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Thermodynamics and Complex Systems in Analytical Chemistry: Theme Issue Honoring Professor Giuseppe Arena on the Occasion of His Retirement

A special issue of Molecules (ISSN 1420-3049). This special issue belongs to the section "Analytical Chemistry".

Deadline for manuscript submissions: closed (1 September 2021) | Viewed by 6861

Special Issue Editors


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Guest Editor
Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche e Ambientali, CHIBIOFARAM, Università degli Studi di Messina, V.le F. Stagno d’Alcontres, 31, 98166 Messina, Italy
Interests: analytical chemistry; chemical speciation; solution equilibria; chemical thermodynamics; modeling of real systems; calculation tools

E-Mail Website
Guest Editor
Dipartimento di Scienze Chimiche, Biologiche, Farmaceutiche e Ambientali, CHIBIOFARAM, Università degli Studi di Messina, V.le F. Stagno d’Alcontres, 31, 98166 Messina, Italy
Interests: analytical chemistry; chemical speciation; solution equilibria; chemical thermodynamics; modeling of real systems; calculation tools

Special Issue Information

Dear Friends, Colleagues and Researchers,

Professor Giuseppe Arena (better known as Pino) obtained the Laurea in Industrial Chemistry from the University of Catania in 1973, where he was enrolled as a Research Assistant soon after.

He spent one year as a post-doctoral fellow at the Chemistry Dept., University of St Andrews, Scotland (1976), where he had the opportunity to meet a PhD student, Peter May, who would soon become a Professor at Murdoch University (Perth, Australia) and a leading expert in speciation. Upon his return to Italy, Professor Arena served as a Lecturer at the University of Catania until 1982, when he was enrolled as an Associate Professor of Analytical Chemistry. In 1985, he became a Full Professor of Analytical Chemistry at the University of Messina, where he served until 1990, when he went back to the University of Catania to become the Analytical Chemistry Chair. 

Pino first went to Brigham Young University (BYU), which at that time was home to several research groups skilled in calorimetry and thermodynamics, in 1984 as a NATO Senior Scientist to learn the principles and practice of titration calorimetry. On this occasion, he served also as a Lecturer. He returned to BYU in 1989 and 1998 as a NATO Senior Scientist and Visiting Professor, respectively, for extended periods. The BYU visits gave him the opportunity to interact actively with well-known researchers such as Dr. Reed M. Izatt, Dr. James J. Christensen, Dr. John D. Lamb, Dr. John L. Oscarson, and Dr. Lee D. Hansen.

Professor Arena had similar experiences with other collaborators/research groups from other universities. He has been responsible for bilateral agreements with Professor Kenneth Raymond (UC Berkeley, USA), Professor Osamu Yamauchi (NUPACE—University of Nagoya, Japan), and was also a Visiting Professor at the University of Cape Town, South Africa. He also collaborated with Professor Richard A. Batsch (Texas Tech University, Lubock, USA) and is still actively collaborating with Professor Vincent L. Pecoraro (University of Michigan, Ann Arbor, USA).

Professor Arena has demonstrated the power of coupling calorimetry with spectral techniques, such as NMR and UV, to determine speciation in complex chemical systems. Determination of species distribution is essential to understand mechanisms of action in chemical reactions and allows results to be interpreted correctly and future experiments to be planned with accuracy. In this connection, he has benefited from the interaction with well-known experts in biomimetic systems and speciation, respectively, such as Professor Enrico Rizzarelli and Professor Silvio Sammartano. Last but not least, he profitably interacted with Professor Rocco Ungaro and his group (University of Parma, Italy) and Professor Peter Gans (University of Leeds, UK), world leaders in calixarene chemistry and data refinement, respectively.

His research has mainly focused on: i. the thermodynamics of bio-functional ligand metal complexes and speciation in aqueous solution; ii. supramolecular chemistry; iii. the optimization of data extraction from calorimetric experiments; and also iv. the use of calixarene-based carriers for the removal/detection of undesired species.

In 1989, Professor Arena received the Stig Sunner Memorial Award of The Calorimetry Conference (USA) in recognition of “the contributions of a young scientist to thermochemistry and thermodynamics”; in 2013, he also received the Canneri Medal of the Division of Analytical Chemistry , Italian Chemical Society,

In 2013, he was elected by his peers to be the Chair of the Division of Analytical Chemistry; Pino was also elected to be the Chair of the Italian Association of Calorimetry and Thermal Analysis in 2014 and kept this assignment up to his retirement.

He has been a Member of a few Editorial Boards of journals, such as Thermochimica Acta and Journal of Inclusion Phenomena and Molecular Recognition and is currently a Member of the Board of Molecules and a Honorary Member of the Editorial Board of the Journal of Thermal Analysis and Calorimetry.

This Special Issue of Molecules, in honor of Prof. Giuseppe Arena, welcomes manuscripts describing original work as well as review articles.

The Guest Editors will be pleased to accept and review manuscripts that address the topics listed below, but not restricted to them:

  • Analytical chemistry
  • Thermodynamics, calorimetry
  • Speciation techniques
  • Biomimetic systems
  • Supramolecular chemistry
  • Sensing systems
  • Separation science

Prof. Dr. Concetta De Stefano
Prof. Dr. Demetrio Milea
Guest Editors

Manuscript Submission Information

Manuscripts should be submitted online at www.mdpi.com by registering and logging in to this website. Once you are registered, click here to go to the submission form. Manuscripts can be submitted until the deadline. All submissions that pass pre-check are peer-reviewed. Accepted papers will be published continuously in the journal (as soon as accepted) and will be listed together on the special issue website. Research articles, review articles as well as short communications are invited. For planned papers, a title and short abstract (about 100 words) can be sent to the Editorial Office for announcement on this website.

Submitted manuscripts should not have been published previously, nor be under consideration for publication elsewhere (except conference proceedings papers). All manuscripts are thoroughly refereed through a single-blind peer-review process. A guide for authors and other relevant information for submission of manuscripts is available on the Instructions for Authors page. Molecules is an international peer-reviewed open access semimonthly journal published by MDPI.

Please visit the Instructions for Authors page before submitting a manuscript. The Article Processing Charge (APC) for publication in this open access journal is 2700 CHF (Swiss Francs). Submitted papers should be well formatted and use good English. Authors may use MDPI's English editing service prior to publication or during author revisions.

Keywords

  • Analytical chemistry
  • Thermodynamics calorimetry
  • Speciation techniques
  • Biomimetic systems
  • Supramolecular chemistry
  • Sensing systems
  • Separation science

Published Papers (3 papers)

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Research

18 pages, 1595 KiB  
Article
Thermodynamic Solution Properties of a Biodegradable Chelant (L-glutamic-N,N-diacetic Acid, L-GLDA) and Its Sequestering Ability toward Cd2+
by Clemente Bretti, Roberto Di Pietro, Paola Cardiano, Olivia Gomez-Laserna, Anna Irto, Gabriele Lando and Concetta De Stefano
Molecules 2021, 26(23), 7087; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26237087 - 23 Nov 2021
Cited by 3 | Viewed by 1906
Abstract
The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect [...] Read more.
The thermodynamics of the interaction of L-glutamic-N,N-diacetic acid (GLDA) with protons was studied potentiometrically at different temperatures, ionic strengths and ionic media. Four protonation constants and corresponding enthalpy changes occurred at infinite dilution together with temperature and ionic strength coefficients. The medium effect was also interpreted in terms of the formation of weak complexes between the ligand and the cations of supporting electrolytes, resulting in a greater tendency of GLDA to chemically interact with Na+ rather than K+ and, in turn, (CH3)4N+. Formation constants of GLDA with Cd2+ were determined in NaCl(aq) at different ionic strength values. Five complex species were found, namely CdL2−, CdHL, CdH2L0(aq), Cd2L0(aq), and Cd(OH)L3−, whose formation constant values at infinite dilution were log β = 12.68, 17.61, 20.76, 17.52, and 1.77, respectively. All the species results were relevant in the pH range of natural waters, although the Cd2L0(aq) was observed only for CCdCGLDA and concentrations of >0.1 mmol dm−3. The sequestering ability of GLDA toward Cd2+, evaluated by means of pL0.5, was maximum at pH~10, whereas the presence of a chloride containing a supporting electrolyte exerted a negative effect. Among new generation biodegradable ligands, GLDA was the most efficient in Cd2+ sequestration. Full article
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9 pages, 7189 KiB  
Article
Critical Reappraisal of Methods for Measuring Urine Saturation with Calcium Salts
by Silvia Berto, Martino Marangella, Concetta De Stefano, Demetrio Milea and Pier Giuseppe Daniele
Molecules 2021, 26(11), 3149; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26113149 - 25 May 2021
Cited by 2 | Viewed by 1883
Abstract
Background: Metabolic and physicochemical evaluation is recommended to manage the condition of patients with nephrolithiasis. The estimation of the saturation state (β values) is often included in the diagnostic work-up, and it is preferably performed through calculations. The free concentrations of constituent [...] Read more.
Background: Metabolic and physicochemical evaluation is recommended to manage the condition of patients with nephrolithiasis. The estimation of the saturation state (β values) is often included in the diagnostic work-up, and it is preferably performed through calculations. The free concentrations of constituent ions are estimated by considering the main ionic soluble complexes. It is contended that this approach is liable to an overestimation of β values because some complexes may be overlooked. A recent report found that β values could be significantly lowered upon the addition of new and so far neglected complexes, [Ca(PO4)Cit]4− and [Ca2H2(PO4)2]. The aim of this work was to assess whether these complexes can be relevant to explaining the chemistry of urine. Methods: The Ca–phosphate–citrate aqueous system was investigated by potentiometric titrations. The stability constants of the parent binary complexes [Cacit] and [CaPO4], and the coordination tendency of PO43− toward [Ca(cit)] to form the ternary complex, were estimated. βCaOx and βCaHPO4 were then calculated on 5 natural urines by chemical models, including or not including the [CaPO4] and [Ca(PO4)cit]4− species. Results: Species distribution diagrams show that the [Ca(PO4)cit]4− species was only noticeable at pH > 8.5 and below 10% of the total calcium. β values estimated on natural urine were slightly lowered by the formation of [CaPO4] species, whereas [Ca(PO4)cit]4− results were irrelevant. Conclusions: While [CaPO4] species have an impact on saturation levels at higher pHs, the existence of ternary complex and of the dimer is rejected. Full article
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16 pages, 2077 KiB  
Article
Thermodynamic Evaluation of the Interactions between Anticancer Pt(II) Complexes and Model Proteins
by Chiara Pelosi, Francesca Saitta, Caterina Zerino, Giovanni Canil, Tarita Biver, Alessandro Pratesi, Celia Duce, Dimitrios Fessas, Chiara Gabbiani and Maria Rosaria Tiné
Molecules 2021, 26(8), 2376; https://0-doi-org.brum.beds.ac.uk/10.3390/molecules26082376 - 19 Apr 2021
Cited by 7 | Viewed by 2176
Abstract
In this work, we have analysed the binding of the Pt(II) complexes ([PtCl(4′-phenyl-2,2′:6′,2″-terpyridine)](CF3SO3) (1), [PtI(4′-phenyl-2,2′:6′,2″-terpyridine)](CF3SO3) (2) and [PtCl(1,3-di(2-pyridyl)benzene) (3)] with selected model proteins (hen egg-white lysozyme, HEWL, and ribonuclease [...] Read more.
In this work, we have analysed the binding of the Pt(II) complexes ([PtCl(4′-phenyl-2,2′:6′,2″-terpyridine)](CF3SO3) (1), [PtI(4′-phenyl-2,2′:6′,2″-terpyridine)](CF3SO3) (2) and [PtCl(1,3-di(2-pyridyl)benzene) (3)] with selected model proteins (hen egg-white lysozyme, HEWL, and ribonuclease A, RNase A). Platinum coordination compounds are intensively studied to develop improved anticancer agents. In this regard, a critical issue is the possible role of Pt-protein interactions in their mechanisms of action. Multiple techniques such as differential scanning calorimetry (DSC), electrospray ionization mass spectrometry (ESI-MS) and UV-Vis absorbance titrations were used to enlighten the details of the binding to the different biosubstrates. On the one hand, it may be concluded that the affinity of 3 for the proteins is low. On the other hand, 1 and 2 strongly bind them, but with major binding mode differences when switching from HEWL to RNase A. Both 1 and 2 bind to HEWL with a non-specific (DSC) and non-covalent (ESI-MS) binding mode, dominated by a 1:1 binding stoichiometry (UV-Vis). ESI-MS data indicate a protein-driven chloride loss that does not convert into a covalent bond, likely due to the unfavourable complexes’ geometries and steric hindrance. This result, together with the significant changes of the absorbance profiles of the complex upon interaction, suggest an electrostatic binding mode supported by some stacking interaction of the aromatic ligand. Very differently, in the case of RNase A, slow formation of covalent adducts occurs (DSC, ESI-MS). The reactivity is higher for the iodo-compound 2, in agreement with iodine lability higher than chlorine. Full article
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