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Metallomics: Recent Advances in Analytical and Biological Sciences of Semimetals/Metalloids

A special issue of International Journal of Molecular Sciences (ISSN 1422-0067). This special issue belongs to the section "Bioinorganic Chemistry".

Deadline for manuscript submissions: closed (31 December 2017) | Viewed by 55821

Special Issue Editors

Laboratory of Toxicology and Environmental Health, Graduate School of Pharmaceutical Sciences, Chiba University, Chuo, Chiba 260-8675, Japan
Interests: selenium; metallomics; speciation; ICP-MS; toxicology
Special Issues, Collections and Topics in MDPI journals
Geochemical Research Center, the University of Tokyo, Bunkyo, Tokyo 113-8654, Japan
Interests: isotope geochemistry; imaging; ICP-MS instrumentation; analytical chemistry; metallomics
Special Issues, Collections and Topics in MDPI journals

Special Issue Information

Dear Colleagues,

This Special Issue “Metallomics: Recent Advances in Analytical and Biological Sciences of Semimetals/Metalloids” will cover the very basic to the latest applications, together with up-to-date review articles, in the field of Metallomics, particularly featuring analytical techniques and biological, physiological and toxicological significance of semimetals/metalloids. Technical papers, critical reviews and commentaries are all welcome.

A variety of noble metals or transition metals are increasingly used in many industries, resulting in their invasion of all aspects of our lives. Semimetals/metalloids are frequently used around us because of their unique physico-chemical properties. However, their biological, physiological, and toxicological impacts are not yet fully understood. For instance, although arsenic is well known historically as a toxic substance, the molecular mechanisms underlying arsenic toxicity are still unclear. Selenium acts as an essential element for animals, in spite of its higher levels of toxicity than arsenic.  The metabolic pathway of selenium is also a puzzles. Tellurium, antimony, tin, germanium, indium and other semimetals/metalloids can also have unique toxic and physiological effects. Further, the recent developments in analytical techniques for monitoring these semimetals/metalloids seems to be also attractive topic. We have reached the conclusion that this themed issue on "Metallomics" is timely to focus on the biological effect of semimetals/metalloids.

Prof. Yasumitsu Ogra
Prof. Takafumi Hirata
Guest Editors

Manuscript Submission Information

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Keywords

  • metalloid/semimetal
  • speciation
  • imaging
  • mass spectrometry
  • laser ablation
  • matrix assisted laser desorption/ionization
  • metabolome
  • environmental sciences
  • molecular biology
  • toxicology

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Published Papers (9 papers)

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Research

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20 pages, 2197 KiB  
Article
Characterization of a Novel Porin-Like Protein, ExtI, from Geobacter sulfurreducens and Its Implication in the Reduction of Selenite and Tellurite
by Mst. Ishrat Jahan, Ryuta Tobe and Hisaaki Mihara
Int. J. Mol. Sci. 2018, 19(3), 809; https://doi.org/10.3390/ijms19030809 - 11 Mar 2018
Cited by 12 | Viewed by 6413
Abstract
The extI gene in Geobacter sulfurreducens encodes a putative outer membrane channel porin, which resides within a cluster of extHIJKLMNOPQS genes. This cluster is highly conserved across the Geobacteraceae and includes multiple putative c-type cytochromes. In silico analyses of the ExtI sequence, [...] Read more.
The extI gene in Geobacter sulfurreducens encodes a putative outer membrane channel porin, which resides within a cluster of extHIJKLMNOPQS genes. This cluster is highly conserved across the Geobacteraceae and includes multiple putative c-type cytochromes. In silico analyses of the ExtI sequence, together with Western blot analysis and proteinase protection assays, showed that it is an outer membrane protein. The expression level of ExtI did not respond to changes in osmolality and phosphate starvation. An extI-deficient mutant did not show any significant impact on fumarate or Fe(III) citrate reduction or sensitivity to β-lactam antibiotics, as compared with those of the wild-type strain. However, extI deficiency resulted in a decreased ability to reduce selenite and tellurite. Heme staining analysis revealed that extI deficiency affects certain heme-containing proteins in the outer and inner membranes, which may cause a decrease in the ability to reduce selenite and tellurite. Based on these observations, we discuss possible roles for ExtI in selenite and tellurite reduction in G. sulfurreducens. Full article
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14 pages, 3203 KiB  
Article
Determination of Proteinaceous Selenocysteine in Selenized Yeast
by Katarzyna Bierla, Ryszard Lobinski and Joanna Szpunar
Int. J. Mol. Sci. 2018, 19(2), 543; https://doi.org/10.3390/ijms19020543 - 11 Feb 2018
Cited by 16 | Viewed by 3737
Abstract
A method for the quantitation of proteinaceous selenocysteine (SeCys) in Se-rich yeast was developed. The method is based on the reduction of the Se-Se and S-Se bridges with dithiotretiol, derivatization with iodoacetamide (carbamidomethylation), followed by HPLC-ICP MS. The chromatographic conditions were optimized for [...] Read more.
A method for the quantitation of proteinaceous selenocysteine (SeCys) in Se-rich yeast was developed. The method is based on the reduction of the Se-Se and S-Se bridges with dithiotretiol, derivatization with iodoacetamide (carbamidomethylation), followed by HPLC-ICP MS. The chromatographic conditions were optimized for the total recovery of the proteinaceous selenocysteine, the minimum number of peaks in the chromatogram (reduction of derivatization products of other Se-species present) and the baseline separation. A typical chromatogram of a proteolytic digest of selenized yeast protein consisted of up to five peaks (including SeMet, carbamidomethylated (CAM)-SeCys, and Se(CAM)2) identified by retention time matching with available standards and electrospray MS. Inorganic selenium non-specifically attached to proteins and selenomethionine could be quantified (in the form of Se(CAM)2) along with SeCys. Selenocysteine, selenomethionine, inorganic selenium, and the water soluble-metabolite fraction accounted for the totality of selenium species in Se-rich yeast. Full article
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2766 KiB  
Article
Anti-Diabetic Effect of Organo-Chalcogen (Sulfur and Selenium) Zinc Complexes with Hydroxy-Pyrone Derivatives on Leptin-Deficient Type 2 Diabetes Model ob/ob Mice
by Takayuki Nishiguchi, Yutaka Yoshikawa and Hiroyuki Yasui
Int. J. Mol. Sci. 2017, 18(12), 2647; https://doi.org/10.3390/ijms18122647 - 07 Dec 2017
Cited by 15 | Viewed by 5388
Abstract
Since the discovery of the anti-diabetic effects of zinc (Zn) complex, we synthesized several Zn complexes and evaluated their effects using the KKAy type 2 diabetes mouse model. Recently, we demonstrated that organo-chalcogen (sulfur and selenium) Zn complexes elicit strong anti-diabetic effects. [...] Read more.
Since the discovery of the anti-diabetic effects of zinc (Zn) complex, we synthesized several Zn complexes and evaluated their effects using the KKAy type 2 diabetes mouse model. Recently, we demonstrated that organo-chalcogen (sulfur and selenium) Zn complexes elicit strong anti-diabetic effects. In this study, we treated leptin-deficient ob/ob mice with organo-chalcogen Zn complexes, and evaluated the resulting anti-diabetic effects in a mouse model of diabetes arising from pathogenic mechanisms different from those in KKAy mice. C57BL/6J ob/ob mice orally received either bis(3-hydroxy-2-methyl-4(H)-pyran-4-thiono)Zn, [Zn(hmpt)2] or bis(3-hydroxy-2-methyl-4(H)-pyran-4-seleno)Zn, [Zn(hmps)2], daily for 28 days. Both Zn complexes elicited potent blood glucose-lowering effects and improved HbA1c values. Moreover, glucose intolerance improved as evidenced by the oral glucose tolerance test, and fasting plasma insulin levels decreased in both types of Zn complex-treated mice. Zn concentrations in the liver and pancreas of [Zn(hmpt)2]-treated mice and in the pancreas of [Zn(hmps)2]-treated mice were increased, respectively. The results suggest that the present Zn complexes mainly exerted an anti-diabetic effect in the liver or pancreas. This study is the first to demonstrate that potent Zn complexes elicit anti-diabetic effects in not only KKAy but also ob/ob mice via a normalizing effect on insulin secretion and fasting blood glucose levels. Full article
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2821 KiB  
Article
Low-Concentration Tributyltin Decreases GluR2 Expression via Nuclear Respiratory Factor-1 Inhibition
by Keishi Ishida, Kaori Aoki, Tomoko Takishita, Masatsugu Miyara, Shuichiro Sakamoto, Seigo Sanoh, Tomoki Kimura, Yasunari Kanda, Shigeru Ohta and Yaichiro Kotake
Int. J. Mol. Sci. 2017, 18(8), 1754; https://doi.org/10.3390/ijms18081754 - 11 Aug 2017
Cited by 7 | Viewed by 4358
Abstract
Tributyltin (TBT), which has been widely used as an antifouling agent in paints, is a common environmental pollutant. Although the toxicity of high-dose TBT has been extensively reported, the effects of low concentrations of TBT are relatively less well studied. We have previously [...] Read more.
Tributyltin (TBT), which has been widely used as an antifouling agent in paints, is a common environmental pollutant. Although the toxicity of high-dose TBT has been extensively reported, the effects of low concentrations of TBT are relatively less well studied. We have previously reported that low-concentration TBT decreases α-amino-3-hydroxy-5-methylisoxazole-4-propionic acid (AMPA)-type glutamate receptor subunit 2 (GluR2) expression in cortical neurons and enhances neuronal vulnerability to glutamate. However, the mechanism of this TBT-induced GluR2 decrease remains unknown. Therefore, we examined the effects of TBT on the activity of transcription factors that control GluR2 expression. Exposure of primary cortical neurons to 20 nM TBT for 3 h to 9 days resulted in a decrease in GluR2 mRNA expression. Moreover, TBT inhibited the DNA binding activity of nuclear respiratory factor-1 (NRF-1), a transcription factor that positively regulates the GluR2. This result indicates that TBT inhibits the activity of NRF-1 and subsequently decreases GluR2 expression. In addition, 20 nM TBT decreased the expression of genes such as cytochrome c, cytochrome c oxidase (COX) 4, and COX 6c, which are downstream of NRF-1. Our results suggest that NRF-1 inhibition is an important molecular action of the neurotoxicity induced by low-concentration TBT. Full article
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3896 KiB  
Article
Exploring the Behavior and Metabolic Transformations of SeNPs in Exposed Lactic Acid Bacteria. Effect of Nanoparticles Coating Agent
by Maria Palomo-Siguero and Yolanda Madrid
Int. J. Mol. Sci. 2017, 18(8), 1712; https://doi.org/10.3390/ijms18081712 - 05 Aug 2017
Cited by 18 | Viewed by 4806
Abstract
The behavior and transformation of selenium nanoparticles (SeNPs) in living systems such as microorganisms is largely unknown. To address this knowledge gap, we examined the effect of three types of SeNP suspensions toward Lactobacillus delbrueckii subsp. bulgaricus LB-12 using a variety of techniques. [...] Read more.
The behavior and transformation of selenium nanoparticles (SeNPs) in living systems such as microorganisms is largely unknown. To address this knowledge gap, we examined the effect of three types of SeNP suspensions toward Lactobacillus delbrueckii subsp. bulgaricus LB-12 using a variety of techniques. SeNPs were synthesized using three types of coating agents (chitosan (CS-SeNPs), hydroxyethyl cellulose (HEC-SeNPs) and a non-ionic surfactant, surfynol (ethoxylated-SeNPs)). Morphologies of SeNPs were all spherical. Transmission electron microscopy (TEM) was used to locate SeNPs in the bacteria. High performance liquid chromatography (HPLC) on line coupled to inductively coupled plasma mass spectrometry (ICP-MS) was applied to evaluate SeNP transformation by bacteria. Finally, flow cytometry employing the live/dead test and optical density measurements at 600 nm (OD600) were used for evaluating the percentages of bacteria viability when supplementing with SeNPs. Negligible damage was detected by flow cytometry when bacteria were exposed to HEC-SeNPs or CS-SeNPs at a level of 10 μg Se mL−1. In contrast, ethoxylated-SeNPs were found to be the most harmful nanoparticles toward bacteria. CS-SeNPs passed through the membrane without causing damage. Once inside, SeNPs were metabolically transformed to organic selenium compounds. Results evidenced the importance of capping agents when establishing the true behavior of NPs. Full article
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1032 KiB  
Article
Bioavailability Comparison of Nine Bioselenocompounds In Vitro and In Vivo
by Kazuaki Takahashi, Noriyuki Suzuki and Yasumitsu Ogra
Int. J. Mol. Sci. 2017, 18(3), 506; https://doi.org/10.3390/ijms18030506 - 26 Feb 2017
Cited by 63 | Viewed by 5667
Abstract
Selenium (Se) shows biologically ambivalent characteristics in animals. It is an essential element but becomes severely toxic when the amount ingested exceeds the adequate intake level. Its biological, nutritional, and toxicological effects are strongly dependent on its chemical form. In this study, we [...] Read more.
Selenium (Se) shows biologically ambivalent characteristics in animals. It is an essential element but becomes severely toxic when the amount ingested exceeds the adequate intake level. Its biological, nutritional, and toxicological effects are strongly dependent on its chemical form. In this study, we evaluated the toxicity and bioavailability of nine naturally occurring Se compounds, or the so-called bioselenocompounds, in vivo and in vitro. Selenite and selenocystine showed higher toxicity than the other bioselenocompounds in vitro. In an in vitro membrane permeability study using Caco-2 cells, selenomethionine and Se-methylselenocysteine were more efficiently transported than the other bioselenocompounds. The effect of bioselenocompounds on nutritional availability was quantitatively determined from the recovery of serum selenoproteins in Se-deficient rats by speciation analysis. In contrast to the in vitro study, there were no significant differences in the assimilation of Se into serum selenoproteins among the bioselenocompounds, including selenoamino acids, selenosugar, and inorganic Se species, such as selenite, selenate, and selenocyanate, except trimethylselenonium ion. These results indicate that animals can equally assimilate both inorganic and organic naturally occurring selenocompounds except trimethylselenonium ion, which is the urinary metabolite of excess Se. We confirmed that the bioselenocompounds except trimethylselenonium ion had equivalent nutritional availabilities. Full article
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1668 KiB  
Article
Induction of Syndecan-4 by Organic–Inorganic Hybrid Molecules with a 1,10-Phenanthroline Structure in Cultured Vascular Endothelial Cells
by Takato Hara, Takayuki Kojima, Hiroka Matsuzaki, Takehiro Nakamura, Eiko Yoshida, Yasuyuki Fujiwara, Chika Yamamoto, Shinichi Saito and Toshiyuki Kaji
Int. J. Mol. Sci. 2017, 18(2), 352; https://doi.org/10.3390/ijms18020352 - 08 Feb 2017
Cited by 17 | Viewed by 5192
Abstract
Organic–inorganic hybrid molecules constitute analytical tools used in biological systems. Vascular endothelial cells synthesize and secrete proteoglycans, which are macromolecules consisting of a core protein and glycosaminoglycan side chains. Although the expression of endothelial proteoglycans is regulated by several cytokines/growth factors, there may [...] Read more.
Organic–inorganic hybrid molecules constitute analytical tools used in biological systems. Vascular endothelial cells synthesize and secrete proteoglycans, which are macromolecules consisting of a core protein and glycosaminoglycan side chains. Although the expression of endothelial proteoglycans is regulated by several cytokines/growth factors, there may be alternative pathways for proteoglycan synthesis aside from downstream pathways activated by these cytokines/growth factors. Here, we investigated organic–inorganic hybrid molecules to determine a variant capable of analyzing the expression of syndecan-4, a transmembrane heparan-sulfate proteoglycan, and identified 1,10-phenanthroline (o-Phen) with or without zinc (Zn-Phen) or rhodium (Rh-Phen). Bovine aortic endothelial cells in culture were treated with these compounds, and the expression of syndecan-4 mRNA and core proteins was determined by real-time reverse transcription polymerase chain reaction and Western blot analysis, respectively. Our findings indicated that o-Phen and Zn-Phen specifically and strongly induced syndecan-4 expression in cultured vascular endothelial cells through activation of the hypoxia-inducible factor-1α/β pathway via inhibition of prolyl hydroxylase-domain-containing protein 2. These results demonstrated an alternative pathway involved in mediating induction of endothelial syndecan-4 expression and revealed organic–inorganic hybrid molecules as effective tools for analyzing biological systems. Full article
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3879 KiB  
Article
Phenylarsine Oxide Can Induce the Arsenite-Resistance Mutant PML Protein Solubility Changes
by Yu Han Jiang, Ye Jia Chen, Chao Wang, Yong Fei Lan, Chang Yang, Qian Qian Wang, Liaqat Hussain, Yasen Maimaitiying, Khairul Islam and Hua Naranmandura
Int. J. Mol. Sci. 2017, 18(2), 247; https://doi.org/10.3390/ijms18020247 - 25 Jan 2017
Cited by 7 | Viewed by 4894
Abstract
Arsenic trioxide (As2O3) has recently become one of the most effective drugs for treatment of patient with acute promyelocytic leukemia (APL), and its molecular mechanism has also been largely investigated. However, it has been reported that As2O [...] Read more.
Arsenic trioxide (As2O3) has recently become one of the most effective drugs for treatment of patient with acute promyelocytic leukemia (APL), and its molecular mechanism has also been largely investigated. However, it has been reported that As2O3 resistant patients are frequently found in relapsed APL after consolidation therapy, which is due to the point mutations in B-box type 2 motifs of promyelocytic leukemia (PML) gene. In the present study, we for the first time establish whether organic arsenic species phenylarsine oxide (PAO) could induce the mutant PML-IV (A216V) protein solubility changes and degradation. Here, three different PML protein variants (i.e., PML-IV, PML-V and mutant PML-A216V) were overexpressed in HEK293T cells and then exposed to PAO in time- and dose-dependent manners. Interestingly, PAO is found to have potential effect on induction of mutant PML-IV (A216V) protein solubility changes and degradation, but no appreciable effects were found following exposure to high concentrations of iAsIII, dimethylarsinous acid (DMAIII) and adriamycin (doxorubicin), even though they cause cell death. Our current data strongly indicate that PAO has good effects on the mutant PML protein solubility changes, and it may be helpful for improving the therapeutic strategies for arsenic-resistant APL treatments in the near future. Full article
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Review

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1206 KiB  
Review
A Summary of New Findings on the Biological Effects of Selenium in Selected Animal Species—A Critical Review
by Bozena Hosnedlova, Marta Kepinska, Sylvie Skalickova, Carlos Fernandez, Branislav Ruttkay-Nedecky, Thembinkosi Donald Malevu, Jiri Sochor, Mojmir Baron, Magdalena Melcova, Jarmila Zidkova and Rene Kizek
Int. J. Mol. Sci. 2017, 18(10), 2209; https://doi.org/10.3390/ijms18102209 - 21 Oct 2017
Cited by 150 | Viewed by 14126
Abstract
Selenium is an essential trace element important for many physiological processes, especially for the functions of immune and reproductive systems, metabolism of thyroid hormones, as well as antioxidant defense. Selenium deficiency is usually manifested by an increased incidence of retention of placenta, metritis, [...] Read more.
Selenium is an essential trace element important for many physiological processes, especially for the functions of immune and reproductive systems, metabolism of thyroid hormones, as well as antioxidant defense. Selenium deficiency is usually manifested by an increased incidence of retention of placenta, metritis, mastitis, aborts, lowering fertility and increased susceptibility to infections. In calves, lambs and kids, the selenium deficiency demonstrates by WMD (white muscle disease), in foals and donkey foals, it is associated with incidence of WMD and yellow fat disease, and in pigs it causes VESD (vitamin E/selenium deficiency) syndrome. The prevention of these health disorders can be achieved by an adequate selenium supplementation to the diet. The review summarizes the survey of knowledge on selenium, its biological significance in the organism, the impact of its deficiency in mammalian livestock (comparison of ruminants vs. non-ruminants, herbivore vs. omnivore) and possibilities of its peroral administration. The databases employed were as follows: Web of Science, PubMed, MEDLINE and Google Scholar. Full article
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