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Inorganics, Volume 9, Issue 1 (January 2021) – 8 articles

Cover Story (view full-size image): Thin films of the metal–organic framework UiO-66-X where X = H, NH2, and NO2 were synthesized on Au coated QCM crystal surfaces and exposed to gas-phase benzene, toluene, ethylbenzene, and xylene isomers. The experimental results suggest that defects strongly influence adsorption capacity. Specifically, the results suggest that UiO-66-NO2 films contain more missing linker defects than UiO-66-NH2 films. It was estimated that UiO-66-NH2 films have at least 2 missing linkers per unit cell and UiO-66-NO2 film have 3–4 missing linkers per unit cell. A greater number of missing linker defects in UiO-66-NO2 films effectively increases the pore size, which can accommodate more molecules per unit cell. View this paper.
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Open AccessEditorial
Acknowledgment to Reviewers of Inorganics in 2020
Inorganics 2021, 9(1), 8; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010008 - 19 Jan 2021
Viewed by 311
Abstract
Peer review is the driving force of journal development, and reviewers are gatekeepers who ensure that Inorganics maintains its standards for the high quality of its published papers [...] Full article
Open AccessReview
A Structural Survey of Poly-Functional Dithiocarbamate Ligands and the Aggregation Patterns They Sustain
Inorganics 2021, 9(1), 7; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010007 - 15 Jan 2021
Cited by 1 | Viewed by 480
Abstract
An overview is presented of the crystal structures of transition metal, main group element, and lanthanide compounds containing poly-functional dithiocarbamate ligands, namely species containing two or more connected NCS2 residues. In all, there are 40 different ligands of this type that [...] Read more.
An overview is presented of the crystal structures of transition metal, main group element, and lanthanide compounds containing poly-functional dithiocarbamate ligands, namely species containing two or more connected NCS2 residues. In all, there are 40 different ligands of this type that have been characterised crystallographically in their heavy-element compounds with up to six NCS2 residues; all are bridging. In most cases, the resulting aggregates are zero-dimensional, often di-nuclear, but aggregates of up to 36 metal (gold) atoms are noted. There are smaller numbers of one-, two-, and three-dimensional architectures sustained by poly-functional dithiocarbamate ligands in their respective crystals. The survey highlights the opportunities afforded by this generally under-studied class of ligand. Full article
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Open AccessEditorial
Transition Metals in Catalysis: The Functional Relationship of Fe–S Clusters and Molybdenum or Tungsten Cofactor-Containing Enzyme Systems
Inorganics 2021, 9(1), 6; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010006 - 13 Jan 2021
Viewed by 452
Abstract
Following the “Molybdenum and Tungsten Enzyme conference—MoTEC2019” and the satellite meeting on “Iron–Sulfur for Life”, we wanted to emphasize the link between iron–sulfur clusters and their importance for the biosynthesis, assembly, and activity of complex metalloenzymes in this Special Issue of Inorganics, [...] Read more.
Following the “Molybdenum and Tungsten Enzyme conference—MoTEC2019” and the satellite meeting on “Iron–Sulfur for Life”, we wanted to emphasize the link between iron–sulfur clusters and their importance for the biosynthesis, assembly, and activity of complex metalloenzymes in this Special Issue of Inorganics, entitled “Transition Metals in Catalysis: The Functional Relationship of Fe–S Clusters and Molybdenum or Tungsten Cofactor-Containing Enzyme Systems” [...] Full article
Open AccessCommunication
Breast Cancer Stem Cell Active Copper(II) Complexes with Naphthol Schiff Base and Polypyridyl Ligands
Inorganics 2021, 9(1), 5; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010005 - 07 Jan 2021
Viewed by 733
Abstract
Breast cancer stem cells (CSCs) are a sub-population of tumour cells that can promote breast cancer relapse and metastasis. Current treatments are unable to completely remove breast CSCs, therefore it is essential to develop new chemotherapeutics that can remove breast CSCs at clinically [...] Read more.
Breast cancer stem cells (CSCs) are a sub-population of tumour cells that can promote breast cancer relapse and metastasis. Current treatments are unable to completely remove breast CSCs, therefore it is essential to develop new chemotherapeutics that can remove breast CSCs at clinically compatible doses. Here we present the synthesis, characterisation, and anti-breast CSC properties of copper(II) complexes, [Cu(L2)(1,10-phenanthroline)]PF6 (2) and [Cu(L3)(1,10-phenanthroline)]PF6 (3) comprising of a tridentate (O,N,S) coordinated naphthol Schiff base ligand (L2 = (E)-1-(((2-(methylthio)ethyl)imino)methyl)naphthalen-2-ol or L3 = (E)-1-(((2-(ethylthio)ethyl)imino)methyl)naphthalen-2-ol and 1,10-phenanthroline. The copper(II) complexes (2 and 3) kill breast CSCs, cultured in monolayer and three-dimensional systems, in the micromolar range. Notably, 2 and 3 are more potent towards breast CSC mammospheres than salinomycin (up to 4.5-fold), an established anti-breast CSC agent. Further, cell-based studies indicate that 2 and 3 are readily taken up by breast CSCs and elevate intracellular reactive oxygen species (ROS) levels upon short exposure times (0.5–1 h). The latter is likely to be the underlying mechanism by which 2 and 3 induces breast CSC death. Full article
(This article belongs to the Special Issue Cornerstones in Contemporary Inorganic Chemistry)
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Open AccessArticle
Influence of Substituents in Terephthalate Linker on the Structure of MOFs Obtained from Presynthesized Heterometallic Complex
Inorganics 2021, 9(1), 4; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010004 - 02 Jan 2021
Viewed by 527
Abstract
The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic [...] Read more.
The synthesis of new porous materials with desired properties is a challenging task. It becomes especially difficult if you need to combine several metals in one framework to obtain a heterometallic node. The use of presynthesized complexes for obtaining of new heterometallic metal–organic frameworks could be essential to solve the problem of tailored synthesis. In our study we use presynthesized heterometallic pivalate complex [Li2Zn2(piv)6(py)2] to obtain new MOFs with heterometallic core as a node of the framework. We are managed to obtain four new heterometallic MOFs: [H2N(CH3)2]2[Li2Zn2(bdc)4]·CH3CN·DMF (1), [Li2Zn2(H2Br2-bdc)(Br2-bdc)3]·2DMF (2), [H2N(CH3)2][LiZn2(ndc)3]·CH3CN (3) and [{Li2Zn2(dmf)(py)2}{LiZn(dmf)2}2 (NO2-bdc)6]·5DMF (4). Moreover three of them contain starting tetranuclear core {Li2Zn2} and saves its geometry. We also demonstrate the influence of substituent in terephthalate ring on preservation of tetranuclear core. For compound 1 it was shown that luminescence of the framework could be quenched when nitrobenzene is included in the pores. Full article
(This article belongs to the Special Issue Heterometallic Complexes)
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Open AccessArticle
Effect of Silane Functionalization on Properties of Poly(Lactic Acid)/Palygorskite Nanocomposites
Inorganics 2021, 9(1), 3; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010003 - 02 Jan 2021
Viewed by 525
Abstract
Poly(lactic acid) (PLA)/palygorskite (Paly) nanocomposites were prepared using the melt compounding technique. Paly modified by 3-aminopropyltriethoxysilane (APTES) and vinyltrimethoxysilane (VTMS) was used as nanofiller for PLA with concentrations in the 1–7 wt% range. It has been found that the functionalization allows a covalent [...] Read more.
Poly(lactic acid) (PLA)/palygorskite (Paly) nanocomposites were prepared using the melt compounding technique. Paly modified by 3-aminopropyltriethoxysilane (APTES) and vinyltrimethoxysilane (VTMS) was used as nanofiller for PLA with concentrations in the 1–7 wt% range. It has been found that the functionalization allows a covalent bond between the hydroxyl groups of the Paly and the PLA matrix, evidenced by the improvement in mechanical properties. Paly modification with VTMS has better properties compared with Pale modification with APTES. This indicates a better adhesion between the Paly-VTMS and PLA matrix, and a good dispersion of the nanofiller in the polymer matrix. Full article
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Open AccessCommunication
Investigating the Factors Affecting the Ionic Conduction in Nanoconfined NaBH4
Inorganics 2021, 9(1), 2; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010002 - 01 Jan 2021
Viewed by 531
Abstract
Nanoconfinement is an effective strategy to tune the properties of the metal hydrides. It has been extensively employed to modify the ionic conductivity of LiBH4 as an electrolyte for Li-ion batteries. However, the approach does not seem to be applicable to other [...] Read more.
Nanoconfinement is an effective strategy to tune the properties of the metal hydrides. It has been extensively employed to modify the ionic conductivity of LiBH4 as an electrolyte for Li-ion batteries. However, the approach does not seem to be applicable to other borohydrides such as NaBH4, which is found to reach a limited improvement in ionic conductivity of 10−7 S cm−1 at 115 °C upon nanoconfinement in Mobil Composition of Matter No. 41 (MCM-41) instead of 10−8 S cm−1. In comparison, introducing large cage anions in the form of Na2B12H12 naturally formed upon the nanoconfinement of NaBH4 was found to be more effective in leading to higher ionic conductivities of 10−4 S cm−1 at 110 °C. Full article
(This article belongs to the Section Inorganic Solid-State Chemistry)
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Open AccessArticle
The Effects of Functional Groups and Missing Linkers on the Adsorption Capacity of Aromatic Hydrocarbons in UiO-66 Thin Films
Inorganics 2021, 9(1), 1; https://0-doi-org.brum.beds.ac.uk/10.3390/inorganics9010001 - 26 Dec 2020
Viewed by 720
Abstract
The adsorption of benzene, toluene, ethylbenzene, and xylene isomers, also known as BTEX, from the gas phase into porous thin films of the metal–organic framework UiO-66-X, where X = H, NH2, and NO2, was measured to quantify adsorption capacity. [...] Read more.
The adsorption of benzene, toluene, ethylbenzene, and xylene isomers, also known as BTEX, from the gas phase into porous thin films of the metal–organic framework UiO-66-X, where X = H, NH2, and NO2, was measured to quantify adsorption capacity. The thin films were grown by a vapor-conversion method onto Au-coated quartz microbalance crystals. The MOF thin films were characterized by IR and Raman spectroscopy, X-ray diffraction, X-ray photoelectron spectroscopy and scanning electron microscopy. The thin films were activated by heating under high vacuum and exposed to each gas to calculate the Henry’s constant. The results demonstrate that the functional groups in the organic linker and missing-linkers both play important roles in the adsorption capacity. Several trends can be observed in the data. First, all the compounds in the BTEX family have lower Henry’s constants in the UiO-66-H films compared to the UiO-66-NH2 and UiO-66-NO2 films, which can largely be attributed to the absence of a functional group on the linker. Second, at 25 °C, the Henry’s constants for all the BTEX compounds in UiO-66-NO2 films are larger than UiO-66-NH2 films. Third, the role of missing linkers is addressed by comparing the measured adsorption capacity to ideal pore filling. The results show that the UiO-66-H films are the most defect-free and the UiO-66-NO2 films have the most missing linker defects. Full article
(This article belongs to the Section Organometallic Chemistry)
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