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Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes

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A special issue of Materials (ISSN 1996-1944). This special issue belongs to the section "Metals and Alloys".

Deadline for manuscript submissions: closed (20 November 2022) | Viewed by 21703

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Prof. Dr. Piotr Piszczek

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Faculty of Chemistry, Nicolaus Copernicus University in Toruń, ul. Gagarina 7, 87-100 Toruń, Poland
Interests: nanotechnologies; titanium and titania-based biomaterial; coordination compounds; structural studies and spectral characterization; medical applications
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Prof. Dr. Aleksandra Radtke

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Faculty of Chemistry, Nicolaus Copernicus University in Toruń, 87-100 Toruń, Poland
Interests: titania; nanomaterials; nanocoatings; implants; hydroxyapatite; photodegradation; biointegration; biological activity; CVD; ALD
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

A global crisis related to the prevailing COVID-19 pandemic has revealed the threats arising from the rapid increase in antimicrobial resistance (AMR) and from the possibility of appearance of new kinds of viruses. The wide research currently carried out aims at the production of new materials, to know their microbicidal or antiviral mechanisms and to use them in various areas of our life. The subject matter of the proposed Special Issue would be studies concerning material based on metals, metal oxides, and d-electron metal complexes and their potential applications in different fields of our life, e.g., in medicine, cosmetics, the food industry, agriculture, and environmental protection. Biodegradable materials with the potential to be used in various areas of our life, e.g., as scaffolds supporting tissue reconstruction, systems for the transport and release of drugs or anti-inflammatory agents, and materials with microbicidal surfaces are of particular interest issue and have been studied intensively in recent years, and any studies on them can be included to this Special Issue.

We would like this Special Issue to become a place for presenting research results and exchanging experiences in the field of use of metals, their oxides, and their complexes in various biomedical applications. The results of research on the material synthesis and their physicochemical, mechanical, photocatalytic properties, and biological activity are of interest to us. We expect submissions of reports from conducted research, and full articles, as well as review articles.

Dr. Piotr Piszczek
Dr. Aleksandra Radtke
Guest Editors

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Keywords

functional materials
metals
metal oxides
metal complexes
biological active agents
antiviral and antibacterial properties
different applications in our life

Published Papers (12 papers)

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Editorial

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3 pages, 190 KiB

Open AccessEditorial

Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes

by Piotr Piszczek and Aleksandra Radtke

Materials 2023, 16(5), 1899; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16051899 - 24 Feb 2023

Cited by 1 | Viewed by 690

Abstract

Materials based on metals, metal oxides, and metal complexes play an essential role in various areas of our lives [...] Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

Research

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17 pages, 2748 KiB

Open AccessArticle

The Composites of PCL and Tetranuclear Titanium(IV)–Oxo Complex with Acetylsalicylate Ligands—Assessment of Their Biocompatibility and Antimicrobial Activity with the Correlation to EPR Spectroscopy

by Julia Śmigiel, Piotr Piszczek, Grzegorz Wrzeszcz, Tomasz Jędrzejewski, Patrycja Golińska and Aleksandra Radtke

Materials 2023, 16(1), 297; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16010297 - 28 Dec 2022

Cited by 3 | Viewed by 1507

Abstract

In our research, we have focused on the biological studies on composite materials produced by the dispersion of titanium(IV)–oxo complex (TOC) with acetylsalicylate ligands in a poly(ε-caprolactone) (PCL) matrix, which is a biodegradable thermoplastic polymer increasingly used in the production of medical devices. Using PCL as a matrix for the biologically active compounds, such as antimicrobial agents, antibiotics or other active medical substances, from which these individuals can be gradually released is fully understable. Composites of PCL + nTOC (n = 10, 15 and 20 wt.%) have been produced and, in such a form, the biological properties of TOCs have been estimated. Direct and indirect cytotoxicity studies have been performed in vitro on L929 and human umbilical vein endothelial cells (HUVEC) cell lines. The antibacterial and antifungal activity of the PCL + TOC samples have been assessed against two Staphylococcus aureus (ATCC 6538 and ATCC 25923) reference strains, two Escherichia coli (ATCC 8739 and ATCC 25922) reference strains and yeast of Candida albicans ATCC 10231. Obtained results have been correlated with electron paramagnetic resonance (EPR) spectroscopy data. We could conclude that photoexcitation by visible light of the surface of PCL + nTOC composite foils lead to the formation of different paramagnetic species, mainly O⁻, which slowly disappears over time; however, their destructive effect on bacteria and cells has been proven. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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21 pages, 3894 KiB

Open AccessArticle

Evaluation of the Cathodic Electrodeposition Effectiveness of the Hydroxyapatite Layer Used in Surface Modification of Ti6Al4V-Based Biomaterials

by Michalina Ehlert, Aleksandra Radtke, Michał Bartmański and Piotr Piszczek

Materials 2022, 15(19), 6925; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15196925 - 06 Oct 2022

Cited by 4 | Viewed by 2092

Abstract

The important issue associated with the design and the fabrication of the titanium and titanium alloy implants is the increase of their biointegration with bone tissue. In the presented paper, the research results concerning the conditions used in the cathodic deposition of hydroxyapatite on the surface Ti6Al4V substrates primarily modified by the production of TiO₂ nanoporous coatings, TiO₂ nanofibers, and titanate coatings, are discussed. Despite excellent biocompatibility with natural bone tissue of materials based on hydroxyapatite (HA), their poor adhesion to the substrate caused the limited use in the implants’ construction. In our works, we have focused on the comparison of the structure, physicochemical, and mechanical properties of coating systems produced at different conditions. For this purpose, scanning electron microscopy images, chemical composition, X-ray diffraction patterns, infrared spectroscopy, wettability, and mechanical properties are analyzed. Our investigations proved that the intermediate titanium oxide coatings presence significantly increases the adhesion between the hydroxyapatite layer and the Ti6Al4V substrate, thus solving the temporary delamination problems of the HA layer. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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16 pages, 4343 KiB

Open AccessArticle

Titanium(IV) Oxo-Complex with Acetylsalicylic Acid Ligand and Its Polymer Composites: Synthesis, Structure, Spectroscopic Characterization, and Photocatalytic Activity

by Julia Śmigiel, Tadeusz Muzioł, Piotr Piszczek and Aleksandra Radtke

Materials 2022, 15(13), 4408; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15134408 - 22 Jun 2022

Cited by 3 | Viewed by 1413

Abstract

The titanium oxo complexes are widely studied, due to their potential applications in photocatalytic processes, environmental protection, and also in the biomedical field. The presented results concern the oxo complex synthesized in the reaction of titanium(IV) isobutoxide and acetylsalicylic acid (Hasp), in a 4:1 molar ratio. The structure of isolated crystals was solved using the single-crystal X-ray diffraction method. The analysis of these data proves that [Ti₄O₂(OⁱBu)₁₀(asp)₂]·H₂O (1) complex is formed. Moreover, the molecular structure of (1) was characterized using vibrational spectroscopic techniques (IR and Raman), ¹³C NMR, and UV–Vis diffuse reflectance spectroscopy (UV–Vis DRS). The photocatalytic activity of the synthesized complex was determined with the use of composite foils produced by the dispersion of (1) micrograins, as the inorganic blocks, in a polycaprolactone (PCL) matrix (PCL + (1)). The introduction of (1) micrograins to the PCL matrix caused the absorption maximum shift up to 425–450 nm. The studied PCL + (1) composite samples reveal good activity toward photodecolorization of methylene blue after visible light irradiation. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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16 pages, 3605 KiB

Open AccessFeature PaperArticle

Magnetite Impregnated Lignocellulosic Biomass for Zn(II) Removal

by Christopher Asimbaya, Nelly Maria Rosas-Laverde, Salome Galeas, Alexis Debut, Victor H. Guerrero and Alina Pruna

Materials 2022, 15(3), 728; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15030728 - 19 Jan 2022

Cited by 1 | Viewed by 1620

Abstract

Magnetic composites obtained by impregnation of lignocellulosic biomass with magnetite nanoparticles were used for zinc(II) removal from aqueous synthetic solutions. Laurel, canelo and eucalyptus sawdust, with a particle size between 74 and 150 µm were used as support. Structural and morphological examinations of the composites confirmed the presence of magnetite nanoparticles in the lignocellulosic support. Transmission Electron Microscopy showed nanoparticles with diameters of about 20 nm. The maximum removal efficiencies for 7 g L⁻¹ of modified adsorbent were increased to 98.9, 98.8 and 97.6% for laurel, canelo and eucalyptus magnetic composites, respectively, in comparison to 60.9, 46.0 and 33.3%, for corresponding unmodified adsorbents. Adsorption data was analyzed using pseudo-first, pseudo-second order and intra-particle diffusion kinetic models and various isotherm models. The results determined that Freundlich isotherm fits the Zn ions adsorption on magnetite modified adsorbents while chemisorption and boundary diffusion were dominating the process. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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18 pages, 9864 KiB

Open AccessArticle

Electrochemical Mechanism of Recovery of Nickel Metal from Waste Lithium Ion Batteries by Molten Salt Electrolysis

by Hui Li, Yutian Fu, Jinglong Liang, Chenxiao Li, Jing Wang, Hongyan Yan and Zongying Cai

Materials 2021, 14(22), 6875; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14226875 - 15 Nov 2021

Cited by 4 | Viewed by 1814

Abstract

With the widespread use of lithium-ion batteries, the cumulative amount of used lithium-ion batteries is also increasing year by year. Since waste lithium-ion batteries contain a large amount of valuable metals, the recovery of valuable metals has become one of the current research hotspots. The research uses electrometallurgical technology, and the main methods used are cyclic voltammetry, square wave voltammetry, chronoamperometry and open circuit potential. The electrochemical reduction behavior of Ni³⁺ in NaCl-CaCl₂ molten salt was studied, and the electrochemical reduction behavior was further verified by using a Mo cavity electrode. It is determined that the reduction process of Ni³⁺ in LiNiO₂ is mainly divided into two steps: LiNiO₂ → NiO → Ni. Through the analysis of electrolysis products under different conditions, when the current value of LiNiO₂ is not less than 0.03 A, the electrolysis product after 10 h is metallic Ni. When the current reaches 0.07 A, the current efficiency is 77.9%, while the Li⁺ in LiNiO₂ is enriched in NaCl-CaCl₂ molten salt. The method realizes the separation and extraction of the valuable metal Ni in the waste lithium-ion battery. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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10 pages, 2964 KiB

Open AccessArticle

Study on the Behavior of Electrochemical Extraction of Cobalt from Spent Lithium Cobalt Oxide Cathode Materials

by Hui Li, Haotian Li, Chenxiao Li, Jinglong Liang, Hongyan Yan and Zhengzhen Xu

Materials 2021, 14(20), 6110; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14206110 - 15 Oct 2021

Cited by 6 | Viewed by 1455

Abstract

The molten salt electrochemical method was used to reduce the Co in spent LiCoO₂. The reduction mechanism of Co (III) in LiCoO₂ was analyzed by cyclic voltammetry, square wave voltammetry, and open circuit potential. The reduction process of Co (III) on Fe electrode was studied in NaCl-CaCl₂-LiCoO₂ molten salt system at 750 °C. The results show that the reduction process of Co (III) is a two-step reduction: Co (III) → Co (II) → Co (0) and they are all quasi-reversible processes controlled by diffusion. Phase analysis (XRD) shows that Li⁺ and Cl²⁻ in the molten salt form LiCl electrolysis experiments with different voltages were carried out, which proved the stepwise reduction of Co in LiCoO₂. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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10 pages, 30975 KiB

Open AccessArticle

In-Situ Synthesis of Methyl Cellulose Film Decorated with Silver Nanoparticles as a Flexible Surface-Enhanced Raman Substrate for the Rapid Detection of Pesticide Residues in Fruits and Vegetables

by Qijia Zhang, Guangda Xu, Na Guo, Tongtong Wang, Peng Song and Lixin Xia

Materials 2021, 14(19), 5750; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14195750 - 01 Oct 2021

Cited by 10 | Viewed by 1977

Abstract

The purpose of this study was to develop a flexible substrate methylcellulose-decorated silver nanoparticles (MC/Ag NPs) film and explore its application in fruits and vegetables by surface enhanced Raman spectroscopy (SERS) technology for rapid detection of pesticides. The performance of the MC/Ag NPs film substrate was characterized by Nile blue A (NBA), and the detection limit was as low as 10⁻⁸ M. The substrate also exhibited satisfactory Raman signal strength after two months of storage. The impressive sensitivity and stability were due to the excellent homogeneity of the silver nanoparticles that were grown in situ in the methylcellulose matrix, which generated “hot spots” between the silver nanoparticles without a large amount of aggregation, and resulted in the ultra-high sensitivity and excellent stability of the MC/Ag NPs film substrate. The MC/Ag NPs film substrate was used to detect thiram pesticides on tomato and cucumber peels, and the minimum detectable level of thiram was 2.4 ng/cm², which was much lower than the maximum residue level. These results indicate that the MC/Ag NPs film is sensitive to rapid detection of multiple pesticides in food. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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12 pages, 6026 KiB

Open AccessArticle

Scaling Up the Process of Titanium Dioxide Nanotube Synthesis and Its Effect on Photoelectrochemical Properties

by Mariusz Szkoda, Konrad Trzciński, Zuzanna Zarach, Daria Roda, Marcin Łapiński and Andrzej P. Nowak

Materials 2021, 14(19), 5686; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14195686 - 29 Sep 2021

Cited by 7 | Viewed by 1821

Abstract

In this work, for the first time, the influence of scaling up the process of titanium dioxide nanotube (TiO₂NT) synthesis on the photoelectrochemical properties of TiO₂ nanotubes is presented. Titanium dioxide nanotubes were obtained on substrates of various sizes: 2 × 2, 4 × 4, 5 × 5, 6 × 6, and 8 × 8 cm². The electrode material was characterized using scanning electron microscopy as well as Raman and UV–vis spectroscopy in order to investigate their morphology, crystallinity, and absorbance ability, respectively. The obtained electrodes were used as photoanodes for the photoelectrochemical water splitting. The surface analysis was performed, and photocurrent values were determined depending on their place on the sample. Interestingly, the values of the obtained photocurrent densities in the center of each sample were similar and were about 80 µA·cm². The results of our work show evidence of a significant contribution to wider applications of materials based on TiO₂ nanotubes not only in photoelectrochemistry but also in medicine, supercapacitors, and sensors. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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14 pages, 1929 KiB

Open AccessCommunication

Characterization of Metal-Bound Benzimidazole Derivatives, Effects on Tumor Cells of Lung Cancer

by Anita Raducka, Agnieszka Czylkowska, Katarzyna Gobis, Kamila Czarnecka, Paweł Szymański and Marcin Świątkowski

Materials 2021, 14(11), 2958; https://0-doi-org.brum.beds.ac.uk/10.3390/ma14112958 - 30 May 2021

Cited by 10 | Viewed by 2172

Abstract

Four new ligands and four new copper (II) coordination compounds were prepared and characterized by chemical, elemental analysis, cytotoxicity, and FTIR spectroscopy (Fourier transform infrared spectroscopy). The nature of metal–ligand coordination was investigated. The thermal properties of complexes in the solid state were studied using TG-MS techniques (thermogravimetric analysis coupled with mass spectrometry) under dynamic flowing air atmosphere to analyze the principal volatile thermal decomposition and fragmentation products that evolved during thermolysis. The intermediate and final solid thermolysis products were also determined. The MTT (3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazoliumbromide) assay was used to evaluate active metabolic cells as an IC₅₀ (half maximal inhibitory concentration). The relationship between antitumor activity and the position of nitrogen atoms in the organic ligand has been shown. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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Review

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24 pages, 1083 KiB

Open AccessReview

Application of Iron Nanoparticle-Based Materials in the Food Industry

by Dariusz Góral, Andrzej Marczuk, Małgorzata Góral-Kowalczyk, Iryna Koval and Dariusz Andrejko

Materials 2023, 16(2), 780; https://0-doi-org.brum.beds.ac.uk/10.3390/ma16020780 - 12 Jan 2023

Cited by 5 | Viewed by 2596

Abstract

Due to their different properties compared to other materials, nanoparticles of iron and iron oxides are increasingly used in the food industry. Food technologists have especially paid attention to their ease of separation by magnetic fields and biocompatibility. Unfortunately, the consumption of increasing amounts of nanoparticles has raised concerns about their biotoxicity. Hence, knowledge about the applicability of iron nanoparticle-based materials in the food industry is needed not only among scientists, but also among all individuals who are involved in food production. The first part of this article describes typical methods of obtaining iron nanoparticles using chemical synthesis and so-called green chemistry. The second part of this article describes the use of iron nanoparticles and iron nanoparticle-based materials for active packaging, including the ability to eliminate oxygen and antimicrobial activity. Then, the possibilities of using the magnetic properties of iron nano-oxides for enzyme immobilization, food analysis, protein purification and mycotoxin and histamine removal from food are described. Other described applications of materials based on iron nanoparticles are the production of artificial enzymes, process control, food fortification and preserving food in a supercooled state. The third part of the article analyzes the biocompatibility of iron nanoparticles, their impact on the human body and the safety of their use. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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21 pages, 5634 KiB

Open AccessReview

Recent Advances in Metal-Based Nanoparticle-Mediated Biological Effects in Arabidopsis thaliana: A Mini Review

by Min Geng, Linlin Li, Mingjun Ai, Jun Jin, Die Hu and Kai Song

Materials 2022, 15(13), 4539; https://0-doi-org.brum.beds.ac.uk/10.3390/ma15134539 - 28 Jun 2022

Cited by 3 | Viewed by 1530

Abstract

The widespread application of metal-based nanoparticles (MNPs) has prompted great interest in nano-biosafety. Consequently, as more and more MNPs are released into the environment and eventually sink into the soil, plants, as an essential component of the ecosystem, are at greater risk of exposure and response to these MNPs. Therefore, to understand the potential impact of nanoparticles on the environment, their effects should be thoroughly investigated. Arabidopsis (Arabidopsis thaliana L.) is an ideal model plant for studying the impact of environmental stress on plants’ growth and development because the ways in which Arabidopsis adapt to these stresses resemble those of many plants, and therefore, conclusions obtained from these scientific studies have often been used as the universal reference for other plants. This study reviewed the main findings of present-day interactions between MNPs and Arabidopsis thaliana from plant internalization to phytotoxic effects to reveal the mechanisms by which nanomaterials affect plant growth and development. We also analyzed the remaining unsolved problems in this field and provide a perspective for future research directions. Full article

(This article belongs to the Special Issue Materials Make a Better Life: Functional Metals, Metal Oxides, and Metal Complexes)

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