Recognition of Chiral Carboxylates by Synthetic Receptors

Recognition of anionic species plays a fundamental role in many essential chemical, biological, and environmental processes. Numerous monographs and review papers on molecular recognition of anions by synthetic receptors reflect the continuing and growing interest in this area of supramolecular chemistry. However, despite the enormous progress made over the last 20 years in the design of these molecules, the design of receptors for chiral anions is much less developed. Chiral recognition is one of the most subtle types of selectivity, and it requires very precise spatial organization of the receptor framework. At the same time, this phenomenon commonly occurs in many processes present in nature, often being their fundamental step. For these reasons, research directed toward understanding the chiral anion recognition phenomenon may lead to the identification of structural patterns that enable increasingly efficient receptor design. In this review, we present the recent progress made in the area of synthetic receptors for biologically relevant chiral carboxylates.

Incorporation of Ions into Nanostructured Anodic Oxides—Mechanism and Functionalities

Anodic oxidation of metals leads to the formation of ordered nanoporous or nanotubular oxide layers that contribute to numerous existing and emerging applications. However, there are still numerous fundamental aspects of anodizing that have to be well understood and require deeper understanding. Anodization of metals is accompanied by the inevitable phenomenon of anion incorporation, which is discussed in detail in this review. Additionally, the influence of anion incorporation into anodic alumina and its impact on various properties is elaborated. The literature reports on the impact of the incorporated electrolyte anions on photoluminescence, galvanoluminescence and refractive index of anodic alumina are analyzed. Additionally, the influence of the type and amount of the incorporated anions on the chemical properties of anodic alumina, based on the literature data, was also shown to be important. The role of fluoride anions in d-electronic metal anodizing is shown to be important in the formation of nanostructured morphology. Additionally, the impact of incorporated anionic species, such as ruthenites, and their influence on anodic oxides formation, such as titania, reveals how the phenomenon of anion incorporation can be beneficial.

Role of Anionic Chromium Species in Leather Tanning

Chrome tanned leathers are definitely unique in comparison with leather made from any other known tanning agents, especially in terms of thermal stability, cost and its reactive mechanism with collagen fibers. In our current studies, self basifying chrome tanning materials masked with different percentages of organic acid were prepared and applied after the de-liming stage of leather processing. This eliminated the need for pickling and basification steps. Tanned leathers resisted shrinkage up to 103 and 105±2°C while conventional chrome tanned leathers resisted up to 108±2°C. Also, interaction of anionic chrome species in tanning was studied. It was observed that the percentage of anionic species in the experimental chrome tanning material was higher than conventional chrome tanning material and the shrinkage temperature achieved by application of experimental tanning material proves that anionic species do involve in tanning. Tanned leathers were crusted and analysed for strength and organoleptic properties.

Access to cationic polyhedral carboranes via dynamic cage surgery with N-heterocyclic carbenes

Polyhedral boranes and heteroboranes appear almost exclusively as neutral or anionic species, while the cationic ones are protonated at exoskeletal heteroatoms or they are instable. Here we report the reactivity of 10-vertex closo-dicarbadecaboranes with one or two equivalents of N-heterocyclic carbene to 10-vertex nido mono- and/or bis-carbene adducts, respectively. These complexes easily undergo a reaction with HCl to give cages of stable and water soluble 10-vertex nido-type cations with protonation in the form of a BHB bridge or 10-vertex closo-type cations containing one carbene ligand when originating from closo-1,10-dicarbadecaborane. The reaction of a 10-vertex nido mono-carbene adduct with phosphorus trichloride gives nido-11-vertex 2-phospha-7,8-dicarbaundecaborane, which undergoes an oxidation of the phosphorus atom to P = O, while the product of a bis-carbene adduct reaction is best described as a distorted C2B6H8 fragment bridged by the (BH)2PCl2+ moiety.

Characterisation of inorganic constitutions of condensate and solid residue generated from small-scale ex situ experiments in the context of underground coal gasification

This paper deals with the characterisation of inorganic constitutions generated at various operating conditions in the context of underground coal gasification (UCG). The ex situ small-scale experiments were conducted with coal specimens of different rank, from the South Wales Coalfield, Wales, UK, and Upper Silesian Coal Basin, Poland. The experiments were conducted at various gaseous oxidant ratios (water: oxygen = 1:1 and 2:1), pressures (20 bar and 36 bar) and temperatures (650°C, 750°C and 850°C). Increasing the amount of water in the oxidants proportionately decreased the cationic elements but increased the concentrations of anionic species. The temperature played minor impact, while the high-pressure experiments at temperature optimum to produce methane-rich syngas (750°C) showed significant reduction in cationic element generation. However, both coal specimens produced high amount of anionic species (F, Cl, SO4 and NO3). The “Hard” bituminous coal from Poland produced less gasification residues and condensates than the South Wales anthracitic coal due to its higher reactivity. The inorganic composition found in the solid residue was used in the theoretical calculation to predict the dissolved product concentrations when the solid residue interacts with deep coal seam water in the event of UCG cavity flooding. It was evident from the solubility products of the Cr, Ni and Zn that changes in the groundwater geochemistry occur; hence, their transportation in the subsurface must be studied further.

Influence of Amino Acids on the Mobility of Iodide in Hydrocalumite

In the cement system, hydrocalumite is a candidate adsorbent for low-level 129I anionic species. However, the stability of hydrocalumite after immobilizing I− is unclear when they are exposed to pedosphere characterized by organic substances derived from living organisms. In the present work, five amino acids were selected as simplified models of natural organic substances under alkaline conditions. L-cysteine (H2Cys) and L-aspartic acid (H2Asp) accelerated the release of I− from I-hydrocalumite through ion-exchange. Ion-exchange of Cys2− with I− in I-hydrocalumite was faster than Asp2−, and the interlayer spacing (d003) of Cys-hydrocalumite was smaller than that of Asp-hydrocalumite. DFT simulations not only supported the above results but also predicted that there was a positive correlation between the formation energies and interlayer spacings of amino acids intercalated hydrocalumite, depending on the configurations. Moreover, in the DFT predictions, the interaction between amino acids and metallic hydroxide layers was responsible for the formation of hydrogen bonds and Ca-O chemical bonds between the -COO− groups and [Ca2Al(OH)6]+. The other three amino acids did not show intercalation through ion-exchange. The stability of I-hydrocalumite is influenced differently by coexisting amino acids, depending on the ionic sizes, charge numbers, and hydrophilicity, which cause the second contamination.

Water Treatment Applications of Eco-Friendly Cationic Maltodextrin-Based Adsorbents

The anthropogenic environmental pollution generated during the last decades led to significant consequences for the aquatic ecosystems and to potential risks for human health. For this reason, the research has been focused on studying and develop pollutants-removing technologies. Nowadays, despite the presence of performing techniques applied in e.g. the potabilization and waste-water treatments, new strategies aimed to better meet the industrial needs and the environmental requirements are still widely investigated. In this frame, the pollution caused by the presence of anionic species in water, is still not completely solved. For this reason, this work is focused on studying novel cationic maltodextrin-based adsorbents obtained via sustainable approach, for water treatment applications. The adsorption performances towards nitrates-, sulphates- and phosphates-polluted water solutions have been tested and discussed.

Additive Effects of Lithium Salts with Various Anionic Species in Poly (Methyl Methacrylate)

We report that lithium salts in lithium-ion batteries effectively modify the physical properties of poly (methyl methacrylate) (PMMA). The glass transition temperature (Tg) is an indicator of the heat resistance of amorphous polymers. The anionic species of the salts strongly affected the glass transition behavior of PMMA. We focused on the additive effects of various lithium salts, such as LiCF3SO3, LiCOOCF3, LiClO4, and LiBr, on the Tg of PMMA. The large anions of the former three salts caused them to form macroscopic aggregates that acted as fillers in the PMMA matrix and to combine the PMMA domains, increasing Tg. On the other hand, LiBr salts dispersed microscopically in the PMMA matrix at the molecular scale, leading to the linking of the PMMA chains. Thus, the addition of LiBr to PMMA increased Tg as well as the relaxation time in the range of glass to rubber transition.

Self-assembly of an anion receptor with metal-dependent kinase inhibition and potent in vitro anti-cancer properties

One topical area of supramolecular chemistry is the binding of anionic species but despite the importance of anions in diverse cellular processes and for cancer development, anion receptors or ‘binders’ have received little attention as potential anti-cancer therapeutics. Here we report self-assembling trimetallic cryptands (e.g. [L2(Metal)3]6+ where Metal = Cu2+, Zn2+ or Mn2+) which can encapsulate a range of anions and which show metal-dependent differences in chemical and biological reactivities. In cell studies, both [L2Cu3]6+ and [L2Zn3]6+ complexes are highly toxic to a range of human cancer cell lines and they show significant metal-dependent selective activity towards cancer cells compared to healthy, non-cancerous cells (by up to 2000-fold). The addition of different anions to the complexes (e.g. PO43ˉ, SO42ˉ or PhOPO32ˉ) further alters activity and selectivity allowing the activity to be modulated via a self-assembly process. The activity is attributed to the ability to either bind or hydrolyse phosphate esters and mechanistic studies show differential and selective inhibition of multiple kinases by both [L2Cu3]6+ and [L2Zn3]6+ complexes but via different mechanisms.