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The mineral-like phase Ca3SiO4Cl2, an anthropogenic anhydrous calcium chlorine-silicate from the Chelyabinsk coal basin has been investigated using single-crystal and high-temperature powder X-ray diffraction and Raman spectroscopy. The empirical formula of this phase was calculated as Ca2.96[(Si0.98P0.03)Σ1.01O4]Cl2, in good agreement with its ideal formula. Ca3SiO4Cl2 is monoclinic, space group P21/c, Z = 4, a = 9.8367(6) Å, b = 6.7159(4) Å, c = 10.8738(7) Å, β = 105.735(6)°, V = 691.43(8) Å3. The crystal structure is based upon the pseudo-layers formed by Ca–O and Si–O bonds separated by Cl atoms. The pseudo-layers are parallel to the (100) plane. The crystal structure of Ca3SiO4Cl2 was refined (R1 = 0.037) and stable up to 660 °C; it expands anisotropically with the direction of the strongest thermal expansion close to parallel to the [−101] direction, which can be explained by the combination of thermal expansion and shear deformations that involves the ‘gliding’ of the Ca silicate layers relative to each other. The Raman spectrum of the compound contains the following bands (cm–1): 950 (ν3), 848 (ν1), 600 (ν4), 466 (ν2), 372 (ν2). The bands near 100–200 cm−1 can be described as lattice modes. The compound had also been found under natural conditions in association with chlorellestadite.

Alunogen, Al2(SO4)3·17H2O, occurs as an efflorescent in acid mine drainage, low-temperature fumarolic or pseudofumarolic (at coal fires) terrestrial environments. It is considered as one of the main Al-sulfates of Martian soils demanding comprehensive crystal chemical data of natural terrestrial samples. However, structural studies of natural alunogen were carried out in 1970s without localization of H atoms and have not previously been performed for samples from geothermal fields, despite the fact that these environments are considered as proxies of the Martian conditions. The studied alunogen sample comes from Verkhne-Koshelevsky geothermal field (Koshelev volcano, Kamchatka, Russia). Its chemical formula is somewhat dehydrated, Al2(SO4)3×15.8 H2O. The crystal structure was solved and refined to R1 = 0.068 based on 5112 unique observed reflections with I > 2σ(I). Alunogen crystalizes in P-1 space group, a = 7.4194(3), b = 26.9763(9), c = 6.0549(2) Å, α = 90.043(3), β = 97.703(3), γ = 91.673(3) °, V = 1200.41(7) Å3, Z = 2. The crystal structure consists of isolated SO4 tetrahedra, Al(H2O)6 octahedra and H2O molecules connected by hydrogen bonds. The structure refinement includes Al, S and O positions that are similar to previous structure determinations and thirty-four H positions localized for the natural sample first. The study also shows the absence of isomorphic substitutions in the composition of alunogen despite the iron-enriched environment of mineral crystallization. The variability of the alunogen crystal structure is reflected in the number of “zeolite” H2O molecules and their splitting. The structure complexity of alunogen and its modifications ranges from 333-346 bits/cell for models with non-localized H atoms to 783-828 bits/cell for models with localized H atoms. The higher values correspond to higher hydration state of alunogen.

The synthetic analogue of mineral stillwaterite, Pd8As3, was synthesised and its crystal structure was solved to R1 = 0.0341 based on single crystal X-ray diffraction data. Pd8As3 is trigonal and the space group is P$\bar{3}$. The unit-cell parameters are a = 7.4261(4), c = 10.3097(9) Å and V = 492.38(7) Å3 with Z = 3. The structure builds up by layers of Pd and As atoms. Pd-nets and As-nets are parallel to (110) and stack along the c axis direction. The stacking sequence is ABCDEEDCBA. The relation between structures of minerals with the common formula Pd8T3 (T = As or/and Sb) are discussed. They are formed by nets of pnictogen and palladium atoms. The common feature of the structures is 36 topology of pnictogen nets. The differences are stacking sequences and topology of the palladium nets.

Philipsburgite has been redefined as the intermediate member of the goldhillite–philipsburgite–kipushite isomorphous series with the ideal formula Cu5Zn[(AsO4)(PO4)](OH)6⋅H2O due to the site-selective As–P substitution. The new mineral goldhillite, ideally Cu5Zn(AsO4)2(OH)6⋅H2O [or Cu5Zn(AsO4)(AsO4)(OH)6⋅H2O], is the arsenate end-member of this series. Goldhillite occurs on fracture surfaces in a rock comprised mostly of quartz with iron hydroxides in association with mixite, cornwallite and conichalcite. Goldhillite forms transparent, bright emerald-green, tabular crystals with vitreous lustre, flattened on {100}, up to 1 mm across and in rosettes up to 1.5 mm. The mineral is brittle with uneven fracture and perfect cleavage on {100}; the Mohs hardness is 3.5. The calculated density for the holotype is 4.199 g cm–3. The Raman spectrum is consistent with the presence of H2O-molecules, OH-groups, AsO4 tetrahedra and traces of PO4. Electron microprobe analyses of goldhillite (H2O content based on the crystal structure) provided: CuO 48.91, ZnO 13.18, As2O5 26.06, P2O5 3.25, H2O 8.97, total 100.37 wt.%. The empirical formula for goldhillite based on O = 15 apfu is (Cu4.69Zn1.23)Σ5.92(As0.86P0.18O4)2(OH)5.61⋅H2O. The crystal structures of goldhillite and philipsburgite were determined using single-crystal X-ray diffraction data and refined to R1 = 0.054 (for 2365 I > 2σI reflections) and 0.052 (for 2308 I > 2σI reflections), respectively. Goldhillite is monoclinic, P21/c, a = 12.3573(5), b = 9.2325(3), c = 10.7163(4) Å, β = 97.346(4)°, V = 1212.59(8) Å3 and Z = 4. Philipsburgite is monoclinic, P21/c, a = 12.3095(9), b = 9.2276(3), c = 10.7195(3) Å, β = 97.137(7)°, V = 1208.16(10) Å3 and Z = 4. The strongest lines of the powder X-ray diffraction pattern of goldhillite [d, Å (I, %)(hkl)] are: 4.09 (28)(300), 3.41 (23)(12$\bar{2}$, 221, 311), 2.57 (100)(132, 11$\bar{4}$, 20$\bar{4}$), 2.17 (18)(42$\bar{3}$, 332), 1.95 (22)(432) and 1.54 (20)(13$\bar{6}$, 060). Goldhillite is named after its type locality, the Gold Hill mine, Tooele County, Utah, USA.

Aim to present a clinical case of the remnant of the Ozurdex implant in the vitreous body. Material and methods. One patient was under observation. During the preoperative examination and surgical treatment, two fragments of the Ozurdex implant were found in the vitreous body. Results. The presented clinical case shows that the remnants of the Ozurdex intravitreal implant can persist for 10 months or more after injection. This fact is clinically important for assessing the therapeutic effect and choice of further treatment tactics for a patient.

Supplementary Materials: The following supporting information can be downloaded at: www.mdpi.com/xxx/s1, Table S1: powder X-ray diffraction data for desautelsite sample 80137 including reflections of lizardite and dashkovaite; Table S2: anisotropic displacement parameters (Å2) for desautelsite.

The rapid implementation of membrane processes in the industry requires novel membrane materials. One of the promising ways to obtain a membrane material with improved properties is to combine the advantages of a polymer and a modifier (in particular, carbon nanoparticles). In the present work, novel pervaporation membranes based on hydroxyethyl cellulose (HEC)/polyvinyl alcohol (PVA) blend and HEC/PVA/fullerene derivative (polyhydroxylated fullerene, carboxyfullerene, and fullerene derivative with l-arginine) composites were developed for dehydration. The membrane composition and the cross-linking with maleic acid were optimized. The membranes were studied by Fourier-transform infrared spectroscopy, scanning electron and atomic force microscopies, thermogravimetric analysis, contact angle and swelling measurements. Transport properties of the membranes were studied in the pervaporation dehydration of isopropanol. The cross-linked dense HEC/PVA(30/70 wt%)/carboxyfullerene (5 wt%) membrane had the optimal transport properties in pervaporation dehydration of isopropanol (12–100 wt% water) at 22 °C: permeation flux of 24–1633 g/(m2 h), 99.99–98.3 wt% water in permeate.

Schreibersite, (Fe,Ni)3P, the most abundant cosmic phosphide, is a principal carrier of phosphorus in the natural Fe-Ni-P system and a likely precursor for prebiotic organophosphorus compounds at the early stages of Earth’s evolution. The crystal structure of the mineral contains three metal sites allowing for unrestricted substitution of Fe for Ni. The distribution of these elements across the structure could serve as a tracer of crystallization conditions of schreibersite and its parent celestial bodies. However, discrimination between Fe (Z = 26) and Ni (Z = 28) based on the conventional X-ray structural analysis was for a long time hampered due to the proximity of their atomic scattering factors. We herein show that this problem has been overcome with the implementation of area detectors in the practice of X-ray diffraction. We report on previously unknown site-specific substitution trends in schreibersite structure. The composition of the studied mineral encompasses a Ni content ranging between 0.03 and 1.54 Ni atoms per formula unit (apfu): the entire Fe-dominant side of the join Fe3P-Ni3P. Of 23 schreibersite crystals studied, 22 comprise magmatic and non-magmatic iron meteorites and main group pallasites. The near end-member mineral (0.03 Ni apfu) comes from the pyrometamorphic rocks of the Hatrurim Basin, Negev desert, Israel. It was found that Fe/Ni substitution in schreibersite follows the same trends in all studied meteorites. The dependencies are nonlinear and can be described by second-order polynomials. However, the substitution over the M2 and M3 sites within the most common range of compositions (0.6 < Ni

American mineralogist 105, 1-35 (2020). doi:10.2138/am-2021-7621, Minerals formed at high pressures are sensitive indicators of extreme pressure-temperature conditions that occur in nature. The discovery of the high-pressure polymorph of (Fe,Ni)$_2$P, allabogdanite in the surficial pyrometamorphic rocks of the Hatrurim Formation (the Mottled Zone) surrounding the Dead Sea basin in Israel is the first terrestrial occurrence of a mineral previously only found in iron meteorites. Stepwise annealing experiments demonstrate that allabogdanite is metastable at ambient pressure and that it irreversibly transforms into its low-pressure polymorph, barringerite, upon heating to 850±50°C. High-pressure high-temperature diamond-anvil cell (DAC) experiments confirm the results of annealing experiments. The DAC data indicate that Hatrurim allabogdanite is metastable below 7.4 GPa, and the low- to high-pressure phase transition (barringerite→allabogdanite) occurs at 25±3 GPa and 1400±100°C. The observed transition pressure of Hatrurim allabogdanite is significantly higher than that of pure synthetic Fe$_2$P (8 GPa), due to partial substitution of Fe for Ni (4 wt.%) and Mo (2.5 wt.%). Because the influence of substituting impurities on the conditions of phase transitions can be unexpectedly strong, our findings confirm that caution should be exercised when extrapolating data from experiments on synthetic compounds to natural systems. Based on the discovery of terrestrial allabogdanite (Fe,Ni)$_2$P coupled with experiments probing the phase transitions in this natural composition, we contend that terrestrial allabogdanite formed via transformation from barringerite and posit potential scenarios of its formation., Published by GeoScienceWorld, Alexandria, Va.

Kufahrite, PtPb, is a new mineral (IMA2020-045) from the Ledyanoy Creek placer, Koryak Highlands, Russia. The mineral was found in isoferroplatinum (Pt3Fe) grains extracted from a heavy-mineral concentrate, together with tetraferroplatinum (PtFe), tulameenite (Pt2FeCu), native iridium, hollingworthite (RhAsS) and Cr-rich spinel. Kufahrite occurs as part of alteration rims which are formed together with tetraferroplatinum after isoferroplatinum, or as grains up to 150 μm in size. According to powder X-ray diffraction analyses kufahrite is isotypic to its synthetic analogue, it is hexagonal and crystallises in space groupP63/mmcadopting the nickeline structure type. Its unit-cell parameters are:a =4.2492(6) Å;c =5.486(6) Å;V =85.78 Å3andZ =2. The calculated density is 14.80 g/cm–3. The strongest diffraction lines are [d, Å (I, %) (hkl)]: 3.052 (80) (101), 2.197 (100) (102), 2.125 (28) (110), 1.747 (18) (210), 1.528 (35) (202), 1.240 (18) (212) and 0.958 (22) (312). The Vickers hardness is 295 kg/mm2(range 262–320,n= 5), corresponding to a Mohs hardness of 4. The empirical formula of kufahrite, calculated from a mean value of 23 electron-microprobe analyses is (Pt0.94Rh0.04)Σ0.98(Pb0.83Sb0.19)Σ1.02. The name (pronounced as [ku fa rait]) honours Fahrid Shakirovitch Kutyev (1943‒1993), a geologist from the Institute of Volcanology of USSR Academy of Sciences, who played a key role in the discovery of the Koryak–Kamchatka Platinum Belt, including the Ledyanoy Creek placer platinum deposit, where the new mineral has been discovered.

Nine different samples of fluorellestadite from Chelyabinsk, Kizel and Kuznetsk coal basins were studied by single-crystal X-ray diffraction analysis, thermal X-ray diffraction (25–800 °C), Infrared (IR) and Raman spectroscopy. Fluorellestadite is hexagonal, space group P63/m, the unit-cell parameters for the nine samples studied vary within rather small ranges: a = 9.415(5) – 9.4808(7) A, c = 6.906(2) – 6.938(8) A, V = 530.3(4) – 538.41(9) A3. The mineral is isotypic with apatite, the structure is based upon isolated TO4 tetrahedra, where the T position is statistically occupied by Si4+ and S6+ with the ideal ratio Si:S equal to 1:1. The fluorine atoms are located in channels of the Ca4[(S,Si)O4]6 framework oriented parallel to the c axis. The thermal expansion of fluorellestadite is almost isotropic in the temperature range 25–800 °C (for ambient temperature: αa = 12.0·10−6 °C−1, αc = 11.9·10−6 °C−1; for 800 °C: αa = 18.2·10−6 °C−1, αc = 18.6·10−6 °C−1). A similar thermal behavior had been observed for fluorapatite. Despite the same structure motifs and close conditions of formation, the samples of fluorellestadite show different S/Si/P occupancies for T site and the F/Cl/OH (X-position) ratios.

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.

This work presents a detailed study of platinum-group mineral (PGM) assemblages from the Malaya Kamenushka River placer, whose formation is associated with the weathering of the Kamenushensky Uralian–Alaskan type massif, Middle Urals, Russian Federation. The deposit is characterised by the dominance of isoferroplatinum, together with significant numbers of inclusions of Os–Ir–Ru alloys and platinum-group element (PGE) sulfides. A study of the Os–Ir–Ru alloys permitted recognition of two types of iridium with different morphology and composition. The similarity of the PGM assemblages from the Malaya Kamenushka River placer and the lode mineralisation of the Kamenushensky massif is demonstrated. A comparison of PGM assemblages from the Malaya Kamenushka River placer with other placers and massifs of the Ural platinum belt demonstrates significant differences in the number of Os–Ir–Ru inclusions. Such differences for minerals of refractory elements cannot be explained by the vertical zoning of the lode mineralisation. Most probably this is associated with the enrichment of the primary substrate with Os, Ir and Ru and/or the degree of melting, depending on the chosen model of formation of the Uralian–Alaskan type massifs.

The crystal structure of arsenopalladinite, Pd8As2.5Sb0.5, from the Kaarreoja River, Inari commune, Finnish Lapland, Finland, was solved to R1 = 0.0451 on the basis of single-crystal X-ray diffraction data. The mineral is triclinic, space group P$\bar{1}$. The unit-cell parameters are: a = 7.3344(7), b = 7.3870(8), c = 7.5255(7) Å, α = 98.869(8), β = 102.566(8), γ = 119.096(11)°, V = 331.19(7) Å3 and Z = 2. The crystal structure of arsenopalladinite consists of an alternation of layers made by pnictogen (As, Sb) and layers made by palladium atoms stacked along the c axis. Arsenic and (As, Sb) nets exhibit a triangular topology (A and D nets), whereas palladium layers show triangular or pentagon–triangular nets (B and C nets). The unit-cell contains 6 layers, with the ABCDCBA stacking sequence. Although arsenopalladinite shows characteristics very similar (nets of the same topology) to the closely-related mineral mertieite-II, Pd8Sb2.5As0.5, it has a different stacking sequence.

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%).

A classification of discrete compounds in binary chiral systems of single and different substances (homo- and heteromolecular compounds) is presented. It considers both chemical and crystallographic characteristics of such compounds. Using amino acids as chiral model systems, features of crystal structures of equimolar and non-equimolar heteromolecular compounds are reviewed. In this connection, the concept of homo- and heteromolecular dimers in compounds formed by amino acids is introduced and analyzed. As a result, a correlation between the molecular dimer type and the side chain structure (linear or branched) and the conformation (extended or folded) of the relevant compounds' molecules is derived. Two non-equimolar discrete heterocompounds discovered in the chiral systems L-valine–L-isoleucine and L-valine–L-leucine are discussed using the concepts proposed. The previously studied first system features a 2 : 1 (Val : Ile) compound. A newly investigated second system is found to form a 3 : 1 (Val : Leu) compound, and its crystal structure is described and evaluated.

Novel membranes based on polyphenylene isophthalamide (PA) modified by fullerene derivatives (5 wt% with respect to PA weight) (polyhydroxylated fullerene (fullerenol), carboxyfullerene and fullerene derivative with L-arginine) were developed. The presence of PA/fullerene and PA/fullerene derivative composites and distribution of carbon nanoparticles after ultrasonic treatment in polymer solution was investigated by dynamic light scattering. The influence of carbon modifier on structural characteristics of PA was examined by nuclear magnetic resonance, small-angle X-ray scattering, scanning electron microscopy, atomic force microscopy, sorption experiments, density investigation and contact angle measurements of water. The transport properties were examined by pervaporation separation of industrially important methanol/toluene mixtures in two regimes (1. a series of experiments of different concentrations including azeotropic mixture and 2. only azeotropic mixture) to assess the effect of residual solvent in the PA membranes on their parameters. It was found that all membranes containing fullerene derivatives possessed improved permeation flux compared to pristine PA membrane. The optimal transport characteristics for the separation of methanol/toluene mixtures containing 10–72 wt% methanol were noticed for PA membrane modified by 5 wt% fullerenol due to the highest permeation fluxes (0.084–0.214 kg/(m2h)) and high level of selectivity (95.9 wt% methanol content in the permeate).

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.

The interaction of triethanolamine (TEA) with Cu(II) salts of salicylic, cinnamic and succinic acids was studied for the first time. The structure of the synthesized complexes was investigated by single-crystal X-ray diffraction. TEA complexes with Cu(II) salicylate (1) and cinnamate (2) are binuclear mixed ligand complexes, but interaction of TEA with Cu(II) succinate leads to the formation of cationic mononuclear complex—[Cu(TEA)2](C4H4O4) (3). Cu(II) complexes 1–3 were also characterized by physicochemical and spectroscopic methods. Their antimicrobial activity was investigated.

Novel porous and dense membranes based on polysulfone (PSF) modified by poly(ethylene glycol)–b–poly(propylene glycol)–b– poly(ethylene glycol) (Pluronic F127) were developed. The influence of Pluronic F127 introduction to the casting solution on different types of polymer membrane formation via two different phase inversion techniques—non-solvent induced phase separation (NIPS) for porous membranes and evaporation induced phase separation (EIPS) for dense membranes—was investigated. According to the triangular phase diagram obtained, PSF-Pluronic F127-N,N-dimethylacetamide (DMAc) systems feature lower critical solution temperature and have a tendency to micelle formation due to Pluronic F127 self-assembly. The structure, hydrophilic-hydrophobic balance and physicochemical properties of PSF-Pluronic F127 membranes were characterized by water contact angle measurements, scanning electron microscopy, nuclear magnetic resonance, small-angle X-ray scattering, and atomic force microscopy. The performance of dense membranes in pervaporation separation of water-ethyl acetate mixtures was investigated to reveal the effect of Pluronic F127 on the structure and free volume of the PSF-Pluronic F127 membranes. It was shown that Pluronic F127 introduction to the casting solution during membrane formation via two different techniques (NIPS and EIPS) leads to the increase in the pore size of the porous membranes and free volume of the dense membranes, as well as the increase in flux and surface hydrophilicity for both membrane types. Pluronic F127 was found to improve the antifouling performance of porous PSF-Pluronic F127 membranes in the BSA solution ultrafiltration. The introduction of 3 wt% Pluronic F127 into dense PSF membrane improved permeation flux in 1.7 and 2.7 times (15.1 and 27.3 g/(m2h)) at high selectivity level (100 wt% water in the permeate) during the separation of ethyl acetate-water mixtures (2 and 4 wt% ethyl acetate) compared to pristine PSF membrane.

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 z2 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.

We report a new occurrence of preiswerkite, the rare sodium analog of eastonite, the trioctahedral mica, from marble-hosted noble spinel deposits of the Luc Yen district, northern Vietnam. It is found in marble for the first time. The preiswerkite is anhedral and associated with phlogopite, aspidolite, sadanagaite, pargasite, spinel, corundum, dolomite and calcite. The average compositions of preiswerkite is (Na0.88Ca0.08K0.01)Σ0.97(Mg2.29Al0.72Fe0.04)Σ3.05)[(Al1.95Si2.05)Σ4.00O10](OH)2. The compositions of preiswerkite have a narrow range of Mg# values (0.96–0.99) and define a preiswerkite-aspidolite solid-solution series. Compared with other occurrences, the Luc Yen preiswerkite has a low iron content, which attains 0.09 atoms per formula unit (1.53 wt.% FeO). The formation of preiswerkite is favored by the proportion of Mg, Al and Si in the precursor rocks and the increased activity of sodium and H2O in the fluid phase.

Technogenic steklite, KAl(SO4)2, and unnamed mineral phase (K,Na)3Na3(Fe,Al)2(SO4)6 from burnt dumps of the Chelyabinsk Coal Basin have been investigated by single-crystal X-ray diffraction and electron microprobe analysis. Steklite is trigonal, space group P3&macr, a = 4.7277(3), c = 7.9871(5) &Aring, V = 154.60(2) &Aring, 3. The crystal structure was refined to R1 = 0.026 (wR2 = 0.068). It is based upon the [Al(SO4)2]&minus, layers formed by corner sharing of SO4 tetrahedra and AlO6 polyhedra. The anionic [Al(SO4)2]&minus, layers are parallel to the (001) plane and linked via interlayer K+ ions. The regular octahedral coordination of Al is observed that distinguishes technogenic steklite from that found in Tolbachik fumaroles. The (K,Na)3Na3(Fe,Al)2(SO4)6 phase is trigonal, space group R3&macr, a = 13.932(2), c = 17.992(2) &Aring, V = 3024.4(7) &Aring, 3, R1 = 0.073 (wR2 = 0.108). The crystal structure is based upon the anionic chains [(Fe,Al)(SO4)3]3&minus, running parallel to the c axis and interconnected via K+ and Na+ ions. There are no known minerals or synthetic compounds isotypic to (K,Na)3Na3(Fe,Al)2(SO4)6, due to the presence of separate K and Na sites in its structure.

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&ndash, 90 wt.% water) were achieved: 0.22&ndash, 1.30 kg/(m2h), 99.9 wt.% water in the permeate.

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.

The complexes [Cu{HC(3,5-Me2pz)3}(NCNR2)][BF4] (1–8; R2 = Me2 1, Et2 2, C5H10 3, C4H8O 4, C4H8 5, C3H6C6H4 [NC3H6C6H4 is 1,2,3,4-dihydroisoquinoline-2-yl] 6, (CH2Ph)2 7, (Me)Ph 8) were prepared by the reaction of [Cu(NCMe)4][BF4] with HC(3,5-Me2pz)3 and NCNR2 (CH2Cl2, 20–25 °C) and these species were characterized by C, H, N analyses, high resolution mass-spectrometry with electrospray ionization, 1H, 13C{1H} NMR and FTIR spectroscopic techniques, molar conductivity measurements, thermogravimetry/differential thermal analysis, and also by single-crystal X-ray diffraction for 3. The theoretical topological analysis of the electron density distribution (QTAIM method) together with the NBO analysis were applied to study the nature of Cu N and Cu C coordination bonds in [Cu{HC(3,5-Me2pz)3}(NCNMe2)]+, [Cu{HC(3,5-Me2pz)3}(NCMe)]+, and [Cu{HC(3,5-Me2pz)3}(CNMe)]+ model species. The nature of Cu N coordination bonds in [Cu{HC(3,5-Me2pz)3}(NCNMe2)]+ and [Cu{HC(3,5-Me2pz)3}(NCMe)]+ is very similar, whereas Cu C contact in [Cu({HC(3,5-Me2pz)3}(CNMe)]+ is relatively more covalent. The calculated vertical total energies for the Cu N and Cu C coordination bonds cleavage increase in the following row: [Cu{HC(3,5-Me2pz)3}(NCMe)]+ (36 kcal/mol)

Thermal behavior of three copper molybdates, lindgrenite, Cu3(MoO4)2(OH)2, szenicsite Cu3(MoO4)(OH)4, and cupromolybdite, Cu3O(MoO4)2, has been studied by high-temperature X-ray powder diffraction in the temperature range of 25–900 °C. The decomposition of lindgrenite and formation of cupromolybdite were observed at T > 325 °C according to the reaction: Cu3(MoO4)2(OH)2 → Cu3O(MoO4)2 + H2O. Szenicsite decomposes to cupromolybdite and tenorite at T > 350 °C according to the reaction: 2Cu3(MoO4)(OH)4 → Cu3O(MoO4)2 + 3CuO + 2H2↑. Cupromolybdite is stable up to 825 °C. The thermal expansion of lindgrenite, szenicsite and cupromolybdite is strongly anisotropic; the values of αmax/αmin are 5.6, 11.0 and 4.3, respectively. The maximal/minimal thermal expansion refers to the dominant direction of long/short Cu–O bonds owing to the distortion of CuO6 octahedral geometry due to the Jahn–Teller effect. For all three Cu molybdates, there are more or less aligned orientations of Jahn–Teller-distorted (CuO6) octahedra, which allows calculating the average 〈Cu–O〉 bond lengths along particular crystallographic directions. The 〈Cu–O〉 values observed are found to be in good correlation with the observed anisotropy of thermal expansion. The additional O2− anions in cupromolybdite act as coordination centers that form four strong Cu–O bonds each. These bonds propagate along the direction of the minimal thermal expansion, thus showing that the anion-centered structural motifs in cupromolybdite are the strongest after the Mo6+-centered (MoO4) tetrahedra.

Novel mixed-matrix membranes based on polyvinyl alcohol and its composites with carboxyfullerene were developed. Carboxyfullerene was simultaneously used as a modifier and a cross-linker for polyvinyl alcohol. The structural properties of the developed composites were studied by nuclear magnetic resonance, X-ray diffraction analysis, scanning electron microscopy, and sorption experiments. Thermal properties and stability were investigated by thermogravimetric analysis and differential scanning calorimetry. Surface features were studied by measuring the contact angles by water. The transport properties of the developed membranes were studied in ethanol-water mixtures separation by pervaporation (4.4–90 wt.% water in the feed) at different temperatures (22, 35, 50 °C). All membranes were selective with respect to water. The optimal transport properties were obtained for the PVA-carboxyfullerene (3.5 wt.%) membranes containing catalyst p-toluenesulfonic acid.

A novel effective method is reported for the preparation of 1-amino-1H-pyrazole-4-carboxylic acid derivatives by Fe(II)-catalyzed rearrangement of isoxazoles having (2,4-dinitrophenylhydrazono)methyl substituent at C4. The reaction proceeds smoothly for both E and Z isomers of 4-(hydrazonomethyl)isoxazoles, and this means it is not necessary to separate mixtures of E/Z-isomers of the hydrazones prepared by reaction of 5-methoxy/pirrolidino-4-carbonylisoxazoles and 2,4-dinitrophenylhydrazine. The rearrangement proceeds via the formation of an aziridine intermediate which can be isolated in certain cases. The 2-nitro group in the synthesized 1-[(2,4-dinitrophenyl)amino]-1H-pyrazole-4-carboxylic esters can be selectively reduced in two steps via acylation of the amino group followed by hydrogenation-deacylation using H2-Pd/C.

International audience; Novel supported membranes based on polyvinyl alcohol (PVA) were developed using two strategies: first, by the modification of the PVA network, via so-called bulk modification, with the formation of the selective layer accomplished through the introduction of fullerenol and/or poly(allylamine hydrochloride), and second, by the functionalization of the surface with successive depositions of multilayered films of polyelectrolytes, such as poly(allylamine hydrochloride) and poly(sodium 4-styrenesulfonate) on the PVA surface. The membrane surface modifications were characterized by scanning electron microscopy and contact angle measurements. The modified PVA membranes were examined for their dehydration transport properties by the perva-poration of isopropyl alcohol-water (80/20% w/w), which was chosen as a model mixture. Compared with the pristine PVA membrane, the main improvement was a marked increase in permeance. It was found that the surface modifications mainly gave rise to a higher global flux but with a strong reduction in selectivity. Only the combination of both bulk and surface modifications with PEL could significantly increase the flux with a high water content in the permeate (over 98%). Lastly, it should be noted that this study developed a green procedure to prepare innovative membrane layers for dehydration, making use of only water as a working medium.

Water-soluble forms of a series of 1-alkyl(aryl)imidazole-4,5-dicarboxylic acids were prepared. Anticonvulsant activity of 1-propylimidazole-4,5-dicarboxylic acid and its triethanolammonium salt was studied using the NMDA-induced convulsion model. The triethanolammonium salt of 1-propylimidazole-4,5-dicarboxylic acid was shown to possess anticonvulsant activity whereas the acid itself was a convulsant. The change of pharmacological profile was related to the formation of ion pairs or associates even in polar physiological media. The ability to associate was confirmed using conductivity measurements. An x-ray crystal structure analysis was performed for the triethanolammonium salt of 1-propylimidazole-4,5-dicarboxylic acid.

The new mineral novograblenovite, (NH4,K)MgCl3·6H2O, was found on basaltic lava from the 2012–2013 Tolbachik fissure eruption at the Plosky Tolbachik volcano, Kamchatka Peninsula, Russia. It occurs as prismatic, needle-like transparent crystals together with gypsum and halite. Novograblenovite was formed due to the exposure of the host rocks to eruptive gas exhalations enriched in HCl and NH3. Basalt was the source of potassium and magnesium for the mineral formation. Novograblenovite crystallises in the monoclinic space group C2/c, with unit-cell parameters a = 9.2734(3) Å, b = 9.5176(3) Å, c = 13.2439(4) Å, β = 90.187(2)°, V = 1168.91(2) Å3 and Z = 4. The five strongest reflections in the powder X-ray diffraction pattern [dobs, Å (I, %) (h k l)] are: 3.330 (100) (2 2 0), 2.976 (45) ($\bar{1}\; 1\; 4$), 2.353 (29) ($\bar {2}\; 2\; 4$), 3.825 (26) (2 0 2), 1.997 (25) ($\overline {4\; 2} $ 2). The density calculated from the empirical formula and the X-ray data is 1.504 g cm–3. The mineral is biaxial (+) with α = 1.469(2), β = 1.479(2) and γ = 1.496(2) (λ = 589 nm); 2Vmeas. = 80(10)° and 2Vcalc. = 75.7°. The crystal structure (solved and refined using single-crystal X-ray diffraction data, R1 = 0.0423) is based on the perovskite-like network of (NH4,K)Cl6-octahedra sharing chlorine vertices, and comprises [Mg(H2O)6]2+ groups in framework channels. The positions of all independent H atoms were obtained by difference-Fourier techniques and refined isotropically. All oxygen, nitrogen and chlorine atoms are involved in the system of hydrogen bonding, acting as donors or acceptors. The formula resulting from the structure refinement is [(NH4)0.7K0.3]MgCl3·6H2O. The mineral is named after Prokopiy Trifonovich Novograblenov, one of the researchers of Kamchatka Peninsula, a teacher, naturalist, geographer and geologist.

Philipsburgite, Cu5Zn((As,P)O4)2(OH)6·H2O, from the Middle Pit, Gold Hill Mine, Tooele Co., Utah, USA, was studied by single-crystal X-ray diffraction and scanning electron microscopy. The empirical formula of the studied sample is (Cu4.69Zn1.23)(As0.86P0.18O4)2(OH)5.61·H2O, which agrees well with the previous reports on the mineral. Philipsburgite is monoclinic, P21/c, a = 12.385(6), b = 9.261(4), c = 10.770(5) A, β = 97.10(1)o, V = 1225.7(9) A3 (at 100 K), and Z = 4. The crystal structure was refined to R1 = 0.046 for 2563 unique observed reflections with |Fo| ≥ 4σF. The crystal structure of philipsburgite is isotypic to that of kipushite and can be considered as a complex three-dimensional framework consisting of two types of layers stacked parallel to the a-axis. The A-type layer is formed by the edge-sharing Jahn–Teller-distorted Cuφ6 octahedra [φ = O2−, (OH)−, H2O]. Two adjacent octahedral layers are linked via (As2O4) tetrahedra. The B-type layer is built by corner-sharing (ZnO4) and (As1O4) tetrahedra and is formed by the four- and eight-membered tetrahedral rings. The A:B ratio of the A and B layers is equal to 2:1. The hydrogen bonding network in philipsburgite is rather complex and consists of two- and three-center hydrogen bonds. The As1 site accommodates ca. 18% of P and is a preferable position for the P substitution in philipsburgite. The observed selectivity of the As1 site for P may indicate that, for the intermediate compositions with the P:As ratios close to 1:1, there is a fully ordered species with P prevalent at the As1 site and As prevalent at the As2 site. The intermediate composition would, therefore, be Cu5Zn(AsO4)(PO4)(OH)6·H2O and such a mineral can be considered as a separate species, according to the rules of the International Mineralogical Association (IMA). Philipsburgite should be considered as structurally complex with the Shannon information contents of 4.954 bits/atom and 614.320 bits/cell. The obvious reason for the structural complexity of the mineral is its modularity, i.e., the presence of two structurally distinct modules, the octahedral–tetrahedral (A) and tetrahedral (B) layers.