Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
4.5
2.7
Journals
Applied Sciences
Special Issues
Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications
share announcement

Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications

A special issue of Applied Sciences (ISSN 2076-3417). This special issue belongs to the section "Materials Science and Engineering".

Deadline for manuscript submissions: closed (15 October 2022) | Viewed by 10123

Special Issue Editors

Dr. Giuseppe Cassone

E-Mail Website
Guest Editor
Institute for Chemical-Physical Processes, Italian National Research Council, 98158 Messina, Italy
Interests: chemical physics; metals behavior in liquid solvents; ab initio molecular dynamics; metadynamics; density functional theory; quantum chemistry
Prof. Dr. Claudia Foti

E-Mail Website
Guest Editor
Department of Chemical, University of Messina, 98122 Messina ME, Italy
Interests: metal–ligand complexation in aqueous systems; speciation in natural waters; thermodynamic interaction parameters; metal sequestration
Prof. Dr. Ottavia Giuffrè

E-Mail Website
Guest Editor
Department of Chemical, Biological, Pharmaceutical and Environmental Sciences, University of Messina, 98122 Messina ME, Italy
Interests: speciation in aqueous solution; metal–ligand interactions; thermodynamic parameters; modeling of natural fluids; ligand sequestering ability toward metal cations
Dr. Franz Saija

E-Mail Website
Guest Editor
Institute for Chemical-Physical Processes, Italian National Research Council, 98158 Messina, Italy
Interests: density functional theory and molecular dynamics; computational spectroscopy; soft condensed matter; phase transitions

Special Issue Information

Dear Colleagues,

Natural waters and biological fluids are multielectrolyte aqueous solutions in which a wide number of components is dissolved or dispersed, namely essential or toxic metal cations, and inorganic and organic anions at low and high molecular weight, having very different characteristics and concentrations. Metal complexation in such fluids is a key process for understanding environmental (such as mobility, bioavailability, and toxicity of species) and biological phenomena (such as transport through membranes, antibiotic activity, enzyme catalysis, etc.). The study of formation of complexes is of significant importance from both a theoretical point of view, to understand the chemical physics behind the interactions leading to complexation and the mechanisms of action of the species in natural aqueous systems, and an applicative one, to exploit the formation of complex species in processes such as removal of contaminants from natural waters, chelating therapies for detoxification from metals, transport of drugs in biological fluids, sensors, and so on.

To further develop some of these aspects, we welcome papers on:

  1. Investigations exploiting computational approaches to develop atomistic pictures of the complexation of metals in natural fluids based on either quantum mechanics or classical simulations and to provide reliable and robust microscopic references to the different and several experimental techniques;
  2. Experimental studies aimed at determining formation, distribution, kinetics, stability of metal-complexes in natural fluids: speciation, characterization, thermodynamic parameters, adsorption processes;
  3. Applicative studies aimed at exploiting the formation of metal complexes in remediation methodologies, in clinical use either as metal-based drugs or as delivery drug systems, in the design of sensors used to probe metal ions, anions, and small molecules.

Dr. Giuseppe Cassone
Prof. Claudia Foti
Prof. Ottavia Giuffrè
Dr. Franz Saija
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. Applied Sciences 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 2400 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

  • metal complexation
  • natural waters
  • biological fluids
  • quantum chemistry simulations
  • speciation
  • metal removal
  • sensors
  • density functional theory

Published Papers (6 papers)

Download All Papers
Order results
Result details
Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:

Editorial

Jump to: Research

2 pages, 200 KiB  
Editorial
Special Issue on Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications
by Giuseppe Cassone, Claudia Foti, Ottavia Giuffrè and Franz Saija
Appl. Sci. 2023, 13(5), 3320; https://0-doi-org.brum.beds.ac.uk/10.3390/app13053320 - 06 Mar 2023
Viewed by 918
Abstract
The complexation of metals in natural fluids, such as natural waters and biological fluids, is a key process in the context of environmental and biological phenomena [...] Full article
(This article belongs to the Special Issue Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications)

Research

Jump to: Editorial

13 pages, 817 KiB  
Article
Trace Metal Partitioning in the Salinity Gradient of the Highly Stratified Estuary: A Case Study in the Krka River Estuary (Croatia)
by Saša Marcinek, Ana Marija Cindrić, Jasmin Pađan and Dario Omanović
Appl. Sci. 2022, 12(12), 5816; https://0-doi-org.brum.beds.ac.uk/10.3390/app12125816 - 08 Jun 2022
Cited by 5 | Viewed by 1490
Abstract
A size partitioning of several trace metals (Zn, Cd, Pb, Cu, Ni, Co, Mn, Fe and Al) between five size fractions (<3 kDa, 3 kDa–0.1 µm, 0.1 µm–1.2 µm, 1.2 µm–5 µm and >5 µm) was studied in the vertical salinity gradient of [...] Read more.
A size partitioning of several trace metals (Zn, Cd, Pb, Cu, Ni, Co, Mn, Fe and Al) between five size fractions (<3 kDa, 3 kDa–0.1 µm, 0.1 µm–1.2 µm, 1.2 µm–5 µm and >5 µm) was studied in the vertical salinity gradient of the highly stratified Krka River estuary. The results indicated a dominant river source for Zn, Co, Mn, Fe and Al and a diluting effect on Cd, Pb and Ni. The truly dissolved fraction (<3 kDa) dominated the Zn, Cd, Cu, Ni and Co pool, and a large part of Pb, Mn, Fe and Al was present in >5 µm particles. Pb, Mn, Fe and Al were closely related, showing a precipitation and colloidal aggregation in the surface layers and dissolution in the seawater layer. The highest percentage (30–37%) of colloids (3 kDa–0.1 µm) in the dissolved pool was found for Pb, Cu, Fe and Al. Differences in size distribution between low and high river flow periods revealed that Zn, Pb, Co, Mn, Fe and Al are introduced by the river mostly in the 3 kDa–5 µm size range. Therefore, a low percentage of colloidally bound metals compared to other coastal areas can be explained by a limited riverine input of terrigenous material, characteristic for this estuary. Correlation with PARAFAC components revealed associations of Cu with protein-like substances and Co with humic-like substances. The accumulation of Cu at the freshwater-seawater interface coupled with an increase of its colloidal fraction was observed, apparently governed by biologically produced organic ligands. Full article
(This article belongs to the Special Issue Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications)
►▼ Show Figures

Figure 1

21 pages, 4133 KiB  
Article
Chemical Speciation of Antarctic Atmospheric Depositions
by Stefano Bertinetti, Silvia Berto, Mery Malandrino, Davide Vione, Ornella Abollino, Eleonora Conca, Matteo Marafante, Anna Annibaldi, Cristina Truzzi and Silvia Illuminati
Appl. Sci. 2022, 12(9), 4438; https://0-doi-org.brum.beds.ac.uk/10.3390/app12094438 - 27 Apr 2022
Cited by 2 | Viewed by 1314
Abstract
Both inorganic and organic complexation of metal cations in clouds or rainwater is essential to describe the global biogeochemical cycles of metals, because complexation can increase metal solubility and stabilize some of their oxidation states. Within a Project of the National Research Program [...] Read more.
Both inorganic and organic complexation of metal cations in clouds or rainwater is essential to describe the global biogeochemical cycles of metals, because complexation can increase metal solubility and stabilize some of their oxidation states. Within a Project of the National Research Program in the Antarctica, atmospheric depositions were collected during the Antarctic summer 2017–2018 in eight sampling sites. The main ionic components occurring in water extracts of these atmospheric depositions were quantified, and a chemical model was applied, in order to identify the main species occurring in the samples. The speciation study showed that most cations were present as aquoions, except for Fe, which occurred predominantly in hydrolytic forms. The model allowed us to foresee the effect of an increase in the concentration levels of all the solution components, by simulating what could happen when the original particles act as cloud condensation nuclei. The role of inorganic anions as complexing agents becomes important when increasing total concentrations of all the solutes by a factor >100 compared to the water extracts, while the presence of organic acids acquires significance for samples having organic acid concentration higher than 10−5 mol L−1. Moreover, it was possible to pinpoint the formation constants that mostly affect the chemical system, and to gain insight into the behavior of metals in wet depositions, which is fundamental knowledge in atmospheric photochemistry studies and in the modeling of the biogeochemical cycles of metal cations. Full article
(This article belongs to the Special Issue Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications)
►▼ Show Figures

Figure 1

14 pages, 2230 KiB  
Article
Binding of Arsenic by Common Functional Groups: An Experimental and Quantum-Mechanical Study
by Donatella Chillé, Viviana Mollica-Nardo, Ottavia Giuffrè, Rosina Celeste Ponterio, Franz Saija, Jiří Sponer, Sebastiano Trusso, Giuseppe Cassone and Claudia Foti
Appl. Sci. 2022, 12(6), 3210; https://0-doi-org.brum.beds.ac.uk/10.3390/app12063210 - 21 Mar 2022
Cited by 3 | Viewed by 2093
Abstract
Arsenic is a well-known contaminant present in different environmental compartments and in human organs and tissues. Inorganic As(III) represents one of the most dangerous arsenic forms. Its toxicity is attributed to its great affinity with the thiol groups of proteins. Considering the simultaneous [...] Read more.
Arsenic is a well-known contaminant present in different environmental compartments and in human organs and tissues. Inorganic As(III) represents one of the most dangerous arsenic forms. Its toxicity is attributed to its great affinity with the thiol groups of proteins. Considering the simultaneous presence in all environmental compartments of other common functional groups, we here present a study aimed at evaluating their contribution to the As(III) complexation. As(III) interactions with four (from di- to hexa-) carboxylic acids, five (from mono- to penta-) amines, and four amino acids were evaluated via experimental methods and, in simplified systems, also by quantum-mechanical calculations. Data were analyzed also with respect to those previously reported for mixed thiol-carboxylic ligands to evaluate the contribution of each functional group (-SH, -COOH, and -NH2) toward the As(III) complexation. Formation constants of As(III) complex species were experimentally determined, and data were analyzed for each class of ligand. An empirical relationship was reported, taking into account the contribution of each functional group to the complexation process and allowing for a rough estimate of the stability of species in systems where As(III) and thiol, carboxylic, or amino groups are involved. Quantum-mechanical calculations allowed for the evaluation and the characterization of the main chelation reactions of As(III). The potential competitive effects of the investigated groups were evaluated using cysteine, a prototypical species possessing all the functional groups under investigation. Results confirm the higher binding capabilities of the thiol group under different circumstances, but also indicate the concrete possibility of the simultaneous binding of As(III) by the thiol and the carboxylic groups. Full article
(This article belongs to the Special Issue Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications)
►▼ Show Figures

Figure 1

11 pages, 1925 KiB  
Article
A Polymer Inclusion Membrane for Sensing Metal Complexation in Natural Waters
by Berta Alcalde, Enriqueta Anticó and Clàudia Fontàs
Appl. Sci. 2021, 11(21), 10404; https://0-doi-org.brum.beds.ac.uk/10.3390/app112110404 - 05 Nov 2021
Cited by 3 | Viewed by 1501
Abstract
Metal speciation studies are of great importance in assessing metal bioavailability in aquatic environments. Functionalized membranes are a simple tool to perform metal chemical speciation. In this study, we have prepared and tested a polymer inclusion membrane (PIM) made of the polymer cellulose [...] Read more.
Metal speciation studies are of great importance in assessing metal bioavailability in aquatic environments. Functionalized membranes are a simple tool to perform metal chemical speciation. In this study, we have prepared and tested a polymer inclusion membrane (PIM) made of the polymer cellulose triacetate (CTA), the extractant di-(2-ethylhexyl) phosphoric acid (D2EHPA), and the plasticizer 2-nitrophenyloctyl ether (NPOE) as a sensor for Zn and Cu complexation studies. This PIM, incorporated in a device with an 0.01 M HNO3 receiving solution, is shown to effectively transport free metal ions, and it is demonstrated that the presence of ligands that form stable complexes with divalent metallic ions, such as ethylenediaminetetraacetic acid (EDTA) and humic acid (HA), greatly influences the accumulation of the metals in the receiving phase due to the increasing metal fraction complexed in the feed phase. Moreover, the effect of major ions found in natural waters has been investigated, and it is found that the presence of calcium did not decrease the accumulation of either Zn or Cu. Finally, the PIM sensor has been used successfully to evaluate metal complexation in a river water affected by Zn pollution. Full article
(This article belongs to the Special Issue Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications)
►▼ Show Figures

Figure 1

9 pages, 2638 KiB  
Article
Thermodynamic Study on the Dissociation and Complexation of Coumarinic Acid with Neodymium(III) and Dioxouranium(VI) in Aqueous Media
by Luana Malacaria, Giuseppina Anna Corrente and Emilia Furia
Appl. Sci. 2021, 11(10), 4475; https://0-doi-org.brum.beds.ac.uk/10.3390/app11104475 - 14 May 2021
Cited by 3 | Viewed by 1451
Abstract
In the frame of a systematic study on the sequestering ability of natural antioxidants towards metal cations, the complexation of coumarin-3-carboxilic acid (HCCA) with neodymium(III) and dioxouranium(VI) (uranyl, UO22+), and overall stability constants of the resulting complexes, were evaluated from [...] Read more.
In the frame of a systematic study on the sequestering ability of natural antioxidants towards metal cations, the complexation of coumarin-3-carboxilic acid (HCCA) with neodymium(III) and dioxouranium(VI) (uranyl, UO22+), and overall stability constants of the resulting complexes, were evaluated from the pH-potentiometric titration data at 37 °C and in an aqueous solution (i.e., 0.16 mol/L NaClO4). The graphic representation of the complex’s concentration curves is given by the distribution diagrams, which provide a depiction of all the species present in the solution in the selected pH ranges. The protonation constant of HCCA was also determined to evaluate the competition of the ligand for the metal cations and H+. The ligand-to-metal concentration ratio was varied between 1 and 10, and the hydrogen ion concentration was decreased stepwise until the incipient precipitation of a basic salt of the metal, which occurred at different values depending on the specific metal cation and the ligand to metal ratio. Speciation profiles obtained by potentiometric titrations and supported by UV-Vis data show that a complexation occurs at a ligand-to-Nd(III) and to –UO22+ ratio of 1:1 and 2:1, with different degrees of deprotonation: Nd(OH)(CCA)+, UO2(OH)(CCA), UO2(OH)2(CCA)−, and Nd(OH)(CCA)2, UO2(CCA)2 and (UO2)2(OH)2(CCA)2. Full article
(This article belongs to the Special Issue Complexation of Metals in Natural Fluids: Simulations, Experiments and Applications)
►▼ Show Figures

Figure 1

Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:
 
Displaying articles 1-6
Back to TopTop