Nanofiltration Mixed Matrix Membranes from Cellulose Modified with Zn-Based Metal-Organic Frameworks for the Enhanced Water Treatment from Heavy Metal Ions.

Nowadays, nanofiltration is actively used for water softening and disinfection, pre-treatment, nitrate, and color removal, in particular, for heavy metal ions removal from wastewater. In this regard, new, effective materials are required. In the present work, novel sustainable porous membranes from cellulose acetate (CA) and supported membranes consisting of CA porous substrate with a thin dense selective layer from carboxymethyl cellulose (CMC) modified with first-time synthesized Zn-based metal-organic frameworks (Zn(SEB), Zn(BDC)Si, Zn(BIM)) were developed to increase the efficiency of nanofiltration for the removal of heavy metal ions. Zn-based MOFs were characterized by sorption measurements, X-ray diffraction (XRD), and scanning electron microscopy (SEM). The obtained membranes were studied by the spectroscopic (FTIR), standard porosimetry and microscopic (SEM and AFM) methods, and contact angle measurement. The CA porous support was compared with other, prepared in the present work, porous substrates from poly(m-phenylene isophthalamide) and polyacrylonitrile. Membrane performance was tested in the nanofiltration of the model and real mixtures containing heavy metal ions. The improvement of the transport properties of the developed membranes was achieved through Zn-based MOF modification due to their porous structure, hydrophilic properties, and different particle shapes.

Crystal Structure, Raman, FTIR, UV-Vis Absorption, Photoluminescence Spectroscopy, TG-DSC and Dielectric Properties of New Semiorganic Crystals of 2-Methylbenzimidazolium Perchlorate.

Single crystals of 2-methylbenzimidazolium perchlorate were prepared for the first time with a slow evaporation method from an aqueous solution of a mixture of 2-methylbenzimidazole (MBI) crystals and perchloric acid HClO4. The crystal structure was determined by single crystal X-ray diffraction (XRD) and confirmed by XRD of powder. Angle-resolved polarized Raman and Fourier-transform infrared (FTIR) absorption spectra of crystals consist of lines caused by molecular vibrations in MBI molecule and ClO4- tetrahedron in the region ν = 200-3500 cm-1 and lattice vibrations in the region of 0-200 cm-1. Both XRD and Raman spectroscopy show a protonation of MBI molecule in the crystal. An analysis of ultraviolet-visible (UV-Vis) absorption spectra gives an estimation of an optical gap Eg~3.9 eV in the crystals studied. Photoluminescence spectra of MBI-perchlorate crystals consist of a number of overlapping bands with the main maximum at Ephoton ≅ 2.0 eV. Thermogravimetry-differential scanning calorimetry (TG-DSC) revealed the presence of two first-order phase transitions with different temperature hysteresis at temperatures above room temperature. The higher temperature transition corresponds to the melting temperature. Both phase transitions are accompanied by a strong increase in the permittivity and conductivity, especially during melting, which is similar to the effect of an ionic liquid.

Novel Mixed Matrix Membranes Based on Poly(vinylidene fluoride): Development, Characterization, Modeling.

Membrane technology is an actively developing area of modern societies; with the help of high-performance membranes, it is possible to separate various mixtures for many industrial tasks. The objective of this study was to develop novel effective membranes based on poly(vinylidene fluoride) (PVDF) by its modification with various nanoparticles (TiO2, Ag-TiO2, GO-TiO2, and MWCNT/TiO2). Two types of membranes have been developed: dense membranes for pervaporation and porous membranes for ultrafiltration. The optimal content of nanoparticles in the PVDF matrix was selected: 0.3 wt% for porous membranes and 0.5 wt% for dense ones. The structural and physicochemical properties of the developed membranes were studied using FTIR spectroscopy, thermogravimetric analysis, scanning electron and atomic force microscopies, and measuring of contact angles. In addition, the molecular dynamics simulation of PVDF and the TiO2 system was applied. The transport properties and cleaning ability under ultraviolet irradiation of porous membranes were studied by ultrafiltration of a bovine serum albumin solution. The transport properties of dense membranes were tested in pervaporation separation of a water/isopropanol mixture. It was found that membranes with the optimal transport properties are as follows: the dense membrane modified with 0.5 wt% GO-TiO2 and the porous membrane modified with 0.3 wt% MWCNT/TiO2 and Ag-TiO2.

N-Benzylethanolammonium Ionic Liquids and Molten Salts in the Synthesis of 68Ga- and Al18F-Labeled Radiopharmaceuticals.

Ionic liquids (ILs), due to their structural features, have unique physical and chemical properties and are environmentally friendly. Every year, the number of studies devoted to the use of ILs in medicine and pharmaceutics is growing. In nuclear medicine, the use of ILs with self-buffering capacity in the synthesis of radiopharmaceuticals is extremely important. This research is devoted to obtaining new ionic buffer agents containing N-benzylethanolammonium (BEA) cations and anions of carboxylic acids. A series of new BEA salts was synthesized and identified by NMR (1H, 13C), IR spectroscopy and elemental and thermal analysis. The crystal structures of BEA hydrogen succinate, hydrogen oxalate and oxalate were determined by x-ray diffraction. Newly synthesized compounds were tested as buffer solutions in 68Ga- and Al18F-radiolabeling reactions with a series of bifunctional chelating agents and clinically relevant peptides used for visualization of malignancies by positron emission tomography. The results obtained confirm the promise of using new buffers in the synthesis of 68Ga- and Al18F-labeled radiopharmaceuticals.

Pervaporation Polyvinyl Alcohol Membranes Modified with Zr-Based Metal Organic Frameworks for Isopropanol Dehydration.

Metal-organic frameworks (MOFs) are perceptive modifiers for the creation of mixed matrix membranes to improve the pervaporation performance of polymeric membranes. In this study, novel membranes based on polyvinyl alcohol (PVA) modified with Zr-MOFs (MIL-140A, MIL-140A-AcOH, and MIL-140A-AcOH-EDTA) particles were developed for enhanced pervaporation dehydration of isopropanol. Two membrane types (substrateless-freestanding; and formed on polyacrylonitrile support-composite) were prepared. The additional cross-linking of membranes with glutaraldehyde was carried out to circumvent membrane stability in pervaporation dehydration of diluted solutions. The synthesized Zr-MOFs were characterized by scanning electron microscopy, X-ray powder diffraction analysis, and specific surface area measurement. The structure and physicochemical properties of the developed membranes were investigated by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, thermogravimetric analysis, swelling experiments, and contact angle measurements. The PVA and PVA/Zr-MOFs membranes were evaluated in pervaporation dehydration of isopropanol in a wide concentration range. It was found that the composite cross-linked PVA membrane with 10 wt% MIL-140A had optimal pervaporation performance in the isopropanol dehydration (12-100 wt% water) at 22 °C: 0.15-1.33 kg/(m2h) permeation flux, 99.9 wt% water in the permeate, and is promising for the use in the industrial dehydration of alcohols.

Development and Investigation of Hierarchically Structured Thin-Film Nanocomposite Membranes from Polyamide/Chitosan Succinate Embedded with a Metal-Organic Framework (Fe-BTC) for Pervaporation.

Thin-film composite membranes (TFC) obtained by the formation of a selective layer on a porous membrane-substrate via interfacial polymerization (IP) are indispensable for separation procedures in reverse osmosis, nanofiltration, pervaporation, and gas separation. Achieving high selectivity and permeability for TFC membranes is still one of the main challenges in membrane science and technology. This study focuses on the development of thin film nanocomposite (TFN) membranes with a hierarchically structured polyamide (PA)/chitosan succinate (ChS) selective layer embedded with a metal-organic framework of iron 1,3,5-benzenetricarboxylate (Fe-BTC) for the enhanced pervaporation dehydration of isopropanol. The aim of this work was to study the effect of Fe-BTC incorporation into the ChS interlayer and PA selective layer, obtained via IP, on the structure, properties, and performance of pervaporation TFN membranes. The structure and hydrophilicity of the developed TFN membranes were investigated using scanning electron microscopy (SEM) and atomic force microscopy (AFM), along with water contact angle measurements. The developed TFN membranes were studied in the pervaporation dehydration of isopropanol (12-30 wt % water). It was found that incorporation of Fe-BTC into the ChS interlayer yielded the formation of a smoother, more uniform, and defect-free PA ultrathin selective layer via IP, due to the amorpho-crystalline structure of particles serving as the amine storage reservoir and led to an increase in membrane selectivity toward water, and a slight decrease in permeation flux compared to the ChS interlayered TFC membranes. The best pervaporation performance was demonstrated by the TFN membrane with a ChS-Fe-BTC interlayer and the addition of 0.03 wt % Fe-BTC in the PA layer, yielding a permeation flux of 197-826 g·m-2·h-1 and 98.50-99.99 wt % water in the permeate, in the pervaporation separation of isopropanol/water mixtures (12-30 wt % water).

PLA-PEG Implant as a Drug Delivery System in Glaucoma Surgery: Experimental Study.

Excessive postoperative scarring halts the effectiveness of glaucoma surgery and still remains a challenging problem. The purpose of this study was to develop a PLA-PEG-based drug delivery system with cyclosporine A or everolimus for wound healing modulation. METHODS: PLA-PEG implants saturation with cyclosporine A or everolimus as well as their further in vitro release were analyzed. Anti-proliferative activity and cytotoxicity of the immunosuppressants were studied in vitro using human Tenon's fibroblasts. Thirty-six rabbits underwent glaucoma filtration surgery with the application of sham implants or samples saturated with cyclosporine A or everolimus. The follow-up period was six months. A morphological study of the surgery area was also performed at seven days, one, and six months post-op. RESULTS: PLA-PEG implants revealed a satisfactory ability to cumulate either cyclosporine A or everolimus. The most continuous period of cyclosporine A and everolimus desorption was 7 and 13 days, respectively. Immunosuppressants demonstrated marked anti-proliferative effect regarding human Tenon's fibroblasts without signs of cytotoxicity at concentrations provided by the implants. Application of PLA-PEG implants saturated with immunosuppressants improved in vivo glaucoma surgery outcomes. CONCLUSIONS: Prolonged delivery of either cyclosporine A or everolimus by means of PLA-PEG implants represents a promising strategy of wound healing modulation in glaucoma filtration surgery.

Novel Thin Film Nanocomposite Membranes Based on Chitosan Succinate Modified with Fe-BTC for Enhanced Pervaporation Dehydration of Isopropanol.

The application of environmentally friendly and energy-efficient membrane processes allows improvement the ecological safety and sustainability of industrial production. However, the effective application of membrane processes requires novel high-performance thin film composite (TFC) membranes based on biopolymers to solve environmental problems. In this work for the first time novel thin film nanocomposite (TFN) membranes based on biopolymer chitosan succinate (ChS) modified with the metal organic framework iron 1,3,5-benzenetricarboxylate (Fe-BTC) were developed for enhanced pervaporation dehydration. The formation of a selective layer of TFN membranes on the porous membrane-support was carried out by two methods-dynamic technique and physical adsorption. The effect of the membrane formation method and Fe-BTC content in ChS layer on the structure and physicochemical properties of TFN membranes was investigated. The developed TFN ChS-based membranes were evaluated in the pervaporation dehydration of isopropanol (12-30 wt.% water). It was found that TFN ChS-Fe-BTC membranes prepared by two methods demonstrated improved permeation flux compared to the reference TFC ChS membrane. The best transport properties in pervaporation dehydration of isopropanol (12-30 wt.% water) were possessed by TFN membranes with 40 wt.% Fe-BTC prepared by dynamic technique (permeation flux 99-499 g m-2 h-1 and 99.99% water in permeate) and TFN membranes with 5 wt.% Fe-BTC developed by physical adsorption (permeation flux 180-701 g m-2 h-1 and 99.99% water in permeate).

Novel High Flux Poly(m-phenylene isophtalamide)/TiO2 Membranes for Ultrafiltration with Enhanced Antifouling Performance.

Wide application of ultrafiltration in different industrial fields requires the development of new membranes with tailored properties and good antifouling stability. This study is devoted to the improvement of ultrafiltration properties of poly(m-phenylene isophtalamide) (PA) membranes by modification with titanium oxide (TiO2) particles. The introduction of TiO2 particles improved membrane separation performance and increased antifouling stability and cleaning ability under UV irradiation. The developed membranes were characterized by scanning electron and atomic force microscopy methods, the measurements of water contact angle, and total porosimetry. The transport properties of the PA and PA/TiO2 membranes were tested in ultrafiltration of industrially important feeds: coolant lubricant (cutting fluid) emulsion (5 wt.% in water) and bovine serum albumin (BSA) solution (0.5 wt.%). The PA/TiO2 (0.3 wt.%) membrane was found to possess optimal transport characteristics in ultrafiltration of coolant lubricant emulsion due to the highest pure water and coolant lubricant fluxes (1146 and 32 L/(m2 h), respectively), rejection coefficient (100%), and flux recovery ratio (84%). Furthermore, this membrane featured improved ability of surface contamination degradation after UV irradiation in prolonged ultrafiltration of BSA, demonstrating a high flux recovery ratio (89-94%).

Novel Membranes Based on Hydroxyethyl Cellulose/Sodium Alginate for Pervaporation Dehydration of Isopropanol.

Membrane methods, especially pervaporation, are quickly growing up. In line with that, effective membrane materials based on biopolymers are required for the industrially significant mixtures separation. To essentially improve membrane transport characteristics, the application of the surface or/and bulk modifications can be carried out. In the present study, novel dense and supported membranes based on hydroxyethyl cellulose (HEC)/sodium alginate (SA) were developed for pervaporation dehydration of isopropanol using several approaches: (1) the selection of the optimal ratio of polymers, (2) the introduction of fullerenol in blend polymer matrix, (3) the selection of the optimal cross-linking agent for the membranes, (4) the application of layer-by-layer deposition of polyelectrolytes on supported membrane surface (poly(sodium 4-styrenesulfonate) (PSS)/poly(allylamine hydrochloride) (PAH) and PSS/SA). Structural and physicochemical characteristics of the membranes were analyzed by different methods. A cross-linked supported membrane based on HEC/SA/fullerenol (5%) composite possessed the following transport characteristics in pervaporation dehydration of isopropanol (12-50 wt.% water): 0.42-1.72 kg/(m2h) permeation flux, and 77.8-99.99 wt.% water content in the permeate. The surface modification of this membrane with 5 bilayers of PSS/PAH and PSS/SA resulted in the increase of permeation flux up to 0.47-3.0 and 0.46-1.9 kg/(m2h), respectively, with lower selectivity.

Novel Mixed Matrix Membranes Based on Polymer of Intrinsic Microporosity PIM-1 Modified with Metal-Organic Frameworks for Removal of Heavy Metal Ions and Food Dyes by Nanofiltration.

Nowadays, nanofiltration is widely used for water treatment due to its advantages, such as energy-saving, sustainability, high efficiency, and compact equipment. In the present work, novel nanofiltration membranes based on the polymer of intrinsic microporosity PIM-1 modified by metal-organic frameworks (MOFs)-MIL-140A and MIL-125-were developed to increase nanofiltration efficiency for the removal of heavy metal ions and dyes. The structural and physicochemical properties of the developed PIM-1 and PIM-1/MOFs membranes were studied by the spectroscopic technique (FTIR), microscopic methods (SEM and AFM), and contact angle measurement. Transport properties of the developed PIM-1 and PIM-1/MOFs membranes were evaluated in the nanofiltration of the model and real mixtures containing food dyes and heavy metal ions. It was found that the introduction of MOFs (MIL-140A and MIL-125) led to an increase in membrane permeability. It was demonstrated that the membranes could be used to remove and concentrate the food dyes and heavy metal ions from model and real mixtures.

Effect of the Formation of Ultrathin Selective Layers on the Structure and Performance of Thin-Film Composite Chitosan/PAN Membranes for Pervaporation Dehydration.

The aim of the study is to improve the performance of thin-film composite (TFC) membranes with a thin selective layer based on chitosan (CS) via different approaches by: (1) varying the concentration of the CS solution; (2) changing the porosity of substrates from polyacrylonitrile (PAN); (3) deposition of the additional ultrathin layers on the surface of the selective CS layer using interfacial polymerization and layer-by-layer assembly. The developed membranes were characterized by different methods of analyses (SEM and AFM, IR spectroscopy, measuring of water contact angles and porosity). The transport characteristics of the developed TFC membranes were studied in pervaporation separation of isopropanol/water mixtures. It was found that the application of the most porous PAN-4 substrate with combination of formation of an additional polyamide selective layer by interfacial polymerization on the surface of a dense selective CS layer with the subsequent layer-by-layer deposition of five bilayers of poly (sodium 4-styrenesulfonate)/CS polyelectrolyte pair led to the significant improvement of permeance and high selectivity for the entire concentration feed range. Thus, for TFC membrane on the PAN-4 substrate the optimal transport characteristics in pervaporation dehydration of isopropanol (12-90 wt.% water) were achieved: 0.22-1.30 kg/(m2h), 99.9 wt.% water in the permeate.

Extraordinary structural complexity of ilmajokite: a multilevel hierarchical framework structure of natural origin.

The crystal structure of ilmajokite, a rare Na-K-Ba-Ce-titanosilicate from the Khibiny mountains, Kola peninsula, Russia, has been solved using single-crystal X-ray diffraction data. The crystal structure is based on a 3D titanosilicate framework consisting of trigonal prismatic titanosilicate (TPTS) clusters centered by Ce3+ in [9]-coordination. Four adjacent TPTS clusters are linked into four-membered rings within the (010) plane and connected via ribbons parallel to 101. The ribbons are organized into layers parallel to (010) and modulated along the a axis with a modulation wavelength of csinß = 32.91 Šand an amplitude of ∼b/2 = 13.89 Å. The layers are linked by additional silicate tetrahedra. Na+, K+, Ba2+ and H2O groups occur in the framework cavities and have different occupancies and coordination environments. The crystal structure of ilmajokite can be separated into eight hierarchical levels: atoms, coordination polyhedra, TPTS clusters, rings, ribbons, layers, the framework and the whole structure. The information-based analysis allows estimation of the complexity of the structure as 8.468 bits per atom and 11990.129 bits per cell. According to this analysis, ilmajokite is the third-most complex mineral known to date after ewingite and morrisonite, and is the most complex mineral framework structure, comparable in complexity to paulingite-(Ca) (11 590.532 bits per cell).

Isolation and Bioactivity of Secondary Metabolites from Solid Culture of the Fungus, Alternaria sonchi.

The fungus, Alternaria sonchi is considered to be a potential agent for the biocontrol of perennial sowthistle (Sonchus arvensis). A new chlorinated xanthone, methyl 8-hydroxy-3-methyl-4-chloro-9-oxo-9H-xanthene-1-carboxylate (1) and a new benzophenone derivative, 5-chloromoniliphenone (2), were isolated together with eleven structurally related compounds (3-13) from the solid culture of the fungus, which is used for the production of bioherbicidal inoculum of A. sonchi. Their structures were determined by spectroscopic (mostly by NMR and MS) methods. Alternethanoxins A and B, which were reported in A. sonchi earlier, were re-identified as moniliphenone and pinselin, respectively. The isolated compounds were tested for phytotoxic, antimicrobial, insecticidal, cytotoxic and esterase-inhibition activities. They did not demonstrate high phytotoxicity (lesions up to 2.5 mm in diameter/length at a concentration of 2 mg/mL) when tested on leaf disks/segments of perennial sowthistle (Sonchus arvensis) and couch grass (Elytrigia repens). They did not possess acute toxicity to Paramecium caudatum, and showed moderate to low cytotoxicity (IC50 > 25 µg/mL) for U937 and K562 tumor cell lines. However, chloromonilicin and methyl 3,8-dihydroxy-6-methyl-4-chloro-9-oxo-9H-xanthene-1-carboxylate (4) were shown to have antimicrobial properties with MIC 0.5-5 µg/disc. Compound 4 and chloromonilinic acid B were found to have contact insecticidal activity to wheat aphid (Schizaphis graminum) at 1 mg/mL. Compounds 2 and methyl 3,8-dihydroxy-6-methyl-9-oxo-9H-xanthene-1-carboxylate displayed selective carboxylesterase inhibition activity at concentration of 100 µg/mL. Therefore, the waste solid substrate for production of A. sonchi spores can be re-utilized for the isolation of a number of valuable natural products.

Enhanced Pervaporation Properties of PVA-Based Membranes Modified with Polyelectrolytes. Application to IPA Dehydration.

In this work, dense and supported pervaporation polyvinyl alcohol (PVA)-based membranes modified with poly(allylamine hydrochloride) (PAH) and poly(sodium 4-styrenesulfonate)(PSS)/PAH top nanolayers were synthesized. Two main points were investigated: the role of the polyelectrolyte PAH on water selectivity of the selective polymer matrix and the impact of the porous substrate based on polyacrylonitrile (PAN) and aromatic polysulfone amide (UPM-20®), used to get supported high-performance membranes. Various methods of analysis (fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), atomic force microscopy (AFM), small-angle X-ray scattering (SAXS), porosity, contact angles, ultrafiltration) were applied to study the developed membranes. Transport characteristics of the developed membranes were studied in isopropanol dehydration by pervaporation. Obtained results are discussed in the light of the structure and physicochemical characteristics of these PVA/PAH membranes and the types of porous substrate. It was shown that the PAN-supported membrane with the selective layer based on PVA/PAH modified by 10 polyelectrolyte PSS/PAH bilayers possessed ~4.5 times higher permeation flux with the same high selectivity level (99.9 wt % water in the permeate) for the dehydration of the isopropanol (20 wt % water) at 60 °C compared to the commercial analog PERVAPTM 1201.

Stagonolides J and K and Stagochromene A, Two New Natural Substituted Nonenolides and a New Disubstituted Chromene-4,5-dione Isolated from Stagonospora cirsii S-47 Proposed for the Biocontrol of Sonchus arvensis.

Two new natural 10-membered macrolides (1, 2) and one chromene-4,5-dione derivative (3), named stagonolides J and K and stagochromene A, respectively, were isolated from the phytopathogenic fungus Stagonospora cirsii S-47, together with two known compounds, stagonolide A (4) and herbarumin I (5). Stagonolides J and K and stagochromene A were characterized as (5E,7R*,8S*,9R*)-7,8-dihydroxy-9-propyl-5-nonen-9-olide, (5E,7R,9S)-7-hydroxy-9-propyl-5-nonen-9-olide, and (2R*,3R*)-3-hydroxy-2-propyltetrahydro-2H-chromene-4,5(3H,4aH)-dione, respectively, by spectroscopic (mostly by NMR and ESIMS) data. Compounds 1-5 showed different rates of phytotoxic activity on punctured leaf discs of Sonchus arvensis. The antimicrobial, cytotoxic, and antiprotozoal activity of isolated compounds was also evaluated. Based on our data, stagonolide K and herbarumin I can be proposed as a potential scaffold for the development of a new natural herbicide and estimated as possible selection/quality markers of a bioherbicide based on S. cirsii, while stagonolide A can be considered as a mycotoxin.

Structural data of phenanthrene-9,10-dicarbonitriles.

In this data article, we present the single-crystal XRD data of phenanthrene-9,10-dicarbonitriles. Detailed structure analysis and photophysical properties were discussed in our previous study, "Intermolecular interactions-photophysical properties relationships in phenanthrene-9,10-dicarbonitrile assemblies" (Afanasenko et al., 2020). The data include the intra- and intermolecular bond lengths and angles.

(Isocyano Group π-Hole)⋠⋠⋠[d z 2 -MII ] Interactions of (Isocyanide)[MII ] Complexes, in which Positively Charged Metal Centers (d8 -M=Pt, Pd) Act as Nucleophiles.

Inspection of the X-ray structures of the newly prepared trans-[MII (CNXyl)2 (DAPT)2 ]Cl(BF4 ) (M=Pd, Pt; Xyl=2,6-Me2 C6 H3 ; DAPT=4,6-diaminopyrimidine-2(1H)-thione) complexes and the appropriate Hirshfeld molecular surface analysis allowed the recognition of the previously unknown π-hole⋅⋅⋅metal interactions between a ligated isocyano group (acting as a π-hole donor) and the positively charged d8 -PtII and d8 -PdII metal centers (acting as nucleophiles); this is the first identification of π-hole⋅⋅⋅metal interactions with triple-bond species. Results of DFT calculations followed by the topological analysis of the electron density distribution within the framework of Bader's theory (quantum theory of atoms in molecules, QTAIM) confirmed the presence of these contacts. The electrostatic surface potential calculations indicated that π-hole⋅⋅⋅metal contacts are formed upon interaction between the electrophilic isocyano C atom (π-hole donor) and the nucleophilic d z 2 orbital of the metal centers, which act as π-hole acceptors. Available CCDC data were processed from the perspective of the π-hole⋅⋅⋅metal interactions with isocyanide ligands, and their analysis disclosed the role of metal nucleophilicity in the corresponding π-hole acceptor ability.

Allabogdanite, the high-pressure polymorph of (Fe,Ni)2P, a stishovite-grade indicator of impact processes in the Fe-Ni-P system.

Allabogdanite, (Fe,Ni)2P, is the only known natural high-pressure phase reported in the Fe-Ni-P system. The mineral, which was previously described from a single meteorite, the Onello iron, is now discovered in the Santa Catharina and Barbianello nickel-rich ataxites. The occurrence of allabogdanite in Santa Catharina, one of the largest and well-studied meteorites, suggests that this mineral is more common than was believed. The formation of allabogdanite-bearing phosphide assemblages in a given meteorite provides evidence that it experienced peak pressure of at least 8 GPa at a temperature above 800 °C. Since the pressure-temperature stability parameters of allabogdanite fall within the margins of the stishovite (rutile-type SiO2) stability area, the former can be employed as a convenient stishovite-grade indicator of significant impact events experienced by iron and stony-iron meteorites and their parent bodies.

Synthesis of 1-(2-Aminovinyl)indoles and 1,3'-Biindoles by Reaction of 2,2-Diaryl-Substituted 2 H-Azirines with α-Imino Rh(II) Carbenoids.

An effective and operationally simple method for the preparation of 1-(2-(sulfonamido)vinyl)indoles (SAV-indoles) by the Rh(II)-catalyzed reaction of 2,2-diaryl-2 H-azirines with 1-sulfonyl-1,2,3-triazoles has been developed. This method enables the stereoselective synthesis of a variety of 1,2,3-trisubstituted indoles having a Z configuration of the (1-aryl-2-(sulfonamido)vinyl) substituent. The reaction mechanism, supported by DFT calculations, involves the formation of 1,4-diazahexa-1,3,5-trienes, which rapidly cyclize to 2,2-diaryl-1-sulfonyl-1,2-dihydropyrazines. These compounds can be isolated at an early stage of the reaction, but under prolonged heating they isomerize into 7a H-indolium ylides, followed by a barrierless 1,5-prototropic shift to SAV-indoles. The developed methodology was also applied to the preparation of 1,3'-biindoles from 2,2-diaryl-2 H-azirines using 3-diazoindolin-2-imines instead of 1-sulfonyl-1,2,3-triazoles.