Federica Aiello

• PhD in Chemical Sciences
• Researcher at Italian National Research Council

The fascinating optoelectronic properties of Metal Halide Perovskites (MHPs) have renewed interest in the development of innovative photovoltaic devices. Controlling the MHP crystallization process is crucial for achieving high‐performing solar cells especially when scaling up deposition technologies. To this aim, this work leverages a practical to...

Mastering of analytical methods for accurate quantitative determinations of enantiomeric excess is a crucial aspect in asymmetric catalysis, chiral synthesis, and pharmaceutical applications. In this context, the phenomenon of Self‐Induced Diastereomeric Anisochronism (SIDA) can be exploited in NMR spectroscopy for accurate determinations of enanti...

A squaramide-based organocatalyst for asymmetric Michael reactions has been tested as a chiral solvating agent (CSA) for 26 carboxylic acids and camphorsulfonic acid, encompassing amino acid derivatives, mandelic acid, as well as some of its analogs, propionic acids like profens (ketoprofen and ibuprofen), butanoic acids and others. In many cases r...

In the exploration of chiral solvating agents (CSAs) for nuclear magnetic resonance (NMR) spectroscopy designed for the chiral analysis of amino acid derivatives, notable advancements have been made with thiourea–CSAs. 1-TU, derived from 2-[(1R)-1-aminoethyl]phenol and benzoyl isothiocyanate, is effective in the enantiodifferentiation of N-3,5-dini...

Nuclear magnetic resonance (NMR) spectroscopy is an analytical technique largely applied in the analysis of discrimination processes involving enantiomeric substrates and chiral agents, which can interact with the analyte either via covalent bonding or via formation of diastereomeric solvates. However, enantiodiscrimination has been observed, in so...

Halide perovskite nanocrystals (PNCs) have demonstrated their wide potential to fabricate efficient optoelectronic devices and to prepare promising photocatalysts for solar‐driven photo(electro)chemical reactions. However, their use in most of the practical applications is limited due to the instability of PNCs in polar environments. Here, the prep...

Silylated-acetylated cyclodextrin (CD) derivatives have recently been investigated, via nuclear magnetic resonance (NMR) spectroscopy, as chiral sensors for substrates that are endowed and devoid of fluorine atoms, and the importance of Si-F interaction in the discrimination phenomena has been assessed. Here, the contributions of both superficial i...

Engineering the chemical composition of metal‐halide perovskites via halide mixing allows a facile bandgap modulation but renders perovskite materials prone to photoinduced halide segregation. Triple‐halide alloys containing Cl, I, and Br were recently reported as a means to stabilize CsyFA1–yPb(BrxI1–x)3 perovskite under illumination. Herein, thes...

Cyclodextrin derivatives constitute a powerful class of auxiliary agents for the discrimination of apolar chiral substrates. Both host–guest inclusion phenomena and interactions with the derivatizing groups located on the surface of the macrocycle could drive the enantiodiscrimination; thus, it is important to understand the role that these process...

The understanding of the interaction between non-steroidal anti-inflammatory drugs and human serum albumin plays a fundamental role in the development of new drugs and new therapeutic strategies. Several studies have been performed, nevertheless, the interaction phenomena are still not fully understood. In this work, high-field solution Nuclear Mag...

Although it has been exploited since the late 1900s to study hybrid perovskite materials, nuclear magnetic resonance (NMR) spectroscopy has only recently received extraordinary research attention in this field. This very powerful technique allows the study of the physico-chemical and structural properties of molecules by observing the quantum mecha...

Pyrethroids are among the insecticidal compounds indicated by the World Health Organization for mitigation of vector-borne diseases. Active deltamethrin (with chiral configuration α-S,1-R-cis) is one of the most effective pyrethroids characterized by low toxicity to humans, and it is currently tested as active ingredient for insecticidal paints. Ne...

Detection and quantification of low molecular weight components in polymeric samples via NMR spectroscopy can be difficult due to overlapping signal caused by line broadening characteristics of polymers. A way of overcoming this problem could be the exploitation of the difference in relaxation between small molecules and macromolecular species, suc...

This chapter will focus on the use of chiral solvating agents (CSAs) for the detection and quantification of enantiomeric substrates by nuclear magnetic resonance spectroscopy, with the aim of identifying the trend of the researches on this topic in this last decade. The main classes of CSAs will be described, spanning from low-to-medium-sized CSAs...

The evolution from solvated precursors to hybrid halide perovskite film dictates most of the photo-physical and optoelectronic prerogatives of the final polycrystalline material. Specifically, the complex equilibria and the importantly different solubility of lead iodide (PbI2) and methylammonium iodide (MAI) induces an inhomogeneous crystal growth...

The cover picture shows the mechanistic pathway involved in the ring-opening cross-metathesis (ROM-CM) reaction of resorc[4]arene macrocycles. The red ruthenium atoms lead the way in the formation of a dimeric product, starting from a bicyclic olefin and passing through ruthenium–resorc[4]arene complexes. NMR techniques in combination with organic...

Efficient enantiodiscrimination of some alanine-containing di- and tri-peptides by using chiral protonated bis(diamido)-bridged basket resorcin[4]arenes depends on several factors, including the basicity of the amino acid residues at the C- and N-termini of the peptide.

Several cyclodextrins (CDs) were probed in order to counteract the precipitation of riboflavin-5'-phosphate (or flavin mononucleotide, FMN-P) due to the presence of divalent cations, by exploiting Nuclear Magnetic Resonance (NMR) spectroscopy both for quantitative analyses and stereochemical characterizations. Among CDs, β-cyclodextrin (β-CD) showe...

For the first time we describe the detection of a ruthenium-carbene-resorc[4]arene complex produced, as a key intermediate, during an olefin metathesis reaction carried out on a resorc[4]arene bicyclic olefin with [Ru(=CHPh)Cl2(PCy3)2] Grubbs first-generation (G1ST) catalyst. The complex was identified by using high-resolution (600 MHz) ¹H, ³¹P NMR...

Background In the hospital setting, commercially available multi-dose formulations in solution are more practical but also more expensive in comparison with products reconstituted on site. In Italy, cyclophosphamide (CP) is sold by Baxter as a galenic solution with 40 day stability at 2–8°C, including 12 days for microbial release, using safe compo...

Chiral diamides and tetramidic resorcin[4]arenes deriving from (R,R)-1,2-diaminocyclohexane and (S,S)-1,2-diphenylethylendiamine, and a valine containing resorcin[4]arene have been compared by NMR in the enantiodiscrimination of mandelic acid. The relevance of cooperation between side arms and external surface of resorcin[4]arene core has been asce...

Hybrid halide perovskites have emerged as promising active constituents of next generation solution processable optoelectronic devices. During their assembling process, perovskite components undergo very complex dynamic equilibria starting in solution and progressing throughout film formation. Finding a methodology to control and affect these equil...

Mono- and bis-alkaloid chiral auxiliaries with anthraquinone or phenanthryl cores were probed as chiral solvating agents (CSAs) for the enantiodiscrimination of chiral cyclic hemiesters. The dimeric anthraquinone derivative and the monomeric phenanthryl one showed remarkable efficiency in the nuclear magnetic resonance (NMR) differentiation of enan...

Applications of nuclear magnetic resonance (NMR) spectroscopy to the structural characterization of polysaccharides with mucoadhesive characteristics are described together with some limited cases of uses in the detection of affinity to mucin. Structural characterization spans from quantification of monomeric units of polysaccharides following degr...

Nuclear magnetic resonance (NMR) investigations on mixtures containing octakis(3-O-butanoyl-2,6-di-O-pentyl)-γ-cyclodextrin (Lipodex E) and each enantiomer of methyl-2-chloropropionate (MCP) ascertained the role of trace amounts of water in the enantiodiscrimination processes. Water is deeply included into the cyclodextrin and favors the formation...

Quantification and identification of chiral drugs and their metabolites constitutes a significant issue for both the pharmaceutical industry and the regulatory authorities, which led to a continuous growth of research areas devoted to the development of direct methods of discrimination of enantiomers. Stereoisomers frequently differ in terms of the...

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Supplementary Information

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Hedgehog signaling is essential for tissue development and stemness, and its deregulation has been observed in many tumors. Aberrant activation of Hedgehog signaling is the result of genetic mutations of pathway components or other Smo-dependent or independent mechanisms, all triggering the downstream effector Gli1. For this reason, understanding t...

The stereochemical features of 2,8,14,20-tetrakis(d-leucyl-d-valinamido)resorc[4]arenecarboxylic acid and the N-succinyl-l-alanyl-l-alanyl-l-prolyl-l-phenylalanine-4-nitroanilide polypeptide substrate were investigated by nuclear magnetic resonance spectroscopy. Proton selective relaxation parameters gave the basis for the inhibitory activity of re...

Bis(diamido)-bridged basket resorcin[4]arene and its enantiomer proved able to interact with 2'-deoxycytidine () and pyrimidine nucleoside analogs in dimethyl sulfoxide (DMSO) solution. In such a solvent, the resorcinarene hosts adopt a preferential 1,3-alternate-like conformation, with a larger cavity delimited by two syn 3,5-dimethoxyphenyl moiet...