A new 3D porous terbium–organic framework {[Tb4(OH)4(DSOA)2(H2O)8]·(H2O)8}n (Tb-DSOA) has been successfully assembled by Tb3+ ions and a sulfonate–carboxylate linker disodium-2,2′-disulfonate-4,4′-oxydibenzoic acid (Na2H2DSOA). In this metal–organic framework (MOF), tetranuclear terbium clusters can be sensitized by the organic linker to generate the characteristic photoluminescence of TbIII ions. Noncoordinated sulfonate oxygen atoms functionalize its channels, which act as basic sites leading to highly selective Fe3+ ion sensing by luminescence quenching, and also act as hopping sites for proton transfer, resulting in a proton conductivity of 1.66 × 10−4 S cm−1 at 98% RH. Exceptional water-stability makes this MOF compatible for these applications in aqueous solution.

Highly selective Fe3+ sensing and proton conduction in a water-stable sulfonate–carboxylate Tb–organic-framework

Applied and Environmental Chemistry of Animal Manure: A Review

A new series of five lanthanide(III) metal–organic frameworks with a general formula of [Ln3(bcpb)4(μ-HCOO)(μ-H2O)(H2O)2(DEF)]n (1–5) was generated by solvothermal reactions from Ln(NO3)3·6H2O {Ln = Eu (1), Tb (2), Gd (3), Dy (4), and Sm (5)} and 3,5-bis(3-carboxyphenyl)pyridine (H2bcpb) in an aqueous N,N-diethylformamide (DEF) medium. The obtained products were characterized by elemental analysis, FT-IR spectroscopy, thermogravimetric analysis (TGA), and powder and single crystal X-ray diffraction. The latter reveals that all compounds (1–5) are isostructural and feature very intricate 2D metal–organic frameworks. These were topologically analyzed, revealing a very complex hexanodal underlying net that can be simplified further to a binodal 3,5-connected layer with the 3,5L52 topology. Solid-state photoluminescence properties of 1–5 were studied in detail. Compound 1 exhibits a strong red luminescence upon excitation at 338 nm and its lifetime is 532 μs. Compound 2 shows an intense green luminescence upon excitation at 336 and its lifetime is 981 μs. The triplet state (3ππ*) of bcpb2− studied by using the Gd(III) derivative 3 demonstrated that the ligand effectively populates Tb(III) emission (Φ = 70.96%), whereas the corresponding Eu(III) derivative 1 shows a weak luminescence efficiency (Φ = 15.81%) as the triplet state of bcpb2− has a poor match with the 5D0 energy level of Eu(III). A notable feature of 1 is its remarkable sensing ability for Cu2+ ions and 2,4,6-trinitrophenol (TNP). Besides, a series of heterobimetallic Tb-based MOFs, [Tb3(1−x)Eu3x(bcpb)4(μ-HCOO)(μ-H2O)(H2O)2(DEF)]n {x = 0.001, 0.002, 0.003, 0.01, 0.02, 0.03, 0.04, 0.10, 0.15, 0.20} (compounds 2a–2j, respectively), was prepared. The luminescence studies reveal that the simultaneous presence of the characteristic sharp emission bands of Eu3+ and Tb3+ allows the tuning of the photoluminescence colors of such materials by adjusting the doping concentration of the Eu3+ ions.

2D lanthanide MOFs driven by a rigid 3,5-bis(3-carboxy-phenyl)pyridine building block:solvothermal syntheses, structural features, and photoluminescence and sensing properties

In the past few decades, cadmium (Cd) as soil contaminant is a major problem for the mankind. Cd contamination of soil and food crops is a critical environmental concern as it deteriorates the soil quality and creates threat to the food safety and human health. High Cd concentration in soils pose negative effects on the plants at physiological, structural and molecular levels. Secretion of certain secondary metabolites in the rhizosphere is a survival mechanism adopted by plants to tolerate and encounter Cd toxicity. Under metal-stressed conditions, secretion of root exudates in soil increases the external detoxification strategies of the plants. The secreted phytochemicals are gaseous compounds, inorganic and especially organic in composition. In plants, the role of these metabolites to confront Cd toxicity and induce tolerance under Cd distress is underrated. The review paper focuses on Cd sources, factors that affect its bioavailability, uptake and toxicity in the plants. Furthermore, it also highlights the contemporary progression in our understanding on the mechanisms of root exudation in plants and the effect of Cd toxicity on the root exudation. Finally, the review provides important information on the role of different root exudates to subsist Cd stress in plants naturally, particularly by reducing the dependence on synthetic amendments to enhance Cd-tolerance and its aquisition in plants.

Root exudates ameliorate cadmium tolerance in plants: A review

A tetranuclear copper cluster-based MOF with sulfonate–carboxylate ligands exhibiting high proton conduction properties

Technological progress and high market demand contributed to a significant interest in the production of fertilizers based on humic acids. The aim of this study was to evaluate the possibilities of using humic acids obtained from lignite in the production of new commercial products. For this purpose, it is necessary to determine the quality standard requirements for such material. Properties of humic acids depend on source of origin as well as method of its extraction. The humic acids were extracted from polish deposit of lignite–Sieniawa Lubuska by alkaline extraction using for this purpose six kinds of extractants: 0.1 M NaOH and 0.25 M NaOH, 0.1 M KOH and 0.25 M KOH, and 0.1 M Na4P2O7 and 0.25 M Na4P2O7. The humic samples were used in solid powder form and characterized by UV-Vis spectroscopy, 13C NMR spectroscopy, fluorescence spectroscopy, and thermal analysis. The determining factor influencing a degree of humic acids extraction from lignite and their structure is type of extractant. The largest efficiency of extraction (about 50%) was obtained with the use of NaOH solutions. All examined humic acids were generally characterized by simple and heterogeneous molecularly structure with low molecular weight and low aromatic polycondensation. Therefore, it can be concluded that humic acids extracted with NaOH and KOH solutions are less condensed than those extracted with Na4P2O7 solutions. It can suggest that humic acids obtained from lignite using solutions of Na4P2O7 are characterized by a low transformation degree and greater amount of carboxyl groups. Low rank coal can be successfully used in agriculture as a rich source of humic acids. Reagent used in their extraction, apart from high efficiency should have a neutral impact on their structure. Studies on the physicochemical properties of humic acids can be helpful in predicting behaviors of such fertilizer components in the environment and in inventing new products taking the principles of sustainable development into consideration.

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Evaluation of the possibilities of using humic acids obtained from lignite in the production of commercial fertilizers

Three novel alkali metal–cadmium coordination polymers [K2Cd(Hsb)4(H2O)6]3n1, [NaCd(sip)(DMF)2(H2O)2]2n2, and [NaCd2(sip)2(DMF)2(H2O)2]2n·2nHdeta·2nH2O 3 (H2sb = 4-sulfobenzoic acid, H3sip = 5-sulfoisophthalic acid) have been synthesized and characterized by single crystal X-ray diffraction and spectroscopic and thermogravimetric methods. The solid state structure of 1 consists of inorganic layers, formed from Na2O10 and CdO6, polyhedral units, bridged via the sulfonate site of the ligand. The layers are pillared by the organic portions of the ligands to form a three-dimensional framework classified as I2O1. Compounds 2 and 3 display inorganic–organic hybrid layers arranged in 3D via nonspecific (hydrophobic) interactions between the DMF ligands. The two-dimensional frameworks of the layers are classified as I1O1 (in 2) and I0O2 (in 3). The guest diethylammonium ions in 3 are arranged in hydrophobic channels along the [011] crystallographic direction and circumvented by the DMF ligands.

New Heterometallic Hybrid Polymers Constructed with Aromatic Sulfonate-Carboxylate Ligands: Synthesis, Layered Structures, and Properties

Kinetic modelling of cadmium removal from wet phosphoric acid by precipitation method

Influence of selected potassium salts on thermal stability of ammonium nitrate

Fertilisers containing ammonium nitrate are the most efficient sources of nitrogen used in agriculture. The major hazard associated with production, storage and transport of materials containing this compound is its liability to rapid decomposition, or even detonation under certain conditions. Properly selected calcium and magnesium carbonates may increase the thermal stability of ammonium nitrate. The aim of this research was to determine the influence of the carbonate mineral type and composition on phase transitions and decomposition process of fertiliser-grade ammonium nitrate. The article focuses on the methodology of thermal analysis of samples containing ammonium nitrate with carbonates and points out the phenomena and thermal characteristics that should be taken into consideration when testing fertiliser mixtures. Two different sample preparation methods allowed for investigating processes that may occur in inappropriate storage and transport conditions as well as during the production of fertiliser. The measurements were taken using techniques of differential thermal analysis and thermogravimetry coupled with mass spectrometry. The results showed that too high a level of carbonates reactivity can cause problems during the production of fertiliser, reducing the effectiveness of the filler in a final product.

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Józef Hoffmann

Papers

Evaluation of the possibilities of using humic acids obtained from lignite in the production of commercial fertilizers

New Heterometallic Hybrid Polymers Constructed with Aromatic Sulfonate-Carboxylate Ligands: Synthesis, Layered Structures, and Properties

Kinetic modelling of cadmium removal from wet phosphoric acid by precipitation method

Influence of selected potassium salts on thermal stability of ammonium nitrate

Effect of carbonate minerals on the thermal stability of fertilisers containing ammonium nitrate