The chiral optical Tamm state (COTS) is a special localized state at the interface of a handedness-preserving mirror and a structurally chiral medium such as a cholesteric liquid crystal or a chiral sculptured thin film. The spectral behavior of COTS, observed as reflection resonances, is described by the temporal coupled-mode theory. Mode coupling is different for two circular light polarizations because COTS has a helix structure replicating that of the cholesteric. The mode coupling for co-handed circularly polarized light exponentially attenuates with the cholesteric layer thickness since the COTS frequency falls into the stop band. Cross-handed circularly polarized light freely goes through the cholesteric layer and can excite COTS when reflected from the handedness-preserving mirror. The coupling in this case is proportional to anisotropy of the cholesteric and theoretically it is only anisotropy of magnetic permittivity that can ultimately cancel this coupling. These two couplings being equal results in a polarization crossover (the Kopp--Genack effect) for which a linear polarization is optimal to excite COTS. The corresponding cholesteric thickness and scattering matrix for COTS are generally described by simple expressions.

Recurrent neural networks (RNNs) transmit information over time through recurrent connections. In contrast, biological neural networks use many other temporal processing mechanisms. One of these mechanisms is the inter-neuron delays caused by varying axon properties. Recently, this feature was implemented in echo state networks (ESNs), a type of RNN, by assigning spatial locations to neurons and introducing distance-dependent inter-neuron delays. These delays were shown to significantly improve ESN task performance. However, thus far it is still unclear why distance-based delay networks (DDNs) perform bettern than ESNs. In this paper, we show that by optimizing inter-node delays, the memory capacity of the network matches the memory requirements of the task. As such, networks concentrate their memory capabilities to the points in the past which contain the most information for the task at hand. Moreover, we show that DDNs have more total linear memory capacity, with the same amount of non-linear processing power.

We aim to investigate if serum levels of microRNAs: miR-126, mir-197 and mir-223, previously implicated in cardiometabolic disease, are reproducibly associated with incident-diabetes (inc-DM), incident-cardiovascular disease (inc-CVD) and with carotid atherosclerosis (measured for the maximum thickness of the intima-media of the carotid bulb (IMT)). The microRNAs were measured, one: in serum of 553 subjects from the baseline exam of the Swedish prospective cohort, Malmö Diet and Cancer Study (MDC-CC), with 169 subjects who developed CVD and 140 DM (16 years follow-up) and, two: in 1221 subjects from the Malmö Offspring Study (MOS), with 14 de-veloped CVD and 12 DM (3.7 years follow-up). Multivariate logistic and linear regression models were used to investigate the relationship of serum-concentrations of the microRNAs and inc-DM, inc-CVD, IMT-bulb respectively. In MDC-CC, miR-126 showed significant positive association with inc-DM (p= 0.01) whereas in fully adjusted model, the association was borderline significant (p= 0.05). The results were not replicated in MOS. There was no consistent significant association between the microRNAs with IMT or inc-CVD in any cohort. Our results do not support previous reports on significant associations between these microRNAs and the risk of CMD, as they were not reproducible in our cohorts. In addition, the directionality of any associations found were not consistent with those previously reported.

The Performance Assessment for California Teachers (PACT) is a high stakes summative assessment that was designed to measure pre-service teacher readiness. We examined the inter-rater reliability (IRR) of trained PACT evaluators who rated 19 candidates. As measured by Cohen’s weighted kappa, the overall IRR estimate was .17 (poor strength of agreement). IRR estimates ranged from -.29 (worse than expected by chance) to .54 (moderate strength of agreement); all were below the standard of .70 for consensus agreement. Follow up interviews of 10 evaluators revealed possible reasons we observed low IRR, such as departures from established PACT scoring protocol, and lack of, or inconsistent, use of a scoring aid document. Evaluators reported difficulties scoring the materials that candidates submitted, particularly the use of Academic Language. Cognitive Task Analysis (CTA) is suggested as a method to improve IRR in the PACT and other teacher performance assessments such as the edTPA.

As a combination of both concepts of innovation and environmental development, green innovation is of great significance to the sustainable development of the country and industry. Previous literatures have found the separate roles of green entrepreneurial orientation and inter-organizational learning in understanding green innovation issues. However, few studies have done a comprehensive analysis of integrating three streams of research: green entrepreneurial orientation, green innovation and supply chain learning capability. Based on the resource-based view and dynamic capability theory, we examine the direct of green entrepreneurial orientation on green innovation as well as indirect effect through the mediation of supply chain learning capability. Meanwhile, an empirical data set of 228 manufacturing companies in China (Shaanxi, Guangdong, Hebei, Jiangsu, and Shandong) was used to test our hypotheses. Findings from our empirical study suggest that supply chain learning capability partially mediates the positive relationships between green entrepreneurial orientation and its two consequences—green incremental innovation and green radical innovation. In addition, this research implies that when enterprise has a strong green entrepreneurial orientation, the enterprise should make an effort to enhance the level of supply chain learning capability so as to fully develop their green innovation.

The phosphogypsum (PG) pile of solid waste is of immense proportions and poses a grave threat to the ecological environment, with its reserves steadily increasing year after year. The urgent need for large-scale consumption and high-quality utilization of PG in industrial production has become apparent. The present study provides a comprehensive analysis of the correlation be-tween the macroscopic mechanical properties and microstructure of PG, elucidating the crystal morphology characteristics in different phases and outlining the crystallization preparation pro-cess. By integrating the physical and chemical properties of diverse PG phases with the intricacies associated with its preparation process, it is imperative to explore avenues for its high-value utili-zation, investigate possibilities for industrial-scale production, and analyze and predict the appli-cation trends and developmental directions in comprehensive PG utilization. These endeavors hold immense significance in guiding the realization of resource utilization potential inherent in PG.

A new copper(I) complex, [Cu2(L)2dppm](PF6)2 (1) [L = 3-(2-Pyridyl)-5,6-diphenyl-1,2,4-triazine and dppm: Bis(diphenylphosphino)methane] was prepared and characterized by IR, 1H-NMR, 31P-NMR spectroscopy, elemental and thermogravimetric analysis, and single-crystal X-ray diffraction technique. Complex 1 is a dinuclear compound, showing that L and dppm act as tridentate and bidentate chelating ligands, respectively. The two Cu(I) atoms exhibit a distorted tetrahedral coordination sphere embedded in N3P environments. The supramolecular interactions in the solid-state structure are characterized by C−H···N, C−H···F, C-H···π and π···π intermolecular interactions that were analyzed by inspection of the Hirshfeld surface and fingerprint plots. Additionally, the complex was studied experimentally in solution by UV–Vis spectroscopy and cyclic voltammetry; also, theoretical studies with Time-Dependent Density Functional Theory (TD-DFT) were performed. Moreover, the optical and electrochemical properties have been studied, focusing on the band gap. Compound 1 has been used as a co-sensitizer in a dye-sensitized solar cell, showing good activity.

In this paper, a sensitivity sensor of dual-core photonic crystal fiber (DC-PCF) filled with magnetic liquid is introduced and investigated by the finite element method (FEM). To regulate the energy coupling involving the two cores, the magnetic fluid is filled into the pore between the two cores. To adjust the coupling between the supermodes in the DC-PCF, the refractive index of the magnetic fluid-filled air hole may change due to the external magnetic field. This specifically created a magnetic fluid-filled DC-PCF, the magnetic fluid-filled hole is not used as the core for energy transmission, thus avoiding transmission loss. The dip wavelength and the magnetic field displayed an excellent linear connection between 80 and 260 Oe, depending on the numerical data. The detection sensitivity of the magnetic field reached 515.75 pm/Oe at a short fiber length of 482 m. The designed magnetic fluid-filled DC-PCF has high sensitivity and small volume and has great application prospects in medical and industrial field magnetic field detection.

2,7-bis(pyridin-4-ylethynyl)-9H-carbazole (1) was synthesized by reacting 4-ethynylpyridine hydrochloride with 2,7-dibromo-9H-carbazole. The full characterization of compound 1 is presented, and the crystal structure of its monohydrate co-crystal was determined by single-crystal XRD analysis.

Quartz Crystal Microbalance (QCM) is a well-known method to measure the mass of ligands bound to receptor-covered surfaces in various fields, ranging from materials science to biology. Actin molecule is essential in various cellular processes through its function of monomer-to-filament polymerization, forming a double-stranded filament with a 75 nm pitch. In this study, QCM was applied to measure the physical properties of actin, finding that the frequency shifted negatively when monomeric actin bound to the QCM surface, whereas the frequency shifted positively when filaments bound. Using fluorescence light microscopic observations, we have examined whether negative and positive frequency shifts originated from their length. In order to control this process, a severing protein, fragmin was used to change the length of actin filament. When the average length of filaments shortened, the magnitude of positive shift decreased in a concentration-dependent manner. However, shorter filaments showed a negative frequency shift depending on their concentration, showing that the weight derived from the loaded concentration and the function derived from actin polymerization dynamics are detectable. Interestingly, the transition from positive to negative occurred when the average length of actin was ~33 nm, or approximately equal to the half-pitch of filaments. Thus, actin filaments can serve as an excellent standard to measure the mechanical properties of biopolymers. Our results show that the QCM sensor could be both a "weight" and a "function" sensor of biomolecules in vitro.

In contemporary science and technology, photonic sensors are essential. They may be made to be extremely resistant to some physical parameters while also being extremely sensitive to other physical variables. Most photonic sensors may be incorporated on chips and operate with CMOS technology, making them suitable for use as extremely sensitive, compact, and affordable sensors. Photonic sensors can detect electromagnetic (EM) wave changes and convert them into an electric signal due to the photoelectric effect. Depending on the requirements, scientists have found ways to develop photonic sensors based on several interesting platforms. In this work, we extensively reviewed the most generally utilized photonic sensors for detecting vital environmental parameters and personal healthcare. These sensing systems include optical waveguides, optical fibers, plasmonics, metasurfaces, and photonic crystals. Various aspects of light are used to investigate photonic sensors' transmission or reflection spectra. In general, resonant cavity or grating-based sensor configurations that work on wavelength interrogation methods are preferred, so these sensor types are mostly presented. We believe this paper will provide insight into the novel types of available photonic sensors.

It is at the chemistry-biology interface that this work that we have carried out takes place. Indeed, the expected goal is to develop simple molecules, capable of activating the catalytic action of certain metalloenzymes such as tyrosinase. The official name of an enzyme includes the type of reaction catalyzed, the name of the substrates involved. In this work, we carried out the study of the catalytic activity of the complexes of organotin carboxylates synthesized vis-à-vis the oxidation of 3,5-di-tert-butylcatecchol. The results obtained show that the various complexes exhibit good catalytic activity for the oxidation of 3,5-di-tert-butylcatecchol under mild conditions. The complexes that showed good catalytic activity are the compounds C1 and C2.

Native reactive electrophile species (RES) are long-recognized regulators of pathophysiology; yet, knowledge surrounding how RES regulate context-specific biology remains limited. The latest technological advances in profiling and precision decoding of RES sensing and signaling have begun to bring about improved understanding of localized RES regulatory paradigms. However, studies in purified systems—prerequisites for gaining structure/function insights—prove challenging. We here introduce emerging chemical biology tools available to probe RES signaling, and the new knowledge that these tools have brought to the field. We next discuss existing structural data of RES-sensor proteins complexed with electrophilic metabolites or small molecule drugs (limited to < 300 Da), including challenges faced in acquiring homogenous RES-bound proteins. We further offer considerations that could promote enhanced understanding of RES regulation derived from three-dimensional structures of RES-modified proteins.

Current generation witnesses a huge interest in optical waveguide due to their salient feature such as low cost, immune to electromagnetic interference, easy to multiplex, compact size, etc. These features of the optical fibers makes it an useful tool for various sensing applications including medicine, automotive, biotechnology, food quality control, aerospace, physical and chemical monitoring etc. Among all the reported application, the device has been widely exploited to measure the physical and chemical variation in surrounding environment. Optical fiber based temperature sensor plays a crucial role in this decade to detect high fever and tackle COVID like pandemic. Recognizing the major developments in the field of the optical fibers, this article aims to provide recent progress in temperature sensor utilizing several sensing configuration including standard fiber, photonic crystal fiber, and Bragg grating fibers. Additionally, the article also highlights the advantages, limitations, and future possibilities in this area.

Two mononuclear Ru(III) complexes of formula trans-[RuCl4(Hgua)(dmso)]·2H2O (1) and trans-[RuCl4(Hgua)(gua)]·3H2O (2) [Hgua = protonated guanine (gua), dmso = dimethyl sulfoxide] have been synthesized and characterized magnetostructurally. Compounds 1 and 2 crystallize in the monoclinic system with space groups P21/n and Pc, respectively. Each Ru(III) ion in 1 and 2 is six-coordinate and bonded to four chloride ions and one (1) or two (2) nitrogen atoms from guanine molecules and one sulfur atom (1) of a dmso solvent molecule, generating quasi regular octahedral geometries in both cases. In their crystal packing, the Ru(III) complexes are self-assembled mainly through an extended network of N-H⋯Cl hydrogen bonds and π⋯Cl type intermolecular interactions, forming novel supramolecular structures based on this paramagnetic 4d metal ion. Variable-temperature dc magnetic susceptibility measurements performed on microcrystalline samples of 1 and 2 show a different magnetic behavior. While 1 is a ferromagnetic compound at low temperature, 2 exhibits a behavior typical of noninteracting mononuclear Ru(III) complexes with S = 1/2. Ac magnetic susceptibility measurements reveal slow relaxation of the magnetization in the presence of external dc fields only for 2, hence indicating the occurrence of field-induced single-ion magnet (SIM) phenomenon in this mononuclear guanine-based Ru(III) complex.

β-Ga2O3 crystal have attracted great attentions in the fields of photonics and photoelectronics because of its ultra wide-band gap and high thermal conductivity. Here, pure β-Ga2O3 crystal was successfully grown by optical floating zone (OFZ) method, and used as saturable absorbers to realize a passively Q-switched all-solid-state 1μm laser for the first time. By placing the as-grown β-Ga2O3 crystal into the resonator of Nd:GYAP solid-state laser, a Q-switched pulses at the center wavelength of 1080.4 nm are generated under a output coupling of 10%. The maximum output power is 191.5 mW while the shortest pulse width is 606.54 ns, and the maximum repetition frequency is 344.06 kHz. The maximum pulse energy and peak power are 0.567 μJ and 0.93 W, respectively. Our experimental results show that β-Ga2O3 crystal has great potential in the development of all-solid-state 1μm pulsed laser.

Herein, we offer a numerical study on the devising of a unique 2D-heterostructure Photonic crystal (PC) that can split two orthogonally polarized light waves. The analysis is performed via a two-dimensional finite element method (2D-FEM) by utilizing COMSOL Multiphysics software. The device consists of two discrete designs of PC formation. The first PC formation is optimized so that it permits both TE and TM-polarization of light to transmit through it. Whereas the second PC formation possesses a Photonic Bandgap (PBG) only for TE-polarized light. These two formations are combined at an angle of 45 degrees, resulting in a reflection of self-collimated TE-polarized light at an angle of 90 degrees owing to the PBG present in the second PC formation. While permitting the self-collimated TM-polarized light wave to travel uninterrupted. The proposed device has a small footprint of ~10.5 μm2 offering low transmission loss and high polarization extinction ratio which makes it an ideal candidate to be employed as an on-chip polarization division multiplexing system.

Based on the sensitive sum frequency generation cross-correlation frequency-resolved optical gating (SFG-XFROG) measurement setup, besides the pulse broadening, blue shift, red shift and obvious pulse acceleration, we observed the soliton evolution when the low energy soliton pulse with wavelength of 1555nm transmit through the Si photonic crystal waveguide. The measurements were nicely matched with the simulation results, which are achieved with an optimized nonlinear Schrödinger equation (NLSE) modeling. The effects of various parameters of the silicon photonic crystal waveguides and the incident pulses on the pulse transmission were also analyzed, including the nonlinear effects and dispersion such as the self-phase modulation (SPM), self-steepening (SS) and intra-pulse Raman scattering(IRS). The results help us understand further the ultra-fast nonlinear dynamics of soliton in silicon-based waveguides, and even open a novel way for soliton-based functional elements in CMOS-compatible platforms.

Research on piezo-composite actuators has been actively conducted over the past two decades as a response to strong demand for light, compact actuators to replace electro-magnetic motor actuators in micro robots, small flying drones, and compact missile systems. Layered piezo-composite unimorph actuators have been studied to provide active vibration control of thin-walled aerospace structures, control the shapes of aircraft wing airfoils, and control the fins of small missiles, because they require less space and provide better frequency responses than conventional electro-magnetic motor actuator systems. However, based on the limited actuation strains of conventional piezo-composite unimorph actuators with poly-crystalline piezoelectric ceramic layers, they have not been implemented effectively as actuators for small aerospace vehicles. In this study, a lightweight piezo-composite unimorph actuator (LIPCA-S2) was manufactured and analyzed to predict its flexural actuation displacement. It was found that the actuated tip displacement of a piezo-composite cantilever could be predicted accurately using the proposed prediction model based on the nonlinear properties of the piezoelectric strain coefficient and elastic modulus of a piezoelectric single crystal.

A powder synthesis of PbMoO₄ from ancient lead (Pb) and deeply purified commercial MoO₃ powders was performed using a wet chemistry technique to achieve the low radioactivity scintillator for neutrinoless double beta decay search in ¹⁰⁰Mo. The synthesized powders were used to grow single crystals of PbMoO₄ by a Czochralski technique in Ar environment. The luminescence and scintillation properties were measured with excitations using UV, X- and γ-rays in temperature range of 10-300 K. Annealing of the grown PMO crystal in air atmosphere enhanced the scintillation light yield by ~3 orders of magnitude compared to that measured before annealing. The scintillation light yield of grown PMO crystal at 10 K is found to be 127% to that of a reference PMO crystal under 662 keV γ-rays excitation from a ¹³⁷Cs source. The background measurement of the grown crystal performed at 50 K shows negligible activity from ²¹⁰Pb compared to that of reference PMO crystal. These preliminary performances show that the PMO crystal grown from ancient Pb and deeply purified MoO₃ powders has the great potential to be used as cryogenic scintillator for the neutrinoless double beta decay search in ¹⁰⁰Mo.

One ambitious objective of Integrated Computational Materials Engineering (ICME) is to shorten the materials development cycle by using computational materials simulation techniques at different length scales. In this regard, the most important aspects are the prediction of the microstructural evolution during material processing and the understanding of the contributions of microstructural features to the mechanical response of the materials. One possible solution to such a challenge is to apply the Phase Field (PF) method because it can predict the microstructural evolution under the influence of different internal or external stimuli, including deformation. To accomplish this, it is necessary to take into account plasticity or, specifically, non-homogeneous plastic deformation, which is particularly important for investigating the size effects in materials emerging at the micron length scale. In this work, we present quasi-2D simulations of plastic deformation in a face centred cubic system in a finite strain formulation. Our model consists of dislocation-based strain gradient crystal plasticity implemented into a PF code. We apply this model to study the influence of grain size on the mechanical behavior of polycrystals, which includes dislocation storage and annihilation. Furthermore, the initial state of the material before deformation is also considered. The results show that a dislocation-based strain gradient crystal plasticity model can capture the Hall-Petch effect in many aspects. The model reproduced the correct functional dependence of the flow stress of the polycrystal on grain size without assigning any special properties to the grain boundaries. However, the predicted Hall-Petch coefficients are significantly smaller than those found typically in experiments. In any case, we found a good qualitative agreement between our findings and experimental results.

In a depolarizing instrument, such as a broadband imaging spectrometer, the depolarizers are placed on the system for stabilization the optical signal. They are also used to reduce measurements offsets due to strong polarization dependence, which produce drastic deterioration of the signal to noise ratio. Dynamic depolarizer with a controllable degree of polarization is also required to study the effect of noise on quantum information. The article described a new instrument for characterization the variable depolarizer with features which make it different from a polarimetric system. The analysing system based on the simple structural design and has good stability for real-time measurement. A practical application of the described interferometer system for variable depolarizer characterization is also presented.

Bio-based glass-forming materials are now considered for thermal energy storage in building applications. Among them, Xylitol appears as a biosourced seasonal thermal energy storage material with high potential. It has a high energy density, a high and stable undercooling allowing storing solar energy at ambient temperature thus, reducing thermal losses and the risk of spontaneous nucleation (i.e., the risk of losing the stored energy). Generally when the energy is needed, the discharge triggering of the storage system is very difficult as well as reaching a sufficient power delivery. Both are indeed the mains locks for the use of pure Xylitol in seasonal energy storage. Different techniques have been hence considered to crystallize highly undercooled Xylitol. Nucleation triggering of highly undercooled pure Xylitol by using an air lift reactor has been proven here. This method should allow reaching performances matching with building applications (i.e., at medium temperatures, below 100 °C). The advantages of this technique compared to other existing techniques to activate the crystallization are discussed. The mechanisms triggering the nucleation are investigated. The air bubble generation, transportation of nucleation sites and subsequent crystallization are discussed to improve the air injection operating conditions.

A series of Cu(II)-thiocyanato complexes derived from sterically hindered N-donors diamines were synthesized and characterized: catena-[Cu(Me₃en)(μ-NCS)(NCS)] (1), catena-[Cu(NEt₂Meen)(μ-NCS)(NCS)] (2), catena-[Cu(N,N,2,2-Me₄pn)(μ-NCS)(NCS)] (3), the dimeric: [Cu₂(N,N′-isp₂en)₂(μ-NCS)₂(NCS)₂] (4) and the monomeric complex [Cu(N,N′-t-Bu₂en)(NCS)₂] (5), where Me₃en = N,N,N′-Trimethylethylenediamine, NEt₂Meen = N,N-diethyl-N′-methylethylenediamine, N,N,2,2-Me₄pn = N,N,2,2-tetramethylpropylenediamine, N,N′-isp₂en = N,N′-diisopropylethylenediamine and N,N′-t-Bu₂en = N,N′-di(tert-butyl)ethylenediamine. The complexes were characterized by elemental microanalyse, IR and UV-Vis spectroscopy and single crystal X-ray crystallography. Density Functional Theory was used to evaluate the role of steric effects in compounds 4 and 5 and how this may affect the adaption of a specific geometry, NCS-bonding mode and the dimensionality of the resulting complex.

The spectral properties of a one-dimensional photonic crystal bounded by a resonant absorbing nanocomposite layer with the near-zero permittivity have been studied. The problem of calculating the transmittance, reflectance, and absorptance spectra of such structures at the normal and oblique incidence of light has been solved. It is shown that, depending on the permittivity sign near zero, the nanocomposite is characterized by either metallic or dielectric properties. For the first time, the possibility of simultaneous formation of the Tamm plasmon polariton at the photonic crystal/metallic nanocomposite interface and the localized state similar to the defect mode with the field intensity maximum inside the dielectric nanocomposite layer is demonstrated. Specific features of field localization at the Tamm plasmon polariton and defect mode frequencies are analyzed.

Nickel nitrate diammine, Ni(NH₃)₂(NO₃)₂, can be synthesised from the thermal decomposition of the nickel nitrate hexammine, Ni[(NH₃)₆](NO₃)₂. The hexammine decomposes in 2 distinct steps; the first releases 4 equivalents of ammonia while the second involves the release of NO_x, N₂ and H₂O to yield NiO. The intermediate diammine compound can be isolated following the first deammoniation step or synthesised as a single phase from the hexammine under vacuum. Powder X-ray diffraction (PXD) experiments have allowed the structure of Ni(NH₃)₂(NO₃)₂ to be solved for the first time. The compound crystallises in orthorhombic space group Pca2₁ (a = 11.0628 (5) Å, b = 6.0454 (3) Å, c = 9.3526 (4) Å; Z = 4) and contains 11 non-hydrogen atoms in the asymmetric unit. Fourier Transform Infrared (FTIR) spectroscopy demonstrates that the bonding in the ammine is consistent with the structure determined by PXD.

In this article we review the advances that have been made on the understanding of the high-pressure structural, vibrational, and electronic properties of wolframite-type oxides since the first works in the early 1990s. Mainly tungstates, which are the best known wolframites, but also tantalates and niobates, with an isomorphic ambient-pressure wolframite structure, have been included in this review. Apart from estimating the bulk moduli of all known wolframites; the cation-oxygen bond distances and their change with pressure have been correlated with their compressibility. The composition variations of all wolframites have been employed to understand their different structural phase transitions to post-wolframite structures as a response to high pressure. The number of Raman modes and band gap energy changes have been also analyzed in the basis of these compositional differences. The reviewed results are relevant for both fundamental science and for the development of wolframites as scintillating detectors. The possible next research venues of wolframites have also been evaluated.

Two novel inorganic–organic hybrid supramolecular assemblies, namely, (4-HNA)(18-crown-6)(HSO₄) (1) and (4-HNA)₂(18-crown-6)₂(PF₆)₂(CH₃OH) (2) (4-HNA = 4-nitroanilinium), were synthesized and characterized by infrared spectroscopy, single X-ray diffraction, differential scanning calorimetry (DSC), and temperature-dependent dielectric measurements. The two compounds underwent reversible phase transitions at about 255 K and 265 K, respectively. These phase transitions were revealed and confirmed by the thermal anomalies in DSC measurements and abrupt dielectric anomalies during heating. The phase transition may have originated from the [(4-HNA)(18-crown-6)]⁺ supramolecular cation. The inorganic anions tuned the crystal packings and thus influenced the phase-transition points and types. The variable-temperature X-ray diffraction data for crystal 1 revealed the occurrence of a phase transition in the high-temperature phase with the space group of P2₁/c and in the low-temperature phase with the space group of P2₁/n. Crystal 2 exhibited the same space group P2₁/c at different temperatures. The results indicated that crystals 1 and 2 both underwent an iso-structural phase transition.

Children’s beneficial relationships with animals are well known. Companion animals, particularly dogs have become an integral part of family life and children’s material culture. Aside the proven physiological benefits there is little research about what children say about their relationships with animals and how they describe them. In this paper we bring together both horse-human and dog-human interactions, finding common ground for understanding the complexity of human development, well-being and flourishing. Dogs in schools are fast becoming a trend in helping support and enhance children’s learning as well as their social and emotional well-being. Studies have shown that the very presence of a dog can increase children’s concentration, executive function and behavior. Also, equine therapy is gaining momentum and empirical studies are showing noteworthy benefits to children and young people. However, the lack of children’s voices means that the mechanisms for these benefits are somewhat unknown and unclear. In seeking to explore this, the authors utilize a visual, sensory and diffractive ethnographic approach to illuminate and illustrate, experiment and re-enact, how the children relate, share spaces and multiple subjectivities with their classroom canine, “Ted” and companion horse “Henry”. ”Henry” is part of a programme in which youngsters care for and engage in activities with horses.

A single-crystal of ytterbium-doped “mixed” yttrium-lutetium aluminium garnet with a stoichiometric composition of (Y0.601Lu0.233Yb0.166)3Al5O12 was grown by the Czochralski method and its structure, vibronic, spectroscopic and laser properties were studied. The stimulated-emission cross-section for Yb3+ ions was maximized to 2.53×10-20 cm2 at 1031 nm, the emission bandwidth is ~8 nm and the reabsorption-free luminescence lifetime of the 2F5/2 state is 1.063 ms. Pumped at 941 nm, the Yb-laser generated a maximum output power of 1.04 W at 1.03 and 1.05 μm with a high slope efficiency of 76.4% and a laser threshold of 76 mW. A continuous wavelength tuning over a range of 51.6 nm (1026.4 - 1078.0 nm) was also achieved. Power scaling is achieved using a 969 nm-diode pumped microchip cavity. A maximum output power of ~9 W is obtained at 1.05 μm with a slope efficiency of 76% and with an almost circular laser beam profile.

TmMgB5O10 spontaneous crystals were synthesized via flux-growth technique from a K2Mo3O10-based solvent. The crystal structure of the compound was solved and refined within the space group P21/n. The first principles calculations of the electronic structure reveal that TmMg-pentaborate is an insulator with an indirect energy band gap of approximately 6.37 eV. Differential scanning calorimetry measurements and powder X-ray diffraction studies of heat-treated solids show that TmMgB5O10 is an incongruent melting compound. A characteristic band of Tm3+ cation corresponding to the 3H6 → 1D2 transition is observed in the photoluminescence excitation spectra of TmMg-borate. The as-obtained crystals exhibit intense blue emission with the emission peaks centered at 455, 479, 667 and 753 nm. The most intensive band corresponds to the 1D2 3F4 transition.

The study of photonic crystals has emerged as an attractive area of research in nanoscience in the last years. In this work we study the properties of a two-dimensional photonic crystal composed of dielectric rods. The unit cell of the system is composed of six rods organized on the sites of a C6 triangular lattice. We induce a topological phase by introducing an angular perturbation ϕ in the pristine system. The topology of the system is then determined by using the so-called k.p perturbed model. Our results show that the system presents a topological and a trivial phases, depending on the sign of the angular perturbation ϕ. The topological character of the system is probed by evaluating the electromagnetic energy density and analyzing its distribution in the real space, in particular on the maximal Wyckoff points. We also find two edge modes at the interface between the trivial and topological photonic crystals, which present a pseudospin topological behavior. By applying the Bulk-Edge correspondence, we study the pseudospin edge modes and conclude that they are robust against defects, disorder and reflection. Moreover, the localization of the edge modes leads to the confinement of light and the interface behaves as a waveguide for the propagation of electromagnetic waves. Finally, we show that the two edge modes present energy flux propagating in opposite directions, which is the photonic analogue of the quantum spin Hall effect.

We present a theoretical modeling of a cylindrical tunable liquid crystal lens based on the modulation of the anchoring energy. This latter can be easily obtained by means of photoaligning techniques. The liquid crystal cell we propose exhibits strong anchoring at the top substrate and an anchoring energy with parabolic profile at the bottom substrate. The model describes the dependence of the focal length on the applied voltage and presents a theoretical study of lens aberrations. The results obtained are of general relevance and can be used to optimize the performances of every kind of liquid crystal lens with parabolic profile.

This study aims to theoretically address the design and analysis of an efficient pressure sensor designed by using a polymer-based defective 1D annular photonic crystal (APC). The 1D APC comprises an alternate arrangement of Si and SiO2 in a cylindrical fashion, incorporating a central defect layer. The investigation of the reflectance characteristics of the proposed structure is conducted by separately considering the polystyrene (PS) and the polymethyl methacrylate (PMMA) polymer materials as the defect layer. The pressure-sensitive refractive index of the polymers and the constituent materials of the APC plays a vital role in envisaging the pressure-sensing application. The cornerstone of this study is represented by the shift analysis in the wavelength of the defect mode inside the band gap using different applied pressures by employing the modified transfer matrix method (MTMM). Various geometrical parameters like the defect polymer layer’s thickness and the APC period were carefully optimized to achieve higher sensing performance. The proposed design demonstrated a remarkable pressure sensitivity and FoM of 51.29 nm/GPa and 301.7 GPa-1, respectively, which is considerably high in the current research scenario. It is believed that the proposed structure can be an apt candidate as an innovative high-performance pressure sensor, and it can play a key role in photonic integrated circuits.

Single-Molecule Magnets (SMMs) have attracted much interest because of their spin properties and potential technological applications. Besides, a great effort has been devoted to their functionalization, which is made with functional groups convenient to connect suitable SMMs to junction devices or to perform their grafting on surfaces of different substrates. We have synthesized and characterized two lipoic acid-functionalized and oxime-based MnIII compounds, of formula [Mn6(μ3-O)2(H2N-sao)6(lip)2(MeOH)6][Mn6(μ3-O)2(H2N-sao)6(cnph)2(MeOH)6]}·10MeOH (1) and [Mn6(μ3-O)2(H2N-sao)6(lip)2(EtOH)6]·EtOH·2H2O (2) [H2N-saoH2 = salicylamidoxime, lip = lipoate anion, cnph = 2-cyanophenolate anion]. 1 crystallizes in the triclinic system with space group Pī and 2 crystallizes in the monoclinic system with space group C2/c. In their crystal packing, adjacent Mn6 complexes are connected through non-coordinating solvent molecules, which are H-bonded to N atoms of –NH2 groups of salicylamidoxime ligand. In addition, Hirshfeld surfaces of 1 and 2 were calculated to study the variety of intermolecular interactions and different level of importance that take place in their crystal lattice, this type of computed study being the first time performed on Mn6 molecules. The study of the magnetic properties of 1 and 2 through dc magnetic susceptibility measurements reveals the coexistence of ferro- and antiferromagnetic exchange couplings between the Mn(III) metal ions in both compounds, the latter being the predominant magnetic interaction. A ground state spin value of S = 4 was obtained through isotropic simulations of the experimental magnetic susceptibility data for both 1 and 2. Ac magnetic susceptibility measurements show the occurrence of slow relaxation of the magnetization in 1 and 2, which indicate that SMM behavior take place in both compounds.

Luminescent properties of epitaxial Cu2O thin films were studied in 10-300 K temperature range and compared with luminescent properties of Cu2O single crystals. Cu2O thin films were deposited epitaxially by the electrodeposition method on either Cu or Ag substrates at different processing parameters, which determined the epitaxial orientation relationships and encapsulated surface. Cu2O (100) and (111) single crystal samples were cut from a crystal rod grown by the floating zone method. Luminescence spectra of thin films contain the same emission bands as single crystals around 720, 810 and 910 nm, characterizing VO2+, VO+ and VCu defects, correspondingly. Additional emission bands, whose origin is under discussion, are observed around 650-680 nm, while the exciton features are negligibly small. The relative mutual contribution of the emission bands varies depending on the particular thin film sample. Existence of the domains of crystallites with different orientation determines the polarization of luminescence. PL of both Cu2O thin films and single crystals is characterized with negative thermal quenching in the low temperature region, the reason of this phenomenon is discussed.

We evaluated hexadecyltrimethylammonium bromide (HTAB) for use in radio frequency (RF) applications in which liquid crystals (LCs) are used in layered structures that have various cell gap conditions. HTAB is a surfactant that can self-align vertically on the surface of indium tin oxide (ITO) substrates, and can induce homeotropic alignment of the LCs. For implementing RF devices with HTAB and LCs, we should consider limitations caused by the design conditions which are different from conventional liquid crystal displays such as cell gap. We quantified the concentration of HTAB ([HTAB]) that is necessary to form and maintain a sufficiently dense vertical alignment of 5CB (4-Cyano-4'-pentylbiphenyl). The required [HTAB] for full-homeotropic alignment was proportional to the cell gap until it was too large to support the transfer of the surface alignment to the LC, due to the weak anchoring nature of HTAB. We also showed the phase-change characteristic of the LC mixture depended on [HTAB] for the design of RF devices driven by light or heat. This work may help to guide the development of new approaches to designing efficient RF devices that use LCs.

The paramagnetic gadolinium(III) ion is used as contrast agent in magnetic resonance (MR) imaging to improve the lesion detection and characterization. It generates a signal by changing the relaxivity of protons from associated water molecules and creates a clearer physical distinction between the molecule and the surrounding tissues. New gadolinium-based contrast agents displaying larger relaxivity values and specifically targeted might provide higher resolution and better functional images. We have synthesized the gadolinium(III) complex of formula [Gd(thy)2(H2O)6](ClO4)3·2H2O (1) [thy = 5-methyl-1H-pyrimidine-2,4-dione or thymine], which is the first reported compound based on gadolinium and thymine nucleobase. 1 has been characterized through vis-IR, SEM-EDAX and single-crystal X-ray diffraction techniques, and its magnetic and relaxometric properties have been investigated by means of SQUID magnetometer and MR imaging phantom studies, respectively. On the basis of its high relaxivity values, this gadolinium(III) complex can be considered a suitable candidate for contrast enhanced magnetic resonance imaging.

In the application of classical nucleation theory (CNT) and all other theoretical models of crystallization of liquids and glasses it is always assumed that nucleation proceeds only after the supercooled liquid or the glass have completed structural relaxation processes towards the metastable equilibrium state. Only employing such assumption, the thermodynamic driving force of crystallization and the surface tension can be determined in the way it is commonly performed. The present paper is devoted to the theoretical treatment of a different situation when nucleation proceeds concomitantly with structural relaxation. To treat the nucleation kinetics theoretically for such cases, we need adequate expressions for the thermodynamic driving force and the surface tension accounting for the contributions caused by the deviation of the supercooled liquid from metastable equilibrium. In the present paper, such relations are derived. They are expressed via deviations of structural order parameters from their equilibrium values. Relaxation processes result in changes of the structural order parameters with time. As a consequence, the thermodynamic driving force and surface tension, and basic characteristics of crystal nucleation, such as the work of critical cluster formation and the steady-state nucleation rate, also become time-dependent. We show that this scenario may be realized in the vicinity and below the glass transition temperature, and it may occur only if diffusion (controlling nucleation) and viscosity (controlling the alpha-relaxation process) in the liquid decouple. Analytical estimates are illustrated and confirmed by numerical computations for a model system. The theory is successfully applied to the interpretation of experimental data. Several further consequences of this newly developed theoretical treatment are discussed in detail. In line with our previous investigations, we reconfirm that only when the characteristic times of structural relaxation are of similar order of magnitude or longer than the characteristic times of crystal nucleation, elastic stresses evolving in nucleation may significantly affect this process. Completing the analysis of elastic stress effects, for the first time expressions are derived for the dependence of the surface tension of critical crystallites on elastic stresses. As the result, a comprehensive theoretical description of crystal nucleation accounting appropriately for the effects of deviations of the liquid from the metastable states and of relaxation on crystal nucleation of glass-forming liquids, including the effect of simultaneous stress evolution and stress relaxation on nucleation, is now available. As one if its applications, this theoretical treatment provides a new tool for the explanation of the low-temperature anomaly in nucleation in silicate and polymer glasses (the so-called \breakdown" of CNT at temperatures below the temperature of the maximum steady-state nucleation rate). We show that this anomaly results from much more complex features of crystal nucleation in glasses caused by deviations from metastable equilibrium (resulting in changes of the thermodynamic driving force, the surface tension, and the work of critical cluster formation, in the necessity to account of structural relaxation and stress effects) than assumed so far.

We present a high-throughput nanoindentation study of in-situ bending effects on incipient plastic deformation behavior of polycrystalline and single-crystalline pure aluminum and pure copper at ultra-nano depths (<200nm). We find that hardness displays a statistically inverse dependence on in-plane stress for indentation depths smaller than 10nm, and the dependence disappears for larger indentation depths. In addition, plastic noise in the nanoindentation force and displacement displays statistically robust noise features, independently of applied stresses. Our experimental results suggest the existence of a regime in FCC crystals where ultra-nano hardness is sensitive to residual applied stresses, but plasticity pop-in noise is insensitive to it.

Synthesis and characterization of anhydrous LiZn(IO₃)₃ powders prepared from an aqueous solution are reported. Morphological and compositional analyses were carried out by scanning electron microscopy and energy dispersive X-ray measurements. The synthesized powders exhibit a needle-like morphology after annealing at 400°C. A crystal structure for the synthesized compound has been proposed from powder X-ray diffraction and density-functional theory calculations. Rietveld refinements led to a monoclinic structure, which can be described with space group P21, number 4, and unit-cell parameters a = 21.874(9) Å, b = 5.171(2) Å, c = 5.433(2) Å, and beta = 120.93(4)º. Density-functional theory calculations supported the same crystal structure. Infrared spectra were also collected and the vibrations associated to the different modes discussed. The non-centrosymmetric space group determined for this new polymorph of LiZn(IO₃)₃, the characteristics of its infrared absorption spectrum, and the observed second harmonic generation suggest a promising infrared non-linear optical material.

A novel hybrid cobalt phosphite, (H2DAB)[Co(H2PO3)4]·2H2O, has been synthesized by using slow evaporation method, in the presence of cobalt nitrate, phosphorous acid and 1,4- dia-minobutane (DAB= 1,4- diaminobutane) as a structure-directing agent. Single crystal X-ray diffraction analysis showed that the compound crystallizes in the P-1(n.2) triclinic space group, with the following unit cell parameters (Å, °) a = 5.4814 (3), b = 7.5515 (4), c = 10.8548 (6), α = 88.001 (4), β = 88.707 (5), γ = 85.126 (5), and V= 447.33 (4) Å3. The crystal structure was built up from cor-ner-sharing [CoO6] octahedra, forming chains parallel to [001], which are interconnected by H2PO3 pseudo-tetrahedral units. The deprotonated cations, residing between the parallel chains, interacted with the inorganic moiety via hydrogen bonds leading thus to the formation of the 3D crystal structure. The Fourier transform infrared spectrum showed characteristic bands corresponding to the phosphite group and the organic amine. The thermal behavior of the compound consisted mainly of the loss of its organic moiety and the water molecules. The biological tests exhibited significant activity against Candida albicans and Escherichia coli strains in all used concentrations, while less inhibitory activity was pronounced against Staphylococcus epidermidis and Saccharomyces cerevisiae, and in the case of multi-cellular organisms, no activity against the nematode model Steinernema feltiae was detected.

This study analyzed the structural changes of semicrystalline polylactide (PLA) in the form of spun-bonded mulching nonwoven, during outdoor composting. The investigation was carried out at the microstructural, supramolecular and molecular levels using scanning electron microscopy (SEM), wide-angle X-ray diffraction (WAXD) and the viscosity method, respectively. The results showed the varying degree of influence of the climatic condition, prepared compost mixtures and time on the molecular, supramolecular and micromorphological structure of PLA spun-bonded mulching nonwoven and its degradation rate. The obtained experimental results revealed how the popular outdoor composting method, realized under two different European climatic conditions (in Poland and in Bulgary), affects the degradation of PLA nonwoven, designed for agriculture use.

Graph theory plays a crucial role in modeling and designing of chemical structure or chemical network. Chemical Graph theory helps to understand the molecular structure of molecular graph. The molecular graph consists of atoms as vertices and bonds as edges. Topological indices capture symmetry of molecular structures and give it a mathematical language to predict properties such as boiling points, viscosity, the radius of gyrations etc. In this article, we study the chemical graph of carbon Crystal structure of graphite and cubic carbon and compute several degree-based topological indices. Firstly we compute M-Polynomials of these structures and then from these M-polynomials we recover nine degree-based topological indices.

The mesoporous heteroatom molecular sieve MCM-41 bulk crystals with the crystalline phase were synthesized via a one-step hydrothermal method using an ionic complex as template. The ionic complex template was formed by interaction between cetyltrimethylammonium ions and metal complex ion [M (EDTA)]2- (M=Co or Ni ). The materials were characterized by X-ray diffraction, scanning electron microscopy, high-resolution transmission electron microscopy, N2 adsorption–desorption isotherms, and X-ray absorption fine structure spectroscopy. The results showed that the materials possess a highly ordered mesoporous structure with the crystalline phase and possess high uniform ordered arrangement channels. The structure is in the vertical cross directions with a crystalline size of about 12 µm and high specific surface areas. The metal atoms were incorporated into the zeolite frameworks in the form of octahedral coordinate and have a uniform distribution in the materials. The amount of metal complexes formed by metal ion and EDTA is an essential factor for the formation of the vertical cross structure. Comparing to Si-MCM-41, the samples exhibited better conversion, higher selectivity for cumene cracking.

Intelligent transportation systems (ITS) have recently evolved rapidly, which requires development of highly trustworthy and effective communication technologies for uses, including vehicle-to-vehicle (V2V) and vehicle-to-everything (V2X) communication; where Orthogonal Frequency Division Multiplexing (OFDM) is regarded as a strong candidate and highly popular option technique among these methods. However, the movement of vehicles introduces Doppler frequencies which produce inter-carrier interference (ICI), that is frequently occurs in V2X channels. This interference has the potential to compromise the integrity of subcarrier orthogonality within OFDM, leading to lower-quality communication and an increased likelihood of data transmission errors. When employing channels with doubly dispersive fading, OFDM necessitates the usage of a complex equalization based on the minimum mean-square error (MMSE) equalizer, which requires channel matrix inversion. Several low-complexity equalizers for OFDM have been developed and are based on band factorization, time domain LSQR (Least-Square QR) iterative computing, and banded minimum mean squared error (BMMSE). This paper proposes Conjugate Gradient Least Squares (CGLS), which is a novel iterative computation algorithm integrated with nonlinear equalizers. The suggested nonlinear equalization technique determines the trade-off between computations and performance. According to simulation data, the suggested nonlinear equalizer performs better than the current BMMSE and linear CGLS algorithms across doubly dispersive fading channels.

Malaria is one of the leading causes of illnesses and deaths in Africa at large and Nigeria in particular, especially amongst pregnant women and children under the age of five years. Our research revealed that though the government has deployed so many intervention systems to contend with this death-causing vector—the mosquitoes, malaria related deaths (MRDs) have continued to increase. This is because people have not sufficiently adopted those intervention systems to protect themselves. Further enquiries into the ineffective compliance of the people to the intervention systems revealed that the interventions are passive in nature. Based on these, we set up three measurable research outcomes to enable us to determine the appropriateness of persuasive technology in solving the malaria problem. We technically avoided a one-size-fits-all design approach and adopted Participatory System Design (PSD) and User-Centered Design (UCD) approaches in our system design methodologies. Well-structured questionnaires were used to extract information from the participants. The data obtained from the research survey was used in modeling the intervention system. The research was conducted in three phases: baseline, development and deployment of an intervention system—the Malaria Prevention and Control Support System (MPCSS), and an evaluation study to determine the performance of the intervention system. The research led to the following achievements: (1) encouraged an increase in the number of people who participated in malaria prevention and control activities by lowering the rate of malaria cases from 96.9% to 68.5% and increasing ownership of mosquito nets from 54% to 85.5%; (2) demonstrated that persuasive technology could be used to increase public awareness and knowledge of a given subject as noted in our evaluation result; and (3) demonstrated that persuasive technology is a veritable active intervention to combat malaria.

Ecologists use the net biotic interactions among plants to predict fundamental ecosystem features. Following this approach, ecologists have built a giant body of theory founded on observational evidence. However, due to the limitations that a phenomenological approach raises both in empirical and theoretical studies, an increasing number of scientists claim the need for a mechanistic understanding of plant interaction outcomes, and a few studies have taken such a mechanistic approach. In this synthesis, we propose a modeling framework to study the plant interaction mechanistically. We first establish a conceptual ground to frame plant-plant interactions, and then, we propose to formalize this research line theoretically developing a family of individual-based, spatially-explicit models in which biotic interactions are an emergent property mediated by the interaction between plants’ functional traits and the environment. These models allow researchers to evaluate the strength and sign of biotic interactions under different environmental scenarios and thus constitute a powerful tool to investigate the mechanisms underlying facilitation, species coexistence, or the formation of vegetation spatial patterns.

The demand of high data rate and ubiquitous coverage in heterogeneous cellular (HetNets) is increasing progressively. In order to meet this demand, sophisticated model having applied interference reduction scheme and cell association technique is needed. The small base station (sBS)are deployed inside the broadcasting area of macro base station (mBS), in heterogeneous cellular networks (HetNets). Since mBS has high transmission power therefore a large number of users get connected with mBS. This causes disproportion of load distribution across the HetNets. For load balancing users from high power mBS are migrated to low power sBS to increase network capacity and to decrease the load from mBS. This results in interference in the communication signal because of strong mBS Interference. Hence, we need interference management technique to mitigate interference and user association and to efficiently use sBSs’ resources. Inter-cell interference (ICI) limit the HetNets’ performance. Additionally, there exist deliberate jamming interference which depends on jammers transmission power and its proximity with the target, which notably degrades the network performance. In this paper, we employ reverse frequency allocation scheme (RFA) to reduce inter cell interference, deliberate jamming interference and to accomplish load balancing. The proposed setup is analyzed inquisitively and with the help of simulations. The result shows reduction in interferences as well as balance of load distribution in the network achieved by employing RFA scheme together with cell association.

The critical period (CP) phenomenon in language development ranks among the 125 conundrums facing scientists in the 21st century, according to Science. While the phenomenon itself has been noncontroversial in first language acquisition, it still warrants an adequate explanation. Predicated on language acquisition as a complex process, questions among the first to be raised include: How do children accomplish this remarkable feat in such a short amount of time? And how do nature and nurture come together to influence language learning? In second language acquisition, however, both the notion of CP, albeit popular, and its empirical evidence have remained contested to this date - among the questions, whether the observed evidence counts as CP-specific and/or whether or not it warrants an isomorphic attribution to maturational constraints. Entwined in this debate are two well-established facets of inter-learner differential attainment. The first is that there exists a stark difference in ultimate attainment between younger and older learners. A second facet is the vast differences in ultimate attainment among older learners. In this article, adopting a social physics approach, we mathematically establish both the relationship between nature and nurture contributions and the presence of a critical period, and, at once, tender a parsimonious and probable theory for the twin phenomena of inter-learner differential attainment.

The reaction between 5-acetylbarbituric acid and 4-dimethylthiosemicarbazide or 4-hexamethyleneiminyl thiosemicarbazide produces 5-acetylbarbituric-4-dimethylthiosemicarbazone (H2AcbDM) and 5-acetylbarbituric-4N-hexamethyleneiminyl thiosemicarbazone (H2Acbhexim). Eight new complexes with different cooper (II) salts have been prepared and characterized using elemental analysis, molar conductance, UV–vis, ESI-HRMS, FT-IR, magnetic moment, EPR and cyclic voltammetry. In addition, three-dimensional molecular structures of [Cu(HAcbDM)(H2O)2](NO3)·H2O (3a), [Cu(HAcbDM)(H2O)2]ClO4 (4), and [Cu(HAcbHexim)Cl] (6) were determined by single crystal X-ray crystallography, and was carried out an analysis of their supramolecular structure. The H-bonded assemblies were further studied energetically using DFT calculations, MEP surface and QTAIM analyses. In these complexes, the thiosemicarbazone coordinates to the metal ion in an ONS-tridentate manner, in the O-enolate/S-thione form. The electrochemical behavior of the thiosemicarbazones and their copper(II) complexes has been investigated at room temperature using the cyclic voltammetry technique in DMFA. The Cu(II)/Cu(I) redox system was found to be consistent with the quasi-reversible diffusion-controlled process.

This work proposes a hollow-core photonic crystal fiber-based edible oil sensor in the terahertz (THz) range (e.g., 1.0THz ≤ f ≤ 3.0THz) and different sensing characteristics are numerically analyzed. The suggested sensor’s performance was assessed by means of COMSOL Multiphysics, a commercial program that uses the finite element approach. The computational results indicate that the relative sensitivity is 85.591%, 84.648%, 82.625%, 82.683%, and 79.161%, respectively, at f = 2.2 THz, for several types of sunflower oil, mustard oil, coconut oil, olive oil and palm oil; and the corresponding effective areas are 7.22×10-8 um2, 7.09×10-8 um2, 6.83×10-8 um2,7.09×10-8 um2, 6.5231 ×10-8 um2. In addition, the effective material loss for sunflower oil, muster oil, coconut oil, olive oil, and palm oil has been found to be 0.02561 cm-1, 0.027054 cm-1, 0.030322 cm-1, 0.028854 cm-1 ,0.035427cm-1 respectively. Moreover, the proposed sensor also has low confinement loss are 1.55×10-8 dB/m, 1.63×10-8 dB/m, 1.31×10-8 dB/m, 1.99×10-8 dB/m, 4.0345×10-8 dB/m.This proposed sensor can be fabricated using extrusion and 3D-printing technologies, and due to its augmented detecting capabilities, it can be a vital part of oil sensing devices implemented in real life such as industry fields.

A systematic study has been conducted on barbiturate complexes of all five alkali metals Li–Cs prepared from the metal carbonates or hydroxide in aqueous solution without other potential ligands present, varying the stoichiometric ratio of metal ion to barbituric acid (BAH). Eight polymeric compounds (two each for Na, K, and Rb and one each for Li and Cs) have been characterised by single-crystal X-ray diffraction. All contain some combination of barbiturate anion BA− (necessarily in a 1:1 ratio with the metal cation M+), barbituric acid, and water. All organic species and water molecules are coordinated to the metal centres via oxygen atoms as either terminal or bridging ligands. Coordination numbers range from 4 (for the Li complex) to 8 (for the Cs complex). Extensive hydrogen bonding plays a significant role in all the crystal structures, almost all of which include pairs of N–H…O hydrogen bonds linking BA− and/or BAH components into ribbons extending in one dimension. Factors influencing the structure adopted by each compound include cation size and reaction stoichiometry as well as hydrogen bonding.

Sumatriptan is a serotonin receptor agonist approved by FDA in 1992 to treat migraines. Its’ solid form used in commercially available drugs Imitrex, Treximet, Onzetra Xsail and Zembrace symtouch is sumatriptan succinate. Herein we report on crystal structure of sumatriptane succinate hemi(ethanol solvate), HSum+·HSucc–·0.5EtOH, its comparison with previously reported solids containing derivatives of sumatriptan.

The reaction of 2-bromo-1-(5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl)ethan-1-one (1) with 4-amino-5-((2,4-dichlorophenoxy)methyl)-4H-1,2,4-triazole-3-thiol (2) in absolute ethanol in the presence of triethyl amine as catalyst gave 2-((4-amino-5-((2,4-dichlorophenoxy)methyl)-4H-1,2,4-triazol-3-yl)thio)-1-(5-methyl-1-(4-nitrophenyl)-1H-1,2,3-triazol-4-yl)ethan-1-one (3) in 73% yield. The structure of the title heterocycle (3) was confirmed by X-ray single crystal diffraction and spectral analyses (NMR and IR).

Management of calcium and phosphate in biofluids is key to maintaining physiological mineral homeostasis (i.e., appropriate mineralization of hard tissues and an absence of mineral deposition in soft tissues). This review describes and contrasts the ways vertebrates manage calcium phosphate in two biological fluids (breast milk and serum) and illustrates the benefits of mineral sequestration by proteins. In milk, phosphoprotein-sequestered calcium magnesium phosphates provide nutritional support, whereas in serum, protein-sequestered calcium phosphates control transport and delivery of calcium and phosphate to tissues for biological function or excretion. In addition, subsets of sequestered phosphates in serum have been identified as culprits underlying ectopic deposition of calcium phosphates and toxicity.

The 11 system in iron-based superconducting family has become one of the most extensively studied materials in the research of high-temperature superconductivity due to their simple structure and rich physical properties. However, the research on 11 iron-based superconductors faces numerous obstacles, mainly stemming from the challenges associated with producing high-quality single crystals. Since the discovery of FeSe superconductivity in 2008, researchers have made significant progress in crystal growth, overcoming the hurdles that initially impeded their studies. Consequently, they have successfully established the complete phase diagrams of 11 iron-based superconductors, including FeSe1-xTex, FeSe1-xSx and FeTe1-xSx. In this paper, we aim to provide a comprehensive summary of the preparation methods employed for 11 iron-based single crystals over the past decade. Specifically, we will focus on hydrothermal, chemical vapor transport (CVT), self-flux, and annealing methods. Additionally, we will discuss the quality, size, and superconductivity properties exhibited by single crystals obtained through different preparation methods. By exploring these aspects, we can gain a better understanding of the advantages and limitations associated with each technique.

The preparation of transition metal salt ammine complexes having oxidizing anions is a great challenge due to the reaction between the ammonia and oxidizing anions during the synthesis of these materials. However, they have an important role in the development of new oxidants in organic chemistry and especially as precursors in the preparation of mixed metal oxides and alloys in controlled temperature thermal decomposition reactions. Therefore, the synthetic procedures to prepare the complexes of transition metal permanganate, pertechnetate, and perrhenate (VIIB group tetraoxometallates) salts with ammonia as ligand or co-ligand have been comprehensively reviewed. The available data about the structure and spectroscopic properties of these compounds, including the hydrogen bonds that act as redox reaction centers under their thermal decomposition are given and evaluated. Their thermal decomposition processes and products have been summarized. The available pieces of information about their role in organic oxidation reactions like the oxidation of benzyl alcohols, and regeneration of oxo-compounds from oximes and phenylhydrazones including the kinetics of these processes have also been collected.

Zinc oxide (ZnO) nanoparticles (NPs) were synthesized using Rosmarinus officinalis leaf extract at 80 ° C (ZnO-80) and 180 ° C (ZnO-180). The biosynthesized ZnO NPs were characterized and their photocatalytic activity was evaluated for the degradation of methylene blue (MB) and crystal violet (CV) under sunlight irradiation. The results of the characterizations by XRD, TEM and SEM showed that the size of the NPs of ZnO-80 was smaller than that of ZnO-180 which exhibited flakier agglomerated spherical structures. Photocatalytic tests showed ZnO-80 which was prepared by a cheap and easy procedure compared to ZnO-180 effectively degrades MB and CV dyes under sunlight. The superior performance of ZnO-80 over ZnO-180 can be explained by the differences in their textural properties. This is because ZnO-80 has a smaller crystallite size, a specific surface area and a higher pore volume than ZnO-180. Fourier-transform infrared spectroscopy (FTIR) analyzes revealed that both samples contained an adsorbed carboxylate group (COO-), and accordingly a mechanism was proposed for the formation of ZnO NPs that include the carboxyl group.

Chemical versatility of organic semiconductors provides nearly unlimited opportunities for tuning their electronic properties. However, despite decades of research, relationship between molecular structure, molecular packing and charge mobility in these materials remains poorly understood. This reduces the search for high-mobility organic semiconductors to the inefficient trial-and-error approach. For clarifying the abovementioned relationship, investigations of the effect of small changes in the chemical structure on OSs properties are particularly important. In this study, we address computationally the impact of substitution of C-H atom pairs by nitrogen atoms (N-substitution) on molecular properties, molecular packing and charge mobility of crystalline oligoacenes. Besides of decreasing frontier molecular orbital levels, N-substitution dramatically alters molecular electrostatic potential yielding pronounced electron-rich and electron-deficient areas. These changes in the molecular electrostatic potential strengthen face-to-face and edge-to-edge interactions in the corresponding crystals and result in the crossover from the herringbone packing motif to π-stacking. When the electron-rich and electron-deficient areas are large, sharply defined and, probably, have certain symmetry, charge mobility increases up to 3-4 cm2V-1s-1. The results obtained highlight the potential of azaacenes for application in organic electronic devices and are expected to facilitate rational design of organic semiconductors for steady improvement of organic electronics.

Calcium carbonate cements have been synthesized by mixing amorphous calcium carbonate and vaterite powders with water to form a cement paste and study how mechanical strength is created during the setting reaction. In-situ XRD was used to monitor the transformation of ACC and vaterite phases into calcite and a rotational rheometer was used to monitor the strength evolution. There are two characteristic time scales of the strengthening of the cement paste. The short timescale of the order 1 hour is controlled by smoothening of the vaterite grains, allowing closer and therefore adhesive contacts between the grains. The long timescale of the order 10-50 hours is controlled by the phase transformation of vaterite into calcite. This transformation is, unlike in previous studies using stirred reactors, found to be mainly controlled by diffusion in the liquid phase. The evolution of shear strength with solid volume fraction is best explained by a fractal model of the paste structure.

This article reveals a best possible design for hybrid dispersion compensating fiber (HyDCF) with high birefringence established on modified broadband compensating structure through S, C and L telecommunication bands. The simulation outcome exhibits relatively higher birefringence of 3.76×10-2 at wavelength of 1550 nm. The suggested fiber also has dispersion compensation characteristics in an inclusive series of wavelengths which covers 1400-1625 nm. The reported design can achieve dispersion quantity of – 606 ps/ (nm.km) at 1550 nm effective wavelength. The reported fiber design matches the relative dispersion slope (RDS) 0.003694 nm-1 similar to single mode fiber at 1550 nm operating wavelength. This fiber demonstrates negatively flattened effective dispersion of – 2.703 ± 0.734 ps/ (nm.km) within 180 nm flat band ranging from 1460-1640 nm wavelength. It is also convenient to optical high bit rate communication systems. The low confinement loss is found 3.756×10-10 dB/m at the operating wavelength. This design also achieves highly nonlinear coefficient of 50.34 W-1km-1. In some cases, it can also be used in sensing applications.

In this paper, we synthesized MC(BeA-co-MMA) copolymer microcapsules through suspension polymerization. The pendent n-behenyl group of BeA is highly crystalline, and it acts as the side-chain in the structure of BeA-co-MMA copolymer. The highly crystalline n-behenyl side-chain provides BeA-co-MMA copolymer thermal-energy-storage capacity. In order to investigate the correlation between thermal properties and crystal structure of BeA-co-MMA copolymer, the effects of monomer ratio, temperature changing and changing rate, as well as synthesis method were discussed. The monomer ratio influenced crystal transition behavior and thermal properties greatly. The DSC results proved that when the monomer ratio of BeA and MMA was 3:1, MC(BeA-co-MMA)3 showed the highest average phase change enthalpy ΔH (105.1 J·g–1). It indicated that the n-behenyl side-chain formed relatively perfect crystal region, which ensured a high energy storage capacity of copolymer. All the DSC and SAXS results proved that the amount of BeA had a strong effect on the thermal-energy-storage capacity of copolymer and the long spacing of crystals, but barely on the crystal lamella. It was found that MMA units worked like defects in the n-behenyl side-chain crystal structure of BeA-co-MMA copolymer. Therefore, a lower fraction of MMA, that is, a higher fraction of BeA contributed to a higher crystallinity of BeA-co-MMA copolymer for providing a better energy storage capacity and thermoregulation property. ST(BeA-co-MMA) copolymer sheets with the same ingredients as microcapsules were also prepared through light-induced polymerization aiming at clarifying the effect of synthesis method. The results proved that synthesis method mainly influenced the copolymer chemical component, but lightly on the crystal packing of n-behenyl side-chain.

In this article, we first present and discuss eighteenth-century descriptions of minerals that contributed decisively to the development of crystallography. Remarkably, these old crystallographic descriptions included morphologies with symmetries incompatible with an internal periodic order of atoms, which, however, have been recognised to be characteristics of quasicrystals. Moreover, we also review a number of studies of minerals with aperiodic crystal structures, including recently reported natural quasicrystals of extra-terrestrial origin. Finally, we discuss the current investigations addressing the search for new quasicrystalline minerals in nature.

Modular steel buildings (MSBs) interlocking inter-module connections (IMCs) have piqued researchers’ interest. However, the existing literature has not yet studied the optimisation of its plate thicknesses. This paper, therefore, focuses on optimising interlocking (IMCs) plate thickness in (MSBs), leveraging previous experimental and numerical simulation methodologies. Various numerical models for four MSBs interlocking (IMCs) with plate thicknesses (4 mm, 6 mm, 10 mm, and 12 mm) were developed under compression loading conditions. The study’s novelty lay in its comprehensive parametric analysis, which evaluated the slip phenomenon in (MSBs) connections and introduced a slip prediction model validated against empirical data. Further innovative machine learning approach was utilised to predict slip values based on applied force through a random forest regression model trained using the 'Treebagger' function. Sensitivity analysis and comparisons with alternative methods were utilised to underscore the reliability and applicability of the findings. The results showed that 11.03 mm was the optimal plate thickness for interlocking (IMCs) in modular steel buildings, with up to 8.08% reduced material costs. Increasing plate thickness boosts its deformation resistance by up to 50.75%. ‘TreeBagger’ random forest for anomaly detection and machine learning improves slip prediction up to 7% at higher force levels.

The development of novel coherent and brilliant sources, such as soft X-ray Free Electron Laser (FEL) and High Harmonic Generation (HHG) enables new ultrafast analysis of the electronic and structural dynamics of a wide variety of materials. Soft X-ray FEL delivers high brilliance beams with short pulse duration, high spatial coherence and photon energy tunability. In com-parison with FELs, HHG X-ray sources are characterized by a wide spectral bandwidth and few to sub-femtosecond pulses. The approach will lead to time-resolved reconstruction of molecular dynamics, shedding light on different photochemical pathways. The high peak brilliance of soft X-ray FELs facilitates investigations in nonlinear regime, while the broader spectral bandwidth of the HHG sources may provide the simultaneous probing of multiple components. Significant technical breakthroughs in these novel sources are under way to improve brilliance, pulse dura-tion, and to control spectral bandwidth, spot size, and energy resolution. Therefore, in the next few years, the new generation of soft X-ray sources combined with novel experimental tech-niques, new detectors, and computing capabilities will allow the study of several extremely-fast dynamics, such as vibronic dynamics. In the present review, we shortly discuss recent devel-opments in experiments, performed with soft X-ray FELs and HHG sources, operating near car-bon K-absorption edge, being a key atomic component in biosystems and soft materials. Differ-ent spectroscopy methods such as time-resolved pump-probe techniques, nonlinear spectrosco-pies and photoelectron spectroscopy studies have been addressed in an attempt of a better un-derstanding of fundamental physico-chemical processes

Connected and Autonomous Vehicle (CAV) combines technologies of autonomous vehicle (AV) and connected vehicles (CV) to develop quicker, more reliable and safer traffic. Artificial Intelligence (AI) based CAV solutions play significant roles in sustainable city. The convergence imposes stringent security requirements for CAV safety and reliability. In practice, vehicles are developed with increased automation and connectivity. Increased automation increases the reliance on the sensor-based technologies and decreases the reliance on driver; increased connectivity increases the exposures of vehicles vulnerability and increases the risk for an adversary to implement a cyber-attack. Much work has been dedicated to identifying the security vulnerabilities and recommending mitigation techniques associated with different sensors, controllers, and connection mechanisms, respectively. However, there is an absence of comprehensive and in-depth studies to identify how the cyber-attacks exploit the vehicles vulnerabilities to negatively impact the performance and operations of CAV. In this survey, we set out to thoroughly review the security issues introduced by AV and CV technologies, analyze how the cyber-attacks impact the performance of CAV, and summarize the solutions correspondingly. The impact of cyber-attacks on the performance of CAV is elaborated from both viewpoints of intra-vehicle system and inter-vehicle system. We pointed out that securing the perception and operations of CAV would be the top requirement to enable CAV to be applied safely and reliably in practice. Also, we suggested to utilize cloud and new AI methods to defend against smart cyber-attacks on CAV.

Due to the rapid developments in aquaculture industry, Artemia franciscana, originally an American species, has been intentionally introduced to the Eurasia, Africa and Australia. In the present study, we used a partial sequence of the mitochondrial DNA Cytochrome Oxidase subunit I (mt-DNA COI) gene and genomic fingerprinting by Inter-Simple Sequence Repeats (ISSRs) to determine the genetic variability and population structure of Artemia populations (indigenous and introduced) from 14 different geographical locations in Western Asia. Based on the haplotype spanning network, Artemia urmiana has exhibited higher genetic variation than native parthenogenetic populations. Although A. urmiana represented a completely private haplotype distribution, no apparent genetic structure was recognized among the native parthenogenetic and invasive A. franciscana populations. Our ISSR findings have documented that despite invasive populations have lower variation than source population in Great Salt Lake (Utah, USA), they have significantly revealed higher genetic variability compare to the native populations in Western Asia. According to the ISSR results, the native populations were not fully differentiated by the PCoA analysis, but the exotic A. franciscana populations were geographically divided in four genetic groups. We believe that during the colonization, invasive populations have experienced substantial genetic divergences, under new ecological conditions in the non-indigenous regions.

Research on titanium oxo complexes (TOCs) are usually focused on their structure and photocatalytic properties. Findings from these investigations spurred our interest in exploring also their potential biological activities. In this study, we focused on the synthesis and structure of a compound with the general formula [Ti8O2(OiPr)20(man)4] (1), which was isolated from the reaction mixture of titanium(IV) isopropoxide with mandelic acid (Hman) in a molar ratio of 4:1. The structure (1) was determined using single-crystal X-ray diffraction, while spectroscopic studies provided insights into its physicochemical properties. To assess the potential practical applications of (1), its microcrystals were incorporated into a polymethyl methacrylate (PMMA) matrix, yielding composite materials of the type PMMA + (1) (2 wt.%, 5 wt.%, 10 wt.%, and 20 wt.%). The next stage of our research involved the antimicrobial activity evaluation of the obtained materials. Investigations carried out demonstrated antimicrobial activity of pure (1) and its composites (PMMA + (1)) against both Gram-positive and Gram-negative strains. Furthermore, MTT tests conducted on the L929 murine fibroblast cell line confirmed the lack of cytotoxicity of these composites. Our study identified (1) as a promising antimicrobial agent, also for producing composite coatings.

A survey of the trends in metal-ligand coordination and hydrogen bonding has been carried out on complexes of singly deprotonated cyanuric acid CY− and alkaline earth metals, synthesised from aqueous solution and characterised by X-ray crystallography. Involvement of cyanurate in the metal coordination increases from Mg through Ca and Sr to Ba relative to coordination by water, in parallel with the increasing ionic radius and coordination number. The incidence of bridging of metal centres by both water and cyanurate also increases in this series. The Mg complex contains hexaaqua-coordinated cations, uncoordinated CY− anions, and additional water molecules. Ca and Sr complexes feature polymeric chains of coordinated metal ions, the Ca complex with uncoordinated anions and the Sr complex with all potential ligands coordinated. The Ba complex has a two-dimensional coordination network. Extensive hydrogen bonding plays a key role in generating a three-dimensional network in all four structures. The competition between cyanurate and water for coordination to the alkaline earth metal cations, and that between coordination and hydrogen bonding propensities of the cyanurate anion, appear to be finely balanced, with the structural outcomes depending on the relative sizes and degrees of hardness of the four cations of the group.

: The silicon single crystals for semiconductor application is usually grown by Czochralski (CZ) method. This paper researches 300mm silicon Czochralski (CZ) crystal growth with CUSP magnetic field for IGBTs substrate application. The different positions of Zero-Gauss plane (ZGP) under CUSP magnetic field are simulated and compared to numerical analysis, investigated melt convection, melt flow velocity near to quartz crucible wall, diffusion boundary layer and effect of initial oxygen concentration in the silicon crystal, and the shape of solid/liquid interface was discussed. The results show that the change of the ZGP of the CMF mainly affects the convection in the melt, which leads to the difference of the thickness of the boundary layer near to the wall of the quartz crucible, and was found to be the key to reduce the oxygen dissolution from the crucible wall and oxygen diffuse into the crystal, along with the differences in the shape of the crystal-melt interface. In addition, we have carried out actual industrial single crystal production under the three configurations. The results show that the experimental data of oxygen content and shape of the crystal-melt interfaces in silicon crystal are consistent with the numerical results.

The correspondence between classical and quaternion quantum equations, permits considering the universe (vacuum) as an ideal elastic solid. Elementary particles would have to be standing or soliton-like waves. Tension induced by the compression and twisting of the elastic medium would increase the energy density, consequently generate a gravity forcing and affect the wave speed. Consequently the gravity could be described by an index of refraction. Theory was created by combining the Cauchy model of the elastic continuum with the Planck-Kleinert crystal hypothesis. The quaternion-imaginary Lagrange’an, the quaternion motion equation and the quaternionic oscillator allowed deriving: - The Schrödinger equation from the functional integral, which identifies the quaternion-imaginary quantum Hamiltonian. - The 2nd order wave equation system describing both the bosons and the gravity in terms of quaternionic Poisson equation. - The first order quaternionic wave equation system. - The family of the second order wave equation systems describing both the particles and the generated quaternionic force-fields (four-potentials). - The fundamental Planck and gravity constants. - The quaternionic continuity equation in an ideal elastic solid.

A new Pd(II) complex of the previously reported ligand N,N′-bis[(2,2′-dihydroxybiphen-3-yl)methyl]-N,N′-dimethylethylenediamine (L) was obtained from a DMF/H2O mixture. It differs from a Pd(II) complex of L previously obtained by sole DMF. The roles in the solid state assembly of solvent molecules and molecular conformation (driven by specific transition metal ions) were studied by comparing six complexes of L containing different metal centers (Ni(II), Cd(II), Cu(II), Pd(II)). Hirshfeld surface analysis, 2D fingerprint plots and energy frameworks calculations were used to investigate the intermolecular interactions within the crystal packing of the six complexes. As suggested by interaction energies, Pd(II) and Ni(II) complexes arrange to form ribbons, while Cd(II) and Cu(II) complexes form 3D networks. Interactions between complexes and solvent molecules in the previous Pd(II) complex are replaced by complex-complex interactions in the new Pd(II) complex, while BuOH and MeOH are interchangeable in the interactions within the crystal packing of the two Ni(II) complexes. Finally, solvent molecules are not involved in the crystal packing of the Cu(II) complex. The present study suggested that the solid state assembly of these systems is mainly driven by the molecular conformation, that depends in turn by the metal ion involved, while the solvent only plays a minor role.

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

The crystal structure of quintinite, Mg4Al2(OH)12(CO3)·3H2O, from Jacupiranga alkaline complex (Cajati, São Paulo, Brazil) has been refined for two samples (91002 and C7029) using single-crystal X-ray diffraction data. The mineral crystallizes in the P-3c1 space group, a = 5.246/5.298, c = 15.110/15.199 Å for the samples 91002/C7029. The crystal structure consists of octahedral sheets with Mg and Al ordering according to the 3 × 3 superstructure. The Mg and Al atoms are coordinated by six hydroxylated oxygen atoms each with the average &lt;Mg–O&gt; and &lt;Al–O&gt; bond distances being in the ranges 2.022–2.053 Å and 1.974–1.978 Å, respectively. The interlayer structures are identical (in contradiction to the previous assumptions) and compose from disordered (CO3)2- groups and (H2O)0 molecules. The samples from Jacupiranga can be identified as quintinite-2T that is the second find of the polytype after the Kovdor alkaline complex (Kola peninsula, Russia). The powder X-ray diffraction pattern of quintinite-2T contains weak superstructure reflection at 4.57 Å (010) indicative of Mg and Al ordering. An important crystal-chemical criterion of quintinite is the interlayer distance (d00n-value) of ~ 7.56 Å, which is steady for natural specimens from various findings worldwide.

The review starts by highlighting the significance of nuclear power plants in contemporary world, especially its indispensable role in the global efforts to reduce CO2 emissions. Then, it describes the impact of irradiation on microstructure and mechanical properties of reactor structural materials. The main part provides the reader with a thorough overview of crystal plasticity models developed to address the irradiation effects so far. All three groups of most important materials are included. Namely, the Zr alloys used for fuel cladding, austenitic stainless steels used for reactor internals and ferritic steels used for reactor pressure vessel. Other materials, especially those considered for construction of future fission and fusion nuclear power plants, are also mentioned. The review pays also special attention to ion implantation and instrumented nanoindentation which are a common way to substitute costly and time-consuming neutron irradiation campaigns.

Chymotrypsin is an important proteolytic enzyme in human digestion system that cleaves milk proteins, through hydrolysis reaction, which makes it interesting subject to study activity of milk proteases. In this work, we compared detection of chymotrypsin by spectrophotometric, dynamic light scattering (DLS) and quartz crystal microbalance (QCM) methods and determined the limit of chymotrypsin detection (LOD), 0.15 ± 0.01 nM for spectrophotometric, 0.67 ± 0.05 nM for DLS and 1.40 ± 0.30 nM for QCM methods, respectively. We discuss peculiarities and give perspective for implementation of detection methods and note that while the optical detection methods are simple to implement, the QCM method is more robust for sample preparation. We give an overview on methods and instruments for detection of chymotrypsin and other milk proteases.

New pharmaceutically acceptable salts of trazodone for the treatment of central nervous system disorders are synthesized and described. Each salt (trazodone hydrogen bromide and trazodone 1-hydroxy-2-naphthoate) was obtained by two or three different methods leading to the same crystalline form. Although trazodone salts are poorly crystalline, single-crystal X-ray diffraction data for trazodone 1-hydroxy-2-naphthoate were collected and analyzed as well as compared to the previously described crystal structure of commercially available trazodone hydrochloride. The powder samples of all new salts were characterized by Fourier transform infrared spectroscopy and 13C solid-state nuclear magnetic resonance spectroscopy. Spectroscopic studies were supported by gauge including projector augmented wave (GIPAW) calculations of carbon chemical shielding constants. The main goal of our research was to find salts with better physicochemical properties and to make an attempt to associate them with both the anion structure and the most prominent interactions exhibited by the protonated trazodone cation. The dissolution profiles of trazodone from tablets prepared from various salts with lactose monohydrate were investigated. The studies revealed that salts with simple anions show a fast release of the drug while the presence of more complex anion, more strongly interacting with the cation, effects a slow-release profile of the active substance and can be used for the preparation of the tables with a delay or prolonged mode of action.

This paper presents a multifunctional reflective digital metasurface of arbitrary base based on voltage tunable liquid crystal (LC). The reflective digital metamaterial can be multiplexed for different desirable functions by properly biasing the LC for different code patterns. Simulation results of three significant functions, beam steering with a steering elevation angle 27° at 75 GHz, RCS reduction of at least 15dB along the incident direction, and beam shaping with different beam shapes have been presented to prove the concept.

We investigated fabrication of neodymium doped thin film optical waveguide-based devices as potential active sources for planar integrated optics. Liquid-phase epitaxial growth was used to fabricate neodymium-doped yttrium aluminum borate films on compatible lattice-matched un-doped yttrium aluminum borate substrates. We observed the refractive index contrast of the doped and un-doped crystal layers by differential interference contrast microscopy. In addition, characterization by X-ray powder diffraction, optical absorption and luminescence spectra demonstrated the crystal quality and uniformity and optical guiding of the resulting thin films.

A realistic implementation of an all-fiber CO₂ sensor, using 74 cm of hollow core PCF fiber as the cavity for light/gas interaction, has been implemented. It is based on CO₂ absorbance in the 2 μm region. The working range is from 2% to 100% CO₂ concentration at 1 atm total pressure. The response time obtained was 10 min. The use of an FBG tuned fiber ring laser, specifically designed for this application, is discussed and preliminary results with this laser are also presented.

The present work reports new mineralogical and whole rock geochemical data from the Breivikbotn silicocarbonatite (Seiland igneous province, North Norway), allowing conclusions to be drawn concerning its origin and the role of late fluid alteration. The rock shows a rare mineral association: calcite + pyroxene + amphibole + zeolite group minerals + garnet + titanite, with apatite, allanite, magnetite and zircon as minor and accessory minerals, and it is classified as silicocarbonatite. Calcite, titanite and pyroxene (Di36-46 Acm22-37 Hd14-21) are primarily magmatic minerals. Amphibole of hastingsitic composition has formed after pyroxene at a late-magmatic stage. Zeolite group minerals (natrolite, gonnardite, Sr-rich thomsonite-(Ca)) were formed during hydrothermal alteration of primary nepheline by fluids/solutions with high Si-Al-Ca activities. Poikilitic garnet (Ti-bearing andradite) has inclusions of all primary minerals, amphibole and zeolites, and presumably crystallized metasomatically during a late metamorphic event (Caledonian orogeny). Whole rock chemical compositions of the silicocarbonatite differs from the global average of calciocarbonatites by elevated silica, aluminium, sodium and iron, but show comparable contents of trace elements (REE, Sr, Ba). Trace element distributions indicate within-plate tectonic setting of the carbonatite. The spatial proximity of carbonatite and alkaline ultramafic rock (melteigite), the presence of “primary nepheline” in carbonatite together with the trace element distributions indicate that the carbonatite was derived from crystal fractionation of a parental carbonated foidite magma. The main prerequisites for the extensive formation of zeolite group minerals in silicocarbonatite are revealed.

Prompt removal of misfolded membrane proteins and misassembled membrane protein complexes is essential for membrane homeostasis. However, the elimination of these toxic proteins from the hydrophobic membrane environment has high energetic barriers. Transmembrane FtsH is the only known ATP-dependent protease responsible for this task, unlike other well-studied soluble ATP-dependent proteases. The mechanisms by which FtsH recognizes, unfolds, translocates, and proteolyzes its substrates remain unclear. Here, we report the crystal structures of the Thermotoga maritima FtsH periplasmic domain (PD) in an associative trimeric state at a 1.5-1.95 Å resolution. We also describe the pH-dependent oligomerization states of the isolated PD using dynamic light scattering. These observations help us understand how FtsH recognizes membrane-anchored misfolded proteins.

The aim of this work is to compare two softwares (MAUD and TOPAS) based on the Rietveld algorithm and to test the concept of tolerance factor using the dissolution at high temperature of yttrium into BaTiO₃. In general, both softwares give up different values of the crystalline parameters however the trends are similar in most cases but the analysis of the strain and crystallite size in the BaTiO₃ crystals suggests that, in this particular case, MAUD offered results more consistent with the expected behavior. Using the crystalline parameters calculated by Rietveld, the tolerance factor values were obtained and these data suggest even better stability in the crystalline structure than that expected using theoretical parameters. Tolerance factor concept also indicates that Ti⁴⁺ should be preferred.

Through an investigation of recently discovered Incantation of Wish-Fulfillment amulets from the Silla kingdom, this paper reveals that early Korea had more diverse forms of dhāraṇī practices than previously assumed. This paper’s analysis of these amulets from Korea contributes toward filling the gap in our current understanding of the material practice pertaining to the Incantation of Wish-Fulfillment widely practiced in medieval East Asia. Based on an interdisciplinary analysis of the two amulet sheets of the Incantation of Wish-Fulfillment from Silla, this paper explored hitherto unknown aspects of early Korean dhāraṇī practice. Previously, the only material dhāraṇī practice in early Korea was thought to be the enshrinement of textual relics in pagodas based on the Pure Light Incantation, which has little connection to contemporaneous Chinese dhāraṇī practice. However, the newly discovered Incantation of Wish-Fulfillment amulets, whose date this paper inferred to be between the eighth and ninth century, show that the Unified Silla also had a dhāraṇī practice closely linked to the Chinese practice. However, unlike the Chinese Incantation of Wish-Fulfillment amulets that were buried in tombs, the Silla amulets were likely enshrined in one of the pagodas erected on Mount Nam, Gyeongju. At the same time, the Silla epigraph from Myogilsang Pagoda at Haeinsa shows that the Incantation of Wish-Fulfillment was placed in the pagoda so as to wish for good afterlives of the soldiers who died at the battle, suggesting that placing the Incantation of Wish-Fulfillment in a pagoda had a function similar to that of burying the Chinese amulet in the tomb.

Bayesian nonlinear mixed effects models for data in the form of continuous, repeated measurements from a population, also known as Bayesian hierarchical nonlinear models, are a popular platform for analysis when interest focuses on individual specific characteristics and relevant uncertainty quantification. Due to the limitation of computational power, this framework was relatively dormant until the late 1980s, but in recent years, the statistical research community saw vigorous development of new methodological and computational techniques for these models, the emergence of software, and wide application of the models in numerous industrial and academic fields. This article presents an overview of the formulation, interpretation, and implementation of Bayesian nonlinear mixed effects models and surveys recent advances and applications.

Tellurium exhibits exceptional intrinsic electronic properties. However, investigations into the modulation of tellurium's electronic properties through physical modification are notably scarce. Here, we present a comprehensive study focused on the evolution of the electronic properties of tellurium crystal flakes under plasma irradiation treatment by employing conductive atomic force microscopy and Raman spectroscopy. The plasma-treated tellurium experienced a process of defect generation through lattice broken. Prior to the degradation of electronic transport performance due to plasma irradiation treatment, a remarkable observation emerged: in the low-energy region of hydrogen plasma-treated tellurium, a notable enhancement in conductivity was unexpectedly detected. The mechanism underlying this enhancement in electronic transport performance was thoroughly elucidated by comparing it with the electronic structure induced by argon plasma irradiation. This study not only fundamentally uncovers the effects of plasma irradiation on tellurium crystal flakes, but also unearths an unprecedented trend of enhanced electronic transport performance at low irradiation energies when utilizing hydrogen plasma. This abnormal trend bears significant implications for guiding the prospective application of tellurium-based 2D materials in the realm of electronic devices.

Single crystals of quaternary adamantine type Cu•GaGeS4 were grown by chemical vapor transport technique using iodine as transport agent. Dark red transparent crystals grew in a temperature gradient of dT = 900–750 °C. Chemical characterization by X-ray fluorescence showed an off-stoichiometric composition of the Cu•GaGeS4 crystals, in particular a slight Ge-deficit. By X-ray diffraction, Cu•GaGeS4 was found to adopt the chalcopyrite-type structure with the space group I-42d. The cation distribution in this structure was analyzed by multiple energy anomalous synchrotron X-ray diffraction and it was found that Cu and vacancies occupy the 4a site, whereas Ga and Ge occupy the 4b site. The band gap energies of several off-stoichiometric Cu•GaGeS4 crystals were determined by UV-Vis spectroscopy and are in the range of 2.1 to 2.4 eV. A non-linear correlation of the band gap energy with the Ge-content of the compound follows the usual bowing behaviour of semiconductor alloys with a bowing parameter of b = 1.45(0.08).

We report the use of four-layer graphene (4LG) as a highly reliable transparent conductive electrode (TCE) for polymer-dispersed liquid crystal (PDLC)-based smart window devices. The adhesion between 4LG and the substrate was successfully improved through a water-induced interface-cleaning (WIIC) process. We compared the performance of a device with a WIIC-processed 4LG electrode with that of devices with a conventional Indium tin oxide (ITO) electrode and a 4LG electrode without a WIIC. With the application of the WIIC process, the PDLC smart window with a 4LG electrode exhibited reduced turn-on voltage and haze compared to 4LG without the WIIC process and characteristics comparable to those of the ITO electrode. Based on our observations, we conclude that 4LG with WIIC is a promising TCE for flexible smart windows.

Bacterial nitroreductase enzymes that convert prodrugs to cytotoxins are valuable tools for creating transgenic targeted ablation models to study cellular function and cell-specific regeneration paradigms. We recently engineered a nitroreductase (“NTR 2.0”) for substantially enhanced reduction of the prodrug metronidazole, which permits faster cell ablation kinetics, cleaner interrogations of cell function, ablation of previously recalcitrant cell types, and extended ablation paradigms useful for modelling chronic diseases. To provide insight into the enhanced enzymatic mechanism of NTR 2.0, we have solved the X-ray crystal structure at 1.85 Angstroms resolution and compared it to the parental enzyme, NfsB from Vibrio vulnificus. We additionally present a survey of reductive activity with eight alternative nitroaromatic substrates, to provide access to alternative ablation prodrugs, and explore applications such as remediation of dinitrotoluene pollutants. The predicted binding modes of four key substrates were investigated using molecular modelling.

The crystal structure of a polymorph of Glycyl-L-alanine HI.H2O was synthesized from chiral cyclic Glycyl-L-alanine dipeptide, known to show molecular flexibility in different environments. The space group is polar (P21) and therefore pyroelectricity and optical second harmonic generation properties are allowed by symmetry. We report a pyroelectric coefficient as high as 45 µC/m2K occurring at 345 K, one order of magnitude smaller than the semi-organic ferroelectric Triglycine Sulphate (TGS) crystal. Furthermore, the polymorph displays a nonlinear optical effective coefficient of 0.14 pm/V, around 14 times smaller than the value from a phase-matched inorganic Barium Borate (BBO) single crystal.

Pairs of pyrrolysyl-tRNA synthetase (PylRS) and tRNAPyl from Methanosarcina mazei and Methanosarcina barkeri are widely used for site-specific incorporations of non-canonical amino acids into proteins (genetic code expansion). Previously, we achieved full productivity of cell-free protein synthesis for bulky non-canonical amino acids, including Ne-((((E)-cyclooct-2-en-1-yl)oxy)carbonyl)-L-lysine (TCO*Lys), by using Methanomethylophilus alvus PylRS with structure-based mutations in and around the amino acid binding pocket (first-layer and second-layer mutations, respectively). Recently, the PylRS•tRNAPyl pair from a methanogenic archaeon ISO4-G1 was used for genetic code expansion. In the present study, we determined the crystal structure of the methanogenic archaeon ISO4-G1 PylRS (ISO4-G1 PylRS) and compared it with those of structure-known PylRSs. Based on the ISO4-G1 PylRS structure, we attempted the site-specific incorporation of Ne-(p-ethynylbenzyloxycarbonyl)-L-lysine (pEtZLys) into proteins, but it was much less efficient than that of TCO*Lys with M. alvus PylRS mutants. Thus, the first-layer mutations (Y125A and M128L) of ISO4-G1 PylRS, with no additional second-layer mutations, increased the protein productivity with pEtZLys up to 578% of that with TCO*Lys, at high enzyme concentrations in the cell-free protein synthesis.

For many decades, X-ray diffraction (XRD) has been used for material characterization. With the recent development in material science understanding and technology, various new materials are being developed, which requires upgrading the existing analytical techniques such that intricate problems can be solved. Although, XRD is a well-established non-destructive technique, it still requires further improvements in its characterization capabilities, especially when dealing with complex mineral structures. The present review conducts comprehensive discussions on atomic crystal structure, XRD principle, its applications, uncertainty during XRD analysis, and required safety precautions, all in one place. It further discusses the future research directions, especially the use of artificial intelligence and machine learning tools for improving the effectiveness and accuracy of XRD technique for mineral characterization. It has been focused that how XRD patterns can be utilized for a thorough understanding of the crystalline structure, size, and orientation, dislocation density, phase identification, quantification, and transformation, information about lattice parameters, residual stress, and strain, and thermal expansion coefficient of materials. All these important discussions on XRD for mineral characterization are compiled in this short yet comprehensive review that would benefit specialists and engineers in the chemical, mining, iron, metallurgy, and steel industries.

We report the effect of doping Cd1-xZnxS/ZnS core/shell quantum dot (CSQDs) in nematic liquid crystal p-methoxybenzylidene p-decylaniline (MBDA) at 0.05 wt/wt%, 0.1 wt/wt%, 0.15 wt/wt%, 0.2 wt/wt%, 0.25 wt/wt% and 0.3 wt/wt% concentrations of CSQDs in MBDA. Dielectric parameters with and without bias with respect to frequency has been investigated. The change in electro - optical parameters with temperature has also been demonstrated. The increase in the mean dielectric permittivity has been found due to large dipole moment of CSQDs which impose stronger interactions with the liquid crystal molecules. The dielectric anisotropy changes sign on doping CSQDs in MBDA liquid crystal. It was concluded that the CSQDs doping noticeably increases the dielectric permittivity of nematic MBDA in the presence of electric field. The doping of CSQDs in nematic MBDA liquid crystal reduces the ion screening effect effectively. This phenomenon is attributed to the competition between the generated ionic impurities during assembling process and the ion trapping effect of the CSQDs. The rotational viscosity of nematic liquid crystal decreases with increasing concentration of the CSQDs with faster response time observed for 0.05 wt/wt% concentration. The birefringence of the doped system increases with the inclusion of CSQDs in MBDA. These results find application in the field of display devices, phase shifters, industries and projectors.

By taking advantage of a stability criterion established recently, the critical temperature T_c is reckoned with help of the microscopic parameters, characterising the normal and superconducting electrons, namely the independent-electron band structure and a repulsive two-electron force. The emphasis is laid on the sharp T_c dependence upon electron concentration and inter-electron coupling, which might offer a practical route toward higher T_c values and help to understand why high-T_c compounds exhibit such remarkable properties.

In this work, we investigated the effects of heat treatment on the microstructure, hydrogen storage characteristics and corrosion rate of a Ti₃₄V₄₀Cr₂₄Fe₂ alloy. The arc melted alloy was divided into three samples, two of which were separately quartz-sealed under vacuum and heated to 1000 °C for 1 h; one of these samples was quenched and the other furnace cooled to ambient temperature. The crystal structures of the samples were studied via X-ray diffractometry and scanning electron microscopy. Absorption/desorption characteristics were investigated using a Sievert apparatus. Potentiostat corrosion tests on the alloys were performed using an AutoLab^® corrosion test apparatus and electrochemical cell. All samples exhibited a mixture of body-center-cubic (BCC) and Laves phase structures. The corrosion rate, maximum absorption, and useful capacities increased after both heat treatments. The annealed sample had the highest absorption and reversible capacity. The plateau pressure of the as-cast alloy increased after quenching. The corrosion rate increased from 0.0004 mm/y in as-cast sample to 0.0009 mm/y after annealing and 0.0017 mm/y after quenching, due to a decrease in the Cr-content of the C14 phase.

Although floods, as well as other natural disasters, can be considered relevant causes of intra-generational inequalities, the frequent catastrophes and the resulting damages to territory reflect the generalized indifference about inter-generational justice. Societal concerns, such as land protection, typically involve the administrative system performing proactive policies in the perspective of inter-generational solidarity, but subsidiarity has made more and more independent the local communities. As a consequence, the attention toward the long run effects – typically concerning the territorial system, as a whole, at the geographical scale – has been dispersed, and the proactive policies coming from the central government has became more ineffective. Regarding the case of the flood happened in 2009 in the Fiumedinisi-Capo Peloro hydraulic basin, in the northeastern part of Sicily, Italy, we propose an economic valuation – carried out by performing the method of the imputed preferences – in order to compare the expenses incurred by the public authorities responsible for protecting the territory to the costs of the rehabilitation of the damaged areas. Some considerations about the economic significance of the proactive policies for the arrangement of territory are addressed according to the role played by the social discount rate in the inter-temporal economic calculation.

If "quantization is an art" then it can be greatly rened by adopting cyclic time formalism. In past papers we have proven the effectiveness of a formulation of physics based on cyclic relativistic time. Now we can demonstrate in a general way, by using theorems of Geometric Quantization, that the Poisson brackets of intrinsically cyclic time dynamics directly imply the ordinary canonical commutation relations and the other Dirac's rules of canonical Quantum Mechanics. In other words, according to our result, canonical quantization is an implicit way of imposing intrinsically cyclic time dynamics without explicitly saying that time is a cyclic dimension.

In the theoretical treatment of crystallization it is commonly assumed that relaxation processes of the liquid proceed fast as compared to crystal nucleation and growth processes. Actually, it is supposed that the liquid is located always in the metastable state corresponding to the current values of pressure and temperature. However, near and below the glass transition temperature, Tg, this condition is commonly not fulfilled. In such cases, in the treatment of crystallization, deviations of the state of the liquid from the respective metastable equilibrium state have to be accounted for in determining the kinetic coefficients governing the crystallization kinetics, the thermodynamic driving force of crystallization, and the surface tension of the aggregates of the newly evolving crystal phase including the surface tension of critical clusters affecting considerably the crystal nucleation rate. These factors may considerably influence the course of the overall crystallization process. A theoretical analysis of the resulting effects is given in the present paper by numerical solutions of the J(ohnson)–M(ehl)–A(vrami)–K(olmogorov)–equation employed as the tool to model the overall crystallization kinetics and by analytical estimates of the crystallization peak temperatures in dependence on cooling and heating rates. The results are shown to be in good agreement with experimental data. Possible extensions of the theory to be explored in future analysis are anticipated.

We report herein high-resolution x-ray diffraction measurements of basal plane bending of homoepitaxial single-crystal diamond (SCD). The results reveal that growth parameters such as temperature, growth time and basal plane bending of the substrate affect the basal plane bending of SCD. First, the basal plane bending of SCD depends mainly on the substrate itself. The basal plane bending of SCD becomes more severe with increasing basal plane bending of the substrate and this type of basal plane bending cannot be recovered. The SCD growth experiments show that the basal plane bending increases at high temperature and with increasing growth time. Finally, to understand the mechanism behind basal plane bending, we investigate the substrate-surface temperature distribution as a function of basal plane bending of SCD fabricated by chemical vapour deposition (CVD). This allows us to propose a bending model and understand the origin of basal plane bending. The results indicate that an uneven temperature distribution on the substrate surface is the main cause of the CVD diamond base-plane bending.