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The structure verification of 5′-oxospiro-(fluorene-9,4′-imidazolidine)-2′-thione by NMR is reported. Toward this aim, 2D NMR techniques including 1H-1H COSY, HMQC, and HMBC experiments were used to assist with the assignment of the 1H and 13C chemical shifts for the corresponding structure. The mutual interpretation of the 1D and 2D NMR spectra ensured a complete and accurate 1H and 13C NMR data assignment for 5′-oxospiro-(fluorene-9,4′-imidazolidine)-2′-thione.

Convection monitoring and forecasting are crucial for air traffic management as they can lead to the development of intense thunderstorms and hazards such as severe turbulence and icing, lightning activity, microbursts and hail that affect aviation safety. The airport of Burgas is located in southeast Bulgaria on the Black Sea coast and occurrences of intense thunderstorms are mainly observed in the warm season between May and September. This work presents an analysis of severe convection over southeast Bulgaria on 17 September 2022. In the late afternoon, a gust front was formed that reached the Burgas airport with a wind speed exceeding 45 m/s, the record for the past 50 years, damaging the instrument landing system of the airport. To analyse the severe weather conditions, we combine state-of-the-art observations from satellite and radar with the upper-air sounding and surface. The studied period was dominated by the presence of a very unstable air mass over southeast Bulgaria ahead of the atmospheric front. As convection developed and moved east towards Burgas, it had four characteristics of severe deep convection, including gravitational waves at the overshooting cloud top, a cold U-shape, a flanking line and a cloud top temperature below −70 °C. The positive integrated water vapour (IWV) rate of change preceded the lightning activity peak by 30 min. Analysis of integrated vapour transport (IVT) gives higher values by a factor of two compared to climatology associated with the atmospheric river covering the eastern Mediterranean sea.

A combination of 1D and 2D NMR techniques, including HMQC, HSQC, 1H-1H COSY and HMBC, was used to provide completely assigned 1H and 13C NMR data for the structures of three 3-[substituted methylidene]-1H,3H-naphtho[1,8-cd]-pyran-1-ones—3-[(4-methoxyphenyl)methylidene]-1H,3H-naphtho[1,8-cd]-pyran-1-one, 3-[(4-fluorophenyl)methylidene]-1H,3H-naphtho-[1,8-cd]-pyran-1-one and 3-[(thiophen-3-yl)methylidene]-1H,3H-naphtho[1,8-cd]-pyran-1-one. The heteronuclear coupling constants 1–4JCF and 3–4JHF were correspondingly determined. Additionally, IR and Raman spectral data were provided in support of the assigned structures.

This paper presents an approach to eliminate one of the most common defects in hyperspectral images—the appearance of spiked points at some wavelengths. The elimination of this defect was carried out by means of polynomial regression. The Bayes Information Criterion (BIC) was used to determine the correct order of the polynomial. Comparison between polynomial regression and classical filtration with the Savitsky–Golay method shows the advantage of the proposed approach, from the point of view of eliminating the defect in a local area, without changing the typical behavior of the spectral feature in the affected image pixels.

Novel fibrous cellulosic substrates impregnated with meta-polybenzimidazole (PBI)-stabilized carbon nanotubes/zinc oxide with different weight content of ZnO and with the use of dimethylacetamide as dispersant media. The pristine ZnO nanoparticle powder was prepared by plant extract-mediated synthesis using Vaccinium vitis-idaea L. The green synthesized ZnO possesses an average crystallite size of 15 nm. The formation of agglomerates from ZnO NPs with size 250 nm–350 nm in the m-PBI@CNTs/ZnO was determined. The prepared materials were investigated by PXRD analysis, XPS, SEM, EDS, AFM, and TEM in order to establish the phase and surface composition, structure, and morphology of the hybrids. The potential of the synthesized hybrid composites to degrade methylene blue (MB) dye as a model contaminant in aqueous solutions under UV illumination was studied. The photocatalytic results show that in the course of the photocatalytic reaction, the m-PBI@CNTs/ZnO 1:3 photocatalyst leads to the highest degree of degradation of the methylene blue dye (67%) in comparison with the other two studied m-PBI@CNTs/ZnO 1:1 and 1:2 composites (48% and 41%). The antibacterial activity of ZnO nanoparticles and the hybrid CNT materials was evaluated by the RMDA and the dynamic contact method, respectively. The profound antibacterial effect of the m-PBI@CNTs/ZnO hybrids was monitored for 120 h of exposition in dark and UV illumination regimes. The photocatalytic property of ZnO nanoparticles significantly shortens the time for bactericidal action of the composites in both regimes. The m-PBI@CNTs/ZnO 1:2 combination achieved complete elimination of 5.105 CFU/mL E. coli cells after 10 min of UV irradiation.

The goal of this study is to synthesize, determine the structure, and examine the antimicrobial properties of novel Cu(II) and Au(III) complexes of 2,4-dithiouracil and its derivatives. These complexes were obtained by mixing aqueous solutions of the corresponding metal salts with the ligand dissolved in DMSO and aqueous NaOH, using a metal-to-ligand ratio of 1:4:2. The structures of the new compounds were analyzed by melting point determination, microwave plasma atomic emission spectrometry (MP-AES) for Cu and Au, inductively coupled plasma optical emission spectrometry (ICP-OES) for S, attenuated total reflection (ATR), solution and solid-state NMR, and Raman spectroscopy. The data for 2,4-dithiouracil obtained from the 1H NMR, 13C NMR, distortionless enhancement by polarization transfer spectrum (DEPT-135), proton–proton homonuclear correlation spectrum (1H-1H COSY), long-range 1H-13C heteronuclear multiple bond correlation experiment (HMBC), and heteronuclear single quantum coherence spectra (HSQC) aided the interpretation of the NMR data for the gold and copper complexes. Furthermore, the antimicrobial effect of the free ligands and their complexes was assessed against Gram-positive and Gram-negative bacteria, as well as yeasts.

The aim of the present study is to synthesize new metal complexes of 6-methyl-2-thiouracil and 6-propyl-2-thiouracil, elucidate their structures, and investigate their biological properties. All metal complexes were obtained after mixing water solutions of the corresponding metal salts and the ligand dissolved in DMSO and water solutions of NaOH in a metal-to-ligand ratio of 1:4:2. The structures of the new compounds are discussed based on melting point analysis (MP-AES) for Cu and Pd, UV-Vis, IR, ATR, 1H NMR, 13C NMR, and Raman spectroscopy. The interpretation of complex spectra is assisted by the data for 6-methyl-2-thiouracil and 6-propyl-2-thiouracil obtained from 1H-1H COSY, DEPT-135, HMBC and HMQC spectra. In addition, the antimicrobial activity of these complexes and the free ligands are assessed against both Gram-positive and Gram-negative bacteria, as well as yeasts. In general, the addition of metal ions improved the antimicrobial activity of both 6-methyl-2-thiouracil and 6-propyl-2-thiouracil. The Cu(II) complex with 6-methyl-2-thiouracil and the Pd(II) complex with 6-propyl-2-thiouracil exhibited the highest activity against the test microorganisms.

The use of biodegradable polyesters derived from green sources and their combination with natural abundantly layered aluminosilicate clay, e.g., natural montmorillonite, meets the requirements for the development of new sustainable, disposable, and biodegradable organic dye sorbent materials. In this regard, novel electrospun composite fibers, based on poly β-hydroxybutyrate (PHB) and in situ synthesized poly(vinyl formate) (PVF), loaded with protonated montmorillonite (MMT-H) were prepared via electrospinning in the presence of formic acid, a volatile solvent for polymers and a protonating agent for the pristine MMT-Na. The morphology and structure of electrospun composite fibers were investigated through SEM, TEM, AFM, FT-IR, and XRD analyses. The contact angle (CA) measurements showed increased hydrophilicity of the composite fibers incorporated with MMT-H. The electrospun fibrous mats were evaluated as membranes for removing cationic (methylene blue) and anionic (Congo red) dyes. PHB/MMT 20% and PVF/MMT 30% showed significant performance in dye removal compared with the other matrices. PHB/MMT 20% was the best electrospun mat for adsorbing Congo red. The PVF/MMT 30% fibrous membrane exhibited the optimum activity for the adsorption of methylene blue and Congo red dyes.

FAU-type zeolite NaX was successfully prepared using hydrothermal synthesis at 90 °C for 6 h. The Mn- and Cu-ion-exchanged NaX zeolites were obtained. After the ion exchange, the zeolite powders were thermally treated at 300 °C. As well as Ag-ion-exchanged zeolite, NaX and zeolite were impregnated with two types of Ag nanoparticle dispersions: citrate surface-stabilized (Cit@Ag NPs) and polymer-stabilized (PVP@Ag) nanoparticles. Silver nanoparticles were synthesized using the electrochemical reduction method. The changes in the phase and chemical composition and structure of the obtained zeolite powders before and after ion exchange or impregnation were investigated by PXRD analysis, FTIR spectroscopy, and XRF analysis. The results show that Mn, Cu-exchanged NaX, and that impregnated with Ag demonstrated catalytic abilities towards ozone decomposition in comparison with pure zeolite (non-catalytic activity).

In times of population growth, climate change, and increasing water scarcity around the world, it is important to take an objective look at water, a fundamental resource for life. Hydrodynamic modeling makes possible the research of different aspects of the water cycle and the evaluation of different hydrological and hydrogeological forecasting scenarios in the short and medium terms. The present research offers a more detailed scope at the hydrodynamic processes and their space-time distributions on a UE pilot in the Júcar River Basin, providing a calibrated and validated hydrodynamic model of 121 km river reach for 45 years period (1974–2019) on a daily scale. The obtained information is about discharge and water depths along the Júcar River reach within the hydrogeological boundaries of the Mancha Oriental Aquifer (MOA). The river–aquifer interactions have been represented as dynamic boundary conditions expressed as a difference between observed discharges measured in 3 gauging stations. The obtained calibration error performance evaluations of observed and simulated values cover two periods, according to observed data availability from gauging station 08036 with resulting R2 for both discharges and water depths over 0.96. The model validation results were obtained for a different gauge 08132 and the determination coefficients R2 also perform very well with value of 0.90. The model developed might be useful for decision making in water resources management and can be used to generate simulated time series of water depths, levels, discharges, and velocities in reaches where gauging measurements are not available with a desired space-time resolution (from meter/second to kilometer/month). Estimation of critical discharge value (1.973 m3s−1) for system equilibrium, based on the balance between losing and gaining sub-reaches of the river, is also made with a statistical significance at 95% for hydrologic years 2007–2010, period influenced by restrictions in groundwater withdrawals. The results of the present research are important for the proper and objective management of the scarce water resources on a watershed scale in Júcar River Basin, a complex case study representing semiarid climate, growing anthropogenic pressures, and complex river–aquifer interactions. The used approach of dynamic representation of the river–aquifer interactions as distributed source boundary condition in the one-dimensional hydrodynamic model might be applied in another study case on similar scale.

Hybrid manufacture of components by combining capabilities of replication and additive manufacturing processes offer a flexible and sustainable route for producing cost-effectively small batches of metal parts. At present, there are open issues related to surface integrity and performance of such parts, especially when utilising them in safety critical applications. The research presented in this paper investigates the ductility amplification of hybrid components produced using metal injection moulding to preform and then build on them customisable sections by laser-based powder bed fusion. The properties of such hybrid components are studied and optimised through the use of non-conventional post treatment techniques. In particular, hot isostatic pressing (HIP) is employed to improve mechanical strength and to produce hybrid components that have consistent properties across batches and throughout the samples, minimising microstructural heterogeneities between fabrication processes. Thus, the investigated post-processing method can offer an extended service life of hybrid components, especially when operating under severe conditions. The optimised post treatment was found to increase the hybrid components’ strength compared to as-built ones by 68% and ~11% in yield strength (YS) and ultimate tensile strength (UTS), respectively. Subsequently, leading to a great pitting resistance, thus, making HIP samples suitable for corrosive environments. The advantages of the HIP treatments in comparison to the conventional heat treatment of hybrid components are discussed and also some potential application areas are proposed.

Today, in industry, laser-based additive manufacturing (LAM) is used to produce high-value parts of very complex designs that are not manufacturable by conventional technologies; this process’ low production throughput and high cost prevent it from being used more extensively. One way to exploit the benefits of LAM in industry is to have it combined with lower-cost manufacturing technologies. In a hybrid approach, LAM can be integrated within an assembly line’s welding station to complete the manufacturing of a product by depositing a foreign material on a substrate only where needed, or by building structures of complex 3D geometries (e.g., lattice structures) directly onto inexpensive preforms. To pave the way for using a hybrid approach design in real applications, as a prime requirement, the chosen technology must grant comparable structural integrity to its products with respect to its conventional counterparts. In this work, different types of surface pretreatments for substrates were investigated as a key enabling factor to tailor the bi-material system’s mechanical properties in use. Hybrid samples were made by depositing AlSi10Mg by direct metal laser sintering onto A356-T6 aluminum bases prefabricated by casting and forging, and their properties were compared with fully homogeneous samples that were conventionally produced. Specifically referring to the automotive use case, both these alloy grades were chosen for their extensive use in the production of motor vehicles. The testing campaign, characterized by microscopy, mechanical testing, and fatigue, revealed that the structural integrity of the hybrid samples is comparable with the benchmarks when standard heat treatments are adopted. This result makes the prospect of the exploitation of the hybridization concept as conceived very promising for the future.

This study evaluates the phytochemical composition and ability of herbal preparation AyuFertin, supplemented shortly after calving, to resume the cyclic ovarian activity in postpartum Bulgarian Murrah buffaloes. In total, 13 healthy Bulgarian Murrah buffaloes at the age of 4–10 years, calved in March–April 2019 were involved in the experiment. Seven experimental buffaloes were treated individually per os with AyuFertin according to producer instruction. All animals were subjected to regular ultrasound examination of ovaries. GC-MS analysis of fatty acids composition and HPLC-DAD analysis of carotenoid and tocopherol content in AyuFertin were conducted. The determination of estrus occurrence and natural mating were done by a fertile bull. The development of the large follicles (12.5–14.3 mm) in 85.7% of treated animals was observed on day 24 postpartum compared to 0% in controls. Clinical signs of estrus were recorded in 71.4% of the animals, followed by an 80% pregnancy rate versus 16% in controls within 70 days after calving. In conclusion, the supplementation of the bioactive herbal product AyuFertin from day 21 postpartum can stimulate the follicular growth in the buffalo’s ovary, which leads to the development of follicles with ovulatory capacity, followed by successful ovulation. The above-mentioned treatment resulted in a better pregnancy rate in the treated multiparous compared to the control buffaloes bred by natural service.

Enteroatmospheric fistulas (EAFs) are still the worst complication of the open abdomen. They lead to a significantly prolonged intensive care unit and hospital stay and to high mortality. Despite the various techniques described in the literature EAFs remain “a nightmare” for the patient, the surgeon, and the hospital. Here we describe a case of right colectomy for obstructing Crohn’s disease in a 26-year-old. On the 19th postoperative day, he developed a superficial EAF. Due to the frozen abdomen, neither resection of the anastomosis, nor implementation of the known techniques for treatment of EAFs were possible. This prompted us to modify the Pepe technique. The EAF was isolated from the upper and lower parts of the wound through deep-skin and subcutaneous sutures and the application of two small pieces of non-adherent plastic foil. The lower holes of a single drain, put through a piece of black foam, were placed over the fistula. The upper holes, which were enveloped with the foam, remained in contact with the wound. The drain was connected to a negative pressure of 125 mmHg. NPWT (negative pressure wound therapy) was also applied by two separate sponges and drains in the upper and lower part. The mainstay of EAF treatment is the isolation of the EAF from the abdominal cavity and subcutaneous tissue, supported by control of the sepsis and adequate nutrition. The proposed technique is applicable in cases with a single, superficial EAF on the background of the frozen abdomen with minimal lateral fascial retraction. As of today, due to the rarity of the condition and lack of randomized trials, EAFs still represents a unique challenge often requiring improvisation.

The hepatoprotective properties of silibinin, as well its therapeutic potential as an anticancer and chemo-preventive agent, have failed to progress towards clinical development and commercialization due to this material’s unfavorable pharmacokinetics and physicochemical properties, low aqueous solubility, and chemical instability. The present contribution is focused on the feasibility of using PEGylated calixarene, in particular polyoxyethylene-derivatized tert-octylcalix[8]arene, to prepare various platforms for the delivery of silibinin, such as inclusion complexes and supramolecular aggregates thereof. The inclusion complex is characterized by various instrumental methods. At concentrations exceeding the critical micellization concentration of PEGylated calixarene, the tremendous solubility increment of silibinin is attributed to the additional solubilization and hydrophobic non-covalent interactions of the drug with supramolecular aggregates. PEG-modified tert-octylcalix[8]arenes, used as drug delivery carriers for silibinin, were additionally investigated for cytotoxicity against human tumor cell lines.

Finding a low-cost and effective method at low temperatures for producing reduced graphene oxide (rGO) has been the focus of many efforts in the research community for almost two decades. Overall, rGO is a promising candidate for use in supercapacitors, batteries, biosensors, photovoltaic devices, corrosion inhibitors, and optical devices. Herein, we report the formation of rGO from two electrically insulating polymers, polytetrafluoroethylene (PTFE) and meta-polybenzimidazole fiber (m-PBI), using an excimer pulsed laser annealing (PLA) method. The results from X-ray diffraction, scanning electron microscopy, electron backscattered diffraction, Raman spectroscopy, and Fourier-transform infrared spectroscopy confirm the successful generation of rGO with the formation of a multilayered structure. We investigated the mechanisms for the transformation of PTFE and PBI into rGO. The PTFE transition occurs by both a photochemical mechanism and a photothermal mechanism. The transition of PBI is dominated by a photo-oxidation mechanism and stepwise thermal degradation. After degradation and degassing procedures, both the polymers leave behind free molten carbon with some oxygen and hydrogen content. The free molten carbon undergoes an undercooling process with a regrowth velocity (−1) that is necessary for the formation of rGO structures. This approach has the potential for use in creating future selective polymer-written electronics.

This paper presents a micromachining process for lithium niobate (LiNbO3) material for the rapid prototyping of a resonant sensor design for medical devices applications. Laser micromachining was used to fabricate samples of lithium niobate material. A qualitative visual check of the surface was performed using scanning electron microscopy. The surface roughness was quantitatively investigated using an optical surface profiler. A surface roughness of 0.526 μm was achieved by laser micromachining. The performance of the laser-micromachined sensor has been examined in different working environments and different modes of operation. The sensor exhibits a Quality-factor (Q-factor) of 646 in a vacuum; and a Q-factor of 222 in air. The good match between the modelling and experimental results shows that the laser-micromachined sensor has a high potential to be used as a resonance biosensor.

The uniform energy distribution of top-hat laser beams is a very attractive property that can offer some advantages compared to Gaussian beams. Especially, the desired intensity distribution can be achieved at the laser spot through energy redistribution across the beam spatial profile and, thus, to minimize and even eliminate some inherent shortcomings in laser micro-processing. This paper reports an empirical study that investigates the effects of top-hat beam processing in micro-structuring and compares the results with those obtainable with a conventional Gaussian beam. In particular, a refractive field mapping beam shaper was used to obtain a top-hat profile and the effects of different scanning strategies, pulse energy settings, and accumulated fluence, i.e., hatch and pulse distances, were investigated. In general, the top-hat laser processing led to improvements in surface and structuring quality. Especially, the taper angle was reduced while the surface roughness and edge definition were also improved compared to structures produced with Gaussian beams. A further decrease of the taper angle was achieved by combining hatching with some outlining beam passes. The scanning strategies with only outlining beam passes led to very high ablation rates but in expense of structuring quality. Improvements in surface roughness were obtained with a wide range of pulse energies and pulse and hatch distances when top-hat laser processing was used.