Linear Free‐Energy Relationships Applied to the 13C NMR Chemical Shifts in 4‐Substituted N‐[1‐(Pyridine‐3‐ and ‐4‐yl)ethylidene]anilines

Two series of 4‐substituted N‐[1‐(pyridine‐3‐ and ‐4‐yl)ethylidene]anilines have been synthesized using different methods of conventional and microwave‐assisted synthesis, and linear free‐energy relationships have been applied to the ¹³C NMR chemical shifts of the carbon atoms of interest. The substituent‐induced chemical shifts have been analyzed using single substituent parameter and dual substituent parameter methods. The presented correlations describe satisfactorily the field and resonance substituent effects having similar contributions for C1 and the azomethine carbon, with exception of the carbon atom in para position to the substituent X. In both series, negative ρ values have been found for C1′ atom (reverse substituent effect). Quantum chemical calculations of the optimized geometries at MP2/6‐31G++(d,p) level, together with ¹³C NMR chemical shifts, give a better insight into the influence of the molecular conformation on the transmission of electronic substituent effects. The comparison of correlation results for different series of imines with phenyl, 4‐nitrophenyl, 2‐pyridyl, 3‐pyridyl, 4‐pyridyl group attached at the azomethine carbon with the results for 4‐substituted N‐[1‐(pyridine‐3‐ and ‐4‐yl)ethylidene]anilines for the same substituent set (X) indicates that a combination of the influences of electronic effects of the substituent X and the π₁‐unit can be described as a sensitive balance of different resonance structures.     

Immobilization of Candida antarctica lipase B on Polystyrene Nanoparticles

Polystyrene (PS) nanoparticles were prepared via a nanoprecipitation process. The influence of the pH of the buffer solution used during the immobilization process on the loading of Candida antarctica lipase B (Cal‐B) and on the hydrolytic activity (hydrolysis of p‐nitrophenyl acetate) of the immobilized Cal‐B was studied. The pH of the buffer solution has no influence on enzyme loading, while immobilized enzyme activity is very dependent on the pH of adsorption. Cal‐B immobilized on PS nanoparticles in buffer solution pH 6.8 performed higher hydrolytic activity than crude enzyme powder and Novozyme 435.

     

Free vibration control of smart composite beams using particle swarm optimized self-tuning fuzzy logic controller

This paper deals with active free vibrations control of smart composite beams using particle-swarm optimized self-tuning fuzzy logic controller. In order to improve the performance and robustness of the fuzzy logic controller, this paper proposes integration of self-tuning method, where scaling factors of the input variables in the fuzzy logic controller are adjusted via peak observer, with optimization of membership functions using the particle swarm optimization algorithm. The Mamdani and zero-order Takagi–Sugeno–Kang fuzzy inference methods are employed. In order to overcome stability problem, at the same time keeping advantages of the proposed self-tuning fuzzy logic controller, this controller is combined with the LQR making composite controller. Several numerical studies are provided for the cantilever composite beam for both single mode and multimodal cases. In the multimodal case, a large-scale system is decomposed into smaller subsystems in a parallel structure. In order to represent the efficiency of the proposed controller, obtained results are compared with the corresponding results in the cases of the optimized fuzzy logic controllers with constant scaling factors and linear quadratic regulator.     

Dimming supernovae without cosmic acceleration

We present a simple model where photons propagating in extragalactic magnetic fields can oscillate into very light axions. The oscillations may convert some of the photons, departing a distant supernova, into axions, making the supernova appear dimmer and hence more distant than it really is. Averaging over different configurations of the magnetic field we find that the dimming saturates at about one-third of the light from the supernovae at very large redshifts. This results in a luminosity distance versus redshift curve almost indistinguishable from that produced by the accelerating Universe, if the axion mass and coupling scale are m approximately 10(-16) eV, M approximately 4 x 10(11) GeV. This phenomenon may be an alternative to the accelerating Universe for explaining supernova observations.     

Stable high-power continuous-wave Yb(3+)-doped silica fiber laser utilizing a point-by-point inscribed fiber Bragg grating

We report on a narrowband 5 W cw fiber laser incorporating a point-by-point fiber Bragg grating inscribed into the core of a Yb(3+)-doped double-clad fiber. The laser featured excellent long-term wavelength and power stability (0.3%), as well as a very narrow (15 pm) linewidth, when passive temperature stabilization of the grating was implemented.     

Comparison of Hydroxyapatite/Poly(lactide-co-glycolide) and Hydroxyapatite/Polyethyleneimine Composite Scaffolds in Bone Regeneration of Swine Mandibular Critical Size Defects: In Vivo Study

Reconstruction of jaw bone defects present a significant problem because of specific aesthetic and functional requirements. Although widely used, the transplantation of standard autograft and allograft materials is still associated with significant constraints. Composite scaffolds, combining advantages of biodegradable polymers with bioceramics, have potential to overcome limitations of standard grafts. Polyethyleneimine could be an interesting novel biocompatible polymer for scaffold construction due to its biocompatibility and chemical structure. To date, there have been no in vivo studies assessing biological properties of hydroxyapatite bioceramics scaffold modified with polyethyleneimine. The aim of this study was to evaluate in vivo effects of composite scaffolds of hydroxyapatite ceramics and poly(lactide-co-glycolide) and novel polyethyleneimine on bone repair in swine’s mandibular defects, and to compare them to conventional bone allograft (BioOss). Scaffolds were prepared using the method of polymer foam template in three steps. Pigs, 3 months old, were used and defects were made in the canine, premolar, and molar area of their mandibles. Four months following the surgical procedure, the bone was analyzed using radiological, histological, and gene expression techniques. Hydroxyapatite ceramics/polyethyleneimine composite scaffold demonstrated improved biological behavior compared to conventional allograft in treatment of swine’s mandibular defects, in terms of bone density and bone tissue histological characteristics.     

Natural Deep Eutectic Solvent (NADES) Extraction Improves Polyphenol Yield and Antioxidant Activity of Wild Thyme (Thymus serpyllum L.) Extracts

Wild thyme (Thymus serpyllum L.) herbal dust has been recognized as a potential underutilized resource for the recovery of antioxidants. The aim of this paper was to optimize natural deep eutectic solvent (NADES) extraction of polyphenols to obtain improved antioxidant activity of extracts determined by selected in vitro assays (DPPH, FRAP, and ABTS). Twenty different NADES systems were investigated in the first step of the screening of the extraction solvent and l-proline (Pro)–glycerine (Gly) based solvents provided the best results. Preliminary experiments organized by 2⁵⁻¹ fractional factorial design narrowed down the number of extraction factors from five (temperature, extraction time, NADES type, water content and L/S ratio) to three and determined their experimental domain for the final step. A face-centered central composite design with temperature (40–55–70 °C), extraction time (60–120–180 min) and L/S ratio (10–20–30 g NADES/g sample) was applied for influence analysis and process optimization. Multi-response optimization suggested a temperature of 65 °C, time of extraction of 180 min and L/S ratio of 28 g NADES/g DW as optimal extraction parameters. Experimental validation confirmed good agreement between experimental and predicted results in the extract obtained at optimal conditions and the interactions in the most suitable NADES (N16; Pro–Gly–H₂O; 1:2:1) were confirmed by the ¹H-NMR.     

Isolation of Garlic Bioactives by Pressurized Liquid and Subcritical Water Extraction

Garlic (Allium sativum L.) is widely used in various food products and traditional medicine. Besides unique taste and flavour, it is well known for its chemical profile and bioactive potential. The aim of this study was to apply subcritical water extraction (SWE) and pressurized liquid extraction (PLE) for the extraction of bioactive compounds from the Ranco genotype of garlic. Moreover, PLE process was optimized using response surface methodology (RSM) in order to determine effects and optimize ethanol concentration (45–75%), number of cycles (1–3), extraction time (1–3 min) and temperature (70–110 °C) for maximized total phenols content (TP) and antioxidant activity evaluated by various in vitro assays. Furthermore, temperature effect in SWE process on all responses was evaluated, while allicin content (AC), as a major organosulphur compound, was determined in all samples. Results indicated that PLE provided tremendous advantage over SWE in terms of improved yield and antioxidant activity of garlic extracts. Therefore, high-pressure processes could be used as clean and green procedures for the isolation of garlic bioactives.     

Carbonised polyaniline and polypyrrole: towards advanced nitrogen-containing carbon materials

Polyaniline (PANI) and polypyrrole (PPY) undergo carbonisation in an inert/reduction atmosphere and vacuum, yielding different nitrogen-containing carbon materials. This contribution reviews various procedures for the carbonisation of PANI and PPY precursors, and the characteristics of obtained carbonised PANI (C-PANI) and carbonised PPY (C-PPY). Special attention is paid to the role of synthetic procedures in tailoring the formation of C-PANI and C-PPY nanostructures and nanocomposites. The review considers the importance of scanning and transmission electron microscopies, XPS, FTIR, Raman, NMR, and EPR spectroscopies, electrical conductivity and adsorption/desorption measurements, XRD, and elemental analyses in the characterisation of C-PANIs and C-PPYs. The application of C-PANI and C-PPY in various fields of modern technology is also reviewed.     

Photoluminescence study of polycrystalline CsSnI3 thin films: Determination of exciton binding energy

We report on the determination of exciton binding energy in perovskite semiconductor CsSnI₃ through a series of steady state and time-resolved photoluminescence measurements in a temperature range of 10–300 K. A large binding energy of 18 meV was deduced for this compound having a direct band gap of 1.32 eV at room temperature. We argue that the observed large binding energy is attributable to the exciton motion in the natural two-dimensional layers of SnI₄ tetragons in this material.