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Ikaite is a calcium carbonate hexahydrate that forms at temperatures close to the freezing point of water; thus, its occurrence is associated with cryogenic conditions. This mineral is metastable and quickly transforms to calcite at temperatures above 5 °C. Pseudomorphs of calcite after ikaite are known as glendonite. The nanostructure of 25 000–43 000 year old glendonite from Victoria cave (Southern Ural, Russia) was investigated in search of structural features indicative of the ikaite-to-calcite transformation. Scanning electron microscope images display several micrometer- to submicrometer-size pores and indicate high intergranular porosity among the loosely aggregated grains. Transmission electron microscopy (TEM) data show evidence of 10–20 nm nanotwins [twin law (1014)] and 10–40 nm overlapping nanograins. Scanning TEM images reveal that the individual grains contain 5–10 nm long and 2–4 nm wide mesopores (sizes between 2 and 50 nm), which are aligned parallel to [1010] of calcite and might be associated with a crystallographically oriented dehydration of the precursor ikaite. Fourier transform infrared spectroscopy reveals no evidence of structural water but absorption bands related to molecular water trapped in fluid inclusions are present. Nitrogen absorption/desorption measurements show that the specific surface area of 5.78 m2/g and the pore volume of ~0.07 cm3/g for calcite, the constituent of glendonite, are comparable to those of a common natural calcite. We suggest that the aligned mesopores, frequently occurring twins, small grain size, presence of aqueous inclusions and the high micrometer- to submicrometer-size intergranular porosity arise from the ikaite-to-calcite transformation and thus may be used as criteria for the former presence of ikaite and hence for cold paleotemperatures. However, since similar features might also be common in biogenic carbonates, the diagnostic macroscopic pseudomorphs after ikaite are equally important for identifying glendonites and inferring cryogenic conditions.

Bizonyos nyomelemek ionos, illetve komplexen kötött vegyületei nélkülözhetetlenek számtalan biokémiai folyamatban, a humán szervezet megfelelő működéséhez. Hiányuk vagy akkumulációjuk számos egészségügyi problémát, betegséget okoz. Korábban az inzulinrezisztencia és a cukorbetegség kezelésében a nyomelemeket kulcsfontosságú faktornak gondolták, azonban a diabetes kialakulásában a nyomelemek hiánya, fontossága vagy a szövődmények kialakulásában és kezelésében a nyomelemstatus megítélése, a pótlás fontossága még ma is ellentmondásos. A szerzők ezért áttekintik a nyomelemek szerepét a diabetes kialakulásában, patogenezisében és progressziójában. Röviden beszámolnak a cink(II), a mangán(II, III), a réz(I, II), a króm(III), a vas(II, III), a kobalt(II), a vanádium(III, IV, V), a molibdén(IV, VI), a jód(I), a szelén(II, IV, VI) és a lítium(I) humán szervezetben ismert legfontosabb folyamatairól és a diabetesszel összefüggő biokémiai változásokról. Részletezik a nyomelemstatus eltéréseit diabetesben, kapcsolatukat a szabad gyökökkel és az antioxidáns védelmi rendszerrel. Rátérnek néhány rizikófaktor tárgyalására, amely súlyosabb mikroelemhiányhoz és szövődmények kialakulásához vezet. Orv Hetil. 2022; 163(33): 1303–1310.

Spray freeze-drying (SFD) is an effective method for reducing the size of thermosensitive organic substances that are sparingly soluble in water. Despite the advantages of the method, its use has not yet become widespread. We aimed at studying SFD technique for metronidazole as a heat-sensitive active pharmaceutical ingredient for reducing its particle size and investigated the morphological and physical parameters of the modified drug.The obtained particles were crystalline in all cases and their sizes were two and one order of magnitude smaller using water or dimethyl sulphoxide solutions, respectively, as compared to the initial reference metronidazole. The particle size varied depending on the experimental parameters (atomization pressure, peristaltic pump speed), although, the operating parameters had a smaller effect on the size of the materials than the applied concentration of starting solution, regardless of the solvent. The as-prepared samples had a microcrystalline structure that is retained for a long time.

One-pot cascade reaction systems offer several process and technological benefits, completed by the opportunity of the second enzyme to act on a convenient concentration of its substrate. Most of the reported cascade reactions involve immobilization of both biocatalysts on a single support, but in this case the catalytic performance of the whole system is affected if the activity of either enzyme drops. In this work, tailor-made immobilization of two β-galactosidases (from Kluyveromyces lactis and Aspergillus oryzae) and a glucose oxidase (from Aspergillus niger) was investigated, to subsequent utilization of the best performing immobilized biocatalyst of each type for the one-pot conversion of lactose to gluconic acid and galacto-oligosaccharides. The immobilization was performed by covalent binding onto amino-terminated Ni0.4Co0.2Zn0.4Fe2O4 and Ni0,5Zn0,5Fe2O4 magnetic particles and commercial amino- and epoxy-functionalized methacrylate supports. The highest activity for β-galactosidases was achieved on Ni0.5Zn0.5-Fe2O4 magnetic particles, meanwhile the glucose oxidase showed higher affinity for the supports with epoxy active groups. The immobilized biocatalysts have been characterized in detail, demonstrating enhanced storage, pH, and thermal stability as well as better operational stability compared to the soluble enzymes.

Copper manganese oxides (CMO) with CuMn2O4 composition are well-known catalysts, which are widely used for the oxidative removal of dangerous chemicals, e.g., enhancing the CO to CO2 conversion. Their catalytic activity is the highest, close to those of the pre-crystalline and amorphous states. Here we show an easy way to prepare a stable CMO material at the borderline of the amorphous and crystalline state (BAC-CMO) at low temperatures (

Two polymorphs and a solvatomorph of a new dimethylammonium polytungstate—decakis(dimethylammonium) dihydrogendodecatungstate, (Me2NH2)10(W12O42)·nH2O (n = 10 or 11)—have been synthesized. Their structures were characterized by single-crystal X-ray diffraction and solid-phase NMR methods. The shape of the dodecatungstate anions is essentially the same in all three structures, their interaction with the cations and water of crystallization, however, is remarkably variable, because the latter forms different hydrogen-bonded networks, and provides a highly versatile matrix. Accordingly, the N–H⋯O and C–H⋯O hydrogen bonds are positioned in each crystal lattice in a variety of environments, characteristic to the structure, which can be distinguished by solid-state 1H-CRAMPS, 13C, 15N CP MAS and 1H–13C heteronuclear correlation NMR. Thermogravimetry of the solvatomorphs also reflect the difference and multiformity of the environment of the water molecules in the different crystal lattices. The major factors behind the variability of the matrix are the ability of ammonium cations to form two hydrogen bonds and the rigidity of the polyoxometalate anion cage. The positions of the oxygen atoms in the latter are favourable for the formation of bifurcated and trifurcated cation–anion hydrogen bonds, some which are so durable that they persist after the crystals are dissolved in water, forming ion associates even in dilute solutions. The H atom involved in furcated hydrogen bonds cannot be exchanged by deuterium when the compound is dissolved in D2O. An obvious consequence of the versatility of the matrix is the propensity of these compounds to form multiple polymorphs.

Detailed vibrational (IR, Raman, far-IR) and thermal (TGA, TG–MS, DSC) analysis has been performed on di[κ1O,κ2O-carbonatotetraamminecobalt(III)] sulfate trihydrate, ([Co(NH3)4CO3]2SO4·3H2O (1). Its isothermic heating at 100 °C leads to formation of [Co(NH3)4CO3]2SO4 (compound 2). UV and IR studies showed that the distorted octahedral arrangement around cis-O2CoN4 core in compound 1 does not change during dehydration, which explains the reversible water loss and ability of compound 2 to rehydrate into compound 1. Compound 2 decomposes at ~ 240 °C in inert atmosphere giving final decomposition products, which are two modifications of nanosized metallic cobalt (hcp-15 nm, fcc-250 nm) and CoO (55 nm). The redox reaction results in N2 as an ammonia oxidation product. The decomposition intermediate is a cobalt(II) compound, Co2O1,14+δ(SO4)0.86 (δ = the oxygen surplus due to the presence of 2.8% of Co(III) ion). The same reaction in air atmosphere resulted in Co2O1.25+δ(SO4)0.75 (δ = the oxygen surplus due to the presence of 5.3% of Co(III) ion (compound 3a). Compound 3a is oxidized in air at 793 °C into Co3O4. The compound 3a exhibits catalytic activity in photodegradation in Congo red. The photodegradation process follows pseudo-first-order kinetic (kapp = 1.0 and 7.0. at pH = 3.4 and 5.25, respectively).

Ionic or complex compounds of certain trace elements are essential for the proper functioning of the human body in numerous biochemical processes. Their absence or accumulation causes many health problems and diseases. In the past, trace elements have been thought to be a key factor in the treatment of insulin resistance and diabetes, however, the importance and lack of trace elements in the development of diabetes or the assessment of trace element status in the development and treatment of complications are still controversial. Therefore, the authors summarize the role of trace elements in the development, pathogenesis, and progression of diabetes. They briefly report on the most important known processes of zinc(II), manganese(II, III), copper(I, II), chromium(III), iron(II, III), cobalt(II), vanadium(III, IV, V), molybdenum(IV, VI), iodine(I), selenium(II, IV, VI), and lithium(I) in the human body and the biochemical changes associated with diabetes. Differences in trace element status in diabetes, their relationship to free radicals, and the antioxidant defense system are detailed. Some risk factors that lead to more severe micronutrient deficiencies and complications are also discussed.Bizonyos nyomelemek ionos, illetve komplexen kötött vegyületei nélkülözhetetlenek számtalan biokémiai folyamatban, a humán szervezet megfelelő működéséhez. Hiányuk vagy akkumulációjuk számos egészségügyi problémát, betegséget okoz. Korábban az inzulinrezisztencia és a cukorbetegség kezelésében a nyomelemeket kulcsfontosságú faktornak gondolták, azonban a diabetes kialakulásában a nyomelemek hiánya, fontossága vagy a szövődmények kialakulásában és kezelésében a nyomelemstatus megítélése, a pótlás fontossága még ma is ellentmondásos. A szerzők ezért áttekintik a nyomelemek szerepét a diabetes kialakulásában, patogenezisében és progressziójában. Röviden beszámolnak a cink(II), a mangán(II, III), a réz(I, II), a króm(III), a vas(II, III), a kobalt(II), a vanádium(III, IV, V), a molibdén(IV, VI), a jód(I), a szelén(II, IV, VI) és a lítium(I) humán szervezetben ismert legfontosabb folyamatairól és a diabetesszel összefüggő biokémiai változásokról. Részletezik a nyomelemstatus eltéréseit diabetesben, kapcsolatukat a szabad gyökökkel és az antioxidáns védelmi rendszerrel. Rátérnek néhány rizikófaktor tárgyalására, amely súlyosabb mikroelemhiányhoz és szövődmények kialakulásához vezet. Orv Hetil. 2022; 163(33): 1303–1310.

Glycerol is an important starting material for the synthesis of many chemical compounds and its selective oxidation represents an efficient way to produce value-added compounds. Glyceric acid, one of these selective oxidation products, is an important intermediate in the food, medicine, cosmetics, and light industries. In this work, four commercially available native laccases were screened for glycerol oxidation using different initiators, and the two most efficient biocatalysts were covalently immobilized on functionalized magnetic and polymethacrylate (Lifetech™) solid supports. Apart from the mostly employed Fe

We reported on the synthesis of nanosized hydroxyapatite particles by wet chemical precipitation method and the consolidation of the nanoparticles by spark plasma sintering. We studied the effect of the synthesis temperature on the particle size and phase composition of the obtained HAp. During synthesis beyond HAp, another phase supposedly nonstoichiometric HAp was also formed as a by-product that can be detected by thermal analysis combined with XRD. Its amount gradually decreased with the increase in synthesis temperature and practically disappeared at 80 °C. Using this nanopowder for sintering, the spark plasma-sintered ceramics retained their nanostructure comprising only HAp phase in contrast to the powders synthesized at lower temperature when transformed products of the nonstoichiometric HAp could also be detected.

Two polymorphs and a solvatomorph of a new dimethylammonium polytungstate-decakis(dimethylammonium) dihydrogendodecatungstate, (Me

Compounds containing redox active permanganate anions and complexed silver cations with reducing pyridine ligands are used not only as selective and mild oxidants in organic chemistry but as precursors for nanocatalyst synthesis in low-temperature solid-phase quasi-intramolecular redox reactions. Here we show a novel compound (4Agpy2MnO4·Agpy4MnO4) that has unique structural features including (1) four coordinated and one non-coordinated permanganate anion, (2) κ1O-permanganate coordinated Ag, (3) chain-like [Ag(py)2]+ units, (4) non-coordinated ionic permanganate ions and an [Ag(py)4]+ tetrahedra as well as (5) unsymmetrical hydrogen bonds between pyridine α-CHs and a permanganate oxygen. As a result of the oxidizing permanganate anion and reducing pyridine ligand, a highly exothermic reaction occurs at 85 °C. If the decomposition heat is absorbed by alumina or oxidation-resistant organic solvents (the solvent absorbs the heat to evaporate), the decomposition reaction proceeds smoothly and safely. During heating of the solid material, pyridine is partly oxidized into carbon dioxide and water; the solid phase decomposition end product contains mainly metallic Ag, Mn3O4 and some encapsulated carbon dioxide. Surprisingly, the enigmatic carbon-dioxide is an intercalated gas instead of the expected chemisorbed carbonate form. The title compound is proved to be a mild and efficient oxidant toward benzyl alcohols with an almost quantitative yield of benzaldehydes.

Wood modification is an excellent and increasingly used method to expand the application of woody materials. Traditional methods, such as chemical or thermal, have been developed for the targeted improvement of some selected properties, unfortunately typically at the expense of others. These methods generally alter the composition of wood, and thus its mechanical properties, and enhance dimensional stability, water resistance, or decrease its susceptibility to microorganisms. Although conventional methods achieve the desired properties, they require a lot of energy and chemicals, therefore research is increasingly moving towards more environmentally friendly processes. The advantage of modern methods is that in most cases, they only modify the surface and do not affect the structure and mechanical properties of the wood, while reducing the amount of chemicals used. Cold plasma surface treatment is one of the cheapest and easiest technologies with a limited burden on the environment. In this review, we focus on cold plasma treatment, the interaction between plasma and wood compounds, the advantages of plasma treatment compared to traditional methods, and perspectives.

[NH4Cu(OH)MoO4] as active photocatalyst in the decomposition of Congo Red when irradiated by UV or visible light has been prepared in an unusual ammonia/water ligand exchange reaction of [tetraamminecopper(II)] molybdate, [Cu(NH3)4]MoO4. [Cu(NH3)4]MoO4 was subjected to moisture of open air at room temperature. Light blue orthorhombic [Cu(NH3)(H2O)3]MoO4 was formed in 2 days as a result of an unexpected solid/gas phase ammonia-water ligand exchange reaction. This complex does not lose its last ammonia ligand on further standing in open air; however, a slow quasi-intramolecular (self)-protonation reaction takes place in 2-4 weeks, producing a yellowish-green microcrystalline material, which has been identified as a new compound, [NH4Cu(OH)MoO4], ( a = 10,5306 A, b = 6.0871 A, c = 8.0148 A, β = 64,153°, C2, Z = 4). Mechanisms are proposed for both the sequential ligand exchange and the self-protonation reactions supported by ab initio quantum-chemical calculations and deuteration experiments as well. The [Cu(NH3)(H2O)3]MoO4 intermediate transforms into NH4Cu(OH)(H2O)2MoO4, which loses two waters and yields [NH4Cu(OH)MoO4]. Upon heating, both [Cu(NH3)4]MoO4 and [Cu(NH3)(H2O)3]MoO4 decompose, losing three NH3 and three H2O ligands, respectively, and stable [Cu(NH3)MoO4] is formed from both. The latter can partially be hydrated in boiling water into [NH4Cu(OH)MoO4. This compound can also be prepared in pure form by boiling the saturated aqueous solution of [Cu(NH3)4]MoO4. All properties of [NH4Cu(OH)MoO4] match those of the active photocatalyst described earlier in the literature under the formulas (NH4)2[Cu(MoO4)2] and (NH4)2Cu4(NH3)3Mo5O20.

Tetrachloroethylene (C2Cl4) has been used widely as a solvent and dry cleaning agent, but was later specified as possible human carcinogen. As a result, its safe treatment became a priority. In this paper, we report on its decomposition in an atmospheric radiofrequency thermal plasma reactor. Main components of the exhaust gases were determined by Fourier transform infrared spectroscopy. We found that complete decomposition can be achieved in either oxidative or reductive conditions but not in neutral one. The solid soot product was characterised by transmission electron microscopy and specific surface area measurement. Organic compounds adsorbed on the surface of the soot were extracted by toluene and comprised, based on gas chromatography mass spectrometry, of various perchlorinated aliphatic (for example hexachlorocyclopentadiene) and aromatic compounds (like hexachlorobenzene, octachloronaphthalene or octachloroacenaphthylene). Several nitrogen containing molecules were also identified whose presence are rare during thermal plasma treatments. Further investigation of the extract by mass spectrometry revealed various higher molar mass chlorinated carbon clusters and two types of fullerenes (C60 and C70).

This paper presents a fast and efficient method of removing the template from silica thin films on polycarbonate. Radiofrequency-generated oxygen plasma induced the decomposition of the non-ionic surfactant. The reference samples were silica coatings on silicon, which had different pore sizes. We removed the surfactant by solvent extraction and calcination from these samples. Grazing incidence angle X-ray diffraction analysis shows a highly ordered arrangement of mesopores. The formation of the face-centred cubic structure of mesopores is independent of the substrate and the template removal method. Atomic force microscopy analysis showed open-pore channels after oxygen plasma etching. It also proved that the ammonia treatment increases the hardness of the layer. A short air-plasma treatment is effective for the consolidation of the silica layer and improves the abrasion resistance of the layer on polycarbonate. Air plasma treatment is an alternative to the long heat treatment process. We performed environmental tests according to the relevant ISO standards for optical coatings. Air plasma treated silica coatings have passed all the weathering tests. Therefore, it can be used in outdoor applications, such as a protective layer for the plastic cover of LED street lights. These thin films on polycarbonate have at least one year of service life and are weather-resistant. Plasma treatment can consolidate the silica network and the thin films on polycarbonate have high light transmission (T = 98.8 %).

A study is presented on the plasma treatment of two different ultra-high molecular weight polyethylene (UHMWPE) and polypropylene (PP) surfaces by using diffuse coplanar surface barrier discharges under atmospheric air conditions. The plasma-treated polymer surfaces are characterized in terms of wettability, surface chemistry, topography, adhesion and tribology. It is found that plasma treatment significantly improves wettability through formation of various oxygen containing functionalities at the surface. The plasma treatment consequently improves adhesion for either polymer/polymer or polymer/steel joints. Under dry sliding conditions the coefficient of friction slightly increases after plasma treatment in parallel with the higher adhesion. In contrast, the coefficient of friction significantly decreases under oil lubrication conditions and it remains low even after cleaning the oil likely due to the improved oil retention capability of the plasma-treated surface. The observed tendencies in adhesion and friction are further analyzed in terms of surface chemistry after plasma treatment and after sliding by use of spectroscopic methods and chemical imaging.

Silicon nitride (Si 3 N 4 ) ceramics exhibit remarkable mechanical, chemical and thermal properties; however, fracture toughness is a decisive characteristic for these advanced ceramics. In this paper, an alternative route to improve the fracture toughness of Si 3 N 4 ceramics is presented. In order to enhance the fracture behaviour, we used ZrO 2 nanofibres to combine two types of toughening effects such as fibre toughening and phase transformation toughening. We characterized the effect of nanofibers on the mechanical properties using instrumented hardness, Young's modulus, fracture toughness and bending tests. In order to compare the effects of nanofibers, we also studied silicon-nitride ceramics containing ZrO 2 particles. The results of fracture toughness and flexural strength measurements show a significant improvement: 15 wt% ZrO 2 fibre exhibits 10.05 ± 0.7 MPa m 1/2 fracture toughness and 543 ± 19 MPa flexural strength, which means 105% and 115% improvements compared to the reinforcement-free samples. We assume that ZrO 2 nanofibres can increase the mechanical properties of the composites in a complex way, including phase transformation toughening and fibre-toughening mechanisms.

Silicon carbide (SiC) ceramics have superior properties in terms of wear, corrosion, oxidation, thermal shock resistance and high temperature mechanical behavior, as well. However, they can be sintered with difficulties and have poor fracture toughness, which hinder their widespread industrial applications. In this work, SiC-based ceramics mixed with 1 wt% and 3 wt% multilayer graphene (MLG), respectively, were fabricated by solid-state spark plasma sintering (SPS) at different temperatures. We report the processing of MLG/SiC composites, study their microstructure and mechanical properties and demonstrate the influence of MLG loading on the microstructure of sintered bodies. It was found that MLG improved the mechanical properties of SiC-based composites due to formation of special microstructure. Some toughening mechanism due to MLG pull-out and crack bridging of particles was also observed. Addition of 3 wt% MLG to SiC matrix increased the Vickers hardness and Young's modulus of composite, even at a sintering temperature of 1700 °C. Furthermore, the fracture toughness increased by 20% for the 1 wt% MLG-containing composite as compared to the monolithic SiC selected for reference material. We demonstrated that the evolved 4H-SiC grains, as well as the strong interactions among the grains in the porous free matrices played an important role in the mechanical properties of sintered composite ceramics.

Amorphous calcium carbonate (ACC) is a precursor of crystalline calcium carbonates that plays a key role in biomineralization and polymorph evolution. Here, we show that several bacterial strains isolated from a Hungarian cave produce ACC and their extracellular polymeric substance (EPS) shields ACC from crystallization. The findings demonstrate that bacteria-produced ACC forms in water-rich environment at room temperature and is stable for at least half year, which is in contrast to laboratory-produced ACC that needs to be stored in a desiccator and kept below 10 °C for avoiding crystallization. The ACC-shielding EPS consists of lipids, proteins, carbohydrates and nucleic acids. In particular, we identified large amount of long-chain fatty acid components. We suggest that ACC could be enclosed in a micella-like formula within the EPS that inhibits water infiltration. As the bacterial cells lyse, the covering protective layer disintegrates, water penetrates and the unprotected ACC grains crystallize to calcite. Our study indicates that bacteria are capable of producing ACC, and we estimate its quantity in comparison to calcite presumably varies up to 20% depending on the age of the colony. Since diverse bacterial communities colonize the surface of cave sediments in temperate zone, we presume that ACC is common in these caves and its occurrence is directly linked to bacterial activity and influences the geochemical signals recorded in speleothems.

Compounds containing redox active permanganate anions and complexed silver cations with reducing pyridine ligands are used not only as selective and mild oxidants in organic chemistry but as precursors for nanocatalyst synthesis in low-temperature solid-phase quasi-intramolecular redox reactions. Here we show a novel compound (4Agpy

The surfaces of two engineering polymers including polyamide 66 (PA66) and polytetrafluoroethylene (PTFE) were treated by diffuse coplanar surface barrier discharges in atmospheric air. We found that plasma treatment improved the adhesion of PA66 for either polymer/polymer or polymer/steel joints, however, it was selective for the investigated adhesive agents. For PTFE the adhesion was unaltered for plasma treatment regardless the type of used adhesive. Tribological properties were slightly improved for PA66, too. Both the friction coefficient and wear decreased. Significant changes, again, could not be detected for PTFE. The occurred variation in the adhesion and tribology was discussed on the basis of the occurred changes in surface chemistry, wettability and topography of the polymer surface.

In this paper we report the synthesis of a N, S co-doped metal free carbon cryogel obtained from a marine biomass derived precursor using urea as nitrogen source. Natural carrageenan intrinsically contains S and inorganic salt. The latter also serves as an activating agent during the pyrolytic step. The overall 11.6 atomic % surface heteroatom concentration comprises 5% O, 4.6% N and 1% S. The purified and annealed final carbon (CA) has a hierarchical pore structure of micro-, meso- and macropores with an apparent surface area of 1070 m2/g. No further treatment was applied. The gas adsorption potential of the samples was probed with H2, CO2 and CH4, while the electrocatalytic properties were tested in an oxygen reduction reaction. The atmospheric CO2 and CH4 storage capacity at 0 °C in the low pressure range is very similar to that of HKUST-1, with the CO2/CH4 selectivity below 20 bar, even exceeding that of the MOF, indicating the potential of CA in biogas separation. The electrocatalytic behavior was assessed in an aqueous KOH medium. The observed specific gravimetric capacitance 377 F/g was exceeded only in B, N dual doped and/or graphene doped carbons from among metal free electrode materials. The CA electrode displays almost the same performance as a commercial 20 wt% Pt/C electrode. The oxygen reduction reaction (ORR) exhibits the 4-electron mechanism. The 500-cycle preliminary stability test showed only a slight increase of the surface charge.

Surface treatments are commonly employed on woven fabrics to render properties such as dyeability, antibacterial feature, self-cleaning, etc. A variety of environmentally benign cold plasma treatments present a viable alternative to the conventional wet chemical processes. The various plasma designs, however, may differ in the efficiency and the effect they exert on the fabrics. In this work a polyester woven fabric was treated by diffuse co-planar surface barrier discharges in atmospheric air for various lengths of time. X-ray photoelectron spectroscopy investigation revealed that changes in surface chemistry occurred within 30 s of treatment. Carbon containing contaminations were removed and the surface became more oxidized, however, new chemical states have not been developed. As an effect, wettability and wickability of the fabric significantly increased. A slight increase in the roughness also occurred after treatment according to AFM measurements. The tensile strength of the fabric showed a gradually decreasing trend with respect to treatment time that could be attributed to damaged sites in the fabric generated by the local excessive etching of the plasma. The results show the detrimental effect of prolonged plasma treatment on the woven poly(ethylene-terephthalate) (PET) fabrics. Employing longer treatment times of 120 s and 180 s the mechanical properties reduced by ca. 40% and 50%, respectively, without significant changes in the surface morphology.

Decomposition of poly(vinyl chloride) (PVC) was studied in inductively coupled radiofrequency thermal plasma in neutral, oxidative and reductive conditions. The exhaust gases were analysed by Fourier transform infrared spectroscopy (FT-IR), and their main components were identified as CO, CO 2 , C 2 H 2 , H 2 O and HCl. The weaker bands in the infrared spectra were assigned by density function theory calculations and P–R separation method. The extent of PVC decomposition was calculated from the amount of solid soot, which was also studied by transmission electron microscopy (TEM) for morphology and composition. Organic compounds adsorbed on the surface of the soot were extracted by toluene and analysed by gas chromatography mass spectrometry (GC/MS). The extracts comprised of various polycyclic aromatic hydrocarbons (PAHs) and their methylated and chlorinated derivatives. Their amount was greatly affected by the experimental conditions. The presence of oxygen decreased the formation of PAHs, while it increased the formation of polychlorinated PAH compounds. In the presence of hydrogen PAH formation was observed. However, dioxin or furan derivatives were not detected in the decomposition products.

[NH

β- d -Galactosidase from Kluyveromyces lactis was for the first time immobilized by entrapment in hybrid organic-inorganic sol–gel materials with microporous structure, obtained from alkoxy silanes and alkyl substituted alkoxy silanes, in different combinations. The immobilization matrix was tailored by fine tuning of several parameters, such as: nature of alkyl group of silane precursors, molar ratio of silane precursors , nature of additives, protein concentration. Unlike other enzymes, β- d -galactosidase showed the best catalytic activity at low alkyl group content in the sol–gel matrix, at a molar ratio of 7:1 between the tetraalkoxysilane alkyl-trialkoxysilane precursor. The immobilized enzyme demonstrated enhanced storage, pH and thermal stability compared to the soluble enzyme. The composite sol–gel materials were characterized by transmission electron microscopy, scanning electron microscopy, fluorescence confocal microscopy, and porosity measurement. The biocatalyst was successfully reused in five reaction cycles, maintaining more than 60% of the initial activity.

In this paper, raw cotton fabric was pretreated with non-thermal atmospheric air-plasma and the accessibility of the surface polymers of the fibers and yarns that act as respective substrates for the enzymes was evaluated. Results proved that plasma slightly destroyed and oxidized the starch size on the surface of warp yarns and partially removed the thin and perfectly hydrophobic waxy coverage of the fibers in weft yarns, creating deep “pits” with a depth of 215 nm. This latter process contributed to the exposure of cellulose and pectin located under the waxy outer layer of the elementary fibers in the weft yarns, and significantly increased the surface roughness of the fibers (from Rq of 25 to 67 nm for the raw and 180 s plasma-treated samples, respectively). Amount of the reducing sugars released during the amylase and cellulase digestion of the plasma-treated fabrics confirmed that air-plasma significantly increased the accessibility of the starch and cellulose, respectively, to the enzymes and resulted in an enhanced solubilization of both polymers. Since the plasma-treated substrates displayed significantly faster enzyme reactions, the time of enzymatic treatments can be sharply reduced.

Transmission electron microscopy (TEM), X-ray diffractometry (XRD), in situ diffuse reflectance ultra violet – visible (UV–Vis) spectroscopy, and temperature-programmed reduction by hydrogen (H 2 -TPR) were used to identify the vanadia forms in vanadium-containing SBA-15 preparations (VO x /SBA-15). Wacker type supported Pd/VO x /SBA-15 catalysts were obtained by introducing Pd into VO x /SBA-15 samples using conventional impregnation method. The activity of the catalysts was tested in the gas phase partial oxidation of ethylene by O 2 in the presence of H 2 O (Wacker oxidation). VO x /SBA-15 sample was obtained by micelle-templated synthesis using vanadium-containing synthesis gel. The vanadium became incorporated in the silica structure from the gel in near to atomic dispersion. This catalyst was quite active in ethylene oxidation to CO 2 but had low Wacker activity. Isolated, polymeric and bulk vanadia species were identified in the VO x /SBA-15 prepared by wet impregnation/calcination method. The specific surface area of the sample was found to be smaller than that of the neat SBA-15 support because some pores were blocked by vanadia agglomerates. The corresponding Pd/VO x /SBA-15 catalyst showed high selectivity for acetaldehyde formation but the activity was relatively low due to low accessible active surface. A third VO x /SBA-15 sample was obtained by applying directed surface reaction between silanol groups of dehydrated SBA-15 and anhydrous solution of vanadyl acetylacetonate. Large number of accessible Pd/VO x sites were present in the corresponding Pd/VO x /SBA-15 catalyst. Latter catalyst induced ethylene oxidation to acetaldehyde with high yield at temperatures ≤160 °C and with good yield to acetic acid at temperatures ≥160 °C.

Volatile carboxylic acids (mainly acetic acid) can be produced efficiently by simple thermochemical or biological degradation of various biomasses. For the processing of such oxygenates in hydrogen atmosphere, acetic acid (AA) hydroconversion was studied in detail over zeolite-based Ni and bimetallic InNi catalysts in a flow-through reactor at 21 bar total pressure and 240–380 °C. Efficient hydrogenating contacts were already obtained by in situ reduction of Ni-zeolites (A, X, P) and mainly co-reduction of their mixtures with In2O3 in H2 flow at 21 bar and 450 °C. Under these conditions, the bulk of charge-compensating nickel cations remained unreduced and therefore a large portion of the microporous zeolite structure was still preserved. Modification of the formed Ni particles with indium quest metal generated bimetallic NiIn/Ni,H-zeolite catalysts having higher hydroconversion activity with much lowered hydrodecarbonylation and with enhanced ethanol selectivity than the parent partially destructed Ni/Ni,H-zeolite. The activity dependence on the reactant partial pressure denotes rate-controlling surface reaction according to the Langmuir–Hinshelwood mechanism.

Step by step alkylation of acetone (A) with ethanol (E) in a ratio of 1 : 2 was investigated. A fixed bed flow-through reactor system was used at a total pressure of 21 bar and in the temperature range of 150–350 °C in inert He or a reducing H2 medium. Following the hydrogen borrowing methodology, two types of catalysts were prepared; using neutral activated carbon (AC) and alkaline hydrotalcite (HT) supports, namely 5 wt% Pd/AC in the presence of alkaline additives (10, 20 and 30 wt% KOH or 20% K3PO4); 9 wt% Cu/HT and 5 wt% Pd/HT. The catalysts were activated in a H2 flow at 350 °C. Different yields of mono- or dialkylated ketones were observed. In a hydrogen medium over the same catalyst systems the ketone products could be reduced to alcohols. In this study the Pd/HT catalyst seems to be the most promising for fuel production based on biomass fermentation.

Solid, nanoporous silica-based spherical mesoporous MCM-41 and KIL-2 with interparticle mesoporosity as well as nanosized zeolite BEA materials differing in morphology and pore size distribution, were used as carriers for the preparation of resveratrol-loaded delivery systems. Two preparation methods have been applied: (i) loading by mixing of resveratrol and mesoporous carrier in solid state and (ii) deposition in ethanol solution. The parent and the resveratrol loaded carriers were characterized by XRD, TEM, N2 physisorption, thermal analysis, and FT-IR spectroscopy. The influence of the support structure on the adsorption capacity and the release kinetics of this poorly soluble compound were investigated. Our results indicated that the chosen nanoporous silica supports are suitable for stabilization of trans-resveratrol and reveal controlled release and ability to protect the supported compound against degradation regardless of loading method. The solid-state dry mixing appears very effective for preparation of drug formulations composed of poorly soluble compound. - Graphical abstract: trans-Resveratrol was stabilized in the pores of BEA zeolite, MCM-41and KIL2 mesoporous silicas. - Highlights: • BEA, KIL-2 and MCM-41 materials were used as carriers for resveratrol loading. • Resveratrol encapsulation in ethanol solution and solid state procedure were applied. • The solid-state preparation appears very effective formore » stabilization of trans-resveratrol.« less

Transformation of ethylbenzene (EB, 22 wt%)- m -xylene (78 wt%) mixture was carried out over zeolite MCM-22 catalysts with different acidities. The modification of the number and strength of the acid sites was attained by: (i) dealumination by steaming and successive acid treatment and (ii) isomorphous substitution of framework Al for boron ([Al,B]MCM-22). The effect of platinum introduction was also investigated. The strong decrease in the Bronsted acidity, concomitant to the dealumination procedure, appears unfavorable since it leads to a drastic diminish of the degree of EB conversion, not compensated by satisfactory level of m -xylene isomerization. [Al,B]MCM-22 is a modification with much better performance, most probably because it contains both strong, Al-connected acid sites but in lower amount than in the parent sample, and weaker boron-generated sites and practically no any Lewis sites. Parent zeolite [Al]MCM-22 as well as B-substitution possess promising properties for ethylbenzene- m -xylene mixture transformation catalyst with adequate degree of EB conversion and extent of p -xylene approach to equilibrium as well as low xylene loss.

Continuous synthesis of TiB x ( x ≈0.5–2) nanoparticles from various low cost solid precursors such as titanium and titanium dioxide admixed with boron and/or carbon in radiofrequency thermal plasma was studied. Feasibility of TiB 2 formation was predicted by thermodynamic equilibrium calculations in the 500–5000 K temperature range. In all the investigated system high temperature reactions resulted in nanometer-sized TiB x powders with a mean size varying between 13 and 83 nm. The yield of particular runs ranged from 38% to 97%. Among the synthesized products in addition to TiB x , oxidized precursor residues were also found in smaller quantities. Although addition of carbon to the precursors could not completely prevent surface oxidation of boride particles, it contributed to the reduction of the mean particle size of the formed TiB 2 .

Copper and iron modified SBA-15 and SBA-16 materials were prepared by incipient wetness impregnation technique and characterized by X-ray diffraction (XRD), transmission electron microscopy (TEM), N2 physisorption, temperature-programmed reduction (TPR-TGA), UV–Vis diffuse reflectance and Mossbauer spectroscopy. Formation of finely dispersed copper and iron-oxide species was observed on both supports, whereas copper ferrite could be evidenced only on SBA-15. It was found that the structural and surface properties of the mesoporous supports determine the type of formed metal oxides, their dispersion, reducibility and the catalytic activity in total oxidation of toluene. On SBA-16 support penetration of metal salt into the bimodal channel system is hindered therefore separate copper- and iron-oxide phases are formed on the outer surface of catalysts. The catalytic activity and stability are lower due to the easier agglomeration of particles. On SBA-15 support finely dispersed metal-oxides can be found in the mesoporous channels. Their interaction is favored to form bimetallic phases enhancing the catalytic activity and stability in total oxidation of toluene.

Volatile fatty acids (VFAs) can be produced efficiently by simple thermochemical or biological biomass degradation. For the processing of these organic acids in hydrogen atmosphere, the consecutive reactions of acetic acid (AA) hydroconversion were studied in details looking for conditions of selective ethanol production over a novel and advantageous bimetallic composite applying indium as co-catalyst. The reactions were investigated in vapor phase at 240–380 °C, 7–21 bar hydrogen and 0.5–3.5 bar acetic acid partial pressures in a fixed bed flow-through reactor using supported copper catalysts. In2O3 admission can significantly increase AA hydroconversion activity of copper catalysts supported on various oxides and the yield of the produced ethanol. Efficient hydrogenating catalysts, containing finely dispersed metal particles were obtained by in situ reduction with H2 at 450 °C. In the catalysts modified with In2O3 additive, formation of an intermetallic compound (Cu2In) was strikingly observed resulting in a different, more advantageous catalytic behavior as of pure copper particles supported on different oxide supports. On comparing a commercial, conventionally used catalysts (Adkins: 72 wt% CuCr2O4 + 28 wt% CuO) with the bimetallic alumina supported composite (Cu2In/Al2O3) the new catalyst proved to be much more active and selective for producing ethanol. A schematic representation of reactions involved in the hydroconversion of acetic acid was explored and verified. The activity dependence on the reactant partial pressures denotes rate-controlling surface reaction according to Langmuir–Hinshelwood mechanism.