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The Role of Metal Ions in Biology, Biochemistry and Medicine

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

Deadline for manuscript submissions: closed (30 September 2020) | Viewed by 47839

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Prof. Dr. Michael Moustakas

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Department of Botany, Aristotle University of Thessaloniki, 54124 Thessaloniki, Greece
Interests: plant ecophysiology; biotic stress; abiotic stress; photosynthesis; antioxidative mechanisms; photoprotective mechanisms; mineral nutrition; ROS
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Dear Colleagues,

Metal ions are fundamental elements for the maintenance of lifespan of plants, animals and humans. Their substantial role in biological systems was recognized a long time ago. They are essential for the maintenance of life and their absence can cause growth disorders, severe malfunction, carcinogenesis or death. They are protagonists as macro or microelements in several structural and functional roles, participating in many biochemical reactions and arise in several forms. They participate in intra and inter cellular communications, in maintaining electrical charges and osmotic pressure, in photosynthesis and electron transfer processes, in the maintenance of pairing, stacking and the stability of nucleotide bases, in regulation of DNA transcription, proper functioning of nerve cells, muscle cells, brain and heart, transport of oxygen and in many other biological processes up to the point that we cannot even imagine a life without metals. With the application of new modern methods to study biological and biochemical systems, new and sophisticated roles of metal ions in living systems can be revealed in articles in this Special Issue that aims to highlight some of the new advances.

We would like to invite experts in the field to contribute both original research papers, as well as review articles, covering basic aspects and future directions in the field.

Prof. Michael Moustakas
Guest Editor

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Keywords

Metal Ions
Metal Deficiency and Toxicity
Micro-Macronutrients
Metal Transport
Metalloenzymes
Metallothionins
Metallomics
Metal Ions and Nucleotides
Metals in Health and Disease
Metal Homeostasis
Metal Hyperaccumulation
Metal Imaging and Sensing
Metal Ions and Cancer
Metallopharmaceuticals
Metallic Nanoparticles

Published Papers (11 papers)

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Editorial

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4 pages, 200 KiB

Open AccessEditor’s ChoiceEditorial

The Role of Metal Ions in Biology, Biochemistry and Medicine

by Michael Moustakas

Materials 2021, 14(3), 549; https://doi.org/10.3390/ma14030549 - 24 Jan 2021

Cited by 60 | Viewed by 4014

Abstract

Metal ions are fundamental elements for the maintenance of the lifespan of plants, animals and humans [...] Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

Research

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18 pages, 2839 KiB

Open AccessArticle

Zn(II) Complex of Plant Phenolic Chlorogenic Acid: Antioxidant, Antimicrobial and Structural Studies

by Monika Kalinowska, Justyna Sienkiewicz-Gromiuk, Grzegorz Świderski, Anna Pietryczuk, Adam Cudowski and Włodzimierz Lewandowski

Materials 2020, 13(17), 3745; https://doi.org/10.3390/ma13173745 - 24 Aug 2020

Cited by 38 | Viewed by 3302

Abstract

The structure of the Zn(II) complex of 5-caffeoylquinic acid (chlorogenic acid, 5-CQA) and the type of interaction between the Zn(II) cation and the ligand were studied by means of various experimental and theoretical methods, i.e., electronic absorption spectroscopy UV/Vis, infrared spectroscopy FT-IR, elemental, thermogravimetric and density functional theory (DFT) calculations at B3LYP/6-31G(d) level. DPPH (2,2-diphenyl-1-picrylhydrazyl), ABTS (2,2′-azino-bis(3-ethylbenzothiazoline-6-sulfonic acid), FRAP (ferric reducing antioxidant power), CUPRAC (cupric reducing antioxidant power) and trolox oxidation assays were applied in study of the anti-/pro-oxidant properties of Zn(II) 5-CQA and 5-CQA. The antimicrobial activity of these compounds against Escherichia coli, Pseudomonas aeruginosa, Bacillus subtilis, Staphylococcus aureus, Salmonella enteritidis and Candida albicans was tested. An effect of Zn(II) chelation by chlorogenic acid on the anti-/pro-oxidant and antimicrobial activities of the ligand was discussed. Moreover, the mechanism of the antioxidant properties of Zn(II) 5-CQA and 5-CQA were studied on the basis of the theoretical energy descriptors and thermochemical parameters. Zn(II) chlorogenate showed better antioxidant activity than chlorogenic acid and commonly applied natural (L-ascorbic acid) and synthetic antioxidants (butylated hydroxyanisol (BHA) and butylated hydroxytoluene (BHT)). The pro-oxidant activity of Zn(II) 5-CQA was higher than the ligand and increased with the rise of the compound concentration The type of Zn(II) coordination by the chlorogenate ligand strongly affected the antioxidant activity of the complex. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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15 pages, 1698 KiB

Open AccessArticle

Comparison of Inflammatory Effects in THP-1 Monocytes and Macrophages after Exposure to Metal Ions

by Henrike Loeffler, Anika Jonitz-Heincke, Kirsten Peters, Brigitte Mueller-Hilke, Tomas Fiedler, Rainer Bader and Annett Klinder

Materials 2020, 13(5), 1150; https://doi.org/10.3390/ma13051150 - 05 Mar 2020

Cited by 10 | Viewed by 3553

Abstract

Monocytes and macrophages are the first barrier of the innate immune system, which interact with abrasion and corrosion products, leading to the release of proinflammatory mediators and free reactive molecules. The aim of this study was to understand inflammation-relevant changes in monocytes and macrophages after exposure to corrosion products. To do this, the THP-1 cell line was used to analyze the effects of metal ions simultaneously in monocytes and differentiated macrophages. Cells were stimulated with several concentrations of metal salts (CoCl₂, NiCl₂, CrCl₃× 6H₂O) to analyze viability, gene expression, protein release and ROS production. Untreated cells served as negative controls. While exposure to Cr(3+) did not influence cell viability in both cell types, the highest concentration (500 µM) of Co(2+) and Ni(2+) showed cytotoxic effects mirrored by significantly reduced metabolism, cell number and a concomitant increase of ROS. The release of IL-1β, IL-8, MCP-1 and M-CSF proteins was mainly affected in macrophages after metal ion exposure (100 µM), indicating a higher impact on pro-inflammatory activity. Our results prove that monocytes and macrophages react very sensitively to corrosion products. High concentrations of bivalent ions lead to cell death, while lower concentrations trigger the release of inflammatory mediators, mainly in macrophages. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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14 pages, 2887 KiB

Open AccessArticle

Spatial Heterogeneity of Cadmium Effects on Salvia sclarea Leaves Revealed by Chlorophyll Fluorescence Imaging Analysis and Laser Ablation Inductively Coupled Plasma Mass Spectrometry

by Michael Moustakas, Anetta Hanć, Anelia Dobrikova, Ilektra Sperdouli, Ioannis-Dimosthenis S. Adamakis and Emilia Apostolova

Materials 2019, 12(18), 2953; https://doi.org/10.3390/ma12182953 - 12 Sep 2019

Cited by 34 | Viewed by 3155

Abstract

In this study, for a first time (according to our knowledge), we couple the methodologies of chlorophyll fluorescence imaging analysis (CF-IA) and laser ablation inductively coupled plasma mass spectrometry (LA-ICP-MS), in order to investigate the effects of cadmium (Cd) accumulation on photosystem II (PSII) photochemistry. We used as plant material Salvia sclarea that grew hydroponically with or without (control) 100 μM Cd for five days. The spatial heterogeneity of a decreased effective quantum yield of electron transport (Φ_PSΙΙ) that was observed after exposure to Cd was linked to the spatial pattern of high Cd accumulation. However, the high increase of non-photochemical quenching (NPQ), at the leaf part with the high Cd accumulation, resulted in the decrease of the quantum yield of non-regulated energy loss (Φ_NO) even more than that of control leaves. Thus, S. sclarea leaves exposed to 100 μM Cd exhibited lower reactive oxygen species (ROS) production as singlet oxygen (¹O₂). In addition, the increased photoprotective heat dissipation (NPQ) in the whole leaf under Cd exposure was sufficient enough to retain the same fraction of open reaction centers (q_p) with control leaves. Our results demonstrated that CF-IA and LA-ICP-MS could be successfully combined to monitor heavy metal effects and plant tolerance mechanisms. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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17 pages, 1545 KiB

Open AccessArticle

Analysis of Cellular Activity and Induction of Inflammation in Response to Short-Term Exposure to Cobalt and Chromium Ions in Mature Human Osteoblasts

by Anika Jonitz-Heincke, Marie-Luise Sellin, Anika Seyfarth, Kirsten Peters, Brigitte Mueller-Hilke, Tomas Fiedler, Rainer Bader and Annett Klinder

Materials 2019, 12(17), 2771; https://doi.org/10.3390/ma12172771 - 28 Aug 2019

Cited by 22 | Viewed by 2617

Abstract

In aseptic loosening of endoprosthetic implants, metal particles, as well as their corrosion products, have been shown to elicit a biological response. Due to different metal alloy components, the response may vary depending on the nature of the released corrosion product. Our study aimed to compare the biological effects of different ions released from metal alloys. In order to mimic the corrosion products, different metal salts (CoCl₂, NiCl₂ and CrCl₃ × 6H₂O) were dissolved and allowed to equilibrate. Human osteoblasts were incubated with concentrations of 10 µM to 500 µM metal salt solutions under cell culture conditions, whereas untreated cells served as negative controls. Cells exposed to CoCr28Mo6 particles served as positive controls. The cell activity and expression of osteogenic differentiation and pro-osteolytic mediators were determined. Osteoblastic activity revealed concentration- and material-dependent influences. Collagen 1 synthesis was reduced after treatment with Co(2+) and Ni(2+). Additionally, exposure to these ions (500 µM) resulted in significantly reduced OPG protein synthesis, whereas RANKL as well as IL-6 and IL-8 secretion were increased. TLR4 mRNA was significantly induced by Co(2+) and CoCr28Mo6 particles. The results demonstrate the pro-osteolytic capacity of metal ions in osteoblasts. Compared to CoCr28Mo6 particles, the results indicated that metal ions intervene much earlier in inflammatory processes. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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17 pages, 9280 KiB

Open AccessFeature PaperArticle

Leaf Age-Dependent Effects of Foliar-Sprayed CuZn Nanoparticles on Photosynthetic Efficiency and ROS Generation in Arabidopsis thaliana

by Ilektra Sperdouli, Julietta Moustaka, Orestis Antonoglou, Ioannis-Dimosthenis S. Adamakis, Catherine Dendrinou-Samara and Michael Moustakas

Materials 2019, 12(15), 2498; https://doi.org/10.3390/ma12152498 - 06 Aug 2019

Cited by 29 | Viewed by 3482

Abstract

Young and mature leaves of Arabidopsis thaliana were exposed by foliar spray to 30 mg L⁻¹ of CuZn nanoparticles (NPs). The NPs were synthesized by a microwave-assisted polyol process and characterized by dynamic light scattering (DLS), X-ray diffraction (XRD), and transmission electron microscopy (TEM). CuZn NPs effects in Arabidopsis leaves were evaluated by chlorophyll fluorescence imaging analysis that revealed spatiotemporal heterogeneity of the quantum efficiency of PSII photochemistry (Φ_PSΙΙ) and the redox state of the plastoquinone (PQ) pool (q_p), measured 30 min, 90 min, 180 min, and 240 min after spraying. Photosystem II (PSII) function in young leaves was observed to be negatively influenced, especially 30 min after spraying, at which point increased H₂O₂ generation was correlated to the lower oxidized state of the PQ pool. Recovery of young leaves photosynthetic efficiency appeared only after 240 min of NPs spray when also the level of ROS accumulation was similar to control leaves. On the contrary, a beneficial effect on PSII function in mature leaves after 30 min of the CuZn NPs spray was observed, with increased Φ_PSΙΙ, an increased electron transport rate (ETR), decreased singlet oxygen (¹O₂) formation, and H₂O₂ production at the same level of control leaves.An explanation for this differential response is suggested. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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15 pages, 13844 KiB

Open AccessFeature PaperArticle

Zinc Uptake, Photosynthetic Efficiency and Oxidative Stress in the Seagrass Cymodocea nodosa Exposed to ZnO Nanoparticles

by Paraskevi Malea, Katerina Charitonidou, Ilektra Sperdouli, Zoi Mylona and Michael Moustakas

Materials 2019, 12(13), 2101; https://doi.org/10.3390/ma12132101 - 29 Jun 2019

Cited by 44 | Viewed by 3423

Abstract

We characterized zinc oxide nanoparticles (ZnO NPs) by dynamic light scattering (DLS) measurements, and transmission electron microscopy (TEM), while we evaluated photosystem II (PSII) responses, Zn uptake kinetics, and hydrogen peroxide (H₂O₂) accumulation, in C. nodosa exposed to 5 mg L⁻¹ and 10 mg L⁻¹ ZnO NPs for 4 h, 12 h, 24 h, 48 h and 72 h. Four h after exposure to 10 mg L⁻¹ ZnO NPs, we noticed a disturbance of PSII functioning that became more severe after 12 h. However, after a 24 h exposure to 10 mg L⁻¹ ZnO NPs, we observed a hormetic response, with both time and dose as the basal stress levels needed for induction of the adaptive response. This was achieved through the reduced plastoquinone (PQ) pool, at a 12 h exposure, which mediated the generation of chloroplastic H₂O₂; acting as a fast acclimation signaling molecule. Nevertheless, longer treatment (48 h and 72 h) resulted in decreasing the photoprotective mechanism to dissipate excess energy as heat (NPQ) and increasing the quantum yield of non-regulated energy loss (Φ_NO). This increased the formation of singlet oxygen (¹O₂), and decreased the fraction of open reaction centers, mostly after a 72-h exposure at 10 mg L⁻¹ ZnO NPs due to increased Zn uptake compared to 5 mg L⁻¹. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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13 pages, 4795 KiB

Open AccessArticle

High Efficiency Mercury Sorption by Dead Biomass of Lysinibacillus sphaericus—New Insights into the Treatment of Contaminated Water

by J. David Vega-Páez, Ricardo E. Rivas and Jenny Dussán-Garzón

Materials 2019, 12(8), 1296; https://doi.org/10.3390/ma12081296 - 19 Apr 2019

Cited by 13 | Viewed by 4089

Abstract

Mercury (Hg) is a toxic metal frequently used in illegal and artisanal extraction of gold and silver which makes it a cause of environmental poisoning. Since biosorption of other heavy metals has been reported for several Lysinibacillus sphaericus strains, this study investigates Hg removal. Three L. sphaericus strains previously reported as metal tolerant (CBAM5, Ot4b31, and III(3)7) were assessed with mercury chloride (HgCl₂). Bacteria were characterized by scanning electron microscopy coupled with energy dispersive spectroscopy (EDS-SEM). Sorption was evaluated in live and dead bacterial biomass by free and immobilized cells assays. Hg quantification was achieved through spectrophotometry at 508 nm by reaction of Hg supernatants with dithizone prepared in Triton X-114 and by graphite furnace atomic absorption spectroscopy (GF-AAS). Bacteria grew up to 60 ppm of HgCl₂. Non-immobilized dead cell mixture of strains III(3)7 and Ot4b31 showed a maximum sorption efficiency of 28.4 µg Hg/mg bacteria during the first 5 min of contact with HgCl₂, removing over 95% of Hg. This process was escalated in a semi-batch bubbling fluidized bed reactor (BFB) using rice husk as the immobilization matrix leading to a similar level of efficiency. EDS-SEM analysis showed that all strains can adsorb Hg as particles of nanometric scale that can be related to the presence of S-layer metal binding proteins as shown in previous studies. These results suggest that L. sphaericus could be used as a novel biological method of mercury removal from polluted wastewater. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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14 pages, 3417 KiB

Open AccessArticle

Chlorophyll Fluorescence Imaging Analysis for Elucidating the Mechanism of Photosystem II Acclimation to Cadmium Exposure in the Hyperaccumulating Plant Noccaea caerulescens

by Gülriz Bayçu, Julietta Moustaka, Nurbir Gevrek and Michael Moustakas

Materials 2018, 11(12), 2580; https://doi.org/10.3390/ma11122580 - 18 Dec 2018

Cited by 57 | Viewed by 4648

Abstract

We provide new data on the mechanism of Noccaea caerulescens acclimation to Cd exposure by elucidating the process of photosystem II (PSII) acclimation by chlorophyll fluorescence imaging analysis. Seeds from the metallophyte N. caerulescens were grown in hydroponic culture for 12 weeks before exposure to 40 and 120 μM Cd for 3 and 4 days. At the beginning of exposure to 40 μM Cd, we observed a spatial leaf heterogeneity of decreased PSII photochemistry, that later recovered completely. This acclimation was achieved possibly through the reduced plastoquinone (PQ) pool signaling. Exposure to 120 μM Cd under the growth light did not affect PSII photochemistry, while under high light due to a photoprotective mechanism (regulated heat dissipation for protection) that down-regulated PSII quantum yield, the quantum yield of non-regulated energy loss in PSII (Φ_NO) decreased even more than control values. Thus, N. caerulescens plants exposed to 120 μM Cd for 4 days exhibited lower reactive oxygen species (ROS) production as singlet oxygen (¹O₂). The response of N. caerulescens to Cd exposure fits the ‘Threshold for Tolerance Model’, with a lag time of 4 d and a threshold concentration of 40 μM Cd required for the induction of the acclimation mechanism. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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13 pages, 1626 KiB

Open AccessArticle

Photosystem II Is More Sensitive than Photosystem I to Al³⁺ Induced Phytotoxicity

by Julietta Moustaka, Georgia Ouzounidou, Ilektra Sperdouli and Michael Moustakas

Materials 2018, 11(9), 1772; https://doi.org/10.3390/ma11091772 - 19 Sep 2018

Cited by 41 | Viewed by 3657

Abstract

Aluminium (Al) the most abundant metal in the earth’s crust is toxic in acid soils (pH < 5.5) mainly in the ionic form of Al³⁺ species. The ability of crops to overcome Al toxicity varies among crop species and cultivars. Here, we report for a first time the simultaneous responses of photosystem II (PSII) and photosystem I (PSI) to Al³⁺ phytotoxicity. The responses of PSII and PSI in the durum wheat (Triticum turgidum L. cv. ‘Appulo E’) and the triticale (X Triticosecale Witmark cv. ‘Dada’) were evaluated by chlorophyll fluorescence quenching analysis and reflection spectroscopy respectively, under control (−Al, pH 6.5) and 148 μM Al (+Al, pH 4.5) conditions. During control growth conditions the high activity of PSII in ‘Appulo E’ led to a rather higher electron flow to PSI, which induced a higher PSI excitation pressure in ‘Appulo E’ than in ‘Dada’ that presented a lower PSII activity. However, under 148 μM Al the triticale ‘Dada’ presented a lower PSII and PSI excitation pressure than ‘Appulo E’. In conclusion, both photosystems of ‘Dada’ displayed a superior performance than ‘Appulo E’ under Al exposure, while in both cultivars PSII was more affected than PSI from Al³⁺ phytotoxicity. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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Review

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24 pages, 3803 KiB

Open AccessReview

Fueling a Hot Debate on the Application of TiO₂ Nanoparticles in Sunscreen

by Shweta Sharma, Rohit K. Sharma, Kavita Gaur, José F. Cátala Torres, Sergio A. Loza-Rosas, Anamaris Torres, Manoj Saxena, Mara Julin and Arthur D. Tinoco

Materials 2019, 12(14), 2317; https://doi.org/10.3390/ma12142317 - 20 Jul 2019

Cited by 40 | Viewed by 8630

Abstract

Titanium is one of the most abundant elements in the earth’s crust and while there are many examples of its bioactive properties and use by living organisms, there are few studies that have probed its biochemical reactivity in physiological environments. In the cosmetic industry, TiO₂ nanoparticles are widely used. They are often incorporated in sunscreens as inorganic physical sun blockers, taking advantage of their semiconducting property, which facilitates absorbing ultraviolet (UV) radiation. Sunscreens are formulated to protect human skin from the redox activity of the TiO₂ nanoparticles (NPs) and are mass-marketed as safe for people and the environment. By closely examining the biological use of TiO₂ and the influence of biomolecules on its stability and solubility, we reassess the reactivity of the material in the presence and absence of UV energy. We also consider the alarming impact that TiO₂ NP seepage into bodies of water can cause to the environment and aquatic life, and the effect that it can have on human skin and health, in general, especially if it penetrates into the human body and the bloodstream. Full article

(This article belongs to the Special Issue The Role of Metal Ions in Biology, Biochemistry and Medicine)

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