Next Issue
Volume 9, July
Previous Issue
Volume 9, May
 
 
Search for Articles:
Title / Keyword
Author / Affiliation / Email
Journal
Article Type
 
 
Advanced Search
 
Section
Special Issue
Volume
Issue
Number
Page
 
4.0
2.9
Journals
Inorganics
Volume 9
Issue 6
share announcement

Inorganics, Volume 9, Issue 6 (June 2021) – 10 articles

Cover Story (view full-size image): Solution-based synthesis routes to cerium dioxide materials, where one or more elements are included in place of a proportion of the cerium, yield unusual compositions with crystal morphology on the nanoscale. Chemical elements from all parts of the periodic table are considered, from transition metals to main group elements and the rare earths, including isovalent and aliovalent cations. This provides functional materials with applications in contemporary applications, such as heterogeneous catalysis, electrodes for solid oxide fuel cells, photocatalysis, luminescence and biomedicine. We identify the challenges that are still remaining, including detailed structural characterisation, the understanding of crystallisation mechanisms and the scale-up of synthesis. View this paper.
  • Issues are regarded as officially published after their release is announced to the table of contents alert mailing list.
  • You may sign up for e-mail alerts to receive table of contents of newly released issues.
  • PDF is the official format for papers published in both, html and pdf forms. To view the papers in pdf format, click on the "PDF Full-text" link, and use the free Adobe Reader to open them.
Order results
Result details
Section
Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:
13 pages, 5500 KiB  
Article
Binding Properties of a Dinuclear Zinc(II) Salen-Type Molecular Tweezer with a Flexible Spacer in the Formation of Lewis Acid-Base Adducts with Diamines
by Gabriella Munzi, Giuseppe Consiglio, Salvatore Failla and Santo Di Bella
Inorganics 2021, 9(6), 49; https://doi.org/10.3390/inorganics9060049 - 16 Jun 2021
Cited by 5 | Viewed by 2438
Abstract
In this paper we report the binding properties, by combined 1H NMR, optical absorption, and fluorescence studies, of a molecular tweezer composed of two Zn(salen)-type Schiff-base units connected by a flexible spacer, towards a series of ditopic diamines having a strong Lewis [...] Read more.
In this paper we report the binding properties, by combined 1H NMR, optical absorption, and fluorescence studies, of a molecular tweezer composed of two Zn(salen)-type Schiff-base units connected by a flexible spacer, towards a series of ditopic diamines having a strong Lewis basicity, with different chain length and rigidity. Except for the 1,2-diaminoethane, in all other cases the formation of stable 1:1 Lewis acid-base adducts with large binding constants is demonstrated. For α,ω-aliphatic diamines, binding constants progressively increase with the increasing length of the alkyl chain, thanks to the flexible nature of the spacer and the parallel decreased conformational strain upon binding. Stable adducts are also found even for short diamines with rigid molecular structures. Given their preorganized structure, these latter species are not subjected to loss of degrees of freedom. The binding characteristics of the tweezer have been exploited for the colorimetric and fluorometric selective and sensitive detection of piperazine. Full article
(This article belongs to the Section Coordination Chemistry)
►▼ Show Figures

Graphical abstract

25 pages, 1516 KiB  
Review
Insights into the Antimicrobial Potential of Dithiocarbamate Anions and Metal-Based Species
by Chien Ing Yeo, Edward R. T. Tiekink and Jactty Chew
Inorganics 2021, 9(6), 48; https://doi.org/10.3390/inorganics9060048 - 14 Jun 2021
Cited by 16 | Viewed by 4126
Abstract
Bacterial infection remains a worldwide problem that requires urgent addressing. Overuse and poor disposal of antibacterial agents abet the emergence of bacterial resistance mechanisms. There is a clear need for new approaches for the development of antibacterial therapeutics. Herein, the antibacterial potential of [...] Read more.
Bacterial infection remains a worldwide problem that requires urgent addressing. Overuse and poor disposal of antibacterial agents abet the emergence of bacterial resistance mechanisms. There is a clear need for new approaches for the development of antibacterial therapeutics. Herein, the antibacterial potential of molecules based on dithiocarbamate anions, of general formula R(R’)NCS2(−), and metal salts of transition metals and main group elements, is summarized. Preclinical studies show a broad range of antibacterial potential, and these investigations are supported by appraisals of possible biological targets and mechanisms of action to guide chemical syntheses. This bibliographic review of the literature points to the exciting potential of dithiocarbamate-based therapeutics in the crucial battle against bacteria. Additionally, included in this overview, for the sake of completeness, is mention of the far fewer studies on the antifungal potential of dithiocarbamates and even less work conducted on antiparasitic behavior. Full article
(This article belongs to the Special Issue Metal Dithiocarbamate Complexes: Versatile Ligands in Coordination Chemistry with Applications in Medicine, Materials Science, and Beyond)
►▼ Show Figures

Graphical abstract

15 pages, 1684 KiB  
Article
DFT Investigation of the Molecular Properties of the Dimethylglyoximato Complexes [M(Hdmg)2] (M = Ni, Pd, Pt)
by Maryam Niazi and Axel Klein
Inorganics 2021, 9(6), 47; https://doi.org/10.3390/inorganics9060047 - 07 Jun 2021
Cited by 7 | Viewed by 3759
Abstract
Important applications of the NiII, PdII and PtII complexes [M(Hdmg)2] (H2dmg = dimethylglyoxime) stem from their metal...metal stacked virtually insoluble aggregates. Given the virtual insolubility of the materials, we postulated that the rare [...] Read more.
Important applications of the NiII, PdII and PtII complexes [M(Hdmg)2] (H2dmg = dimethylglyoxime) stem from their metal...metal stacked virtually insoluble aggregates. Given the virtual insolubility of the materials, we postulated that the rare reports on dissolved species in solution do not represent monomolecular species but oligomers. We thus studied the structural and spectral properties of the monomolecular entities of these compounds using density functional theory (DFT) and time-dependent DFT computations in dimethyl sulfoxide (DMSO) as a solvent. The molecular geometries, IR and UV-vis spectra, and frontier orbitals properties were computed using LANL2DZ ecp and def2TZVP as basis sets and M06-2X as the functional. The results are compared with the available experimental and other calculated data. The optimised molecular geometries proved the asymmetric character of the two formed O–H…O bonds which connect the two Hdmg‒ ligands in the completely planar molecules. Calculated UV-vis spectra revealed the presence of three absorptions in the range 180 to 350 nm that are red-shifted along the series Ni–Pd–Pt. They were assigned to essentially ligand-centred π−π* transitions in part with metal(d) to ligand(π*) charge transfer (MLCT) contributions. The notorious d‒p transitions dominating the colour and electronics of the compounds in the solid-state and oligomeric stacks are negligible in our monomolecular models strongly supporting the idea that the previously reported spectroscopic observations or biological effects in solutions are not due to monomolecular complexes but rather to oligomeric dissolved species. Full article
(This article belongs to the Section Coordination Chemistry)
►▼ Show Figures

Graphical abstract

15 pages, 2044 KiB  
Review
Strike a Balance: Between Metals and Non-Metals, Metalloids as a Source of Anti-Infective Agents
by Tiziano Marzo and Diego La Mendola
Inorganics 2021, 9(6), 46; https://doi.org/10.3390/inorganics9060046 - 04 Jun 2021
Cited by 12 | Viewed by 3670
Abstract
Most of the commercially available anti-infective agents are organic molecules. In fact, though, during the pioneering times of modern medicine, at the beginning of the 20th century, several inorganic compounds of transition metals were used for medicinal application, to date, only a small [...] Read more.
Most of the commercially available anti-infective agents are organic molecules. In fact, though, during the pioneering times of modern medicine, at the beginning of the 20th century, several inorganic compounds of transition metals were used for medicinal application, to date, only a small number of inorganic drugs are used in clinical practice. Beyond the transition metals, metalloids—or semimetals—offer a rich chemistry in between that of metallic and non-metallic elements, and accordingly, peculiar features for their exploitation in medicinal chemistry. A few important examples of metalloid-based drugs currently used for the treatment of various diseases do exist. However, the use of this group of elements could be further expanded on the basis of their current applications and the clinical trials they entered. Considering that metalloids offer the opportunity to expand the “chemical-space” for developing novel anti-infective drugs and protocols, in this paper, we briefly recapitulate and discuss the current applications of B-, Si-, As-, Sb- and Te-based anti-infective drugs. Full article
(This article belongs to the Special Issue Metal-Based Antimicrobials)
►▼ Show Figures

Figure 1

25 pages, 7383 KiB  
Review
Volumetrics of Hydrogen Storage by Physical Adsorption
by Sai Smruti Samantaray, Seth T. Putnam and Nicholas P. Stadie
Inorganics 2021, 9(6), 45; https://doi.org/10.3390/inorganics9060045 - 04 Jun 2021
Cited by 19 | Viewed by 6159
Abstract
Physical adsorption remains a promising method for achieving fast, reversible hydrogen storage at both ambient and cryogenic conditions. Research in this area has recently shifted to focus primarily on the volumetric (H2 stored/delivered per volume) gains achieved within an adsorptive storage system [...] Read more.
Physical adsorption remains a promising method for achieving fast, reversible hydrogen storage at both ambient and cryogenic conditions. Research in this area has recently shifted to focus primarily on the volumetric (H2 stored/delivered per volume) gains achieved within an adsorptive storage system over that of pure H2 compression; however, the methodology for estimating a volumetric stored or delivered amount requires several assumptions related to the ultimate packing of the adsorbent material into an actual storage system volume. In this work, we critically review the different assumptions commonly employed, and thereby categorize and compare the volumetric storage and delivery across numerous different porous materials including benchmark metal-organic frameworks, porous carbons, and zeolites. In several cases, there is a significant gain in both storage and delivery by the addition of an adsorbent to the high-pressure H2 storage system over that of pure compression, even at room temperature. Lightweight, low-density materials remain the optimal adsorbents at low temperature, while higher density, open metal-containing frameworks are necessary for high-density room temperature storage and delivery. Full article
(This article belongs to the Special Issue Metal Hydrogen Systems: Fundamental Properties and Current Applications for Energy Storage and Conversion)
►▼ Show Figures

Graphical abstract

11 pages, 1529 KiB  
Article
Tris-{Hydridotris(1-pyrazolyl)borato}lanthanide Complexes: Synthesis, Spectroscopy, Crystal Structure and Bonding Properties
by Christos Apostolidis, Attila Kovács, Alfred Morgenstern, Jean Rebizant and Olaf Walter
Inorganics 2021, 9(6), 44; https://doi.org/10.3390/inorganics9060044 - 03 Jun 2021
Cited by 6 | Viewed by 2462
Abstract
Complexes of trivalent lanthanides (Ln) with the hydridotris(1-pyrazolyl)borato (Tp) ligand Ln[η3-HB(N2C3H3)3]3 (LnTp3) were subjected to a joint experimental–theoretical analysis. X-ray diffraction experiments have been performed on CeTp3, NdTp [...] Read more.
Complexes of trivalent lanthanides (Ln) with the hydridotris(1-pyrazolyl)borato (Tp) ligand Ln[η3-HB(N2C3H3)3]3 (LnTp3) were subjected to a joint experimental–theoretical analysis. X-ray diffraction experiments have been performed on CeTp3, NdTp3, SmTp3, GdTp3, and TbTp3 in the nine-fold coordination and on DyTp3, HoTp3, ErTp3, TmTp3, YbTp3, and LuTp3 in the eight-fold coordination form. Density functional theory (DFT) calculations were carried out for all 15 LnTp3 complexes. They extended the X-ray diffraction data available on the LnTp3 compounds and facilitated a straightforward interpretation of trends in the structural parameters. As a result of the joint analysis, significant steric strain in the equatorial coordination sites of the nine-coordinate structures was recognized. Trends in the bonding properties were elucidated by energy decomposition and quantum theory of atoms in molecules (QTAIM) analysis of the electron density distribution. These results revealed the major electrostatic character of the Ln…Tp bonding and fine variation of charge transfer effects across the Ln row. Full article
(This article belongs to the Section Coordination Chemistry)
►▼ Show Figures

Graphical abstract

23 pages, 1642 KiB  
Review
New Trends in Nanoclay-Modified Sensors
by Esperanza Pavón, Rosa Martín-Rodríguez, Ana C. Perdigón and María D. Alba
Inorganics 2021, 9(6), 43; https://doi.org/10.3390/inorganics9060043 - 02 Jun 2021
Cited by 16 | Viewed by 3988
Abstract
Nanoclays are widespread materials characterized by a layered structure in the nano-scale range. They have multiple applications in diverse scientific and industrial areas, mainly due to their swelling capacity, cation exchange capacity, and plasticity. Due to the cation exchange capacity, nanoclays can serve [...] Read more.
Nanoclays are widespread materials characterized by a layered structure in the nano-scale range. They have multiple applications in diverse scientific and industrial areas, mainly due to their swelling capacity, cation exchange capacity, and plasticity. Due to the cation exchange capacity, nanoclays can serve as host matrices for the stabilization of several molecules and, thus, they can be used as sensors by incorporating electroactive ions, biomolecules as enzymes, or fluorescence probes. In this review, the most recent applications as bioanalyte sensors are addressed, focusing on two main detection systems: electrochemical and optical methods. Particularly, the application of electrochemical sensors with clay-modified electrodes (CLME) for pesticide detection is described. Moreover, recent advances of both electrochemical and optical sensors based on nanoclays for diverse bioanalytes’ detection such as glucose, H2O2, organic acids, proteins, or bacteria are also discussed. As it can be seen from this review, nanoclays can become a key factor in sensors’ development, creating an emerging technology for the detection of bioanalytes, with application in both environmental and biomedical fields. Full article
(This article belongs to the Special Issue Inorganic Nanostructures)
►▼ Show Figures

Graphical abstract

17 pages, 2809 KiB  
Article
Acute Toxicity Evaluation of Non-Innocent Oxidovanadium(V) Schiff Base Complex
by Lidiane M. A. Lima, Heide Murakami, D. Jackson Gaebler, Wagner E. Silva, Mônica F. Belian, Eduardo C. Lira and Debbie C. Crans
Inorganics 2021, 9(6), 42; https://doi.org/10.3390/inorganics9060042 - 24 May 2021
Cited by 20 | Viewed by 3877
Abstract
The vanadium(V) complexes have been investigated as potential anticancer agents which makes it essential to evaluate their toxicity for safe use in the clinic. The large-scale synthesis and the acute oral toxicity in mice of the oxidovanadium(V) Schiff base catecholate complex, abbreviated as [...] Read more.
The vanadium(V) complexes have been investigated as potential anticancer agents which makes it essential to evaluate their toxicity for safe use in the clinic. The large-scale synthesis and the acute oral toxicity in mice of the oxidovanadium(V) Schiff base catecholate complex, abbreviated as [VO(HSHED)dtb] containing a redox-active ligand with tridentate Schiff base (HSHED = N-(salicylideneaminato)-N’-(2-hydroxyethyl)-1,2-ethylenediamine) and dtb = 3,5-di-(t-butyl)catechol ligands were carried out. The body weight, food consumption, water intake as well biomarkers of liver and kidney toxicity of the [VO(HSHED)dtb] were compared to the precursors, sodium orthovanadate, and free ligand. The 10-fold scale-up synthesis of the oxidovanadium(V) complex resulting in the preparation of material in improved yield leading to 2–3 g (79%) material suitable for investigating the toxicity of vanadium complex. No evidence of toxicity was observed in animals when acutely exposed to a single dose of 300 mg/kg for 14 days. The toxicological results obtained with biochemical and hematological analyses did not show significant changes in kidney and liver parameters when compared with reference values. The low oral acute toxicity of the [VO(HSHED)dtb] is attributed to redox chemistry taking place under biological conditions combined with the hydrolytic stability of the oxidovanadium(V) complex. These results document the design of oxidovanadium(V) complexes that have low toxicity but still are antioxidant and anticancer agents. Full article
(This article belongs to the Special Issue New Trends on Vanadium Chemistry, Biochemistry, and Medicinal Chemistry)
►▼ Show Figures

Graphical abstract

9 pages, 605 KiB  
Article
Effects of Glymes on the Distribution of Mg(B10H10) and Mg(B12H12) from the Thermolysis of Mg(BH4)2
by Ba L. Tran, Tamara N. Allen, Mark E. Bowden, Tom Autrey and Craig M. Jensen
Inorganics 2021, 9(6), 41; https://doi.org/10.3390/inorganics9060041 - 23 May 2021
Cited by 9 | Viewed by 2461
Abstract
We examined the effects of concentrations and identities of various glymes, from monoglyme up to tetraglyme, on H2 release from the thermolysis of Mg(BH4)2 at 160–200 °C for 8 h. 11B NMR analysis shows major products of Mg(B [...] Read more.
We examined the effects of concentrations and identities of various glymes, from monoglyme up to tetraglyme, on H2 release from the thermolysis of Mg(BH4)2 at 160–200 °C for 8 h. 11B NMR analysis shows major products of Mg(B10H10) and Mg(B12H12); however, their relative ratio is highly dependent both on the identity and concentration of the glyme to Mg(BH4)2. Selective formation of Mg(B10H10) was observed with an equivalent of monoglyme and 0.25 equivalent of tetraglyme. However, thermolysis of Mg(BH4)2 in the presence of stoichiometric or greater equivalent of glymes can lead to unselective formation of Mg(B10H10) and Mg(B12H12) products or inhibition of H2 release. Full article
(This article belongs to the Special Issue Metal Hydrogen Systems: Fundamental Properties and Current Applications for Energy Storage and Conversion)
►▼ Show Figures

Graphical abstract

34 pages, 14929 KiB  
Review
Solvothermal Synthesis Routes to Substituted Cerium Dioxide Materials
by James W. Annis, Janet M. Fisher, David Thompsett and Richard I. Walton
Inorganics 2021, 9(6), 40; https://doi.org/10.3390/inorganics9060040 - 21 May 2021
Cited by 10 | Viewed by 4245
Abstract
We review the solution-based synthesis routes to cerium oxide materials where one or more elements are included in place of a proportion of the cerium, i.e., substitution of cerium is performed. The focus is on the solvothermal method, where reagents are heated above [...] Read more.
We review the solution-based synthesis routes to cerium oxide materials where one or more elements are included in place of a proportion of the cerium, i.e., substitution of cerium is performed. The focus is on the solvothermal method, where reagents are heated above the boiling point of the solvent to induce crystallisation directly from the solution. This yields unusual compositions with crystal morphology often on the nanoscale. Chemical elements from all parts of the periodic table are considered, from transition metals to main group elements and the rare earths, including isovalent and aliovalent cations, and surveyed using the literature published in the past ten years. We illustrate the versatility of this synthesis method to allow the formation of functional materials with applications in contemporary applications such as heterogeneous catalysis, electrodes for solid oxide fuel cells, photocatalysis, luminescence and biomedicine. We pick out emerging trends towards control of crystal habit by use of non-aqueous solvents and solution additives and identify challenges still remaining, including in detailed structural characterisation, the understanding of crystallisation mechanisms and the scale-up of synthesis. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
►▼ Show Figures

Graphical abstract

Show export options expand_more Show export options expand_less
Select all
Export citation of selected articles as:
 
Displaying articles 1-10
Previous Issue
Next Issue
Back to TopTop