomaterials show a very high overall sensitization, allowing under a single wavelength excitation to obtain many different colors (one per nanoparticle) in emission wit...

Fast and efficient energy transfer among dyes confined in nanocontainers provides the basis of outstanding functionalities in new-generation luminescent probes. This feature article provides an overview of recent research achievements on luminescent Pluronic-Silica NanoParticles (PluS NPs), a class of extremely monodisperse core-shell nanoparticles...

Non-fluorescent nanoparticles resulting from the self-assembly of a new perylene diimide behave as fluorogenic probes for biological cells under physiological conditions giving a dosage-dependent green or red fluorescence and showing very low cytotoxicity. The emission colour can be tuned by photo-irradiation to achieve multicolour labelling.

The quinoline urea derivatives 1,3-di(quinolin-5-yl)urea (DQ5U), 1-phenyl-3-(quinolin-6-yl)urea (PQ6U), 1-(isoquinolin-5-yl)-3-phenylurea (PiQ5U) and 1-phenyl-3-(3,5-bis(pyrid-2-yl)-1,2,4-triazol-4-yl)urea (PPT4U) have been synthesised and structurally characterized by powder and single crystal X-ray diffraction. Their gelator behaviour in the form...

The photophysical properties of two 7-aminocoumarin molecules with flexible and rigid alkyl moieties at the 7-nitrogen atom have been investigated in ethanol and in Pluronic-silica nanoparticles (PluS NPs) by means of time-resolved emission spectroscopy (TRES) and time-dependent density functional theory (TDDFT). Although the two coumarin derivativ...

Stars that shine bright: A high local dye concentration in doped silica-based core-shell nanoparticles causes self-quenching and spectral broadening (top images). This phenomenon jeopardizes the potential advantages of heavily doped systems. Förster resonance energy transfer (FRET) to an acceptor co-included in the silica led to ultrabright nanopar...

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 p...

5,10,15-Triaryltetrabenzocorrole complexes of aluminum, gallium, germanium, and phosphorus were synthesized by coordination of these metal ions in the preformed triaryltetrabenzocorrole macrocycle, opening a way to the investigation of different metal complexes. The UV-vis spectra of these derivatives exhibit a red shift and broadening of all absor...

Mineralized tissues grow through biologically controlled processes in which specific macromolecules are involved. Some of these molecules, which are present in very low concentrations and are difficult to localize and characterize, become entrapped inside the mineralized tissue. Herein, a protein fragment, GP, which was obtained by the alkaline dig...

Background and methods Despite the recent introduction of targeted bio-drugs, the scarcity of successful therapeutic options for advanced colorectal cancer remains a limiting factor in patient management. The efficacy of curative surgical interventions can only be extended through earlier detection of metastatic foci, which is dependent on both the...

Characterization of the fluorescent SPNs. (A) TEM analysis of SPN silica cores for the evaluation of size distribution. (B) Dynamic light scattering distribution of the nanoparticle hydrodynamic diameter. Exemplary graphs referred to CGIYRLRS-(Rhod)-SPNs are shown. Abbreviations: SPN, silica-poly(ethylene glycol) nanoparticles; TEM, transmission el...

Single-color targeted SPNs recognize human hepatic metastases ex vivo Frozen sections (10-μm ) of matched (grossly) normal liver and hepatic metastasis were fixed in 4% formaldehyde before being incubated with 5 × 1012 of either untargeted, CGIYRLRS-, or (A) CGVYSLRS-(Rhod)- or (B) (Cy5)-SPNs for 4 h at RT. After 3 washes in TBS-T, the SPN-emitted...

This review aims to give an overview on the state of the art in the precise context of metal complexes-based ECL dyes directly adsorbed on, included in or interacting with nanoparticles of various nature. Electrogenerated chemiluminescence, or electrochemiluminescence (ECL), is the process through which species generated at electrodes undergo homog...

Devices are systems able to perform specific functions, which result from the coordinated action of different components. The design of these systems is, hence, based on the identification or the development of the necessary parts, and in their integration in a suitable supramolecular architecture. The main challenge in such a process is undoubtedl...

Fancy a copper? A sensing system for copper(I) ions, based on the interplay between a "classical" chemosensor and a fluorescent silica nanoparticle, is presented (see scheme). The occurrence of properly designed energy transfer processes and the observed increase of the affinity of the nanosystem towards Cu + improve sensor performance at low metal...

We present a simple and versatile mechanism for the reversible photoswitching of dye-doped core-shell nanoparticles. Photochromic dithienylethenes are incorporated into the outer shell, close enough to the dyes entrapped in the core to efficiently quench them by energy transfer when photoconverted with UV light. The emission can be switched back on...

Hybrid microspheres of calcium carbonate/fullerenol were synthesized and characterized. Their morphology depends on the concentration of the fullerenol solutions. XRD and FT-IR measurements proved that the mineral phase is consistently calcite, while fluorescence confocal microscopy indicated that fullerenol is homogenously included in the crystall...

Seven new bioinspired chemosensors (2-4 and 7-10) based on fluorescent peptides were synthesized and characterized by elemental analysis, (1)H and (13)C NMR, melting point, matrix-assisted laser desorption-ionization time-of-flight mass spectrometry (MALDI-TOF-MS), and IR and UV-vis absorption and emission spectroscopy. The interaction with transit...

Feines Gespür: Eine Auflösung auf molekularem Niveau beim Nachweis kurzkettiger Alkohole in der Gasphase bietet ein fluoreszierender Cavitandensensor. Der Transduktionsmechanismus, der ausschließlich duch die Art der Komplexierung aktiviert wird, beruht auf einer Änderung der Elektronendichte im Fluorophor als Folge der Bildung einer Intrakavitäts-...

Siliciumdioxidnanopartikel verfügen über besondere Eigenschaften, z. B. eine geringe Toxizität, und stellen eine vielseitige Plattform für die Nanotechnologie dar. Ein geeignetes Design oder eine geeignete Derivatisierung führen zu selbst unter physiologischen Bedingungen stabilen Kolloiden und ermöglichen verschiedenste Funktionen. Insbesondere be...

Silica nanoparticles are versatile platforms with many intrinsic features, such as low toxicity. Proper design and derivatization yields particularly stable colloids, even in physiological conditions, and provides them with multiple functions. A suitable choice of dyes and synthetic strategy may, in particular, yield a very bright nanosystem. Silic...

A strong coupling between shear, confinement and microstructure governs the flow of dense colloidal suspensions through narrow channels. In this paper we explore the additional complexity that arises when the channel is partially blocked by a constriction in the centre of the channel. The reduction of the particle flux due to the constriction induc...

The field of nanoparticles is amazingly many-sided and consequently their applications range between many different areas from industry to bio-analysis and catalysis. In particular, luminescent nanoparticles attract close attention in the areas of biology, medical diagnosis and therapy, where they already find many applications. In this so fascinat...

Very monodisperse water-soluble silica core-surfactant shell nanoparticles (SCSS NPs) doped with a rhodamine B derivative were prepared using micelles of F127 as nanoreactors for the hydrolysis and condensation of the silica precursor tetraethoxysilane (TEOS). The functionalization of the rhodamines with a triethoxysilane group allowed the covalent...

The careful design of dye doped silica nanoparticles in order to induce controllable energy transfer processes can yield very sophisticated species able to perform precious and complex functions. They can be therefore exploited in many fields of great economical and social importance, such as medical diagnostics, molecular biology, and solar energy...

A set of modular components was designed, synthesized, and combined to yield an innovative, robust, and reliable methodology for the self-assembly of large supramolecular structures on silicon wafers. Specific host-guest and H-bonding motifs were embedded in a single molecule by exploiting the remarkable complexing properties of tetraphosphonate ca...

The reaction of 5,10,15-triarylcorrole with 4-amino-4H-1,2,4-triazole provides another example of corrole ring expansion to give the corresponding 6-azahemiporphycene, a novel porphyrin analogue. The facile oxidation of the corrole ring is a required step for the ring expansion and for this reason the reaction fails in the case of corroles bearing...

Die Änderung des Redoxzustands eines Paraphenylendiamin-Azakronenether-Konstrukts, das als selbstorganisierte Monoschicht an eine Elektrodenoberfläche gebunden ist, führt zur zeitlich und räumlich steuerbaren Freisetzung pikomolarer Ca2+-Mengen. Der Prozess läuft binnen Millisekunden ab und ist irreversibel, wenn das oxidierte Redoxzentrum nicht wi...