Mechanochemically Synthesised Dicyanamide Hybrid Organic-Inorganic Perovskites and their Melt-Quenched Glasses

Here we present efficient and scalable mechanochemical formation of hybrid organic-inorganic perovskites of the form [TPrA][M(dca)₃] (M = Mn²⁺, Co²⁺) and the subsequent formation of their bulk melt-quenched glass samples. The thermal, chemical and adsorptive properties of the materials are also investigated.

Indirect Flow Diversion for Off-Centered Bifurcation Aneurysms and Distant Small-Vessel Aneurysms, a Retrospective Proof of Concept Study From Five Neurovascular Centers

Background: Treatment of cerebral aneurysms using hemodynamic implants such as endosaccular flow disruptors and endoluminal flow diverters has gained significant momentum during recent years. The intended target zone of those devices is the immediate interface between aneurysm and parent vessel. The therapeutic success is based on the reduction of aneurysmal perfusion and the subsequent formation of a neointima along the surface of the implant. However, a subset of aneurysms–off-centered bifurcation aneurysms involving the origin of efferent branches and aneurysms arising from peripheral segments of small cerebral vessels–oftentimes cannot be treated via coiling or implanting a hemodynamic implant at the neck level for technical reasons. In those cases, indirect flow diversion–a flow diverter deployed in the main artery proximal to the parent vessel of the aneurysm–can be a viable treatment strategy, but clinical evidence is lacking in this regard.Materials and Methods: Five neurovascular centers contributed to this retrospective analysis of patients who were treated with indirect flow diversion. Clinical data, aneurysm characteristics, anti-platelet medication, and follow-up results, including procedural and post-procedural complications, were recorded.Results: Seventeen patients (mean age: 60.5 years, range: 35–77 years) with 17 target aneurysms (vertebrobasilar: n = 9) were treated with indirect flow diversion. The average distance between the flow-diverting stent and the aneurysm was 1.65 mm (range: 0.4–2.4 mm). In 15/17 patients (88.2%), perfusion of the aneurysm was reduced immediately after implantation. Follow-ups were available for 12 cases. Delayed opacification (OKM A3: 11.8%), reduction in size (OKM B1-3: 29.4%) and occlusion (D1: 47.1%) were observable at the latest investigation. Clinically relevant procedural complications and adverse events in the early phase and in the late subacute phase were not observed in any case.Conclusion: Our preliminary data suggest that indirect flow diversion is a safe, feasible, and effective approach to off-centered bifurcation aneurysms and distant small-vessel aneurysms. However, validation with larger studies, including long-term outcomes and optimized imaging, is warranted.

Methodological approaches to efficiency evaluation foreign economic activity agricultural enterprises

The article is devoted to topical issues of development of existing and establishment of new approaches to the methodology of assessing the effectiveness of foreign economic activity of agricultural enterprises with the subsequent formation of strategies for its development. Thanks to the successful operation of domestic agricultural enterprises in foreign markets and effective and fruitful cooperation with foreign partners, economic growth of the country as a whole is achieved. Therefore, in modern economic conditions, the increase in foreign economic activity requires a thorough methodological approach to assessing the effectiveness of foreign economic activity of agricultural enterprises. The theoretical and methodological basis of research were the works of leading domestic and foreign economists and the work of leading analysts on the problems and methodology of modeling foreign economic activity, comprehensive approaches based on a combination of economic analysis and methods of economic and mathematical modeling. The following research methods were used in solving the tasks: monographic, analysis and synthesis, expert evaluations, deduction method and abstract-logical. In order to implement the organizational and economic mechanism for determining the foreign economic activity of agricultural enterprises, we propose to use a universal method of foreign economic activity analysis and at the micro level in order to compare the obtained calculations to assess trends in the development of foreign economic activity of agricultural enterprises. If an agricultural enterprise is engaged in both exports and imports, then to assess its performance in the foreign market for a certain period can be calculated integrated indicators of foreign trade, which provide for the comparability of results achieved for the whole set of export-import operations at full cost. The initial methodological basis for assessing and analyzing the foreign economic activity of agricultural enterprises should be a systematic analysis and a comprehensive, dialectical approach, which necessitates the study of individual elements and the system as a whole in constant motion, change, in the process of constant renewal. This is important not only for understanding the essence of economic categories but also for formulating conclusions on their practical application, making management decisions at different levels of the hierarchical management system in the agricultural sector of Ukraine. The practical significance of the results of the study lies in the substantiation of the methodology, which allows to calculate and fully assess the effectiveness of foreign economic activity of any agricultural enterprise.

The biosynthesis of thymol, carvacrol, and thymohydroquinone in Lamiaceae proceeds via cytochrome P450s and a short-chain dehydrogenase

Thymol and carvacrol are phenolic monoterpenes found in thyme, oregano, and several other species of the Lamiaceae. Long valued for their smell and taste, these substances also have antibacterial and anti-spasmolytic properties. They are also suggested to be precursors of thymohydroquinone and thymoquinone, monoterpenes with anti-inflammatory, antioxidant, and antitumor activities. Thymol and carvacrol biosynthesis has been proposed to proceed by the cyclization of geranyl diphosphate to γ-terpinene, followed by a series of oxidations via p-cymene. Here, we show that γ-terpinene is oxidized by cytochrome P450 monooxygenases (P450s) of the CYP71D subfamily to produce unstable cyclohexadienol intermediates, which are then dehydrogenated by a short-chain dehydrogenase/reductase (SDR) to the corresponding ketones. The subsequent formation of the aromatic compounds occurs via keto–enol tautomerisms. Combining these enzymes with γ-terpinene in in vitro assays or in vivo in Nicotiana benthamiana yielded thymol and carvacrol as products. In the absence of the SDRs, only p-cymene was formed by rearrangement of the cyclohexadienol intermediates. The nature of these unstable intermediates was inferred from reactions with the γ-terpinene isomer limonene and by analogy to reactions catalyzed by related enzymes. We also identified and characterized two P450s of the CYP76S and CYP736A subfamilies that catalyze the hydroxylation of thymol and carvacrol to thymohydroquinone when heterologously expressed in yeast and N. benthamiana. Our findings alter previous views of thymol and carvacrol formation, identify the enzymes involved in the biosynthesis of these phenolic monoterpenes and thymohydroquinone in the Lamiaceae, and provide targets for metabolic engineering of high-value terpenes in plants.

Removal of Organic Dyes from Water and Wastewater Using Magnetic Ferrite-Based Titanium Oxide and Zinc Oxide Nanocomposites: A Review

Heterogeneous photocatalysis using titanium dioxide (TiO2) and zinc oxide (ZnO) has been widely studied in various applications, including organic pollutant remediation in aqueous systems. The popularity of these materials is based on their high photocatalytic activity, strong photosensitivity, and relatively low cost. However, their commercial application has been limited by their wide bandgaps, inability to absorb visible light, fast electron/hole recombination, and limited recyclability since the nanomaterial is difficult to recover. Researchers have developed several strategies to overcome these limitations. Chief amongst these is the coupling of different semi-conductor materials to produce heterojunction nanocomposite materials, which are both visible-light-active and easily recoverable. This review focuses on the advances made in the development of magnetic ferrite-based titanium oxide and zinc oxide nanocomposites. The physical and magnetic properties of the most widely used ferrite compounds are discussed. The spinel structured material had superior catalytic and magnetic performance when coupled to TiO2 and ZnO. An assessment of the range of synthesis methods is also presented. A comprehensive review of the photocatalytic degradation of various priority organic pollutants using the ferrite-based nanocomposites revealed that degradation efficiency and magnetic recovery potential are dependent on factors such as the chemical composition of the heterojunction material, synthesis method, irradiation source, and structure of pollutant. It should be noted that very few studies have gone beyond the degradation efficiency studies. Very little information is available on the extent of mineralization and the subsequent formation of intermediate compounds when these composite catalysts are used. Additionally, potential degradation mechanisms have not been adequately reported.

Asynchrony of Apical Polarization, Luminogenesis, and Functional Differentiation in the Developing Thyroid Gland

Follicular thyroid tissue originates from progenitors derived from a midline endodermal primordium. Current understanding infers that folliculogenesis in the embryonic thyroid designates the latest morphogenetic event taking place after the final anatomical shape and position of the gland is established. However, this concept does not consider the fact that the thyroid isthmus develops chronologically before the lobes and also contains all progenitors required for lobulation. To elucidate whether cells committed to a thyroid fate might be triggered to differentiate asynchronously related to maturation and developmental stage, mouse embryonic thyroid tissues from E12.5-17.5 were subjected to immunofluorescent labeling of biomarkers (progenitors: NKX2-1; differentiation: thyroglobulin/TG); folliculogenesis: E-cadherin/CDH1; luminogenesis: mucin 1/MUC1; apical polarity: pericentrin/PCNT; basement membrane: laminin; growth: Ki67), quantitative RT-PCR analysis (Nkx2.1, Tg, Muc1) and transmission electron microscopy. Tg expression was detectable as early as E12.5 and gradually increased >1000-fold until E17.5. Muc1 and Nkx2.1 transcript levels increased in the same time interval. Prior to lobulation (E12.5-13.5), MUC1 and TG distinguished pre-follicular from progenitor cells in the developing isthmus characterized by intense cell proliferation. Luminogenesis comprised redistribution of MUC1+ vesicles or vacuoles, transiently associated with PCNT, to the apical cytoplasm and the subsequent formation of MUC1+ nascent lumens. Apical polarization of pre-follicular cells and lumen initiation involved submembraneous vesicular traffic, reorganization of adherens junctions and ciliogenesis. MUC1 did not co-localize with TG until a lumen with a MUC1+ apical membrane was established. MUC1 delineated the lumen of all newly formed follicles encountered in the developing lobes at E15.5-17.5. Folliculogenesis started before establishment of a complete follicular basal lamina. These observations indicate that embryonic thyroid differentiation is an asynchronous process consistent with the idea that progenitors attaining a stationary position in the connecting isthmus portion undergo apical polarization and generate follicles already at a primordial stage of thyroid development, i.e. foregoing growth of the lobes. Although the thyroid isthmus eventually comprises minute amounts of the total thyroid volume and contributes little to the overall hormone production, it is of principal interest that local cues related to the residence status of cells – independently of a prevailing high multiplication rate – govern the thyroid differentiation program.

Indications of Deep Marine Fans in the Early Miocene Foredeep of Lower Austria: A Potential New Play

The petroleum province in Lower Austria resulted from the Alpine collision and the subsequent formation of the Vienna Basin. OMV is active in this area since its foundation in 1956. Several plays have been successfully tested and produced in this complex geological region. The main exploration focus is currently on the deep plays. However, this paper proposes a so far unrecognized and therefore undrilled play in a shallower level to broaden OMV's portfolio in Austria. Seismic re-interpretations of reprocessed 3D seismic data and structural reconstructions were used to review some of the existing plays and get novel ideas from improved understanding of processes. In the frontal accretion zone of the Alpine wedge, the Waschberg-Ždánice zone discoveries are limited to the frontal thrust unit and associated structures. The more internal parts of the thrust belt have only sparsely been drilled and are perceived not to have high-quality reservoir rocks. The detailed structural interpretations indicated that the foredeep axis during the Early Miocene was positioned in the thrust sheet located directly in front of the advancing Alpine wedge (comprising the eroding Rhenodanubian Flysch in its frontal part). Seismic amplitude anomalies can be interpreted to represent Lower Miocene basin floor and slope fans. Nearby wells did not penetrate these fans but drilled instead shale-dominated lithologies. Thus, the presence of potential sand-rich fans in front of the advancing alpine wedge is considered a potential new play in Lower Austria. Analogues are found in Upper Austria some 250 km to the West, where several large gas fields in Lower Miocene deposits located in front of the advancing Alpine wedge have been discovered by another operator. In that area the fans are only partly involved in the fold-thrust belt. In Lower Austria, these fans are located within the rear thrust sheet(s), providing a structural component to a mixed structural-stratigraphic trap. Two potential charge mechanism can be considered: a) biogenic gas charge from the organic matter of surrounding shales (like the Upper Austria analogues) or b) oil charge via the thrust fault planes from the Jurassic Mikulov Formation (the proven main source rock in the broader area). Our results add to the understanding of the Miocene structural-stratigraphic evolution of the Alpine collision zone. The definition of a potential new play may add significant value to OMV's upstream efforts in a very mature hydrocarbon province.

The Genetic Backdrop of Hypogonadotropic Hypogonadism

The pituitary is an organ of dual provenance: the anterior lobe is epithelial in origin, whereas the posterior lobe derives from the neural ectoderm. The pituitary gland is a pivotal element of the axis regulating reproductive function in mammals. It collects signals from the hypothalamus, and by secreting gonadotropins (FSH and LH) it stimulates the ovary into cyclic activity resulting in a menstrual cycle and in ovulation. Pituitary organogenesis is comprised of three main stages controlled by different signaling molecules: first, the initiation of pituitary organogenesis and subsequent formation of Rathke’s pouch; second, the migration of Rathke’s pouch cells and their proliferation; and third, lineage determination and cellular differentiation. Any disruption of this sequence, e.g., gene mutation, can lead to numerous developmental disorders. Gene mutations contributing to disordered pituitary development can themselves be classified: mutations affecting transcriptional determinants of pituitary development, mutations related to gonadotropin deficiency, mutations concerning the beta subunit of FSH and LH, and mutations in the DAX-1 gene as a cause of adrenal hypoplasia and disturbed responsiveness of the pituitary to GnRH. All these mutations lead to disruption in the hypothalamic–pituitary–ovarian axis and contribute to the development of primary amenorrhea.

Effect of Tantalum Pentoxide Addition on the Radiopacity Performance of Bi2O3/Ta2O5 Composite Powders Prepared by Mechanical Milling

Among the various phases of bismuth oxide, the high temperature metastable face-centered cubic δ phase attracts great attention due to its unique properties. It can be used as an ionic conductor or an endodontic radiopacifying material. However, no reports concerning tantalum and bismuth binary oxide prepared by high energy ball milling and serving as a dental radiopacifier can be found. In the present study, Ta2O5-added Bi2O3 composite powders were mechanically milled to investigate the formation of these metastable phases. The as-milled powders were examined by X-ray diffraction and scanning electron microscopy to reveal the structural evolution. The as-milled composite powders then served as the radiopacifier within mineral trioxide aggregates (i.e., MTA). Radiopacity performance, diametral tensile strength, setting times, and biocompatibility of MTA-like cements solidified by deionized water, saline, or 10% calcium chloride solution were investigated. The experimental results showed that subsequent formation of high temperature metastable β-Bi7.8Ta0.2O12.2, δ-Bi2O3, and δ-Bi3TaO7 phases can be observed after mechanical milling of (Bi2O3)95(Ta2O5)5 or (Bi2O3)80(Ta2O5)20 powder mixtures. Compared to its pristine Bi2O3 counterpart with a radiopacity of 4.42 mmAl, long setting times (60 and 120 min for initial and final setting times) and 84% MG-63 cell viability, MTA-like cement prepared from (Bi2O3)95(Ta2O5)5 powder exhibited superior performance with a radiopacity of 5.92 mmAl (the highest in the present work), accelerated setting times (the initial and final setting time can be shortened to 25 and 40 min, respectively), and biocompatibility (94% cell viability).

Bleaching of Microcrystalline Cellulose Produced by Gas-Phase Hydrolysis

One of the main consumers of microcrystalline cellulose (MCC) is the pharmaceutical industry, where MCC is used as a binder and filler in direct compression of tablets. MCC is produced by acidic hydrolysis of cellulose, which usually results in a decrease in whiteness. This is due to the destruction of sugars formed during hydrolysis and the subsequent formation of colored products. The composition and properties of these products depend on the method of hydrolysis, acid concentration, temperature, and process duration. One of the most promising methods for producing MCC is gas-phase hydrolysis of cellulose with hydrogen chloride gas-air mixtures. The method has a high rate of hydrolysis, low reagent and energy consumption. The requirements of the pharmaceutical industry determine the need to produce MCC with high whiteness. The research purpose is to select bleaching modes for MCC using sodium hypochlorite and hydrogen peroxide as bleaching agents. MCC produced by gas-phase hydrolysis of bleached wood pulp was used during the study. The whiteness and intensity of the yellow tint of MCC in the bleaching process were determined by digital colorimetry on a flatbed scanner. The paper shows that sodium hypochlorite and hydrogen peroxide allow achieving the whiteness not less than 90 % and the intensity of the yellow tint not more than 3 standard units. High-quality bleaching can be carried out even for MCC samples with an initial whiteness of about 40 %. The most effective bleaching agent is sodium hypochlorite when the pH of the bleaching solution is 2–3. Hydrogen peroxide also provides high whiteness of MCC at pH of 10–11. However, the consumption of active oxygen (AO) for bleaching is more than three times higher in comparison with the consumption of active chlorine (ACh). It was found that the dyes of MCC produced by gas-phase hydrolysis consist of two chromophore groups that decolorize at different rates. The easily oxidized group of components makes up about 90 % of the total amount of dyes, and the resistant to oxidation components make up about 10 % and determine the intensity of the yellow tint of MCC. The modes of bleaching MCC with sodium hypochlorite and hydrogen peroxide to product samples with whiteness comparable to that of imported samples were determined. For citation: Sizov A.I., Pimenov S.D., Stroiteleva A.D., Stroiteleva K.D. Bleaching of Microcrystalline Cellulose Produced by Gas-Phase Hydrolysis. Lesnoy Zhurnal [Russian Forestry Journal], 2021, no. 6, pp. 173–183. DOI: 10.37482/0536-1036-2021-6-173-183