Alessandro D'Urso

Alessandro D'Urso
University of Catania | UNICT · Department of Chemical Sciences

Professor

About

78
Publications
6,681
Reads
How we measure 'reads'
A 'read' is counted each time someone views a publication summary (such as the title, abstract, and list of authors), clicks on a figure, or views or downloads the full-text. Learn more
1,443
Citations
Introduction
My research activity is mainly focused on the characterization of the interactions between porphyrin macrocycles and biomolecules as DNA, RNA, aminoacids, peptide and proteins, with the aim to use porphyrins as active molecules, conformational probes and useful tools to study chiral transfer processes.
Additional affiliations
March 2014 - June 2014
University of Catania
Position
  • Professor
Description
  • Supramolecular Chemistry
November 2012 - present
University of Catania
Position
  • Researcher
July 2012 - September 2012
Columbia University
Position
  • PostDoc Position

Publications

Publications (78)
Article
The functionalization of carbon dots with dyes by exploiting supramolecular interactions represents a huge resource in nanomaterials science. Desired properties, and especially the optical ones, can be obtained starting from the knowledge of surface-related interactions, which can be exploited to originate the complex. In this context, the present...
Article
The possibility to design rational carbon dots surface functionalization for specific analytical and bioanalytical applications is hindered by the lack of a full knowledge of the surface chemical features driving fluorescent properties. In this model study, we have synthesized four different peptides, three of which are isobaric and not distinguish...
Article
Full-text available
Cationic porphyrins exhibit an amazing variety of binding modes and inhibition mechanisms of 20S proteasome. Depending on the spatial distribution of their electrostatic charges, they can occupy different sites on α rings of 20S proteasome by exploiting the structural code responsible for the interaction with regulatory proteins. Indeed, they can a...
Article
The self-assembly process appears as a powerful and attractive strategy for constructing complex supramolecules by the spontaneous organization of appropriate building blocks. In this scenario, water-soluble porphyrinoids lend themselves as ideal paradigms to disclose the self-assembly phenomenon by exploiting their well-known tendency to build agg...
Article
Mussels-inspired melanin coatings from L-DOPA are getting growing attention by virtue of their facile synthesis and low-cost production. However, the spontaneous DOPA-melanin deposition is often affected by numerous experimental factors which hinder the preparation of robust adhesive films for practical application. Hence, we have set up a feasible...
Article
Full-text available
Porphyrinoids are extremely attractive for their electronic, optical, and coordination properties as well as for their versatile substitution at meso/β-positions. All these features allow porphyrinoids to behave as chiroptical hosts for chiral recognition by means of non-covalent interactions towards chiral guests. Over the years, chiral discrimina...
Article
Full-text available
The pivotal role played by potassium ions in the noncovalent synthesis of discrete porphyrin-calixarene nanostructures has been examined. The flattened-cone conformation adopted by the two cavities of octa-cationic calix[4]tube C4T was found to prevent the formation of complexes with well-defined stoichiometry between this novel water-soluble calix...
Article
Full-text available
Chiral porphyrin hetero-aggregates, produced from meso-tetrakis(4-N-methylpyridyl) porphyrin H 2 T4 and copper(II) meso-tetrakis(4-sulfonatophenyl)porphyrin CuTPPS by an imprinting effect in the presence of L-3,4-dihydroxyphenylalanine (L-DOPA), are shown herein to serve as templates for the generation of chiral structures during the oxidative conv...
Article
Full-text available
The present study provides new evidence that cationic porphyrins may be considered as tunable platforms to interfere with the structural “key code” present on the 20S proteasome α-rings and, by consequence, with its catalytic activity. Here, we describe the functional and conformational effects on the 20S proteasome induced by the cooperative bindi...
Article
In this work, we have characterized the interactions of monospermine porphyrin derivative with calf thymus DNA (ct‐DNA) and poly (dG‐dC)2 in both B and Z conformation. By several spectroscopic techniques (UV–vis, electronic circular dichroism and resonance light scattering), the binding modes of monospermine porphyrin derivative with different DNA...
Article
Full-text available
Antibiotics represent essential drugs to contrast the insurgence of bacterial infections in humans and animals. Their extensive use in livestock farming, including aquaculture, has improved production performances and food safety. However, their overuse can implicate a risk of water pollution and related antimicrobial resistance. Consequently, inno...
Article
Full-text available
Zinc oxide (ZnO) nanorods grown by chemical bath deposition (CBD) on the surface of polyetheresulfone (PES) electrospun fibers confer antimicrobial properties to the obtained hybrid inorganic-polymeric PES/ZnO mats. In particular, a decrement of bacteria colony forming units (CFU) is observed for both negative (Escherichia coli) and positive (Staph...
Article
The hierarchical assembly, in aqueous solution, of a new multi‐metalloporphyrin/calixarene aggregate has been accomplished. In this supramolecular system transfer of chirality, from the outermost components to the central porphyrin reporter, takes place as a result of favorable and fully noncovalent long‐range electronic communication. Hierarchical...
Article
Full-text available
Mature microRNAs are short non-coding RNA sequences which upon incorporation into the RISC ribonucleoprotein complex, play a crucial role in regulation of gene expression. However, miRNAs can exist within the cell also as free molecules fulfilling their biological activity. Therefore, it is emerging that in addition to sequence even the structure a...
Article
We synthetized and characterized a mono spermine porphyrin derivative by NMR, UV-vis and fluorescence spectroscopy. The photophysical properties and the protonation equilibria of 5-(4-carboxyphenylspermine)-10,15,20-triphenylporphyrin have been investigated, showing that porphyrin does not aggregate in acidic solutions, differently from what occurs...
Article
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 ma...
Article
Full-text available
The dispersion of para-nitroaniline (p-NA) in water poses a threat to the environment and human health. Therefore, the development of functional adsorbents to remove this harmful compound is crucial to the implementation of wastewater purification strategies, and electrospun mats represent a versatile and cost-effective class of materials that are...
Article
Full-text available
We report of the interactions between four amino acids lysine (Lys), arginine (Arg), histidine (His), and phenylalanine (Phe) with the J-aggregates of the protonated 5,10,15,20-tetrakis(4-sulfonatophenyl)-porphyrin H4TPPS. Several aspects of these self-assembled systems have been analyzed: (i) the chiral transfer process; (ii) the hierarchical effe...
Article
Full-text available
G-rich DNA sequences have the potential to fold into non-canonical G-Quadruplex (GQ) structures implicated in aging and human diseases, notably cancers. Because stabilization of GQs at telomeres and oncogene promoters may prevent cancer, there is an interest in developing small molecules that selectively target GQs. Herein, we investigate the inter...
Article
Full-text available
The chirality of (nano)structures is paramount in many phenomena, including biological processes, self-assembly, enantioselective reactions, and light or electron spin polarization. In the quest for new chiral materials, metallo-organic hybrids have been attractive candidates for exploiting the aforementioned scientific fields. Here, we show that c...
Article
Full-text available
Hybrid poly(ether sulfones) (PES)–TiO2 electrospun mats are used as selective filters to remove lead and zinc ions from water. Presence of TiO2 is functional to trigger fiber’s surface charge that allows for better performances in terms of ionic adsorption with respect to bare PES mats. Temperature increase promotes a speed up of ion removal. Abili...
Article
Cationic polylysine promotes, at neutral conditions, the spontaneous aggregation in water of opposite charged ZnTPPS. Spectroscopic investigations evidence a different pre‐organization of ZnTPPS onto the polypeptides matrix depending on the chain length. Spinodal Decomposition Theory in confined geometry is used to model this mechanism by consideri...
Article
Cationic polylysine promotes, at neutral conditions, the spontaneous aggregation in water of opposite charged ZnTPPS. Spectroscopic investigations evidence a different pre‐organization of ZnTPPS onto the polypeptides matrix depending on the chain length. Spinodal Decomposition Theory in confined geometry is used to model this mechanism by consideri...
Article
Porphyrinoids are ideal compounds to be incorporated into DNA due to their peculiar spectroscopic characteristics, fascinating photochemistry and synthetic versatility. The ability to act as photosensitizers in the presence of oxygen promoted interest of the scientific community to study the non-covalent binding of porphyrins with DNA in order to u...
Article
Spontaneous formation of meso-tetra(N-methyl-4-pyridyl)porphirin (H2T4) layers on glass surface is proven effective to assess sensitive and selective solid chemosensors for spectrometric detection (at sub-pmm level) of Pb2+ and Zn2+ ions in water. The obtained results, achieved by a simple, low cost and repeatable non covalent glass surface functio...
Article
Full-text available
The importance of allosteric proteasome inhibition in the treatment of cancer is becoming increasingly evident. Motivated by this urgent therapeutic need, we have recently identified cationic porphyrins as a highly versatile class of molecules able to regulate proteasome activity by interfering with gating mechanisms. In the present study, the mapp...
Article
Tritopic tris-calix[4]arene TC4 –possessing three divergent cavities linked to a tris-aminophenylamine core– forms, in the presence of tetra-anionic Cu(II) porphyrins CuTPPS or a combination of different metallo-porphyrins (CuTPPS, NiTPPS and MnTPPS), discrete 3:1 porphyrin/tris-calixarene complexes. The 3:1-(CuTPPS/TC4) complex in particular is sh...
Article
The interaction of the porphyrin derivative H2TCPPSpm4, having spermine pendants in the four meso positions, with the G-quadruplex (GQ) structure formed by the DNA aptamer TGGGAG has been investigated by means of UV, electronic circular dichroism and PAGE studies. The results here reported demonstrate that porphyrin derivative is capable of stabili...
Article
Acid-base properties of tetra-anionic zinc meso-5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin (ZnTPPS) in presence of cationic and anionic polyelectrolytes are studied by UV-visible spectroscopy. In fact, spectral modifications related to the out-of-plane deformation of porphyrins after protonation allow for an easy probing of the protonation ev...
Article
Graphene oxide (GO) is one of the most appealing bidimensional materials able to interact non-covalently with achiral molecules and to act as chiral inducers. Vortexes can tune chirality and, consequently transfer a specific handedness to non-covalent host molecules, either when dispersed in water or when deposited on a solid surface.
Article
Herein, we exploit the induction of chirality by chiral Zn(ii) Schiff-base complexes, followed by their spontaneous dissociation in aqueous solution, providing for the first time a possibility of overcoming the template removal steps, to demonstrate memorization of chirality in porphyrin hetero-aggregates.
Article
Full-text available
The 20S proteasome is a barrel-shaped enzymatic assembly playing a critical role in proteome maintenance. Access of proteasome substrates to the catalytic chamber is finely regulated through gating mechanisms which involve aromatic and negatively charged residues located at the N-terminal tails of α subunits. However, despite the importance of gate...
Article
A diiminoisoindolo-pyrazino unit was annulated to the β-pyrrolic position of the Zn complex of tetraphenylporphyrin, giving a macrocycle with an expanded π system in satisfying yields. The crystal structure of this derivative evidenced the formation of a hydrogen bond network. The interaction of the β-fused isoindoline porphyrin derivative with nuc...
Article
The octaanionic 5,11,17,23-tetrasulfonato-25,26,27,28-tetrakis(hydroxycarbonylmethoxy)-calix[4]arene (cone conformation) (C4TsTc) was investigated as a sensor for the biogenic tetracationic polyamine, spermine .(H4Spe4+). Fluorescence titration experiments of the water-soluble calixarene with spermine showed the formation of the 2:1 and 1:1 calixar...
Article
Noncovalent porphyrin deposition onto polylysinated surfaces proceeds by obeying the self-assembly rules experienced in aqueous solution. In particular, the porphyrin’s ability to stack in a face-to-face arrangement, leading to H-aggregate formation, strongly depends on the central metal coordination, even during deposition on surfaces. This aspect...
Article
In this study we show the outstanding agreement between simulation and experimental data concerning the efficient stabilization effect by NaCl of Z conformation. We demonstrate by circular dichroism (CD) experiments that Na(+) not only is able to induce a B to Z form transition in a short (GC)3 alternated portion of a sequence having 17 basis, but...
Article
Full-text available
We designed and synthesized a new porphyrin-spermine derivative that self-assembles under hierarchical control. Its aggregation processes depend on the protonation of both the spermine units and central core nitrogen atoms. Therefore, the time duration of pH titrations and/or the direct protonation of a specific site allow for choosing the desired...
Article
Cysteine is a sulfur-containing amino acid that easily coordinates to soft metal ions and grafts to noble metal surfaces. Recently, chiroptical activity of Ag+/Cysteine coordination polymers has been widely studied, whilst, on the other hand, the appearance of a plasmon-enhanced circular dichroic signal (PECD), at the plasmonic spectral region (λ>...
Article
In this paper we extend an integrated QM/MM/Polarizable Continuum Model (PCM) method, which combines a fluctuating charge (FQ) approach to the MM polarization with the PCM, to describe Electronic Circular Dichroism (ECD) spectra of systems in aqueous solution. The main features of the approach are presented and then applications to the UV and ECD s...
Chapter
The porphyrin–DNA binding modes depend on both the structural properties of the porphyrinoid derivatives and the DNA sequences and conformations. The experimental conditions, that is, the molar ratio of porphyrin to DNA and the ionic strength also influence the binding mode. This chapter explores the non-covalent interactions of porphyrins with dif...
Article
Full-text available
A chiral organic-inorganic hybrid material, based on a porous silicon surface functionalized with a chiral cavitand, was designed and synthesized. The affinity of this device in water toward a bromine-marked alkyl-ammonium salt has been evaluated using XPS detection. UV and CD measurements highlight the enantioselective extraction from a racemic mi...
Article
A stepwise surface functionalization procedure, based on hybrid covalent and non-covalent approach is herein proposed to anchor tetra-anionic meso-tetrakis(4-sulfonatophenyl)porphyrin on ZnO nanorods. Carboxyalkylphosphonic acids have been proven effective to form stable self-assembled monolayers through the surface grafting of –PO3H2 headgroups. T...
Chapter
Due to their unique physicochemical aspect porphyrinoid–DNA complexes have been widely studied for long time to develop a novel range of supramolecular constructs for application in medicinal chemistry. Owing to the intriguing properties of porphyrinoid macrocycles, they have been used for several applications in many scientific fields: biosensoris...
Article
The successful transferring of a porphyrin complex assembly from a solution to a solid surface is important for an economical development of functional materials, biomaterials, and sensing devices. The understanding of the mechanisms and factors that drive spontaneous and stable deposition, in water, of porphyrins (and their complex species) onto i...
Article
We report the chiroptical signature and binding interactions of cationic (meso-tetrakis(4-N-methylptridyl)porphyrin, 2HT4) and anionic (meso-tetrakis(4-sulfonatophenyl)porphyrin, 2HTPPS) porphyrins and their zinc(II) and nickel(II) derivatives (ZnT4, ZnTPPS, NiT4, and NiTPPS) with right-handed B-form and two forms of left-handed Z-form of alternati...
Article
In this manuscript a multi-technique approach is proposed to characterize the interaction between new tri-N-methylpyridyl corrole (TMPC) and its Germanium (IV) derivative (GeTMPC), with single and double stranded nucleic acid homopolymers and calf thymus DNA. The specificity of each spectroscopic technique has been exploited to analyze the differen...
Article
The paper published by C. M. Drain and J.-M. Lehn in 1994 in Chemical Communications offered a new, elegant way of synthesizing, in high yield, porphyrin species with controlled structure and stoichiometry. It also suggested to chemists a new approach: from the understanding to the imitation and exploitation of the wonderful machinery of Nature.
Article
Self-organization is the driving force that led to the evolution of life. Rationalization of the spontaneous self-assembly paradigm will offer tremendous potentialities to obtain a wide variety of complex systems, having specific functionality and properties. Herein, we will propose an overview of the developments in non-covalent syntheses of multi...
Article
The aim of this study is to verify if water-soluble porphyrins can be used as proteasome inhibitors. We have found that cationic porphyrins inhibit proteasome peptidase activities much more effectively than the corresponding anionic derivatives. The relevance of electrostatics in driving porphyin-proteasome interactions has been confirmed by the ob...
Article
CD and UV-vis measurements were carried out to demonstrate chirality induction-promoted by chiral covalently linked groups and non-covalently bound Δ- and Λ-[Ru(phen)(3)](2+) enantiomers-in metallo-porphyrin-calixarene and metallo-porphyrin-bis-calixarene non-covalent assemblies, respectively.
Article
We report a very selective and sensitive spectroscopic detection of Z-DNA embedded in B-DNA in condensed as well as non-condensed DNA using anionic Ni(II) meso-tetrakis(4-sulphonatophenyl)porphyrin, NiTPPS. A combination of micromolar concentrations of Ni(II) and spermine(4+) allowed us to prepare left-handed Z-DNA in short oligonucleotides without...
Article
Anionen machen den Unterschied! Gegenionen, die während der Säure-geförderten Selbstorganisation von Monomervorstufen des AB-Typs freigesetzt werden, docken an designierte Hilfsbindungsstellen an und erleichtern somit den Poymerisierungsprozess, während sie ihre molekularen Eigenschaften auf die gesamte supramolekulare Struktur übertragen (siehe Bi...
Article
Full-text available
Using UV-vis absorption and circular dichroism (CD) spectroscopies, we explored the binding interactions of 3,3'-diethylthiatricarbocyanine iodide (Cy7) with polynucleotides of different sequences and helicity. CD showed to be a very diagnostic tool giving different spectroscopic chiroptical signatures for all explored DNA sequences upon Cy7 bindin...
Article
For the first time it has been shown by spectroscopic studies such as circular dichroism and UV/Vis that cationic zinc porphyrin serves as a selective spectroscopic sensor that is able to recognize short left-handed Z-DNA tracts embedded in the B-Z-B sequences.
Chapter
Full-text available
Transfer of chirality is an intriguing issue worth studying to understand better the origin of life and for possible technological applications. In the last few years we have been working in this area studying the chain of events that begins with induction, reaches a permanent transfer (chiral memory) and extends in some cases to a (quasi-)reversib...
Article
The use of a water-soluble octacationic bis-calix[4]arene with divergent cavities (BC(4)) as a templating agent for the assembly of a tetraanionic porphyrin (CuTPPS) has allowed the noncovalent synthesis of 2D or 3D multiporphyrin assemblies. Self-assembly of CuTPPS and BC(4) molecules proceeded under hierarchical control in a stepwise fashion to y...
Article
Self-aggregation processes are rarely reproducible owing to their dependence on various experimental parameters (aging of stock solutions, their concentration, concentration of working solutions, ionic strength, etc.). However, by enucleating the dependence from one parameter (in this case, the dependence of aggregation from the concentration of th...
Article
The left-handed Z-DNA form of the short unmodified alternating guanine-cytosine oligonucleotides, 5'-(dGdC)(24) and 5'-(dGdC)(18), was selectively detected under physiological ionic strength and pH conditions using the anionic nickel(II) porphyrin, NiTPPS. No spectroscopic signal was observed for NiTPPS with any right-handed oligonucleotides under...
Article
(Figure Presented) J-aggregates respond dynamically to vortexes created by stirring. The CD signal inverts with stirring sense and its intensity increases. Prolonged stirring leads to deposition of chiral aggregates on the cuvette wall, the chirality of the deposits depends on the stirring sense. Stirring shifts the equilibrium of a racemic mixture...