Nicola Demitri

Nicola Demitri
Sincrotrone Trieste S.C.p.A. · Hard X-ray Diffraction Beamlines and Structural Biology Lab

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159
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Publications

Publications (159)
Article
The reactivity of palladium(II) indenyl derivatives and their applications are topics relatively little studied, though in recent times these compounds have been used as pre-catalysts able to promote challenging cross-coupling processes. Herein, we propose the first systematic study concerning the nucleophilic attack on Palladium(II) coordinated in...
Article
Halogenation, generally introduced on aromatic aminoacids, is becoming a key supramolecular tool in peptides. Herein, we report the crystal structures and DFT study of two bis-halogenated tyrosines showing the subtle relation between hydrogen and halogen bonds in promoting their supramolecular self-assembly
Article
Invited for the cover of this issue is the collaborative research team coordinated by Arie van der Lee at the University of Montpellier. The image depicts chiral channels with highly mobile water molecules resulting from the robust self-organization of a simple achiral acetamide. Fully reversible release and re-uptake of water molecules takes place...
Article
Chiral channels with highly mobile water molecules result from the robust self‐organization of a simple achiral acetamide. Fully reversible release and re‐uptake of water molecules takes place near ambient conditions, with efficient water transport and a good selectivity against NaCl suggesting it to be an efficient candidate for desalination proce...
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In this paper we tackle the challenge of gaining control of the photophysical properties of PAHs through a site-specific N-doping within the structural aromatic framework. By developing a simple predictive tool that identifies C(sp2)-positions that if substituted with a heteroatom would tailor the changes in the absorption and emission spectral env...
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Crystallization of atomically precise nanoclusters is gaining increasing attention, due to the opportunity of elucidating both intracluster and intercluster packing modes, and exploiting the functionality of the resulting highly pure crystallized materials. Herein, we report the design and single-crystal X-ray structure of a superfluorinated 20 kDa...
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A straightforward synthetic route to a selection of new ferrocenyl complexes bearing different organopalladium fragments is reported. The target complexes were fully characterized by Nuclear Magnetic Resonance, High Resolution Mass Spectrometry, Infrared Spectroscopy, X‐ray Diffraction, and electrochemical techniques. All compounds, with the except...
Article
The Front Cover shows novel allyl and indenyl palladates with a promising biological activity. A wide range of these peculiar Pd(II) derivatives were prepared by a solvent‐free method consisting of grinding the corresponding Pd precursors with different azolium salts. These complexes are stable in chlorinated and polar solvents, and most of them sh...
Article
The catalytic and biological properties of dirhodium tetracarboxylates ([Rh2(μ-O2CR)4L2], L = axial ligand and R = CH3-, CH3CH2-, etc.) largely depend on the nature of bridging carboxylate equatorial μ-O2CR ligands, which can be easily exchanged by solvent molecules when R is CF3 (i.e. μ-O2CR is trifluoroacetate, tfa). Here, we prepared the [Rh2(OA...
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The synthesis and isolation of one of the few examples of a π-extended diamagnetic phenazine dication have been achieved by oxidizing a phenanthrene-based dihydrophenazine precursor. The resulting dication was isolated and fully characterized, highlighting an aromatic distorted structure, generated by the conformational change upon the oxidation of...
Article
Achiral 2‐hydroxy‐N‐(diphenylmethyl)acetamide (HNDPA) crystallizes in the P 6 1 chiral space group as a hydrate, building up permeable chiral crystalline helical water channels. The crystallization driven chiral self‐resolution process is highly robust, with the same air stable crystalline form readily obtained from a variety of conditions. Interes...
Article
The mechanochemical syntheses of allyl and indenyl palladate complexes are reported. All compounds were obtained in quantitative yields and microanalytically pure without the need of any workup. These complexes are stable in chlorinated and polar (DMSO or DMSO/H 2 O solutions) solvents. In chlorinated solvents, they appear as ionic pairs of which c...
Article
Dirhodium complexes of general formula [Rh2(O2CR)4]L2 are a well-known class of bimetallic compounds that are used as efficient catalysts for a variety of reactions and have been shown to be potent antibacterial and anticancer agents. The catalytic and biological properties of these complexes largely depend on the nature of the bridging carboxylate...
Article
This work is focused on a polymorphic and crystallographic study of a novel p-type organic semiconductor 2,7-bis(2-(2-methoxyethoxy)ethoxy)benzo[b]benzo[4,5]thieno[2,3-d]thiophene (OEG-BTBT). The well-known BTBT core is functionalized by eight-atom-long oligoethylene glycol side chains. Our results demonstrate the discovery of three crystal forms o...
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Iodination has long been employed as a successful labelling strategy to gain structural insights into proteins and other biomolecules via several techniques, including Small Angle X-ray Scattering, Inductively Coupled Plasma Mass Spectrometer (ICP-MS), and single-crystal crystallography. However, when dealing with smaller biomolecular systems, inte...
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A series of Pt(0)-η²-olefin complexes bearing 1,3,5-triaza-7-phosphaadamantane (PTA) or N-heterocyclic carbenes are prepared following different synthetic strategies depending on the nature of coordinated alkene and spectator ligands. These new platinum(0) derivatives have been tested in vitro as anticancer agents toward three different tumor (huma...
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The structure, stability, and enzymatic activity of the adduct formed upon the reaction of the V–picolinato (pic) complex [VIVO(pic)2(H2O)], with an octahedral geometry and the water ligand in cis to the V═O group, with the bovine pancreatic ribonuclease (RNase A) were studied. While electrospray ionization-mass spectrometry, circular dichroism, an...
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After almost two years from its first evidence, the COVID-19 pandemic continues to afflict people worldwide, highlighting the need for multiple antiviral strategies. SARS-CoV-2 main protease (Mpro/3CLpro) is a recognized promising target for the development of effective drugs. Because single target inhibition might not be sufficient to block SARS-C...
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Two new solvates of the widely used anthelminthic Praziquantel (PZQ) were obtained through mechanochemical screening with different liquid additives. Specifically, 2-pyrrolidone and acetic acid gave solvates with 1:1 stoichiometry (PZQ-AA and PZQ-2P, respectively). A wide-ranging characterization of the new solid forms was carried out by means of p...
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Tetraphenylmethane appended with four pyridylpyridinium units works as a scaffold to self‐assemble four ruthenium porphyrins in a tetrahedral shape‐persistent giant architecture. The resulting supramolecular structure has been characterised in the solid state by X‐ray single crystal analysis and in solution by various techniques. Multinuclear NMR s...
Article
The synthesis and characterization of silver and palladium allyl complexes bearing imidazo [1,5-a]pyridine-3-ylidene and dipyridoimidazolinylidene ligands is reported. NMR analysis of the starting azolium salts revealed the weaker σ-donor character of these NHC ligands compared to the most common imidazol-2-ylidenes and imidazolin-2-ylidenes. All c...
Preprint
Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e. related to the interactions with the dielectric layer), especially for n-type materials. Internal dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular)...
Article
Full-text available
Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both internal and external (i.e., related to interactions with the dielectric layer), especially for n‐type materials. Internal dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) si...
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Full-text available
Aromatic amino acids such as L-tyrosine and L-tryptophan are deployed in natural systems to mediate electron transfer (ET) reactions. While tyrosine oxidation is always coupled to deprotonation (proton-coupled electron-transfer, PCET), both ET-only and PCET pathways can occur in the case of the tryptophan residue. In the present work, two novel con...
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Compound repurposing is an important strategy for the identification of effective treatment options against SARS-CoV-2 infection and COVID-19 disease. In this regard, SARS-CoV-2 main protease (3CL-Pro), also termed M-Pro, is an attractive drug target as it plays a central role in viral replication by processing the viral polyproteins pp1a and pp1ab...
Article
Background: Ribosome-binding factor A from the pathogenic bacterium Pseudomonas aeruginosa (PaRbfA) is a small ribosome assembly factor, composed by a single KH domain, involved in the maturation of the 30S subunit. These domains are characterized by the ability to bind RNA or ssDNA and are often located in proteins involved in a variety of cellula...
Article
In this study we describe the crystal structures of the apoform, the binary and the ternary complexes of a double bond reductase from Malus domestica L. (MdDBR) and explore a range of potential substrates. The overall fold of MdDBR is similar to that of the medium chain reductase/dehydrogenase/zinc-dependent alcohol dehydrogenase-like family. Struc...
Article
Antibacterial adjuvants are of great significance, since they allow the therapeutic dose of conventional antibiotics to be lowered and reduce the insurgence of antibiotic resistance. Herein, we report that an O-acetylserine sulfhydrylase (OASS) inhibitor can be used as a colistin adjuvant to treat infections caused by Gram-positive and Gram-negativ...
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Multi‐functionalization and isomer‐purity of fullerenes are crucial tasks for the development of fullerene chemistry in various fields. In both current main approaches – tether‐directed covalent functionalization and supramolecular masks – the control of regioselectivity requires multi‐step synthetic procedures to prepare the desired tether or mask...
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By incorporating azobenzene photochromic units in the double functionalization of [60]fullerene, the regiochemistry of the double cyclopropanation reaction could be controlled by using either the E or the Z isomeric forms of the photoswitch. Once covalently linked to the C60 sphere, the azobenzene unit changes its light‐ and thermally‐induced isome...
Preprint
Full-text available
Compound repurposing is an important strategy for the identification of effective treatment options against SARS-CoV-2 infection and COVID-19 disease. In this regard, SARS-CoV-2 main protease (3CL-Pro), also termed M-Pro, is an attractive drug target as it plays a central role in viral replication by processing the viral polyproteins pp1a and pp1ab...
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Full-text available
Building on the MOF approach to prepare porous materials, herein we report the engineering of porous BN-doped materials using tricarboxylic hexaarylborazine ligands, that are laterally decorated with functional groups at the full-carbon ‘inner shell’. Whilst an open porous 3D entangled structure could be obtained from the double interpenetration of...
Article
Background: In continuation of a previous work concerned with the anticancer activity of some 8-alkyl-2,4-bisarylidene-8-nortropan-3-ones, this work focuses on further modification to the tropane/pyran fused skeleton aiming to obtain improved anticancer activity. Methodology: Reaction of 8-alkyl-2,4-bisarylidene-8-nortropan-3-ones 1–21 with malonon...
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The asymmetric n-type Ph-BTBT-C10 derivative 2-decyl-7-phenyl-[1]benzothieno[3,2-b][1]benzothiophene S,S,S′,S′-tetraoxide is structurally investigated in the thin film regime. After film preparation by spin coating and physical vapor deposition, a rather disordered structure is observed, with a strong change of its internal degree of order upon hea...
Article
The copper(II) complexes of general formula [Cu(GL)(Cl)] (1–3, G = OMe, H and NO2, respectively), bearing tridentate Schiff base ligands (GL−) and a chloride as a fourth labile one, are here reported. The Schiff bases derive from the monocondensation of ethylenediamine and substituted salicylaldehyde, where the electronic properties are modulated b...
Article
We take advantage of the Pummerer oxidative annulation reaction to extend PAHs through the formation of an intramolecular C-O bond with a suitable phenol substituent. Depending on the peripheral topology of the PAH precursor (e.g., pyrene, boron-dipyrromethene, or perylene diimide) five-, six-, and seven-membered O-containing rings could be obtaine...
Article
Biogenic crystals produced by organisms have been known for several decades to exhibit intracrystalline organic macromolecules. Here, using a reductionist approach, we tackle the question of whether the incorporation of single amino acids is driven by kinetics or by thermodynamics. We show that when calcite is grown in the presence of amino acids u...
Article
In this paper we report a comprehensive account of our synthetic efforts to prepare borazino‐doped hexabenzocoronenes using the Friedel‐Crafts‐type electrophilic aromatic substitution. We showed that hexafluoro‐functionalized aryl‐borazines , bearing an ortho fluoride leaving group on each N ‐ and B ‐aryl rings, could lead to cascade‐type electroph...
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Abstract Here, we demonstrate that introduction of halogen atoms at the tyrosine 10 phenol ring of the DSGYEV sequence derived from the flexible amyloid‐β N‐terminus, promotes its self‐assembly in the solid state. In particular, we report the crystal structures of two halogen‐modified sequences, which we found to be stabilized in the solid state by...
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Herein we report an efficient synthesis to prepare O‐doped nanographenes, which derive from the longitudinally and latitudinally p‐extension of pyrene. The derivatives are highly fluorescent and feature low‐oxidation potentials. Exploiting electrooxidation, crystals of cationic mixed valence (MV) complexes were grown in which the organic salts orga...
Article
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Herein we report an efficient synthesis to prepare O‐doped nanographenes, which derive from the longitudinally and latitudinally p‐extension of pyrene. The derivatives are highly fluorescent and feature low‐oxidation potentials. Exploiting electrooxidation, crystals of cationic mixed valence (MV) complexes were grown in which the organic salts orga...
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Full-text available
Given its potential role in the synthesis of novel prebiotics and applications in the pharmaceutical industry, a strong interest has developed in the enzyme levansucrase (LSC, EC 2.4.1.10). LSC catalyzes both the hydrolysis of sucrose (or sucroselike substrates) and the transfructosylation of a wide range of acceptors. LSC from the Gram-negative ba...
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Since their first appearance, organic-inorganic perovskite absorbers have been capturing the attention of the scientific community. While high efficiency devices highlight the importance of band level alignment, very little is known on the origin of the strong n-doping character observed in the perovskite. Here, by means of a highly accurate photoe...
Article
A rotated Doehlert matrix was utilized to explore the experimental design space around the milling parameters of Praziquantel (PZQ) polymorph B formation in terms of frequency and milling time. Three experimental responses were evaluated on the resulting ground samples: two quantitative responses, i.e. median particle size by Laser Light scattering...
Preprint
Charge transport in organic semiconductors is notoriously extremely sensitive to the presence of disorder, both intrinsic and extrinsic, especially for n-type materials. Intrinsic dynamic disorder stems from large thermal fluctuations both in intermolecular transfer integrals and (molecular) site energies in weakly interacting van der Waals solids...
Article
Solvens-Gast-Austausch und gleitende Netzwerke lösen die Bildung von Eugenol-Nanoaggregaten in den Poren eines flexiblen, säulenförmigen Metall-organischen Gerüsts aus. Kristallographische Momentaufnahmen liefern eine detaillierte Beschreibung der verschiedenen Schritte der Gastmolekül-Aggregation in der Nanoumgebung. Abstract The crystalline spon...
Article
The crystalline sponge method (CSM) primary application has been the unambiguous structural determination via Single Crystal X‐ray Diffraction (SCXRD) of a single analyte encapsulated inside a porous MOF. As the host‐guest systems often show severe disorder, their reliable crystallographic determination is very demanding thus the dynamics of the gu...
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(R)-9-hydroxystearic acid, (R)-9-HSA, is a chiral nonracemic hydroxyacid of natural origin possessing interesting properties as an antiproliferative agent against different cancer types. Considering its potential application for medical and pharmaceutical purposes, the structures and rheological properties of (R)-9-HSA were investigated. Oscillator...
Article
It is widely accepted that drug-target association and dissociation rates directly affect drug efficacy and safety. To rationally optimize drug binding kinetics, one must know the atomic arrangement of the protein-ligand complex during the binding/unbinding process in order to detect stable and metastable states. Whereas experimental approaches can...
Article
In this paper, we describe the synthetic routes for preparing a novel switchable BNC˗based chromophore, composed of a borazine core peripherally functionalized with azobenzene moieties. Capitalizing on the Pd˗catalyzed Suzuki cross˗coupling reaction between a tris˗triflate borazine and an organoboron azobenzene derivative, a photoswticheable azo˗bo...
Article
Here we describe the synthesis and spectroscopic and structural characterization of various borazine-doped polyphenylenes displaying high doping dosages (16–18%). Capitalizing on the condensation reaction approach, the desired products were formed using a mixture of p-phenylendiamine and aniline with BCl3, followed by the addition of an aryl lithiu...
Article
In this paper, we describe three new stereoisomers of the already known 2 + 2 metallacycle of porphyrins [ trans, cis, cis-RuCl2(CO)2(4' cisDPyP)]2 (2, 4' cisDPyP = 5,10-bis(4'-pyridyl)-15,20-diphenylporphyrin), namely [{ trans,cis,cis-RuCl2(CO)2}(4' cisDPyP)2{ cis,cis,cis-RuCl2(CO)2}] (14) and [ cis,cis,cis-RuCl2(CO)2(4' cisDPyP)]2 (15), in which...
Article
In land plants and algae, the Calvin–Benson (CB) cycle takes place in the chloroplast, a specialized organelle in which photosynthesis occurs. Thioredoxins (TRXs) are small ubiquitous proteins, known to harmonize the two stages of photosynthesis through a thiol-based mechanism. Among the 11 enzymes of the CB cycle, the TRX target phosphoribulokinas...
Article
Erwinia tasmaniensis is an epiphytic bacterium related to the plant pathogen Erwinia amylovora, the etiological agent of fire blight. In this study the levansucrase from E. tasmaniensis (EtLsc) has been compared with the homologous enzyme from E. amylovora (EaLsc). We characterized the enzymatic activity and compared the products profile of both en...
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In the version of this Article originally published, in the graphical abstract the y-axis units of the plot read ‘mA cm–2’, but should have read ‘μA cm–2’. Additionally, an erroneous gap appeared in the red trace. These errors have now been corrected.
Article
A series of four arrays made of a central Sn(IV) porphyrin as scaffold axially connected, via carboxylate functions, to two free-base porphyrins has been prepared and fully characterized. Three arrays in the series feature the same free-base unit and alternative tin-porphyrin macrocycles, and one consists of a second type of free-base and one chose...
Article
The AvrRpt2 protein of the phytopathogenic bacterium Erwinia amylovora (AvrRpt2 EA ) is a secreted type III effector protein, which is recognised by the FB_MR5 resistance protein of Malus × robusta 5, the only identified resistance protein from a Malus species preventing E. amylovora infection. The crystal structure of the immature catalytic domain...
Article
We report on the synthesis and characterization of novel substituted 1,1'‐biperylene‐2,2'‐diols in which the dihedral angle between the two PAH units is tailored from ~60° to ~90° by introduction of cyclo‐etheric straps or sterically hindered groups such as TIPS. Depending on the type of substitution, we lock the dihedral angle between the peryleny...
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The oxygen in Earth’s atmosphere is there primarily because of water oxidation performed by photosynthetic organisms using solar light and one specialized protein complex, photosystem II (PSII). High-resolution imaging of the PSII ‘core’ complex shows the ideal co-localization of multi-chromophore light-harvesting antennas with the functional react...
Article
The beneficial effects of transmetalation on MOFs’ functional behaviours are well-known as it endows the material with novel functionalities. Even though the structural adaptation of the framework to the new metal ion has a great impact on the properties of the resulting material, this subject still remains poorly understood. Herein we present a de...