Synthesis and Thermal Decomposition of High-Entropy Layered Rare Earth Hydroxychlorides.

The synthesis of multicomponent and high-entropy compounds has become a rapidly developing field in advanced inorganic chemistry, making it possible to combine the properties of multiple elements in a single phase. This paper reports on the synthesis of a series of novel high-entropy layered rare earth hydroxychlorides, namely, (Sm,Eu,Gd,Y,Er)2(OH)5Cl, (Eu,Gd,Tb,Y,Er)2(OH)5Cl, (Eu,Gd,Dy,Y,Er)2(OH)5Cl, and (Eu,Gd,Y,Er,Yb)2(OH)5Cl, using a homogeneous hydrolysis technique under hydrothermal conditions. Elemental mapping proved the even distribution of rare earth elements, while luminescence spectroscopy confirmed efficient energy transfer between europium and other rare earth cations, thus providing additional evidence of the homogeneous distribution of rare earth elements within the crystal lattice. The average rare earth cation radii correlated linearly with the unit cell parameters (0.868 < R2 < 0.982) of the high-entropy layered rare earth hydroxychlorides. The thermal stability of the high-entropy layered rare earth hydroxychlorides was similar to that of individual hydroxychlorides and their binary solid solutions.

Cinnamate-Intercalated Layered Yttrium Hydroxide: UV Light-Responsive Switchable Material.

In recent years, there has been an increasing interest in stimuli-responsive host-guest materials due to the high potential for their application in switchable devices. Light is the most convenient stimulus for operating these materials; a light-responsive guest affects the host structure and the functional characteristics of the entire material. UV-transparent layered rare earth hydroxides intercalated with UV-switchable anions are promising candidates as stimuli-responsive host-guest materials. The interlayer distance in the layered rare earth hydroxides depends on the size of the intercalated anions, which could be changed in situ, e.g., via anion isomerisation. Nevertheless, for layered rare earth hydroxides, the possibility of such changes has not been reported yet. A good candidate anion that is capable of intercalating into the interlayer space is the cinnamate anion, which undergoes UV-assisted irreversible trans-cis isomerisation. In this work, both trans- and cis-cinnamate anions were intercalated in layered yttrium hydroxide (LYH). Upon UV-irradiation, the interlayer distance of trans-cinnamate-intercalated layered yttrium hydroxide suspended in isopropanol changed from 21.9 to 20.6 Å. For the first time, the results obtained demonstrate the possibility of using layered rare earth hydroxides as stimuli-responsive materials.

Matrix is everywhere: extracellular DNA is a link between biofilm and mineralization in Bacillus cereus planktonic lifestyle.

To date, the mechanisms of biomineralization induced by bacterial cells in the context of biofilm formation remain the subject of intensive studies. In this study, we analyzed the influence of the medium components on the induction of CaCO3 precipitation by the Bacillus cereus cells and composition of the extracellular matrix (ECM) formed in the submerged culture. While the accumulation of extracellular polysaccharides and amyloids appeared to be independent of the presence of calcium and urea during the growth, the accumulation of extracellular DNA (eDNA), as well as precipitation of calcium carbonate, required the presence of both ingredients in the medium. Removal of eDNA, which was sensitive to treatment by DNase, did not affect other matrix components but resulted in disruption of cell network formation and a sixfold decrease in the precipitate yield. An experiment with a cell-free system confirmed the acceleration of mineral formation after the addition of exogenous salmon sperm DNA. The observed pathway for the formation of CaCO3 minerals in B. cereus planktonic culture included a production of exopolysaccharides and negatively charged eDNA lattice promoting local Ca2+ supersaturation, which, together with an increase in the concentration of carbonate ions due to pH rise, resulted in the formation of an insoluble precipitate of calcium carbonate. Precipitation of amorphous CaCO3 on eDNA matrix was followed by crystal formation via the ACC-vaterite-calcite/aragonite pathway and further formation of larger mineral aggregates in complex with extracellular polymeric substances. Taken together, our data showed that DNA in extracellular matrix is an essential factor for triggering the biomineralization in B. cereus planktonic culture.

Switchable Nanozyme Activity of Porphyrins Intercalated in Layered Gadolinium Hydroxide.

In this study, organo-inorganic nanohybrids LHGd-MTSPP with enzyme-like activity were prepared by in situ intercalation of anionic 5,10,15,20-tetrakis-(4-sulfonatophenyl)porphyrin and its complexes with Zn(II) and Pd(II) (MTSPP, M = 2H, Zn(II) and Pd(II)) into gadolinium layered hydroxide (LHGd). The combination of powder XRD, CHNS analysis, FT-IR, EDX, and TG confirmed the layered structure of the reaction products. The basal interplanar distances in LHGd-MTSPP samples were 22.3-22.6 Å, corresponding to the size of an intercalated tetrapyrrole molecule. According to SEM data, LHGd-MTSPP hybrids consisted of individual lamellar nanoparticles 20-50 nm in thickness. The enzyme-like activity of individual constituents, LHGd-Cl and sulfoporphyrins TSPP, ZnTSPP and PdTSPP, and hybrid LHGd-MTSPP materials, was studied by chemiluminescence analysis using the ABAP/luminol system in phosphate buffer solution. All the individual porphyrins exhibited dose-dependent antioxidant properties with respect to alkylperoxyl radicals at pH 7.4. The intercalation of free base TSPP porphyrin into the LHGd preserved the radical scavenging properties of the product. Conversely, in LHGd-MTSPP samples containing Zn(II) and Pd(II) complexes, the antioxidant properties of the porphyrins changed to dose-dependent prooxidant activity. Thus, an efficient approach to the design and synthesis of advanced LHGd-MTSPP materials with switchable enzyme-like activity was developed.

Tetranuclear Cr-Ln ferrocenecarboxylate complexes with a defect-dicubane structure: synthesis, magnetism, and thermolysis.

Using ferrocenecarboxylic acid (FcCO2H) and triethanolamine (H3tea) as ligands, the isostructural heterotrimetallic complexes [LnIII2CrIII2(OH)2(FcCO2)4(NO3)2(Htea)2]·2MePh·2THF (Ln = Tb (1), Dy (2), Ho (3), Er (4), and Y (5); Fc = (η5-C5H4)(η5-C5H5)Fe; H3tea = N(CH2CH2OH)3) were obtained. In all of the complexes which possess a defective dicubane structure, two doubly deprotonated triethanolamine ligands chelate the chromium ions. However, during the synthesis of 1, an isomeric complex 1a in which Tb3+ is chelated by triethanolamine as a tetradentate ligand, was also isolated as a few single crystals. Magnetic susceptibility measurements revealed dominant antiferromagnetic interactions in the {LnIII2CrIII2} cores of 1-4 leading to the formation of complexes with an uncompensated magnetic moment, while weak Cr-Cr ferromagnetic interactions were detected in the Y analogue. Complexes 1, 2, and 3 exhibit single-molecule magnet properties dominated by an Orbach-type relaxation mechanism with magnetization reversal barriers (Δ/kB) estimated around 54, 75, and 47 K, respectively. The Dy complex exhibits a magnetization hysteresis in an applied magnetic field at temperatures below 4 K. Thermolysis of the complexes was studied by TGA and DSC techniques; the final products obtained under an air atmosphere contain mixed oxide Cr0.75Fe1.25O3 and heterotrimetallic oxide LnCr1-xFexO3 (with x ≈ 0.75) phases.

Hydrophobic up-conversion carboxylated nanocellulose/fluoride phosphor composite films modified with alkyl ketene dimer.

Hydrophobic up-conversion nanocomposite films have been developed based on TEMPO-oxidized cellulose nanofibrils (TOCNF) modified with alkyl ketene dimer (AKD) as a matrix and MF2:Ho (M = Ca, Sr) as a phosphor. Fabrication of homogeneous, strong and translucent TOCNF/MF2:Ho-AKD films with water contact angle of 123 ±â€¯2° was accomplished with mild drying at 110 °C. These hydrophobic nanocomposite films demonstrated stable up-conversion luminescence in the visible spectral range upon excitation of the 5I7 level of Ho3+ ions by laser irradiation at 1912 nm both under ambient conditions and in a humid atmosphere (92 ±â€¯2% humidity). The absence of luminescence quenching in a high humidity atmosphere for TOCNF/MF2:Ho-AKD composite films was considered to be due to the reliable shielding effect of the hydrophobic TOCNF-AKD matrix. The films show promise for visualizing 2 µm laser radiation in medicine and monitoring of the atmosphere.

1D Ceric Hydrogen Phosphate Aerogels: Noncarbonaceous Ultraflyweight Monolithic Aerogels.

Ceric hydrogen phosphate gels possess a very unique spatial organization, being nearly amorphous materials with a fibrous structure. Using a sol-gel approach, we succeeded in preparing bulky gels containing as much as 20,000 molecules of water per cerium atom. Supercritical treatment of these gels made it possible to obtain the first ultralight monolithic noncarbonaceous aerogels with a density as low as 1 mg/cm3.

High-temperature resistive gas sensors based on ZnO/SiC nanocomposites.

Increasing requirements for environmental protection have led to the need for the development of control systems for exhaust gases monitored directly at high temperatures in the range of 300-800 °C. The development of high-temperature gas sensors requires the creation of new materials that are stable under these conditions. The stability of nanostructured semiconductor oxides at high temperature can be enhanced by creating composites with highly dispersed silicon carbide (SiC). In this work, ZnO and SiC nanofibers were synthesized by electrospinning of polymer solutions followed by heat treatment, which is necessary for polymer removal and crystallization of semiconductor materials. ZnO/SiC nanocomposites (15-45 mol % SiC) were obtained by mixing the components in a single homogeneous paste with subsequent thermal annealing. The composition and microstructure of the materials were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS). The electrophysical and gas sensing properties of the materials were investigated by in situ conductivity measurements in the presence of the reducing gases CO and NH3 (20 ppm), in dry conditions (relative humidity at 25 °C RH25 = 0) and in humid air (RH25 = 30%) in the temperature range 400-550 °C. The ZnO/SiC nanocomposites were characterized by a higher concentration of chemisorbed oxygen, higher activation energy of conductivity, and higher sensor response towards CO and NH3 as compared with ZnO nanofibers. The obtained experimental results were interpreted in terms of the formation of an n-n heterojunction at the ZnO/SiC interface.

Eu-Doped layered yttrium hydroxides sensitized by a series of benzenedicarboxylate and sulphobenzoate anions.

A number of Eu-doped layered yttrium hydroxides intercalated with various benzenedicarboxylate (phthalate, isophthalate and terephthalate) and sulphobenzoate (2-, 3- and 4-sulphobenzoate) anions were obtained using hydrothermal microwave (HTMW) treatment. For the first time, phthalate, isophthalate and sulphobenzoate anions were intercalated into layered rare-earth hydroxides (LRHs). Two approaches for the synthesis of intercalated layered yttrium hydroxides were used: ion exchange reactions and homogeneous hydrolysis of rare-earth cations in the presence of intercalated anions. Ion-exchange reactions between layered rare-earth hydroxides and a series of benzenedicarboxylic and sulphobenzoic acid salts were performed under the conditions of HTMW treatment, which significantly increased the rate of intercalation. The structure of the first representative of layered rare-earth hydroxides intercalated with sulphobenzoate-type anions, namely layered yttrium hydroxide intercalated with 4-sulphobenzoate of the composition Y3(OH)7(C7H4O5S)·H2O, was solved. Intercalation of benzenedicarboxylate and sulphobenzoate anions into Eu-doped layered yttrium hydroxides led to a substantial sensitization of Eu3+ luminescence. The local symmetry of Eu3+ was greatly decreased by intercalation of benzenedicarboxylate and sulphobenzoate anions.

closo-Dodecaborate Intercalated Yttrium Hydroxide as a First Example of Boron Cluster Anion-Containing Layered Inorganic Substances.

The first member, Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O, of a new family of boron-containing substances, closo-dodecaborate intercalated layered rare-earth hydroxides, was synthesized using a microwave-assisted hydrothermal method. The structure and composition of this compound were studied by X-ray diffraction, transmission and scanning electron microscopy, thermal analysis, inductively coupled plasma mass spectrometry, IR spectroscopy, and X-ray photoelectron spectroscopy. The title compound had the composition Y2(OH)5.46(B12H12)0.23Cl0.08·4.98H2O and crystallized in a form of plate-like, aggregated particles less than 10 nm thick. The coordination of closo-dodecaborate anions with yttrium hydroxide host layers was demonstrated.