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January 2018 - September 2019
January 2010 - present
Publications
Publications (80)
Throughout the many diverse synthesis methods for CsPbBr3 nanocrystals (NCs), a binary ligand system composed of aliphatic carboxylic acids and primary amines of various chain lengths is commonly employed. In this work, we have carried out a systematic study examining how the concentration of ligands (oleylamine and oleic acid) and the resulting ac...
We propose here a new colloidal approach for the synthesis of both all-inorganic and hybrid organic-inorganic lead halide perovskite nanocrystals (NCs). The main limitation the protocols that are currently in use, such as the hot-injection and the ligand assisted reprecipitation routes, is that they employ PbX2 (X= Cl, Br, or I) salts as both lead...
Abstract The synthesis of microcrystalline cellulose (MCC) and 9,10,16-hydroxyhexadecanoic (aleuritic) acid ester-based bioplastics was investigated through acylation in a mixed anhydride (trifluoroacetic acid (TFA)/trifluoroacetic acid anhydride (TFAA)), chloroform co-solvent system. The effects of chemical interactions and the molar ratio of aleu...
Absolute analyte quantification by nuclear magnetic resonance (NMR) spectroscopy is rarely pursued in metabolomics, even though this would allow researchers to compare results obtained using different techniques. Here we report on a new protocol that permits, after pH-controlled serum protein removal, the sensitive quantification (limit of detectio...
Herein we report on a novel series of multitargeted compounds obtained by linking together galantamine and memantine. The compounds were designed by taking advantage of the crystal structures of acetylcholinesterase (AChE) in complex with galantamine derivatives. Sixteen novel derivatives were synthesized, using spacers of different lengths and che...
In this study, we synthesized a phosphonium-based ligand, trimethyl(tetradecyl)phosphonium bromide (TTP-Br), and employed it in the postsynthesis surface treatment of Cs-oleate-capped CsPbBr3 nanocrystals (NCs). The photoluminescence quantum yield (PLQY) of the NCs increased from ∼60% to more than 90% as a consequence of replacing Cs-oleate with TT...
Perovskite nanocrystal superlattices are being actively studied after reports have emerged on collective excitonic properties at cryogenic temperatures, where energetic disorder is minimized due to the frozen lattice vibrations. However, an important issue related to structural disorder of superlattices at low temperatures has received little atten...
Perovskite nanocrystal superlattices are being actively studied after reports have emerged on collective excitonic properties at cryogenic temperatures, where energetic disorder is minimized due to the frozen lattice vibrations. However, an important issue related to structural disorder of superlattices at low temperatures has received little atten...
We report a colloidal synthesis of blue emissive, stable cube-shaped CsPbBr3 quantum dots (QDs) in the strong quantum confinement regime via a dissolution-recrystallization starting from pre-synthesized (KxCs1-x)4PbBr6 nanocrystals which are then reacted with PbBr2. This is markedly different from the known case of Cs4PbBr6 nanocrystals that react...
Lead halide perovskite nanocrystals (LHP NCs) are generally prone to surface defect formation during the purification process, resulting in a reduced photoluminescence (PL) quantum yield. The purification of LHP NCs using antisolvents leads to the detachment of surface atoms and ligandsin the form of alkylammonium‐halides or A‐carboxylates (A: Cs,...
We report a colloidal synthesis of blue emissive, stable cube-shaped CsPbBr3 quantum dots (QDs) in the strong quantum confinement regime via dissolution–recrystallization starting from pre-syntesized (KxCs1–x)4PbBr6 nanocrystals which are then reacted with PbBr2. This is markedly different from the known case of Cs4PbBr6 nanocrystals that react wit...
We have approached the synthesis of colloidal InAs nanocrystals (NCs) using amino-As and ligands that are different from the commonly employed oleylamine (OA). We found that carboxylic and phosphonic acids led only to oxides, whereas tri-n-octylphosphine, dioctylamine, or trioctylamine (TOA), when employed as the sole ligands, yielded InAs NCs with...
One major concern toward the performance and stability of halide perovskite-based optoelectronic devices is the formation of metallic lead that promotes nonradiative recombination of charge carriers. The origin of metallic lead formation is being disputed whether it occurs during the perovskite synthesis or only after light, electron, or X-ray beam...
We show how, in the synthesis of yellow-emissive Bi-doped Cs2Ag1-xNaxInCl6 double perovskite nanocrystals (NCs), preventing the transient formation of Ag0 particles increases the photoluminescence quantum yield (PLQY) of the NCs from ∼30% to ∼60%. Calculations indicate that the presence of even a single Ag0 species on the surface of a NC introduces...
Polyethylene resistance to biochemical attack is a well-known limit, preventing the development of green strategies, based on enzymatic catalysis, for the bioconversion of waste polyethylene into smaller molecules and subsequently second-life products. This inertness derives from the chemical structure of the polymer, consisting of repeating methyl...
Maximizing loading while modulating the release of therapeutic molecules from nanoparticles and implantable drug delivery systems is key to successfully address deadly diseases like brain cancer. Here, four different conjugates of the potent chemotherapeutic molecule docetaxel (DTXL) were realized to optimize the pharmacological properties of 1,000...
Tridecafluorononanoic acid (TFNA), a C6-fluorinated carboxylic acid, was esterified with cellulose at different molar ratios (0:1, 1:1, 2:1, and 3:1) in a trifluoroacetic acid (TFA):trifluoroacetic anhydride (TFAA):CHCl3 (2:1:1, v:v:v) solvent mixture. Free-standing films were obtained for all formulations and are presented as alternatives to compo...
We utilize the solvent acidolysis crystallization technique to grow mixed dimethylammonium/methylammonium lead tribromide (DMA/MAPbBr3) crystals reaching the highest dimethylammonium incorporation of 44% while maintaining the 3D cubic perovskite phase. These mixed perovskite crystals show suppression of the orthorhombic phase and a lower tetragonal...
The interaction of lead bromide perovskite nanocrystals with charged ligands, such as salts, zwitterions, or acid–base pairs, has been extensively documented over the past few years. On the other hand, little is known about the reactivity of perovskite nanocrystals toward neutral ligands. To fill this gap, in this work we study the interaction of C...
The encapsulation of colloidal lead halide perovskite nanocrystals within silica (SiO2) is one of the strategies to protect them from polar solvents and other external factors. Here, we demonstrate the overcoating of CsPbBr3 perovskite nanocrystals with silica by exploiting the anhydride-induced transformation of Cs4PbBr6 nanocrystals. CsPbBr3@SiO2...
We report a one-step synthesis of halide perovskite nanocrystals embedded in amphiphilic polymer (poly(acrylic acid)-block-poly(styrene), PAA-b-PS) micelles, based on injecting a dimethyl-formamide solution of PAA-b-PS, PbBr 2 , ABr (A = Cs, formamidinium, or both) and "additive" molecules in toluene. These bifunctional or trifunctional short chain...
Cellulose ester films were prepared by esterification of cellulose with a multibranched fluorinated carboxylic acid, “BRFA” (BRanched Fluorinated Acid), at different anhydroglucose unit:BRFA molar ratios (i.e., 1:0, 10:1, 5:1, and 1:1). Morphological and optical analyses showed that cellulose-BRFA materials at molar ratios 10:1 and 5:1 formed flat...
Polyvinylpyrrolidone (commonly known as povidone or PVP) rapidly dissolves in water. This significantly hinders its use in sustained release formulations developed for the biomedical field. Electrospun fibers of PVP dissolve even faster due to larger surface to volume ratio. In this work, we propose a way to circumvent this problem by developing an...
We employed oleylphosphonic acid (OLPA) for the synthesis of CsPbBr3 nanocrystals (NCs). Compared to phosphonic acids with linear alkyl chains, OLPA features a higher solubility in apolar solvents, allowing us to work at lower synthesis temperatures (100 °C), which in turn offer a good control over the NCs size. This can be reduced down to 5.0 nm,...
Various strategies have been proposed to engineer the band gap of metal halide perovskite nanocrystals (NCs) while preserving their structure and composition and thus ensuring spectral stability of the emission color. An aspect that has only been marginally investigated is how the type of surface passivation influences the structural/color stabilit...
Understanding and tuning the ligand shell composition in colloidal halide perovskite nanocrystals (NCs) has been done systematically only for Pb-based perovskites, while much less is known on the surface of Pb-free perovskite systems. Here, we reveal the ligand shell architecture of Bi-doped Cs2Ag1-x Na
x
InCl6NCs via nuclear magnetic resonance an...
Cystic fibrosis (CF) is a life-threatening autosomal recessive disease, caused by mutations in the CF transmembrane conductance regulator (CFTR) chloride channel. CFTR modulators have been reported to address the basic defects associated with CF-causing mutations, partially restoring the CFTR function in terms of protein processing and/or channel g...
Various strategies have been proposed to engineer the band gap of metal halide perovskite nanocrystals (NCs) while preserving their structure and composition and thus ensuring spectral stability of the emission color. An aspect that has only been marginally investigated is how the type of surface passivation influences the structural/color stabilit...
Differing sensitivity is the main obstacle for a direct combination of HPTLC with nuclear magnetic NMR spectroscopy. A sufficient amount of the isolated compound zone must be provided by HPTLC for subsequent offline NMR detection (HPTLC//NMR). To fill the gap, a straightforward procedure was developed using the same analytical HPTLC system for both...
Correction for ‘Transforming colloidal Cs 4 PbBr 6 nanocrystals with poly(maleic anhydride- alt -1-octadecene) into stable CsPbBr 3 perovskite emitters through intermediate heterostructures’ by Dmitry Baranov et al. , Chem. Sci. , 2020, 11 , 3986–3995, DOI: 10.1039/D0SC00738B.
The preparation of strongly emissive CsPbBr3 perovskite nanocrystals with a robust surface passivation is a challenge in the field of lead halide perovskite nanomaterials. We report an approach to prepare polymer-capped CsPbBr3 perovskite nanocrystals by reacting oleylammonium/oleate-capped s4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-octa...
Multi-dentate ligands enabling a quick and high yield water transfer of inorganic nanocrystals (NCs) via ligand exchange process is of great interest to promote the applications of NCs in biomedical...
Nuclear Magnetic Resonance (NMR) is an analytical technique extensively used in almost every chemical laboratory for structural identification. This technique provides statistically equivalent signals in spite of using spectrometer with different hardware features and is successfully used for the traceability and quantification of analytes in food...
The preparation of strongly emissive CsPbBr3 perovskite nanocrystals with a robust surface passivation is a challenge in the field of lead halide perovskite nanomaterials. We report an approach to prepare polymer-capped CsPbBr3 perovskite nanocrystals by reacting oleylammonium/oleate-capped Cs4PbBr6 nanocrystals with poly(maleic anhydride-alt-1-oct...
The LIBRA compound library is a collection of 522 non-commercial molecules contributed by various Italian academic laboratories. These compounds have been designed and synthesized during different medicinal chemistry programs and are hosted by the Italian Institute of Technology. We report the screening of the LIBRA compound library against Trypano...
We devised a colloidal approach for the synthesis of CsPbBr3 nanocrystals (NCs) in which the only ligands employed are alkyl phosphonic acids. Compared to more traditional syntheses of CsPbBr3 NCs, the present scheme delivers NCs with the following distinctive features: i) The NCs do not have cubic, but truncated octahedron shape enclosed by Pb-ter...
A detailed investigation into the synthesis of green-emitting powders of Cs4PbBr6 and CsPbBr3 materials by antisolvent precipitation from CsBr-PbBr2 precursor solutions in dimethylformamide (DMF) and dimethyl sulfoxide (DMSO) is reported. Various solvated lead bromide and polybromide species (PbBr2, [PbBr3]⁻, [PbBr4]²⁻, and possibly [PbBr5]³⁻ or [P...
ε-caprolactone-p-coumaric acid copolymers at different mole ratios (ε-caprolactone:p-coumaric acid 1:0, 10:1, 8:1, 6:1, 4:1, and 2:1) were synthesized by melt-polycondensation and using 4-dodecylbenzene sulfonic acid as catalyst. Chemical analysis by NMR and GPC showed that copolyesters were formed with decreasing molecular weight as p-coumaric aci...
Post-synthesis ligand exchange has been employed extensively on lead halide perovskite (LHP) nanocrystals (NCs), but the com-plex ligand shell composition of the starting NCs prevented a clear understanding of the exchange process and the surface chem-istry of the final NCs remained poorly characterized. Here, we de-scribe a ligand exchange strateg...
Polyvinylpyrrolidone (PVP) is probably one of the most utilized pharmaceutical polymers with applications ranging from blood plasma substitute to nanoparticle drug delivery, since its synthesis in 1939. It is highly biocompatible, non-toxic and transparent film forming polymer. Although high solubility of PVP in aqueous environment is advantageous,...
Fully inorganic cesium lead halide perovskite (CsPbX3) nanocrystals (NCs) have been extensively studied due to their excellent optical properties, especially their high photoluminescence quantum yield (PLQY) and the ease with which the PL can be tuned across the visible spectrum. So far, most strategies for synthesizing CsPbX3 NCs are highly sensit...
We report an amine-free synthesis of lead halide perovskite (LHP) nanocrystals, using trioctylphosphine oxide (TOPO) instead of aliphatic amines, in combination with a protic acid (e.g., oleic acid). The overall synthesis scheme bears many similarities to the chemistry behind the preparation of LHP thin films and single crystals, in terms of ligand...
Cellulose acetate oleate ester has been synthesized from oleic acid and cellulose acetate by using a mixed anhydride system based on a mixture of trifluoroacetic acid and trifluoroacetic acid anhydride with chloroform as a co-solvent. In absence of oleic acid, cellulose acetate was deacetylated in this mixed anhydride system. However, when oleic ac...
We report the synthesis of various binary and ternary inorganic and hybrid organic-inorganic iodide nanocrystals (NCs) starting from molecular iodine (I2). The synthesis described herein utilizes a reaction between I2 and oleylamine, which re-sults in oleylammonium iodide - an iodide precursor that can be directly used in the preparation of iodide...
In cystic fibrosis (CF), deletion of phenylalanine 508 (F508del) in the CFTR channel is associated with misfolding and premature degradation of the mutant protein. Among the known proteins associated with F508del-CFTR processing, the ubiquitin ligase RNF5/RMA1 is particularly interesting. We previously demonstrated that genetic suppression of RNF5...
Colloidal nanocrystals can self-assemble into highly ordered superlattices. Recent studies have focused on changing their morphology by tuning the nanocrystal interactions via ligand-based surface modification for simple particle shapes. Here we demonstrate that this principle is transferable to and even enriched in the case of a class of branched...
Cellulose is the most abundant natural biopolymer in our planet. For this reason, it offers a renewable alternative for replacing non-degradable oil-based polymer products. Nowadays, the combination of cellulose with organic and inorganic molecules has been demonstrated very effective in order to modify cellulose’s chemical structure and to improve i...
Tissue engineering using adult mesenchymal stem cells (MSCs), a promising approach for cartilage repair, is highly dependent on the nature of the matrix scaffold. Thermoresponsive, photocrosslinkable hydrogels were fabricated by functionalizing pepsin-soluble decellularized tendon and cartilage extracellular matrices (ECM) with methacrylate groups....
Water insoluble monohydrochloride monohydrate free ciprofloxacin (Cipro) antibiotic was incorporated in polyvinylpyrrolidone (PVP) polymer matrix by using acetic acid co-solvent in water. The resultant solutions were cast into fully transparent antimicrobial films. Proper concentrations of acetic acid eliminated in situ crystallization of the antib...
Abstract Water insoluble monohydrochloride monohydrate free ciprofloxacin (Cipro) antibiotic was incorporated in polyvinylpyrrolidone (PVP) polymer matrix by using acetic acid co-solvent in water. The resultant solutions were cast into fully transparent antimicrobial films. Proper concentrations of acetic acid eliminated in situ crystallization of...
We report chemical routes for the synthesis of both nanocrystals and bulk crystals of methylammonium (MA) lead halide perovskites employing N-methylformamide (NMF) as source of MA ions. Colloidal nanocrystals were prepared by a transamidation reaction between NMF and an alkyl amine (oleylamine). The nanocrystals had photoluminescence quantum yields...
Acid ceramidase (AC) is a lysosomal cysteine amidase responsible for the cleavage of ceramide into sphingosine, which is then phosphorylated to sphingosine 1-phosphate. AC regulates the intracellular levels of ceramide and sphingosine, and AC inhibition may be useful in the treatment of disorders, such as cancer, in which ceramide-mediated signali...
The NMR spectra and data reported in this article refer to the research article titled “A simple and accurate protocol for absolute polar metabolite quantification in cell cultures using q-NMR” [1]. We provide the 1H q-NMR spectra of cell culture media (DMEM) after removal of serum proteins, which show the different efficiency of various precipitat...
The availability of nanofibrous substrates with engineered properties, such as controlled porosity, mechanical conformability, biodegradation profile and drug release, is of strategic importance in the biomedical sector. Here, we demonstrate that N-methacrylate glycol chitosan, a photo-polymerisable, biocompatible and water-soluble derivative of ch...
The 1HNMR characterization of the encapsulation of bisplatinum complex CT-3610 by cucurbit[7]uril is reported. The formation of the intermediate monoinclusion complex can be easily detected in the 1HNMR spectrum, and the pD dependence of the equilibrium has also been assessed. No significant differences were observed in cytotoxicity experiments bet...
Boronic esters are key intermediates in the synthesis of biologically active compounds such as thrombin and proteasome inhibitors. However, they have low hydrolytic stability both during synthetic reactions and in biological media. We report the preparation of several boronic esters and a comparative study of their stability to hydrolysis vs. the c...
3-Aryl-4-hydroxycoumarins have been obtained in satisfactory yields and selectivity through a Rh(II)-mediated arylation of diazocoumarin. The utility of this approach is demonstrated by synthesis of the natural product derrusnin.
Two different groups of liver fatty acid-binding proteins (L-FABPs) are known: the mammalian type and the basic type. Very few members of this second group of L-FABPs have been characterized and studied, whereas most of the past studies were concerned with the mammalian type. The interactions of chicken liver basic fatty acid-binding protein (Lb-FA...
A preparation of chicken liver (basic) fatty acid binding protein was purified to homogeneity in multicompartment electrolyzers with isoelectric membranes. Large amounts of the isoelectric point (pI) 9.7 protein were collected into a compartment delimited by pI 8.8 and 11.0 membranes. The protein thus purified produced crystals which diffract to hi...