Direct electron transfer (DET)-type bioelectrocatalysis, which couples electrode reactions and catalytic functions of redox enzymes without any redox mediator, is one of the most intriguing subjects studied over the past decades in the field of bioelectrochemistry. In order to realize the DET-type bioelectrocatalysis and to improve the performance, nanostructures of the electrode surface have to be carefully tuned for each enzyme. In addition, enzymes can also be tuned by protein engineering approach for the DET-type reaction. This review summarizes the resent progresses in this field of the research, while taking into consideration of the importance of nanostructure of electrodes as well as redox enzymes. Described are basic concepts and theoretical aspects of DET-type bioelectrocatalysis, significance of nanostructures as scaffolds for DET-type reactions, protein engineering approached for DET-type reactions, and concepts and facts of bidirectional DET-type reactions, from a cross-disciplinary viewpoint.

Electroactive microorganisms have received a lot of interest in the field of environmental engineering and biotechnology because of their extracellular electron transfer (EET) capability of energy recovery and environmental remediation. However, the low efficiency of EET remains a barrier to its practical implementation. This review presents an introduction to EET, followed by addressing strategies for enhancing EET through different approaches including enhancing EET by mediator materials, external electricity, photo, and magnetism as well as integrated strategies, that is, the combination of multiple means to promote extracellular electron transport and improve the performance of microbial electrochemical systems. Finally, the challenges, perspectives, and new directions for EET enhancement will be discussed.

With metal oxide semiconductors being a promising candidate for accurate indoor air quality assessments, multiple drawbacks of the gas sensors prevent their widespread use. Examples include poor selectivity, instability over time, and sensor poisoning. Complex calibration methods and advanced operation modes can solve some of those drawbacks. However, this leads to long calibration times, which are unsuitable for mass production. In recent years, multiple attempts to solve calibration transfer have been made with the help of direct standardization, orthogonal signal correction, and many more methods. Besides those, a new promising approach is transfer learning from deep learning. This article will compare different calibration transfer methods, including direct standardization, piecewise direct standardization, transfer learning for deep learning models, and global model building. The machine learning methods to calibrate the initial models for calibration transfer are feature extraction, selection, and regression (established methods) and a custom convolutional neural network TCOCNN. It is shown that transfer learning can outperform the other calibration transfer methods regarding the root mean squared error, especially if the initial model is built with multiple sensors. It was possible to reduce the number of calibration samples by up to 99.3 % (from 10 days to approximately 2 hours) and still achieve an RMSE for acetone of around 18 ppb (15 ppb with extended individual calibration) if six different sensors were used for building the initial model. Furthermore, it was shown that the other calibration transfer methods (direct standardization and piecewise direct standardization) also work reasonably well for both machine learning approaches, primarily when multiple sensors are used for the initial model.

The elimination of superoxide radical anions (O2•−) by 5-amino-2-hydroxybenzoic acid (mesalazine, 5-ASA), 4-amino-2-hydroxybenzoic acid (4-ASA), and related compounds used for ulcerative colitis treatment was investigated using cyclic voltammetry and electron spin resonance (ESR) analyses aided by density functional theory (DFT) calculations. Quasi-reversible O2/O2•− redox was found to be modified by the compounds, suggesting that an acid-base reaction in which a hydroperoxyl radical (HO2•) is formed from O2•− occurs. However, the deprotonated 5-ASA anion can eliminate O2•− through proton-coupled electron transfer (PCET), forming a radical product. This electron transfer (ET) was confirmed by ESR analysis. The 4-aminophenol moiety in 5-ASA plays an important role in the PCET involving two proton transfers and one ET based on -conjugation. The electrochemical and DFT results indicated that O2•− elimination by 5-ASA proceeds efficiently viathrough the PCET mechanism after deprotonation of the 1-carboxyl group. Thus, 5-ASA may act as an anti-inflammatory agent in the alkali intestine through PCET-based O2•− elimination.

In this review, photoinduced electron transfer processes in specifically designed assembled ar-chitectures have been investigated on the basis of recent results reported from our laboratories. A convenient and useful way to study these kinds of systems has been described in order to under-stand the rules that drive to a light induced charge separation and its subsequent decay to the ground state, also with the aim of offering a tutorial for young researchers. Assembled systems of covalent or supramolecular nature have been presented and some functional multicomponent systems for the conversion of light energy into chemical energy have been discussed.

Abstract: Scavenging of electrogenerated superoxide radical anion (O2•−) by pyrogallol (PyH3) was investigated on the basis of cyclic voltammetry and in situ electrolytic electron spin resonance spectrum in N,N-dimethylformamide with the aid of density functional theory (DFT) calculations. Quasi-reversible dioxygen/O2•− redox coupe was modified by the presence of PyH3, suggesting that O2•− was scavenged by PyH3 through proton-coupled electron transfer (PCET) involving two proton transfer and one electron transfer. The DFT calculation suggested that the formation of hydrogen bond (HB) complex and the subsequent concerted-two-proton coupled electron transfer (2PCET) characterized by catechol moiety in PyH3 is plausible mechanism which embodies the superior kinetics of the O2•− scavenging by PyH3 as shown in the electrochemical results. Furthermore, it was clarified that three hydroxyl groups of PyH3 promote the formation of prereactive HB complex, in comparative analyses using related compounds, resulting the promotion of the O2•− scavenging.

Redox reactions are of great importance in environmental catalysis. Gold nanoparticles (NPs) have attracted much attention because of their catalytic activity and their localized surface plasmon resonance (LSPR). In the present study, we investigated in details the reduction of ferricyanide (III) ion into ferrocyanide (II) ion catalyzed by spherical gold nanoparticles of two different sizes 15 nm and 30 nm and excited at their LSPR band. Experiments were conducted in the presence (or not) of sodium thiosulfate. This catalysis is enhanced in the presence of Au-NPs under visible light excitation. This reduction takes also place even without sodium thiosulfate. Our results demonstrate the implication of hot electrons in this reduction.

We have investigated the interfacial dislocations in InxGa1–xN/GaN (0 ≤ x ≤ 0.20) heterostructures using diffraction contrast analysis in a transmission electron microscopy. The analysis indicate that the structural properties of the interface dislocations depend on the indium composition. For lower indium composition up to x = 0.09, we observed that the screw-type dislocations and dislocation half loops occurred at the interface even though the former do not contributes toward elastic relaxation of the misfit strain in the InGaN layer. With the increase of indium composition (0.13 ≤ x ≤ 0.17), in addition to the network of screw-type dislocations, edge-type misfit dislocations were found generated with their density gradually increasing. For higher indium composition (0.18 ≤ x ≤ 0.20), all the interfacial dislocations are transformed into a network of straight misfit dislocations along the <10-10> directions leading to partially relaxation of the InGaN epilayer. The presence of dislocation half loops may be explained by slip on the basal plane, the formation of misfit dislocations are attributed to punch-out mechanism.

Biohydrogen is a versatile energy carrier for the generation of electric energy from renewable sources. Hydrogenases can be used in enzymatic fuel cells to oxidize dihydrogen. The rate of electron transfer (ET) at the anodic side between the [NiFe]-hydrogenase enzyme distal iron-sulfur cluster and the electrode surface can be described by the Marcus equation. All parameters for the Marcus equation are accessible from DFT calculations. The distal cubane FeS-cluster has a three cysteine and one histidine coordination [Fe₄S₄](His)(Cys)₃ first ligation sphere. The reorganization energy (inner- and outer-sphere) is almost unchanged upon a histidine-to-cysteine substitution. Differences in rates of electron transfer between the wild-type enzyme and the all-cysteine mutant can be rationalized by a diminished electronic coupling between the donor and acceptor molecules in the [Fe₄S₄](Cys)₄ case. The fast and efficient electron transfer from the distal iron-sulfur cluster is realized by a fine-tuned protein environment which facilitates the flow of electrons. This study enables the design and control of electron transfer rates and pathways by protein engineering.

The critical role of global electron density transfer (GEDT) in increasing the reaction rate of polar organic reactions has been studied within the framework of Molecular Electron Density Theory (MEDT). To this end, the series of the polar Diels-Alder (P-DA) reactions of cyclopentadiene with cyanoethylene derivatives, for which experimental kinetic data are available, have been chosen. A complete linear correlation between the computed activation Gibbs free energies and the GEDT taking place at the polar transition state structures (TSs) is found; the higher the GEDT at the TS, the lower the activation Gibbs free energy. An interacting quantum atoms (IQA) energy partitioning analysis allows establishing a complete linear correlation between the electronic stabilization of the electrophilic ethylene frameworks and the GEDT taking place at the polar TSs. This finding supports Parr’s proposal for the definition of the electrophilicity  index (J. Am. Chem. Soc., 1999, 121, 1922). The present MEDT study allows establishing the critical role of the GEDT in the acceleration of polar reactions, since the electronic stabilization of the electrophilic framework with the electron density gain is greater than the destabilization of the nucleophilic one, making a net favorable electronic contribution to the decrease of the activation energy.

Abstract: Elimination of superoxide radical anion (O2•−) by tocopherols (TOH), and related compounds was investigated on the basis of cyclic voltammetry and in situ electrolytic electron spin resonance spectral measurements in N,N-dimethylformamide (DMF) with the aid of density functional theory (DFT) calculations. Quasi-reversible O2/O2•− redox was modified by the presence of TOHs, suggesting that the electrogenerated O2•− was eliminated by α-, β-, γ-TOH through proton-coupled electron transfer (PCET), but not by δ-TOH. The structure–activity correlation of α-, β-, γ-, and δ-TOH characterized by methyl group on the 6-chromanol ring was experimentally confirmed, where the methyl group promotes the PCET mechanism. Furthermore, comparative analyses using some related chemical analogues suggested that methoxyl group of the 6-chromanol ring is required for a successful electron transfer (ET) to O2•− through the PCET. The electrochemical and DFT results in dehydrated DMF suggested that the PCET mechanism involves preceding proton transfer (PT) forming hydroperoxyl radical followed by a concerted PCET (ET–PT). The O2•− elimination by TOH proceeds efficiently along the net PCET mechanism involving one ET and two PTs.

The goal of this paper is to propose a dual version of the direct cosine simplex algorithm (DDCA) for general linear problems. Unlike the two-phase and the big-M methods, our technique does not involve artificial variables. Our technique solves the dual Klee-Minty problem in two iterations and solves the dual Clausen’s problem in four iterations. The utility of the proposed method is evident from the extensive computational results on test problems adapted from NETLIB. Preliminary results indicate that this dual direct cosine simplex algorithm (DDCA) reduces the number of iterations of two-phase method.

Graphene-based composites have been widely explored for electrode and electrocatalyst materials for electrochemical energy systems. In this paper, a novel composite material of the reduced graphene oxide nanosheets (rGON) with gold nanoparticles (NPs) (rGON-AuNP) is synthesized, and its morphology, structure and composition are characterized by SEM, HRTEM, XRD, EDX, FTIR, Raman, and UV-Vis techniques. To confirm this material’s electrochemical activity, a glucose oxidase (GOD) is chosen as the target reagent to modify the rGON-AuNP layer to form GOD/rGON-AuNP/glassy carbon (GC) electrode. Two pairs of distinguishable redox peaks, corresponding to the redox processes of two different conformational GOD on AuNP, are observed on the cyclic voltammograms of GOD/rGON-AuNP/GC electrode. Both cyclic voltammetry and electrochemical impedance spectroscopy are employed to study the mechanism of direct electron transfer from GOD to GC electrode on the rGON-AuNP layer. In addition, this GOD/rGON-AuNP/GC electrode shows catalytic activity toward glucose oxidation reaction.

This paper aims to provide an adaptation of the TL-moments method to censored data. The present study concentrates on Type-I censored data. The idea of using TL-moments with censored data may seem conflicting. But our perspective in that, we may use data censored from one side and trimmed from the other side. This study is applied to estimate the two unknown parameters of the Weibull distribution. The suggested point is compared with Direct L-moments and ML methods. A Monte Carlo simulation study is carried out to compare these method in terms of estimate average, root of mean square error (RMSE) and relative absolute biases (RAB).

Surface passivation, which has been intensively studied recently, is essential for the perovskite solar cells (PSCs), due to the intrinsic defects in perovskite crystal. A series of chemical or physical methods have been published for passivating the defects of perovskite, which effectively suppressed the charge recombination and enhanced the photovoltaic performance. In this study, the n-type semiconductor of [6,6]-phenyl-C61-butyric acid methyl ester (PCBM) is dissolved in chlorobenzene (CB) for the surface passivation during the spin-coating process for depositing the two-dimensional (2D) perovskite film. This approach simplifies the fabrication process of 2D PSCs and benefits the film quality. As a result, the defects of perovskite film are effectively passivated by this method. A better perovskite/PCBM heterojunction is generated, exhibiting an increased film coverage and improved film morphology of PCBM. It is found that this technology results in an improved electron transporting performance as well as suppressed charge recombination for electron transport layer. As a result, PSCs based on the one-step formed perovskite/PCBM heterojunctions exhibit the optimized power conversion efficiency of 15.69% which is about 37% higher than that of regular perovskite devices. The device environmental stability is also enhanced due to the quality-improved electron transport layer.

In this paper, we analyze the generalized Ulam-Hyers stability of affine type AQ Functional Equation in various Banach Spaces using Direct and Fixed Methods

The conformational dependence of the matrix element for spin-orbit coupling and of the electronic coupling for charge separation are determined for an electron donor-acceptor system containing a pyrene acceptor and a dimethylaniline donor. Different kinetic and energetic aspects that play a role in the spin-orbit charge transfer intersystem crossing (SOCT-ISC) mechanism are discussed. This includes parameters related to initial charge separation and the charge recombination pathways using the (Semi-Classical) Marcus Theory for electron transfer. The spin-orbit coupling, which plays a significant role in charge recombination to the triplet state can be probed by (TD-)DFT, using the latter as a tool to understand and predict the SOCT-ISC mechanism. The matrix elements for spin-orbit coupling for acetone and 4-thio-thymine are used for benchmarking. (Time Dependent-) Density Functional Theory (DFT and TD-DFT) calculations are applied using the quantum chemical program Amsterdam Density Functional (ADF).

Recent advancements in the study of the protein complex photosystem II have clarified the sequence of events leading to the formation of oxygen during the S3->S4->S0 tran-sition, wherein the inorganic Mn4Ca(µ-O)6(OHx)4 cluster finishes photo-catalyzing the water splitting reaction (Greife et al, Nature 2023, 617, 623-628; Bhowmick et al, Nature 2023, 617, 629-636) . During this final step a tyrosine radical (TyrZ), stable for a couple of milliseconds, oxidizes a cluster bound oxygen while the hydrogen bonding patterns of nearby waters shift a proton away. A treatment of this redox reaction within the context of accepted transition state theories predicts rate constants that are significantly higher than experimentally recovered values (10^12s^-1 versus 10^3s^-1). In an effort to understand this disparity, temperature dependent experiments have revealed large entropic con-tributions to the rates with only a moderate energy of activation. We suggest that the entropic source may be related to the observed proton rearrangements, and further possible near isoenergetic variations in the nearby extended h-bonding network de-laying the realization of an ‘ideal’ transition state. In the following we explore this re-lation in the context of Eyring’s transition state theory and Marcus’ electron transfer theory, and evaluate their compatibility with the experimental evidence.

Extracellular electron transfer (EET) is key to the success of microbial fuel cells (MFCs). Clostridium sp. often occurs in MFC anode communities, but its ability to perform EET remains controversial. We have employed Clostridium pasteurianum DSM 525 as biocatalyst in a glycerol-fed MFC, designated MFC_DSM. We have also followed the EET of this biocatalyst in the presence of a mediator, namely soluble neutral red (NR), soluble methyl viologen (MV), neutral red film (FNR), or methyl viologen film (FMV). MFC_DSM provided power and current densities (j) of 0.39 mW.cm^-2 and 2.47 mA.cm^-2, respectively, which evidenced that the biocatalyst performs direct electron transfer (DET). Introducing 150.0 µM NR or MV into the MFC_DSM improved the current density by 7.0- and 3.7-fold (17.05 and 8.45 mA.cm^-2), respectively. After 20 cyclic voltammetry (CV) cycles, the presence of FNR in the MFC_DSM anodic chamber provided almost twofold higher current density (30.76 µA.cm^-2) compared the presence of NR in the MFC_DSM. Introducing MV or FMV into the MFC_DSM anodic chamber gave practically the same current density after 10 CV cycles. The MFC_DSM anodic electrode might interact with FMV weakly than with FNR, so FNR is more promising to enhance C. pasteurianum DSM 525 EET within MFC_DSM.

Photosystem I is a key component of primary energy conversion in oxygenic photosynthesis. Electron transfer reactions in Photosystem I take place across two, parallel, electron transfer chains that converge after a few electron transfer steps, sharing both the terminal electron acceptors, that are a series of three Iron-Sulphur (Fe-S) clusters known as , and , and the terminal donor, . The two electron transfer chains show kinetic differences which are, due to their close geometrical symmetry, mainly attributable to the tuning of the physical-chemical reactivity of the bound cofactors, exerted by the protein surroundings. The factors controlling the rate of electron transfer between the terminal Fe-S clusters are still not fully understood because of the difficulties of monitoring these events directly. Here we present a discussion concerning the driving forces associated to electron transfer between and as well as and , employing a tunnelling-based description of the reaction rates coupled to the kinetic modelling of forward and recombination reactions. It is concluded that the reorganisation energy for oxidation shall be lower than 1 eV. Moreover, it is suggested that the analysis of mutants with altered redox properties can also provide useful information concerning the upstream, phylloquinone, cofactor energetics.

Bioelectrochemical systems (BESs) have great potential in renewable energy production technologies. BES can generate electricity via Microbial Fuel Cell (MFC) or use the electric current for the synthesis of valuable commodities in Microbial Electrolysis Cells (MECs). The number of various reactor configurations and operational protocols increasing rapidly although, the industrial scale operation is still facing difficulties. This article reviews the recent BES related to literature, with special attention to electrosynthesis and the most promising reactor configurations. We also attempted to clarify the numerous definitions proposed for BESs. The main components of BES are highlighted. Although the comparison of the various fermentation systems is we collected useful and generally applicable operational parameters to be used for comparative studies. A brief overview to link the appropriate microbes to the optimal reactor design is given.

This study presents structural analysis and optimization for the lightweight design of a buoyant rotor-type permanent magnet (BRPM) generator, which was first presented in Bang (2010), and compares its structural performances to a conventional generator with a spoke arm-type rotor and stator. The main benefit of a BRPM is that it can be realized as a bearing-less drive system, free from the mechanical failure of rotor bearings, by using a buoyant rotor. Also, the deformation of a generator by blade vibration can be effectively suppressed using joint couplings between the blades and the rotor. For the design optimization, the objective is set as the mass of the rotor and the stator, and the maximum deformation of the airgap clearance between the rotor and the stator by external forces is constrained below 10% of the gap width. The commercial software Optistruct is used for the analysis and optimization. In this investigation, the analysis and optimization are conducted for a 10 MW wind turbine generator. However, the proposed methods can be extended to larger generator designs without requiring considerable modification. The mass of the opti-mized 10MW BRPM generator is 160.7 tons (19.3 tons for the rotor and 141.4 tons for the stator) while that of an optimized conventional spoke arm-type generator is obtained as 325.6 tons.

This paper introduces new improvements to the modified version of the BIRECT (BI secting RECTangles) algorithm referred to as BIRECTv. We explore various approaches, by first including a grouping strategy for hyper-rectangles having almost the same sizes by categorizing them into different classes. Therefore constraining them not to exceed a certain pre-defined threshold (a small positive value to define the tolerance level). This approach allows for more efficient computation and can be particularly useful when dealing with a large number of hyper-rectangles with varying sizes. To avoid over-sampling, and preventing redundant or excessive sampling, at some shared vertices in descendant subregions, a particular vertex database is used to limit the number of samples taken within each subregion to two. The experimental investigation shows that these improvements have a positive impact on the performance of the BIRECTv(imp.) algorithm and the proposal is a promising global optimization algorithm compared to the original BIRECTv algorithm and its variants. Additionally, the BIRECTv(imp.) algorithm showed particular efficacy in solving high-dimensional problems.

Noninvasive brain stimulation technique can be used for modulation of motor behaviors such as reaction time (RT). The main aim of this study was to investigate whether RT during a sequential visual isometric pinch task (SVIPT) can be affected by anodal transcranial direct current stimulation (a-tDCS) over three different stimulation sites such as dorsolateral prefrontal cortex (DLPFC), primary motor cortex (M1) or posterior parietal cortex (PPC). We also aimed to assess if stimulation of these cortical sites affect the transfer of learning during SVIPT. A total of 48 right-handed healthy participants were randomly assigned to one of the four a-tDCS groups: 1) left M1, 2) left DLPFC, 3) left PPC and 4) sham. A-tDCS was applied concurrent with SVIPT in which the participants were precisely controlled their forces to reach seven different target forces from 10 to 40% of maximum voluntary contraction (MVC) presenting on a computer screen with right dominant hand. Four test blocks were randomly performed at baseline and 15 min after the intervention including sequence and random blocks with either hand. Our results showed significant differences between a-tDCS groups on ratio RT in the sequence blocks of both the right trained (P = .041) and left untrained hands (P = .023) for target forces of 15% and 30 % of MVC, respectively. In sequence blocks, M1 showed significant elongation in ratio RT for the target force of 15% and 30 % MVC compared to PPC and Sham groups in the right hand. In sequence blocks with left hand, this negative effect were found between M1-DLPFC and M1-Sham groups. In random blocks, no significant differences were found among four groups at each target forces for the left hand while there were significant differences for 15% (P =. 04) and 40% MVC (P =. 035) in the right hand. Our findings suggest that three different stimulation sites (DLPFC, M1 or PPC) were differentially affected by a single session of a-tDCS at some target forces during SVIPT. The effects of a-tDCS on ratio RT were transferred in the left untrained hand for sequence blocks but not random blocks. Further research is needed to understand fundamental aspects of these main areas of the brain on temporal processing in a precision control task such as SVIPT.

Photophysics properties such as fluorescence quenching, and photoexcitation dynamics of bimolecular non-covalent systems consisting of cationic poly[(9,9-di(3,3’-N,N’-trimethyl-ammonium) propyl fluorenyl-2,7-diyl)-alt-co-(9,9-dioctyl-fluorenyl-2,7-diyl)] diiodide salt (PFN) and anionic graphene carboxylate (GC) have been discovered for the first time by the steady state and time-resolved femtosecond transient absorption (TA) spectroscopy with broadband capabilities. The steady-state fluorescence of PFN is quenched with high efficiency by GC acceptor. Fluorescence lifetime measurements revealed that the quenching mechanism of PFN by GC is static. Here, the quenching mechanisms are well proven by TA spectra of PFN/GC systems. For PFN/GC systems, the photo electron transfer (PET) and charge recombination (CR) processes are ultrafast (within few tens of ps) related to static interactions whereas for PFN/DCB systems the PET takes place in few hundreds ps (217.50 ps)1 suggesting diffusion-controlled PET process. In the latter case, the PFN+•-DCB-• radical ion pairs as the result of PET from the PFN to DCB are clearly resolved and they are long-lived. The slow CR process (in 30 ns time scales)1 suggest PFN+• and DCB-• may already form separated radical ion pairs through charge separation (CS) process, which recombined back to the initial state with a characteristic time constant of 30 ns. The advantage of the present positively charged polyfluorene used in this work is the control over the electrostatic interactions and electron transfers in non-covalent polyfluorene/quencher systems in DMSO solution.

The evaluation of HAADF-STEM images of a sample with the composition Nb18W16O93 provided new insights in its real structure. The basic structure comprises an intact octahedral framework of the tetragonal tungsten bronze (TTB) type. The partial occupation of the pentagonal tunnels (PT) by metal-oxygen strings determines the oxygen to metal ratio (O/SM with M = Nb,W). For a large area, the O/SM was determined to be 2.755 which is smaller than the value of Nb18W16O93 which is O/SM = 2. 735. To a large extent, the threefold TTB superstructure structure of Nb8W9O47 with a high oxygen content is present (O/SM = 2.765). In addition, a new fourfold TTB superstructure was found in small domains: Nb12W11O63 with an O/SM = 2.739 obviously accommodates a part of the sample’s metal excess compared to the stable phase Nb8W9O47.

Surface processes such as coatings, corrosion, photocatalysis, and tribology are greatly diversified by acid-base interaction at the surface overlayer. This study focuses on the action of metallic copper surface as an electron donor/acceptor related to inactivation of viruses; it was found that regarding Cu2O or Cu materials electrostatic interaction plays a major role in virus inactivation. We applied TPPE method to clarify the mechanism of electron transfer (ET) occurring at light irradiated copper surfaces. The TPPE characteristics was strongly influenced by the environments, which correspond to the temperature and environment dependence of the total count of emitted electrons in the incident light wavelength scan (PE total count, NT), the photothreshold, and further the activation energy (E) analyzed from Arrhenius plot of NT values obtained in the temperature-increase and subsequent temperature-decrease processes. In this study we reexamined the dependence of the TPPE data from two types of Cu metal surfaces: Sample A, which was mechanically abraded in alcohols, water, and air, and Sample C, which was only ultrasonically cleaned in these liquids. The NT for both Samples slowly increased with increasing temperature, reached a maximum (NTmax) at 250C (maximum temperature, Tmax), and after that decreased. For Sample A the NTmax value decreased in the order H2O > CH3OH > C2H5OH > (CH3)2CHOH > C3H7OH, although the last alcohol gave Tmax = 100C, while with Sample C the NTmax value decreased in the order: C3H7OH > (CH3)2CHOH > C2H5OH > CH3OH > H2O. Interestingly, both orders of the liquids were completely opposite: this means that Cu surface can possess two-way character. The NT intensity was found to be strongly associated with the change of the hydroxyl group (Cu-OH) to the oxide oxygen (O2) in the O1s spectra in the XPS measurement. The difference between the above orders was explained by the acid-base interaction mode of the Cu-OH group with the adsorbed molecule on the surfaces. The H2O adsorbed on Sample A produces the electric dipole Cu-OH+---:OH2 (--- hydrogen bond), while the C3H7OH and (CH3)2CHOH adsorbed on Sample C produce ROH+---:O(H)-Cu (R = alkyl groups). Gutmann’s acceptor number (AN) representing the basicity of the liquid molecules was found to be related to the TPPE characteristics: (CH3)2CHOH (33.5), C2H5OH (37.1), CH3OH (41.3), H2O (54.8) (the AN of C3H7OH could not be confirmed). With Sample A the values of NTmaxa and EaUp1 both increased with increasing AN (Up1 means the 1st temperature-increase process). On the other hand, with Sample C the values of NTmaxc and EcUp1 both decreased with increasing AN. These findings suggest that Sample A acts as an acid, while Sample C functions as a base. However, in the case of both types of Samples A and C the NTmax values were found to increase with increasing EUp1. It was explained that the EUp1 values depending on the liquids originate from the difference in the energy level of the hydroxyl group radical at the surface denoted. This is able to attract electrons in the neighborhood of the Fermi level of the base metal by tunnelling. After that due to Auger emission electrons are released, leading to the ET in the overlayer. These electrons are considered to have a strong ability of reducibility.

In general, a superconductor has zero resistance, although it requires significant refrigeration or high pressures with high manufacturing costs, which prevents it into practical applications. In other words, solving these issues implies main superconducting researches. To solve these problems, this paper describes a new type of superconductivity, which is independent for temperatures and which operates without pressures. The principles of the presented system are as follows:First a voltage source, a current source and a load are connected in series. Then, the voltage of the voltage source is adjusted to balance the voltage of the load. Under this condition, the balance of the two voltages provides a zero voltage between the taps of the current source and the generated current from the voltage source becomes zero because of the internal infinite resistance of the current source. As a result, the electric powers generated by the two sources are zero, and therefore, the load cannot generate Joule heating because of energy conservation. However, the current from the current source (not the voltage source) is not zero; therefore, we can predict that the resistance of the load must be zero. As a theory, we derived a new electric field and transient attractive force, which result in a very short coherence of an electron pair because there is not the Coulomb repulsive force due to the existence of the above transient attractive force. Note that both the forces are derived by the Poisson equation, which implies that they cannot be compatible. Therefore, the pair combination energy from spins becomes extremely strong, which is not destroyed by the normal heat energy. Moreover, every center-of-mass motion of electron pair results in the Bose-Einstein condensation and the macroscopic wave function, which produces the London equation (i.e., the Meissner effect). Moreover, by introducing the equivalent circuit, this paper conducted numerical calculations. As a result, we could derive numerically zero resistance and responses for additional static magnetic fields as a discharged current, which implies the Meissner effect. Note that this paper has prepared Appendix section, which provides a guide to reproduce actual experiments and preliminary experimental results. These results in the Appendix indicate the zero resistances and Meissner effects.

Plasma plays an important role in semiconductor processes. With the recent miniature and integration, the control of plasma became essential for the success in critical dimension of a few nanometers and etch narrow and deep holes with high aspect ratios. Recently, the etching process has reached physical limitations due to a significant increase in wafer surface temperature under the elevated amount of RF power, affecting not only the warpage phenomenon but also etching uniformity and etching profiles. Therefore, the plasma characteristics are identified using invasive single Langmuir probe (SLP) for wafer temperature diagnosis. Optical data is obtained through a non-invasive optical emission spectroscopy (OES) and the plasma parameters are derived to compare and verify with the SLP. Two variables, electron temperature and electron density, are substituted for the heat flux formula to derive the heat flux according to its location. Using a wafer-type temperature sensor, check the derived heat flux values and compare trends. Such studies are expected to be able to calculate heat flux values in real time, anticipate wafer temperatures, and solve existing problems.

In this paper, we present a preliminary study and conceptual idea concerning 3D printing water-sensitive glass by exemplifying with a borosilicate glass with high alkali and alkaline oxide contents using direct ink writing. The investigated material was prepared in the form of a glass frit, which was further ground in order to obtain a fine powder of desired particle size distribution. In a following step, inks were prepared by mixing the fine glass powder with Pluoronic F-127 hydrogel. The acquired pastes were rheologically characterized and printed using a Robocasting device. DSC experiments were performed for base materials and the obtained green bodies. After sintering, SEM and XRD analyses were carried out in order to examine microstructure and the eventual presence of crystalline phase inclusions. Results confirmed that obtained inks exhibit stable rheological properties despite the propensity of glass to undergo hydrolysis and could be adjusted to desirable values for 3D printing. No additional phase was observed, supporting the suitability of the designed technology for the production of water sensitive glass inks. SEM micrographs of the sintered samples revealed the presence of closed porosity, which may be the main reason of light scattering.

Scanning electron microscopy (SEM) is a powerful tool in the domain of material science, mining, and geology, owing to its enormous potential to provide unique insights into the micro and nanoscale worlds. This comprehensive review discusses the background development of SEM, basic SEM operation including the specimen preparation and imaging process, and fundamental theoretical calculations underlying the SEM operation. It provides foundational understanding to the engineers and scientists, who never got a chance to dig in-depth into the SEM, to understand the working and development of this robust analytical technique. The present review covers how SEM has been serving as a crucial tool in mineral characterization, with specific discussions on the working and research fronts of SEM-EDX, SEM-AM, SEM-MLA, and QEMSCAN. With automation gaining pace in the development of all spheres of technology, the understanding of uncertainties in SEM measurements is very important. The constraints in mineral phase identification by EDS spectra and sample preparation are conferred. In the end, future research directions for SEM are analyzed with the possible incorporation of machine learning, deep learning, and artificial intelligence tools, for automating the process of mineral identification, quantification, and efficient communication with the researchers, so that the analytical process robustness and objectivity can be improved, and the analysis time and the involved costs can be brought down. This review also discusses the idea of integrating robotics with SEM, to make the equipment portable, so that further mineral characterization insights can be gained not only on earth but also on other terrestrial grounds.

The invariant mass of free particles is used to derive a bound-state equation for several particle atomic systems at rest. This relativistic-kinematic bound-state equation is applied to the hydrogen and helium atoms. The derived equation has the well-known solutions for the single-electron bound states of the hydrogen atom, and the two-electron states of the helium atom. For the hydrogen atom, existence of the two-particle bound states, for which the electron and the proton kinetic energies are of the same order of magnitude, is predicted. The three-particle bound states with the same feature of the kinetic energies can exist in the helium atom. Radiative operators for processes involving the hydrogen two-particle bound states, are obtained. It is discussed that these new two- and three-particle bound states should be optically inactive.

The main aspects of material research: material synthesis, material structure, and material properties, are interrelated. Acquiring atomic structure information of electron beam sensitive materials by electron microscope, such as porous zeolites, organic-inorganic hybrid perovskites, metal-organic frameworks, is an important and challenging task. The difficulties in characterization of the structures will inevitably limit the optimization of their synthesis methods and further improve their performance. The emergence of integrated differential phase contrast scanning transmission electron microscopy (iDPC-STEM), a STEM characterization technique capable of obtaining images with high signal-to-noise ratio under lower doses, has made great breakthroughs in the atomic structure characterization of these materials. This article reviews the developments and applications of iDPC-STEM in electron beam sensitive materials, and provides an outlook on its capabilities and development.

The [3+2] cycloaddition (32CA) reactions of strongly nucleophilic norbornadiene (NBD) with simplest diazoalkane (DAA) and three DAAs of increased electrophilicity have been studied within the Molecular Electron Density Theory (MEDT) at the MPWB1K/6-311G(d,p) computational level. These pmr-type 32CA reactions follow an asynchronous one-step mechanism with activation enthalpies ranging from 17.7 to 27.9 kcal·mol-1 in acetonitrile. The high exergonic character of these reactions makes them irreversible. The presence of electron-withdrawing (EW) substituents in the DAA increases the activation enthalpies, in complete agreement with the experimental slowing-down of the reactions, but contrary to the Conceptual DFT prediction. Despite the nucleophilic and electrophilic character of the reagents, the global electron density transfer at the TSs indicates rather non-polar 32CA reactions. The present MEDT study allows establishing that the depopulation of the NNC core in this series of DAAs with the increase of the EW character of the substituents present at the carbon center is responsible for the experimentally found deceleration.

Multi-parameter families of Lax pairs for the modified Korteweg-de Vries (mKdV) equation are defined by applying a direct method developed in the present study. The gauge transformations converting the defined Lax pairs to some simpler forms and reducing the variety of the Lax pairs this way are found. The direct method and its possible applications to other types of evolution equations are discussed.

Atrial fibrillation (AF) is an increasingly recognized comorbidity in patients with cancer. Indeed, cancer patients have a significantly higher incidence of AF than that observed in the general population. A reciprocal relationship between these two diseases has been observed, as much as some assume AF as a marker for occult cancer screening, especially in older adults. The pathophysiological mechanisms are many and varied, including the underlying pro-inflammatory state, specific treatments (chemo and radiotherapy) and surgery. The therapeutic management of patients with cancer and AF involves the same rhythm and frequency control strategies as the general population; however, the numerous interactions with chemotherapeutics, which lead to a significant increase in side effects, as well as the extreme fragility of the patient should be considered. Anticoagulant therapy is also a complex challenge to address, as bleeding and stroke risk scores have not been fully assessed in this subpopulation. Furthermore, in large studies establishing the efficacy of direct oral anticoagulants (DOACs), cancer patients have been underrepresented. In this review, we elaborate on mechanisms linking AF to cancer patients with a particular focus on therapeutic challenges in this population.

The effects of 0.4wt.% Sc addition on a typical Al-Si10-Mg alloy were systematically investigated in the present research. Samples with and without Sc produced refined dendritic arranged microstructures with sensitivity to the aging treatment after solidification, particularly in the case of the alloy without Sc. After being exposed to 300°C for 90 minutes, the dendritic spacing nearly doubled in the Al-10wt.%Si-0.45wt.%Mg samples. The rapidly solidified microstructures were constituted by the -Al dendritic phase surrounded by eutectic phases/intermetallics such as Si, Mg2Si and Al3Sc (in the case of the alloy containing Sc). 255°C and 300°C were deemed most appropriate temperatures for aging treatments, with four exposure times of up to 120 minutes tested for each alloy. The heat treatments allowed the Vickers hardness profiles to be plotted and compared. Moreover, in order to detect both Sc- and Mg- precipitates after aging, specific samples have been prepared for either SEM or TEM analyses. At first, the results pointed to a strong precipitate-related hardening effect formed as a result of the Sc addition to the alloy. All samples containing Sc showed a higher hardness value when compared to their respective treated samples without Sc. Secondly, when comparing the Al-10Si-Mg-Sc alloy samples among themselves after being treated at different conditions, high temperatures and excessive treatment times can become detrimental to the hardness. This was due to the growth of larger Sc-bearing precipitates of approximately 1 µm in size under such conditions, having less pronounced hardening effect. The best condition (255°C for 60 min) for as centrifuged samples in Cu-mold produced very fine dispersion of Mg- and Sc- intermetallics (~200 nm in size) with a peak hardness of 110 HV.

A hybrid smart process and material design system for nanoimprinting is proposed, which combines with a learning system based on experimental and numerical simulation results. Instead of carrying out extensive learning experiments for various condition, the simulation learning results are partially complimented where the results can be theoretically predicted by numerical simulation. In other word, the lacking data in experimental learning are complimented by simulation-based learning results. Therefore, the prediction of nanoimprint results under various conditions without experimental learning could be realized even for unknown materials. In this study, material and process design for a low-temperature nanoimprint process using glycerol-containing polyvinyl alcohol are demonstrated. Experimental results under limited conditions are learned to investigate optimum Glycerol concentrations and process temperatures. On the other hand, simulation-based learning is used to predict the dependence on press pressure and shape parameters. The prediction results for unknown Glycerol concentrations agreed well with the follow-up experiments.

This paper aims to research whether there is link between FDI inflows and Economic growth in the Republic of Seychelles Island. The ordinary least square results obtained shows that in the impact of FDI inflows on economic growth is low. Small Island Developing States attracts less FDI inflow because they are limited to few resources that attracts overseas firms which results in retarded development. The research lighted that impact of foreign direct investment on host countries does not only depend on the quality and quantity of the FDI inflows but some other variables such as the internal policies and the management skills, market structures, economic trends among others.

In this paper, we propose an assumption of which the relation between electron and phonon is discussed and investigated based on the experiment of γ photon and electric interconverting with each other. We calculated the charge of a particular standing wave topology with Maxwell’s equation rotated in accordance space with the SO3 transformation. The derived charge value is 1.6035 × 10E−19C around 0.0826% different from the experimental data, indicating the proposal is a promising theory to explain the origin of charge and spin of electron particle. Electron spin angular momentum comes from the orbital angular momentum of photon rotation (electromagnetic field rotation), and electron charge comes from photon, that is, the space-time rotation effect of electromagnetic wave.

The present study investigation, our results on characterization of commercially pure-Ti alloy brazed with metallic glass ribbons of Ti20Zr20Cu60-xNix (x = 30, 40, and 50) metallic glass ribbons were produced using a vacuum melt spinner. These ribbons were then used as filler materials for vacuum brazing of two Ti alloy plates at 1268, 1277 and 1279 K for a period of 10 min. Field-Emission Scanning Electron Microscopy (FESEM), Transmission Electron Microscopy (TEM) and the energy dispersive X-ray spectroscopy (EDX). The as-spun ribbons showed fully amorphous structure when examined on both surfaces by XRD and also verified by TEM investigation. The brazing joint of two Ti-plates using the metallic glass ribbon when brazed with Ni50 was found to be of very high strength. FESEM characterization of the cross-section of the brazed joints shows sub-micron size grains uniformly distributed in the matrix with brighter appearance. FESEM and EDX analysis revealed that the sub-micron grains are rich in Ti & Ni while the matrix phase mainly consisted of Ti. BSE image along with EDS Analysis indicated that the brazed joint has a presence of NiTi2 and Cu2 (Ni Zr) phases which could be responsible for increase in the strength of the brazed joint.

An innovative superconducting mechanism was developed based on a patented discovery of room temperature superconductivity in several thorium (Th) salts or compounds. The rationale behind this discovery is through the experimental results about the unique electrical and magnetic properties of these Th salts. Accordingly, this new superconducting mechanism for these Th salts was obtained through the analyses of the compounds’ molecular configurations and the packings of their relevant crystal structures. Owing to the distinctive properties of the Th compounds in this discovery, we further established a different electron pairing scheme as opposed to the pairing of the Cooper pairs. Compared to the long distance electron pairing of the Cooper pairs, the new electron pairing in our mechanism is constructed by two closely correlated electrons that reside on the same atomic orbital of the Th cation as an electron lone pair. In this new superconducting mechanism, the Th cation is sitting on a relevant crystallographic lattice arrangement or a network of the relevant Th compounds. This network is constructed by many Th cations along certain crystallographic lattice arrangement where each Th cation contains one electron lone pair. This network allows the electron lone pairs on the Th cations to be delocalized over the network, “in pair”, and thus, reveals the electron lone pair in presence in a long distance fashion. The closely correlated electron lone pairs hop on this network and thus, construct the supercurrent over the network. This explanation about the superconductivity laid the basis for our superconducting mechanism. All these conclusions came from the previous studies about these compounds that illustrated their unusual features of a coexistence of high electrical conductivity and diamagnetism. These electrical and magnetic properties fall in line with that of superconductors but, surprisingly, these Th compounds have such properties at the ambient condition, meaning under room temperature and atmosphere pressure. We expect that this mechanism may be appropriate to be utilized to other superconducting cases, either conventional or unconventional, and therefore, can be adapted to describe the superconducting phenomenon for other superconductors.

Machine Learning deals with creating algorithms capable of learning from the provided data. These systems have a wide range of applications and can also be a valuable tool for scientific research which in recent years has been focused on finding new diagnostic techniques for particle accelerator beams. In this context SPARC_LAB is positioned, a facility located at the Frascati National Laboratories of INFN, where the progress of beam diagnostics is one of the main developments of the entire project. With this in mind, you aim to present the design of two neural networks aimed at predicting the spot size of the electron beam of the plasma-based accelerator at SPARC_LAB, which powers an undulator for the generation of x-ray Free Electron Laser (XFEL). Data-driven algorithms use two different data preprocessing techniques, namely autoencoder neural network and PCA. With both approaches, the predicted measurements can be obtained with an acceptable margin of error and most importantly without activating the accelerator, thus saving time, even compared to a simulator that can produce the same result but much more slowly. The goal is to lay the groundwork for creating a digital twin of linac and conducting virtualized diagnostics using an innovative approach.

The dimethylaminophenyl-substituted silver phthalocyanine [dmaphPcAg] can be used as a UV-vis photoinitiator for in situ preparation of a silver/polymer nanocomposite. To verify early steps of the supposed mechanism of radical polymerization, we performed quantum chemical calculations of m[dmaphPcAg]q complexes with charges q = +1 to -2 in the two lowest spin states m, of a free ligand and its dehydrogenated/deprotonated products m[dmaphPcHn]q, n = 2 to 0, q= 0, -1 or -2, in the lowest spin states m. The calculated electronic structures and electron transitions of all the optimized structures in CHCl3 solutions are compared with experimental EPR and UV-vis spectra, respectively. The unstable 3[dmaphPcAg]+ species deduced only from previous EPR spin trap experiments was identified. In addition to 2[dmaphPcAg]0, our results suggest the coexistence of both reaction intermediates 1[dmaphPcAg]- and 3[dmaphPcAg]- in reaction solutions. Silver nanoparticle formation is a weak point of the supposed reaction mechanism from the energetic, stereochemistry, and electronic structure points of view.

Over the past two decades, covalent organic frameworks (COFs) have become the most widely studied porous crystalline materials. Its specific physical and chemical properties are determined by the arrangement of atoms (crystal structure). Therefore, the determination of its structure is arguably the most important characterization step for COFs. Although single crystal X-ray diffraction (SCXRD) is the most widely used method for structure determination, the size of COF crystals is too small, or their crystal quality is so poor that confirmation of their structure is limited to lattice fringes by transmission electron microscopy (TEM). At present, many 2D-COFs have clear PXRD patterns, but not all 2D-COFs can obtain specific lattice fringes. This severely hinders the development of the COF field. Here, we discover the lattice shrinkage behavior of COFs under electron beam irradiation by comparing the lattice fringes of 2D-COFs under different conditions. By comparing the lattice fringes of TAPT-TFPT COF at room temperature and under liquid nitrogen freezing conditions, we found that the lattice fringes are in good agreement with the Powder X-ray diffraction (PXRD) and theoretical values of COF (2.213 nm) under freezing conditions, however, the lattice fringe spacing is only 1.656 nm at room temperature. The discovery not only provides new insights into the TEM characterization of COFs, but also further expands the range of crystalline COF materials.

This report is on magneto-electric (ME) interactions in bulk composites with coaxial nanofibers of nickel zinc ferrite and PZT. Core-shell fibers of PZT and Ni1-x Znx Fe2 O4 (NZFO) with x = 0-0.5 were made by electrospinning. Both kind of fibers, either with ferrite- or PZT-core and with diameters in the range 1-3 m were made. Electron- and scanning probe microscopy images indicted well-formed fibers with uniform core and shell structures and defect free interface. X-ray diffraction data for fibers annealed at 700-900 C did not show any impurity phases. Magnetization, magnetostriction, ferromagnetic resonance, and polarization P versus electric field E measurements confirmed the ferroic nature of the fibers. For ME measurements the fibers were pressed into disks and rectangular platelets and then annealed at 900-1000 C for densification. Strengths of strain mediated ME coupling were measured by H-induced changes in remnant polarization Pr and by low-frequency ME voltage coefficient (MEVC). The fractional change in Pr under H increased in magnitude, from +3% for disks of NFO– PZT to -82% for NZFO (x=0.3)-PZT, and further increase in x resulted in a decrease to a value of -3% for x=0.5. Low-frequency MEVC measured in disks of the core-shell fibers ranged from 6 mV/cm Oe to 37 mV/cm Oe. The fractional changes in Pr and the MEVC values were an order of magnitude higher than for bulk samples containing mixed fibers with random distribution of NZFO and PZT. The bulk composites with coaxial fibers have the potential for use as magnetic field sensors and in energy harvesting applications.

The dynamic nature of international business necessitates a strategic approach to achieve sustainable value creation. This paper supports the hypothesis that understanding institutional constraints and leveraging organizational resources provides the foundation for sustainable value creation during international expansion. These elements provide a solid foundation for firms seeking to expand internationally by enabling them to effectively navigate the complexities of foreign markets. Using the context supplied by Peng (2023), the subsequent sections and subsections delve into critical facets of international expansion, including market integration, the role of entrepreneurial firms, entry strategies, supply chain establishment, multinational strategies, and the impact of global trade and foreign direct investment (FDI).

A single water pollution by dyes is a huge environmental problem; there is a necessity to produce new decolorization methods that are effective, cost-attractive, and suitable in industrial use. Magnetic chitosan polymers offer the advantage of easy separation from the dye solution. In this work, a Chitosan-Fe polymer was synthesized, characterized, and tested for removal of the azo dye Direct Red 83:1 from water. The polymer was characterized in terms of surface morphology (SEM), elemental analysis (EA), differential scanning calorimetry (DSC), thermal gravimetric analysis (TGA), infrared spectrophotometry (IR), X-ray powder diffraction (XRD) and density functional theory (DFT). The reported results hint that 1 g and pH 7.0 were the best conditions to carry out both kinetic and isotherm models. To understand the adsorption behavior of Direct Red 83:1 onto the polymers, adsorption rate and maximum adsorption capacity were calculated using kinetic tests and isotherm curves respectively. The kinetic data and mechanism of the adsorption process were analyzed by three models and the equilibrium data by three adsorption isotherms. The results indicated that the adsorption process follows a pseudo-second-order kinetics (R2= 0.999) and fits the Temkin isotherm (R2= 0.946), indicating that the adsorption occurred on heterogeneous surfaces. The newly synthesized Chitosan-Fe polymer exhibited good adsorption properties and easy separation of cleaned water.

This 16-month study aimed to evaluate the extended effects of administering direct-fed microbials (DFM) on milk yield and components in 150 dairy cows. The cows were randomly divided into two groups: control (n=75) and DFM (n=75) based on parity and days in milk. Throughout the study, the two groups of cows were housed separately in a free stall yard, and each group had their own feeding area. The DFM group received 10 ml/cow of the Lacticaseibacillus- and Lentilactobacillus-based DFM via top dressing of the feed during lactation and drying off. Milk yield and liveweight were recorded daily. Milk samples were collected every two months for milk components analysis. Both groups produced less milk in the second production season due to adverse weather conditions. DFM cows gained more liveweight across the study (19.40 kg, 95% CI 0.44; 38.30) compared to controls. In the second season, DFM cows lost weight at a slower rate (-6.06, 95% CI -10.49; -1.61) during the postpartum period and produced more milk (0.39 L/d 95% CI 0.10; 0.89). Over a full lactation, DFM cows yielded at least 258L (95% CI 252L; 265L) more milk than controls. No significant differences were found in fat yield, protein yield, or somatic cell counts. The study suggests that prolonged DFM administration positively impacted milk production, but further research is needed to understand the underlying mechanism.

Laser patterning of implant materials for bone tissue engineering purposes has shown to be a promising technique to control cell properties such as adhesion or differentiation, resulting in an enhanced osteointegration. However, the perspective of patterning the bone tissue side interface to generate microstructure effects has never been investigated. In the present study, three different laser-generated patterns were machined on the bone surface with the aim to identify the best surface morphology compatible with osteogenic-related cells recolonization. The laser patterned bone tissue was characterized by electron scanning microscopy and confocal microscopy in order to obtain a comprehensive picture of the bone surface morphology. Cortical bone patterning impact upon cell compatibility and cytoskeleton rearrangement to the patterned surfaces was performed with Stromal Cells from Apical Papilla (SCAPs). Results indicated that laser machining had no detrimental effect upon consecutively seeded cells metabolism. Orientation assays revealed that surface patterning characterized by larger hatch distances was correlated with a higher cell cytoskeletal conformation to the laser-machined patterns. For the first time, to our knowledge, bone is considered and assessed here as a potentially engineered-improvable biological interface. Further studies shall focus on in vivo implications of this direct patterning.

Fostering innovation is considered one of the key policy priorities in most governments' agendas in developing countries, and foreign direct investment (FDI) is considered a principal resource for financing sustainable development, corresponding to 17 sustainable development goals (SDGs). This study analyzes the extent to which inward FDI affects innovation (proxied with patent applications) in Sri Lanka using secondary data from 1990 to 2019. We used the Autoregressive Distributed Lag (ARDL) cointegration procedure to examine the long-run relationships between variables. As per the study results, the coefficient of inward FDI is a negative sign while the coefficients of per capita gross domestic product (GDP) and high technology exports (HEX) show positive signs 2.142 and 0.414, respectively, and statistically significant in the long run. It is demonstrated that per capita GDP and high technology exports are an important variable in explaining technological innovation, and inward FDI and education expenditure (EDU) did not contribute towards widening technological innovation in Sri Lanka. Shaping the future of FDI in Sri Lanka is essential to foster innovation capability.

The paper deals with the problems of direct kinematics related to a 2T6R robot, the direct kinematics of the plane mechanism of the robot. The direct kinematics of this proposed new robot help to study the movement, including the dynamic one, to determine the forces in the mechanism and to model the possible trajectories of the final effector point, thus determining the robot's working space and some of its multiple possible uses. Two totally different methods were used to verify the calculation relations, the results obtained by both methods being practically identical. The first method used is an original trigonometric method, and the second is an original geometrically analytical method.

Stroke often results in impaired gait, which can limit community ambulation and the quality of life. Recent works have shown the feasibility of transcranial Direct Current Stimulation (tDCS) as an adjuvant treatment to facilitate gait rehabilitation. Since the cerebellum plays an essential role in balance and movement coordination, which is crucial for independent overground ambulation, so, we investigated the effects of cerebellar tDCS (ctDCS) on the post-stroke overground gait performance in chronic stroke survivors. Fourteen chronic post-stroke male subjects were recruited based on convenience sampling at the collaborating hospitals where ten subjects finally participated in the ctDCS study. We evaluated the effects of two ctDCS montages with 2mA direct current, a) optimized configuration for dentate stimulation with 3.14cm² disc anode at PO10h (10/5 EEG system) and 3.14cm² disc cathode at PO9h (10/5 EEG system), and b) optimized configuration for leg lobules VII-IX stimulation with 3.14cm² disc anode at Exx8 (electrodes defined by ROAST) and 3.14cm² disc cathode at Exx7. We found ctDCS to be acceptable by all the exposed subjects. The ctDCS intervention had an effect on the 'Normalised Step length Affected side' (p=0.1) and 'Gait Stability Ratio' (p=0.0569), which was found using Wilcoxon signed-rank test at 10% significance level. Also, ctDCS montage specific effect was found using a two-sided Wilcoxon rank-sum test at a 5% significance level for 'Step Time Affected Leg' (p=0.0257) and '%Stance Time Unaffected Leg' (p=0.0376). Moreover, the changes in the quantitative gait parameters across both the montages were found to be correlated to the mean electric field strength in the lobules based on partial least squares regression analysis (R² statistic = 0.6574) where the mean electric field strength at the cerebellar lobules, Vermis VIIIb, Ipsilesional IX, Vermis IX, Ipsilesional X, had the most loading. In conclusion, our feasibility study indicated the potential of a single session of ctDCS to contribute to the immediate improvement in the balance and gait performance in terms of gait-related indices and clinical gait measures.

With the advent of Web 3.0, the swift advancement of technology confronts an imminent threat from quantum computing. Security protocols safeguarding the integrity of Web 2.0 and Web 3.0 are growing more susceptible to both quantum attacks and sophisticated classical threats. The article introduces our novel long-distance free-space quantum secure direct communication (LF QSDC) as a method to safeguard against security breaches in both quantum and classical contexts. Differing from techniques like quantum key distribution (QKD), LF QSDC surpasses constraints by facilitating encrypted data transmission sans key exchanges, thus diminishing the inherent weaknesses of key-based systems. The distinctiveness of this attribute, coupled with its quantum mechanics base, protects against quantum computer assaults and advanced non-quantum dangers, harmonizing seamlessly with the untrustworthy tenets of the Web 3.0 age. The focus of our study is the technical design and incorporation of LF QSDC into web 3.0 network infrastructures, highlighting its efficacy for extended-range communication. LF QSDC is based on the memory DL04 protocol and enhanced with our novel Quantum-Aware Low-Density Parity Check (LDPC), Pointing, Acquisition, and Tracking (PAT) technologies, and Atmospheric Quantum Correction Algorithm (AQCA). Utilizing this method not only bolsters the security of worldwide Web 3.0 networks but also guarantees their endurance in a time when quantum and sophisticated classical threats exist simultaneously. Consequently, LF QSDC stands out as a robust security solution, well-suited for Web 3.0 systems amidst the constantly evolving digital environment.

Multipactor is a common discharge phenomenon occurred in space microwave systems. The surface microstructure has been verified to be effective to mitigate multipactor. In this work, we design a square coaxial low-pass filter (SCLPF) with dielectric sheets loaded to check the multipactor dependence on the structure parameters of the loaded dielectric sheets, and further model groove structures on the sensitive area surface to lower the risk of multipactor. Simulation results indicate that the SCLPF loaded with alumina and PTFE exhibits good operational characteristics, and the multipactor threshold is significantly improved after introducing the surface grooves. Then we investigate the effects of three typical groove parameters, groove depth, groove number, and aspect ratio, on the multipactor threshold of the SCLPF device. The results show that the multipactor threshold raise at first as the groove number and groove depth increase, and then the threshold reaches a saturation status. For a deeper analysis of multipactor, we discuss how the grooves shelter the secondary electrons, and further mitigate the electron avalanche. Furthermore, the mechanisms of threshold saturation under the effect of groove parameters are analyzed in detail, and a contour map for the multipactor threshold of PTFE-loaded SCLPFs is given, which makes significant sense for predicting the multipactor threshold of the devices with its sensitive surface being grooved. The regularity of modulating the multipactor threshold by the groove structures obtained in this study is of engineering significance for suppressing multipactor in microwave devices in practical applications.

For many disciplines of science, all conceivable collisional cross sections and reactions must be precisely known. Although the recent decades were a trial of large-scale research to give these data, many essential atomic and molecular cross section data still missing, and the reliability of the existing cross sections has to be validated. In this paper, we present electron stripping, electron capture, and system breakdown cross sections in carbon (C5+) ions and lithium (Li2+) ions collisions with atomic hydrogen based on the Monte Carlo models of classical and quasi-classical trajectories. According to our expectation, the QCTMC results show higher results in comparison to standard CTMC data, emphasizing the role of Heisenberg correction constraint, especially in the low energy regime. On the Other hand, at high energy, the Heisenberg correction term has less influence as a projectile momentum increase. We present the total cross sections of electron stripping, electron capture, and system breakdown in C5+ ions and Li2+ ions collisions with atomic hydrogen in the impact energy range from 10 keV to 160 keV, which is of interest in astrophysical plasmas, atmospheric sciences, plasma laboratories, and fusion research.

Sub-micro dislocation cellular structures formed during rapid solidification break the strength-ductility trade-off in laser powder bed fusion (LPBF)-processed 316L stainless steel through high-density dislocations and segregated elements or precipitates at the cellular boundaries. The high-density dislocation entangled at the cellular boundary accommodates solidification strains among the cellular structures and cooling stresses through elastoplastic deformation. Columnar grains with cellular structures typically form along the direction of thermal flux. However, the ultra-low misorientations between the adjacent cellular structures and their interactions with the cellular boundary formation remain unclear. In this study, we revealed the ultra-low misorientations between the cellular structures in LPBF-processed 316L stainless steel using conventional electron backscatter diffraction (EBSD), transmission Kikuchi diffraction (TKD), and transmission electron microscopy (TEM). The conventional EBSD and TKD analysis results could provide the misorientation angles smaller than 2° while the resolution mainly depends on the specimen quality and scanning step size, and so on. TEM technique with higher spatial resolution provides accurate information between adjacent dislocation cells with misorientation angles smaller than 1°. This study presents that TEM method is the better and more precise analysis method of the misorientation measurement of the cellular structures and provides insights into measuring the small misorientation angles between adjacent dislocation cells and nanograins in nanostructured-metals and alloys with ultrafine-grained microstructures.

To obtain a given structure in 3D building-up modes, it is necessary to use optimal surfacing modes that determine the amount of heat input in local areas. For this purpose, aluminum bronze was surfacing onto a deformed base and the structure and its characteristics in the surfacing and heat-affected zones were studied by the EBSD method. The heterogeneity of the formation of the structure in each selected zone is established, which indicates the heterogeneity of heat input in local areas of the material in one mode of surfacing. For typical cases of crystallization, a molecular dynamics simulation of crystallization processes with different heat input to the base with characteristics specified based on experimental data was carried out. It has been established that the amount of heat input determines the degree of melting and the inherited defectiveness of growing crystals. The formation of misorientation boundaries and crystallization centers of new grains is determined by the conditions of joint growth of grains with given crystallographic parameters of the computational model. Numerical calculations agree with the experimentally observed results.

In the perspective of designing complex concentrated alloys (CCAs) for structural applications, sigma (σ) phase is important. It is generally known to be an embrittling phase leading to a degradation in the mechanical properties of CCAs. This necessitates detailed investigations on the evolution of σ phase in these alloys. In the present study, an equiatomic CoCrCuMnNi CCA is chosen, in which σ phase appears at 800°C, as reported in a recent publication [1]. To this end, the present investigation aims at understanding the evolution of this phase so that its presence can be controlled for the purpose of preventing degradation in mechanical properties. In the present work, a vacuum arc melted alloy, after homogenisation (at 400°C for 5h), is heat-treated for different times ranging from 1 to 9h at 800°C followed by water quenching. Extensive characterisation has been carried out using X-Ray Diffraction (XRD) and Scanning Electron Microscopy (SEM) and Transmission Electron Microscopy (TEM) techniques to understand the sequence of σ phase precipitation at 800°C.

In the Standard Model of elementary particles, the rest mass, magnetic moment and electric charge of the electron are considered to be natural constants. In this article it is proposed that these properties can be calculated in a simple way from the corresponding Planck units using the well-known period doubling phenomenon in nonlinear dynamical systems. Periods corresponding to the values of the electron and positron properties belong to a subset of stable periods. The periodic structures of the rest energy and magnetic moment consist of three internal degrees of freedom, whereas the Coulomb energy of the electric charge consists of four. The number of period doublings for the elementary charge determines the value of the fine structure constant alpha.

Respiratory viral infections (RVI) are common reasons for healthcare consultations. The inpatient management of RVI consumes significant resources. From 2009-2014, we assessed the costs of RVI management in 4776 hospitalized chil-dren aged 0-18 years participating in a quality improvement program, where all ILI patients underwent virologic testing at the National Reference Centre followed by de-tailed recording of their clinical course. The direct (medical or non-medical) and indirect costs of inpatient management outside the ICU (“non-ICU”) versus management requiring ICU-care (“ICU”) added up to 2,767.14€ (non-ICU) vs. 29,941.71€ (ICU) for Influenza, 2,713.14€ (non-ICU) vs. 16,951.06€ (ICU) for RSV infections, and 2,767.33€ (non-ICU) vs. 14,394.02€ (ICU) for human rhinovirus (hRV) infections, respectively. Non-ICU inpatient costs were similar for all 8 RVI studied: Influenza, RSV, hRV, ade-novirus (hAdV), metapneumovirus (hMPV), parainfluenzavirus (hPIV), bocavirus (hBoV) and seasonal coronavirus (hCoV) infections. ICU-costs for Influenza however, ex-ceeded all other RVI. At the time of the study, Influenza was the only RVI with antivi-ral treatment options available for children, but only 9.8% of Influenza patients (non-ICU) and 1.5% of ICU-patients with Influenza received antivirals; only 2.9% were vac-cinated. Future studies should investigate the economic impact of treatment and pre-vention of Influenza-, COVID-19-, and RSV post vaccine introduction.

We have investigated the effect of electron-beam irradiation by a forevacuum-pressure plasma-cathode electron source on the surface roughness and hardness of Al2O3- and AlN-based ceramics. The roughness increases with increasing temperature of the processed surface, while the hardness slightly decreases. For aluminum nitride ceramic, we find that the thermal conductivity increases by a factor of 1.5 to 2 depending on the electron-beam irradiation regime.

The intramolecular ionic Diel-Alder (IIDA) reactions of two dieniminiums have been studied within the Molecular Electron Density Theory (MEDT) at the B97XD/6-311G(d,p) computational level. ELF topological analysis of dieniminiums shows that its electronic structure can been seen as the sum of those of butadiene and ethaniminium. The superelectrophilic character of dieniminiums accounts for the high intramolecular global electron density transfer taking place between the diene and iminium frameworks at the transition state structures (TSs) of these IIDA reactions. The activation enthalpy associated to the IIDA reaction of the experimental dieniminium, 8.7 kcal·mol-1, is closer to that of the ionic Diels-Alder (I-DA) reaction between butadiene and ethaniminium, 9.3 kcal·mol-1. However, the activation Gibbs free energy of the IIDA reaction is 12.7 kcal·mol-1 lower than that of the intermolecular I-DA reaction. The strong exergonic character of the IIDA reaction, higher than 17 kcal·mol-1, makes the reaction irreversible. These IIDA reactions present a total re/exo and si/endo diastereoselectivity, which is controlled by the most favourable chair conformation of the tetramethylene chain. Electron localization function (ELF) topological analysis of the single bond formation indicates that these IIDA reactions take place through a non-concerted two-stage one-step mechanism. Finally, ELF and atoms-in-molecules (AIM) topological analyses of the TS associated to inter and intramolecular processes show the great similitude among them.

Background We aimed to evaluate the effectiveness of the ALRYNGO channel-type video laryngoscope with an AI-based glottis guidance system in senior emergency medicine residents for endotracheal intubation. Methods We enrolled twenty patients would be adequate for each device (direct laryngoscope, Pentax-AWS, and ALRYNGO). Before intubation, six senior residents wore a personal protective equipment. To randomize the device in this clinical study, a sealed envelope containing a device-specific identification card was utilized. When intubation began, the person who measured the intubation time divided the total intubation time into three-time intervals. The primary outcome was the intubation time. The secondary outcomes were the glottis view using the Cormack-Lehane grade (C-L grade) and the glottis guidance performance of ALRYNGO’s artificial intelligence. Results In Pentax-AWS and ALRYNGO, all intubations were successful, but the intubation time was longer than with the direct laryngoscope. And among the three, the ALRYNGO and Pentax-AWS had the highest frequency of C-L grade I (easiest intubation) at 80%, and the direct laryngoscope had the lowest frequency of 10%. Conclusions Even if healthcare professionals without experience with the channel-type video laryngoscope improve their performance on airway mannequins after training, their intubation performance may differ when applied to actual patients.

This work reports the influence of reduced graphene oxide (rGO) support on the catalytic performance of Cu@PtRu/rGO catalysts towards methanol oxidation in acidic medium. These core-shell catalysts are synthesized by the reduction method in two steps being the first using ethylene glycol to obtain Cu/rGO and the second, the reduction of copper atoms synthesized in the previous step to produce Cu@PtRu/rGO. In order to compare the catalytic performance of the prepared catalysts, Pt/C, PtRu/C, Cu@PtRu/C catalysts are also synthesized on Vulcan XC-72R carbon. The theoretical loading of Pt used in the Vulcan XC-72R carbon supported catalysts is equal to that utilized in Cu@PtRu/rGO, and higher in the other prepared catalysts. The surface composition of the nanoparticles, as well as their sizes, particle size distribution and morphology of the catalyst particles are characterized by X-ray diffraction (XRD) and high resolution transmission electron microscopy (HRTEM). Cyclic voltammetry (CV) and chronoamperometry (CA) are employed to measure the electrochemical performance of the prepared catalysts. The anodic scans show that for the region of technological interest (0.1 to 0.4 V), the Cu@PtRu/rGO-16 electrocatalyst exhibits higher current density value than the others as a result of its lower starting oxidation potential (0.250V against 0.437V for Pt/C) and its higher ratio between forward (iF) and reverse (iR) current densities (iF/iR 1.45 against 0.93 for Pt/C). Chronoamperometric tests depict that the current density value of Cu@PtRu/rGO-16 catalyst is about 4 times higher than that of Cu@PtRu/C-16 and Cu@PtRu/C-18 catalysts, ca. 4.8 times higher than that of PtRu/C-30 catalyst and around 6 times higher than that of Pt/C-30. These results suggest that Cu@PtRu/rGO-16 exhibits high bulk activity for the electrooxidation of methanol, high stability and high tolerance to CO poisoning, making it possible to reduce the platinum loading in proton exchange membrane fuel cells (PEMFCs).

Nanoscale structuring/printing is of interest for range of applications in 3D subtractive and additive manufacturing (3D^+/-). Basic principles of light field enhancement and control at the nanoscale are overviewed in this section/chapter for bulk, surface, and localised plasmons (1D, 2D, and 3D localisation, respectively). All these plasmons are resonant phenomena which have common Lorentzian spectral lineshape which relates refractive and absorption properties as well as defining the phase of transmitted and scattered light. Localisation of light at the nanoscale creates the possibility of modification with matching resolution. Harnessing this light enhancement can be demonstrated as a "nano-pen" for direct write nanolithography.

Semantically meaningless strings that are associated with affective attributes (US) can become emotionally valenced CS. Jurchiș et al (2020) recently demonstrated CS-US associations may influence evaluations towards previously-unseen letter strings if the latter share grammar construction rules with CS. We replicated those authors' findings in a modified extension (Experiment 1; N₁ = 108), where happy/angry faces (US) were differentially associated with letter strings (CS) constructed using familiar (English) or non-familiar (Phoenician) alphabets. CS-US sequences were sandwiched by evaluations of strings that never appeared as CS, but shared grammar construction rules. However, post-hoc tests indicated valence effects were restricted to participants classified as 'high awareness' or those who had been exposed to longer stimulus durations, suggesting resource-intense deliberations were central during evaluations. Qualitative awareness checks additionally showcased many participants had attributed valences to recurring elements across conditioned and evaluated exemplars. These limitations were collectively addressed in Experiment 2 (N₂ = 140), where participants viewed Phoenician (/English) CS during conditioning but viewed English (/Phoenician) strings during evaluations, meaning no strings nor elements recurred between phases. We found credible valence effects across English and Phoenician strings, with the latter observed across all awareness categories. Because participants were unable to consciously specify any evaluative strategies while evaluating Phoenician strings, we speculate grammar construction rules (organizing relations) may have been non-consciously acquired during conditioning.

The structure of turbulent flow over non-flat surfaces is a topic of major interest in practical applications in both engineering and geophysical settings. A lot of work has been done in the fully rough regime at high Reynolds numbers where the effect on the outer layer turbulence structure and the resulting friction drag is well documented. It turns out that surface topology plays a significant role on the flow drag especially in the transitional roughness regime and therefore, hard to characterize. Survey of literature shows that roughness function depends on the interaction of roughness height, flow Reynolds number and topology shape. In addition, if the surface topology contains large enough scales then it can impact the outer layer dynamics and in turn modulate the total frictional force. Therefore, it is important to understand the mechanisms underlying drag increase from systematically varied surface undulations in order to better interpret quantifications based on mean statistics such as roughness function. In this study, we explore the mechanisms that modulate the turbulence structure over a two-dimensional (2D) sinusoidal wavy surface with a fixed amplitude, but varying slope. To accomplish this, we model the turbulent flow between two infinitely wide 2D wavy plates at a friction Reynolds number, $Re_{\tau}=180$. We pursue two different but related flavors of analysis. The first one adopts a roughness characterization flavor of such wavy surfaces. The second one focuses on understanding the non-equilibrium near surface turbulence structure and their impact on roughness characterization. Analysis of the different statistical quantifications show strong dependence on wave slope for the roughness function indicating drag increase due to enhanced turbulent stresses resulting from increased production of vertical velocity variance from the surface undulations.

Direct mass spectrometry-based metabolomics has been widely employed in the last years to characterize metabolic alterations underlying to Alzheimer’s disease development and progression. This high-throughput approach presents a great potential for fast and simultaneous fingerprinting of a vast number of metabolites, which can be applied to multiple biological samples such as serum/plasma, urine, cerebrospinal fluid and tissues. In this review article we present the main advantages and drawbacks of metabolomics based on direct mass spectrometry compared with conventional analytical techniques, and provide a comprehensive revision of the literature on the application of these tools in Alzheimer’s disease research.

Quantum revival phenomena, wherein the wave function of a quantum system periodically returns to its initial state after evolving in time, are investigated in this study. Focusing on electrons confined within a quantum box with an impurity, both weak and strong coupling regimes are explored, revealing intricate relationships between impurity parameters and temporal dynamics. The investigation considers the influence of impurity position, impurity strength, and external factors such as aluminum concentration, temperature, and hydrostatic pressure on classical periods and revival times. Through analytical derivations and graphical analyses, the study elucidates the sensitivity of quantum revivals to these parameters, providing valuable insights into the fundamental aspects of quantum mechanics. While no specific physical applications are discussed, the findings offer implications for quantum heat engines and other quantum-based technologies, emphasizing the importance of understanding quantum revivals in confined quantum systems.

We introduce a device for automatic detection and reporting of crawling insects in urban environments. It is a monitoring device for urban pests that complies with the context of smart homes, smart cities and is compatible with the emerging discipline of the Internet of Things (IoT). We believe it can find its place to every room of a hotel, hospital, military camp and residence. This box-shaped device attracts targeted insect pests, senses the entering insect and takes automatically a picture of the internal space of the box. The picture is communicated through the Wi-Fi commonly found in such establishments to an authorized person/stakeholder receiving the picture to take proper action. The e-trap includes strong attractants (pheromone and/or food) to increase capture efficiency. The insect is trapped on the sticky floor of the device. The device carries the necessary optoelectronic sensors to guard all entrances of the trap. As the insect enters it interrupts the infrared light source. This triggers a detection event; a picture is taken, and a time-stamp is set before reporting the event through the Wi-Fi. The device can be integrated seamlessly in urban environments and operates unobtrusively to human activities. We report results on various insect pests and depending on the insect species, can reach a detection accuracy ranging from 96-99%.

As sessile organisms, plants face a wide range of abiotic stresses, with salinity being a prominent constraint affecting their growth, development, and productivity, particularly in arid and semi-arid regions. This study focused on understanding how salinity impacts Jatropha curcas, an important oilseed plant for biodiesel production. By examining the anatomy and ultrastructure of stomata and chloroplasts, we investigated the effects of prolonged salinity stress on J. curcas. This stress led to changes in stomatal density, stomatal index, and ostiole aperture, which case an imbalance of water conductivity in the xylem. Through transmission electron microscopy, we explored the subcellular organization of J. curcas chloroplasts and their contribution to plant photosynthetic efficiency, providing insights into their role in this process. Notably, salinity treatment resulted in a significant increase in starch granules accumulation, leading to impaired the granal and stromal grana lamellae, destroying this ultrastructure. Our findings indicate that the anatomy and ultrastructure of chloroplasts play a crucial role in influencing photosynthetic efficiency and hydraulic conductivity. This study offers new perspectives on the structure and function of chloroplasts in J. curcas, presenting innovative opportunities to develop strategies that enhance biofuel production in areas with high soil salinity.

The ionic Diels-Alder (I-DA) reactions of a series of six iminium cations with cyclopentadiene have been studied within the Molecular Electron Density Theory (MEDT). The superelectrophilic character of iminium cations,  > 8.20 eV, accounts for the high reactivity of these species participating in I-DA reactions. The activation energies are found between 13 and 20 kcal·mol-1 lower in energy than those associated to the corresponding Diels-Alder (DA) reactions of neutral imines. These reactions are low endo selective as a consequence of the cationic character of the TSs, but highly regioselective. Solvents have poor effects on the relative energies, and an unappreciable effect in the geometries. In dichloromethane the activation energies increase slightly as a consequence of the better solvation of the iminium cations than the cationic TSs. ELF topological analysis of the bonding changes along the I-DA reactions shows that they are very similar to those in polar DA reactions. The present MEDT study makes it possible establishing that the global electron density transfer (GEDT) taking place at the TSs of I-DA reactions, and not steric (Pauli) repulsions such as have been recently proposed, are responsible for the features of these type of DA reactions.

The electronic structure and the participation of the simplest azomethine imine (AI) in [3+2] cycloaddition (32CA) reactions have been analysed within the Molecular Electron Density Theory (MEDT) using DFT calculations at the MPWB1K/6-311G(d) level. Electron localisation function (ELF) topological analysis reveals that AI has a pseudoradical structure, while the conceptual DFT reactivity indices characterise this TAC as a moderate electrophile and a good nucleophile. The non-polar 32CA reaction of AI with ethylene takes place through a one-step mechanism with low activation energy, 5.3 kcal/mol-1. A bonding evolution theory (BET) study indicates that this reaction takes place through a non-concerted [2n+2τ] mechanism in which the C–C bond formation is clearly anticipated prior to the C–N one. On the other hand, the polar 32CA reaction of AI with dicyanoethylene takes place through a two-stage one-step mechanism. Now, the more favourable regioisomeric transition state structure (TS) is located 8.5 kcal•mol⁻¹ below the reagents, in complete agreement with the high polar character of the TS. The current MEDT study makes it possible to extend Domingo’s classification of 32CA reactions to a new pra-type of reactivity.

Friction and wear take place on two solid surfaces in sliding contact as a result of the mechanical, thermal and chemical interactions with the participation of environmental species. Electron microscopy and the associated spectroscopic analyses are powerful in probing these mechanisms in spatial resolutions from micro to atomic scale. This article provides a review of the author’s work in the wear and friction mechanisms of PVD hard coatings in which various SEM- and TEM-based microscopic and spectroscopic techniques were employed. Understanding on the failure mechanisms and the origin of self-adaptive friction has been improved to nano-scale. Other related issues are also discussed, such as sample preparation techniques for cross-sectional electron microscopy, energy dispersive X-ray spectroscopy and electron energy loss spectroscopy.

We report a simple and high-performance flexible strain sensor based on liquid metal nanoparticles (LMNPs) on polyimide substrate by laser induced deposition. The LMNPs were prepared by ultrasonic method, and then the femtosecond laser direct writing technology was used to induce the assembly and deposition of the LMNPs to form liquid metal microwires. Laser local sintering enhances the connection between particles, and a wearable strain sensor was fabricated with the high sensitivity as high as 76.18, the good linearity (a correlation coefficient of 0.999) in a wide sensing rage, the fast response/recovery time of 159 ms/120 ms. Attributed to these extraordinary strain sensing performances, the sensor can sense various dynamic strains in real time, monitor both subtle physiological activities and large human motions. It can be adhered to human skin, and well reflect the change of facial expression and realize real-time monitoring of facial expression. And the vocal cord vibration can be detected for speech recognition while the sensor attached to the outside of the throat.

Brushless Synchronous Machines (BSM) are replacing conventional synchronous machines with static excitation in generation facilities due to the absence of sparking and lower maintenance. However, this excitation system makes challenging measuring electric parameters in the rotor. This fact highly difficult the detection of ground faults, which are the most common type of electrical fault in electric machines. In this paper, a ground fault detection method for BSM is proposed. It is based on an inductive AC/DC rotating current sensor installed in the shaft. In case of a ground fault in the rotating parts of the BSM, a fault current will flow through the rotor’s sensor, inducing voltage in its stator. Analyzing the frequency components of the induced voltage the detection of a ground fault in the rotating elements is possible. The ground faults detection method proposed covers the whole rotor and discern between DC and AC sides. To corroborate the detection method, experimental tests have been performed using a prototype of this sensor connected to laboratory synchronous machines achieving satisfactory results.

The laser sintering process and modification of electrophoretic deposition (EPD) YSZ coatings on YSZ air plasma sprayed thermal barrier coatings (TBCs) were investigated. Ni-based superalloy was plasma sprayed using yttria-stabilized zirconia (YSZ) to perform thermal barrier coating with 400 μm thickness. The electrophoretic deposition (EPD) technique was used for depositing nanopowder of YSZ on the surface of YSZ TBCs. In this study, a technology of direct sintering the green EPD layer by laser beam was carried out. The best conditions of deposition YSZ overlay coating using DC current were obtained with applied voltage 40 V, deposition time 5 min, and suspension concentration 10 g/l. Iodine was added to the solutions as the stabilizing agent. To overcome the disadvantages of high sintering temperatures, laser sintering was taken as a new approach. Microstructures for all specimens were studied using Field Emission Scanning Electron Microscopy (FESEM) with EDS analysis. Surface roughness was investigated using AFM analysis and central line average (CLA). The results indicated that the morphology after the direct laser sintering of the EPD layer has a fine and controllable grain size, high hardness, and low roughness. Which is better than the direct laser on plasma-sprayed coatings.

With an increasing concern for global warming, there have been many attempts to reduce greenhouse gas emissions. About 30 % of total energy has been consumed by buildings and much attention has been paid to reducing building energy consumption. While there are many ways of reducing building energy consumption, accurate energy consumption prediction becomes more significant. As mechanical systems are the most energy-consuming components in the building, the present study developed the energy consumption prediction model for a direct-fired absorption chiller by using the ANN technique for the short term. The ANN model was optimized and validated with the actual data collected through a BAS. For the optimization, the numbers of input variables and neurons, and the data size of training were applied. By changing these parameters, the predictive performance was analyzed. In sum, the outcome of the present study can used to predict the energy consumption of the chiller as well as improve the efficiency of the energy management. The outcome of the present study can be used to develop a more accurate prediction model with a few datasets in that it can improve the efficiency of building energy management.

Breast cancer (BC) is a heterogeneous disease representing a substantial economic burden. In order to develop policies that successfully decrease this burden, the factors affecting costs need to be fully understood. Evidence suggests that early detection in Stage I has a lower cost than late detection. We aim to provide conservative estimates of BC's stage-wise medical costs from German healthcare and the payer's perspective. To this end, we conducted a literature review of articles evaluating stage-wise costs of BC in Germany through PubMed, Web of Science, and Econ Lit databases supplemented by Google Scholar. We developed a decision tree model to estimate BC related medical costs in Germany using available treatment and cost information. The review generated seven studies; none estimated the stage-wise costs of BC. The studies were classified into two groups: (1) case scenarios (five studies) and two studies based on administrative data. The first sickness funds data study (Gruber, Stock, et al. 2012) used 1999 information to approach BC attributable cost; their results suggest a range between €3,929 and €11,787 depending on age. The second study (Kreis, Plöthner, et al. 2020) used 2011-2014 data and suggested an initial phase incremental cost of €21,499, an intermediate phase cost of €2,620, and a terminal phase cost of €34,513 per incident case. Our decision tree model based BC stage-wise cost estimates were €21,523 for Stage I, €25,679 for Stage II, €30,156 for Stage III, €42,086 for Stage IV. Alternatively, the modeled cost estimates are €20,284 for the initial phase of care, €851 for the intermediate phase of care, and €34,963 for the terminal phase of care. Our estimates for phases of care are consistent with recent German estimates provided by Kreis and Plöthner et al. Furthermore, the data collected by sickness funds are collected primarily for reimbursement purposes, where the German ICD-10 classification system defines a cancer diagnosis. As a result, claims data lack the clinical information necessary to understand stage-wise BC costs. Our model-based estimates fill the gap and inform future economic evaluations of BC interventions.

The direct radiative effects of atmospheric aerosols are essential for climate, as well as for other societal areas, like the energy sector. The goal of the present study is to exploit the newly devel-oped ModIs Dust AeroSol (MIDAS) dataset for quantifying the direct effects on the downwelling surface solar irradiance (DSSI), induced by the total and dust aerosols amount, under clear-sky conditions and the associated impacts on solar energy for the broader Mediterranean basin, over the period 2003 – 2017. Aerosol optical depth (AOD) and dust optical depth (DOD) derived by the MIDAS dataset, along with additional aerosol and dust optical properties and atmospheric variables were used as inputs to radiative transfer modeling to simulate DSSI components. A 15-year climatology of AOD, DOD and of clear-sky Global Horizontal Irradiation (GHI) and Direct Normal Irradiation (DNI) was derived. The spatial and temporal variability of the aerosol and dust effects on the different DSSI components was assessed. Aerosol attenuation of annual GHI and DNI range from 1-13% and 5-47%, respectively. Significant attenuation by dust 2-10% and 9-37% was found over North Africa and the Middle East, contributing to 45-90% of the total aero-sol effects. The mean GHI and DNI attenuation during extreme dust episodes reached values up to 12% and 44%, respectively, for different areas. After 2008 a decline of aerosol effects on DSSI was found, attributed mainly to the dust component. Sensitivity analysis using different AOD/DOD inputs from Copernicus Atmosphere Monitoring Service (CAMS) reanalysis dataset, revealed CAMS underestimation of aerosol and dust radiative effects compared to MIDAS, due to slight AOD and stronger DOD underestimation, respectively.

Intensive development of many industries, including textile, paper or plastic, which consume large amounts of water and generate huge amounts of wastewaters containing toxic dyes, contribute to pollution of the aquatic environment. Among many known methods of wastewater treatment, adsorption techniques are considered as the most effective. In the present study the weakly basic anion exchangers such as Amberlyst A21, Amberlyst A23 and Amberlyst A24 of the polystyrene, phenol-formaldehyde and polyacrylic matrices were used for C.I. Direct Yellow 50 removal from aqueous solutions. The equilibrium adsorption data were well fitted to the Langmuir adsorption isotherm. Kinetic studies were described by the pseudo-second order model. The pseudo-second order rate constants were in the range of 0.0609-0.0128 g/mg·min for Amberlyst A24, 0.0038-0.0015 g/mg·min for Amberlyst A21 and 1.1945-0.0032 g/mg·min for Amberlyst A23, and decreased with the increasing initial concentration of dye from 100-500 mg/L, respectively. There were observed auxiliaries (Na2CO3, Na2SO4, anionic and non-ionic surfactants) impact on the dye uptake. The polyacrylic resin Amberlyst A24 can be promising sorbent for C.I. Direct Yellow 50 removal as it is able to uptake 666.5 mg/g of the dye compared to the phenol-formaldehyde Amberlyst A23 of the 284.3 mg/g capacity.

The direct radiative effect of aerosols is taken into account in many limited area numerical weather prediction models using wavelength-dependent aerosol optical depths of a range of aerosol species. We study the impact of aerosol distribution and optical properties on radiative transfer, based on climatological and more realistic near real-time aerosol data. Sensitivity tests were carried out using the single column version of the ALADIN-HIRLAM numerical weather prediction system, set up to use the HLRADIA broadband radiation scheme. The tests were restricted to clear-sky cases to avoid the complication of cloud-radiation-aerosol interactions. The largest differences in radiative fluxes and heating rates were found to be due to different aerosol loads. When the loads are large, the radiative fluxes and heating rates are sensitive to the aerosol inherent optical properties and vertical distribution of the aerosol species. Impacts of aerosols on shortwave radiation dominate longwave impacts. Sensitivity experiments indicated the important effects of highly absorbing black carbon aerosols and strongly scattering desert dust.

Objective: Cerebrovascular accidents are the second leading cause of death and the third leading cause of disability worldwide. We hypothesized that cerebellar transcranial direct current stimulation (ctDCS) of the dentate nuclei and the lower-limb representations in the cerebellum can improve standing balance functional reach in chronic (> 6 months’ post-stroke) stroke survivors. Materials and Methods: Magnetic resonance imaging(MRI) based subject-specific electric field was computed across 10 stroke survivors and one healthy MRI template to find an optimal bipolar bilateral ctDCS montage to target dentate nuclei and lower-limb representations (lobules VII-IX). Then, in a repeated-measure crossover study on 5 stroke survivors, we compared 15minutes of 2mA ctDCS based on the effects on successful functional reach(%) during standing balance task. Three-way ANOVA investigated the factors of interest– brain regions, montages, stroke participants, and their interactions.Results: “One-size-fits-all” ctDCS montage for the clinical study was found to be bipolar PO9h – PO10h for dentate nuclei and bipolar Exx7–Exx8 for lobules VII-IX with contalesional anode. Bipolar PO9h–PO10h ctDCS performed significantly (alpha=0.05) better in facilitating successful functional reach (%) when compared to bipolar Exx7–Exx8 ctDCS. Furthermore, a linear relationship between successful functional reach (%) and electric field strength was found where bipolar PO9h–PO10h montage resulted in a significantly (alpha=0.05) higher electric field strength when compared to bipolar Exx7–Exx8 montage for the same 2mA current. Conclusion: We presented a rational neuroimaging based approach to optimize deep ctDCS of the dentate nuclei and lower limb representations in the cerebellum for post-stroke balance rehabilitation.

Understanding the distribution in drought and floods plays an important role in disaster risk management. The present study aims to explore the trends in the standardized precipitation index and extreme precipitation days in China, as well as to estimate the economic losses they cause. We found that in the Northeast China, northern of North China and northeast of Northwest China were severely affected by drought disasters (average damaged areas were 6.44 million hectares) and the most severe drought trend was located in West China. However, in the north of East China and Central China, the northeastern of the Southwest China was severely affected by flood disasters (average damaged areas were 3.97 million hectares) and the extreme precipitation trend is increasing in the northeastern of the Southwest China. In the Yangtze River basin, there were increasing trends in terms of drought and extreme precipitation, especially in the northeastern of the Southwest China, where accompanied by severe disaster losses. By combining the trends in drought and extreme precipitation days with the distribution of damaged areas, we found that the increasing trend in droughts shifted gradually from north to south, especially in the Southwest China, and the increasing trend in extreme precipitation gradually shifted from south to north.

An adaptive operation strategy for on-demand control of DMFC system is proposed as an alternative method to enhance the voltage stability. Based on a single-cell DMFC stack, a newly simplified semi-empirical model is developed from the uniform-designed experimental results to describe the I-V relationship. Integrated with this model, the multi-objective optimization method is utilized to develop an adaptive operation strategy. Although the voltage instability is frequently encountered in unoptimized operations, the voltage deviation is successfully decreased to a required level by adaptive operations with operational adjustments. Moreover, the adaptive operations are also found to be able to extend the range of operating current density or to decrease the voltage deviation according to ones requirements. Numerical simulations are implemented to investigate the underlying mechanisms of the proposed adaptive operation strategy, and experimental adaptive operations are also performed on another DMFC system to validate the adaptive operation strategy. Preliminary experimental study shows a rapid response of DMFC system to the operational adjustment, which further validates the effectiveness and feasibility of the adaptive operation strategy in practical applications. The proposed strategy contributes to a guideline for the better control of output voltage from operating DMFC systems.

It is of great academic significance to understand how the atomic structure of interfaces and boundaries in materials impacts the magnetic coupling nature across the boundaries and encourage development of state-of-the-art magnetic devices. Here, we carry out a systematic investigation of the atomic and electronic structures of twin boundaries (TBs) in LiFe5O8 thin films and determine their concurrent magnetic couplings using atomic-resolution transmission electron microscopy and atomistic first-principles calculations. The results show ferromagnetic or antiferromagnetic coupling can exist across the different TBs in LiFe5O8 (LFO) thin films and electrical structures within a few atomic layers directly rely on the TB atomic core structures. Uncovering one-to-one relationship between the magnetic properties of individual TB and the local atomic structures will clarify a thorough comprehension of numerous fascinating magnetic properties of commonly utilized magnetic materials, which will undoubtedly encourage the progress of sophisticated magnetic materials and devices.

Point-contact spectroscopy has been performed on bulk samples of electron-doped high temperature superconductor Nd2-xCexCuO4-. The samples were characterized by X-ray diffraction and scanning electron microscopy equipped with a wavelength dispersive spectrometer and an electron backscatter diffraction detector. The samples with a Ce content x = 0.15, show the absence of spurious phases and randomly oriented grains, most of which have dimensions of approximately 220 µm2. The low-bias spectra in the tunnelling regime, i.e., high transparency interface, exhibit a gap feature at about ±5 meV and no zero-bias conductance, consistent with the most literature data on oriented samples. The high-bias conductance has also been measured in order to obtain information on the properties of the barrier. A V-shape has been in some cases observed, instead of the parabolic behavior expected for tunnel junctions.

It has been recently demonstrated that inelastic helium-atom scattering from conducting surfaces can provide a direct measurement of the surface electron-phonon coupling constant (mass-enhancement factor ) via the temperature- or the incident-energy-dependence of the Debye-Waller exponent. The analysis of previous published as well as unpublished helium atom scattering diffraction data from the vicinal surfaces of copper (Cu(11),  = 3,5,7) and aluminium (Al(221) and Al(332)) permits to extract  for this class of surfaces, suggesting an enhancement with respect to the corresponding data for the low-index surfaces (111) and (001) above a possible roughening transition temperature. The specific role of steps as compared to that of terraces is briefly discussed.

Our knowledge of electricity is based on two parallel lines of research: one focusing on ‘charge’, the other on ‘electron’. The distinction is blurred. The difficulty is that the fundamental nature of elementary charge is unknown. Here I present evidence that charge is a resting electron and electron is a moving charge – one physical entity two behavioural identities. That is, charge is nonrelativistic electron and electron is relativistic charge. Charges obey the laws of static electricity (electrostatics); electrons obey the laws of moving electricity (electrodynamics). Whether positive or negative, a charge is ejected from the atom at tremendous speed, losing the characteristics of ‘a charge’ and gaining those of ‘an electron’. I conclude that an atom, hence nature in general, contains an equal number of positive and negative electrons, recognised at rest as opposite charges. This solves the mystery of the electron-positron numerical asymmetry. It means that static positions and negatrons (charges) play equivalent roles as subatomic building blocks of matter, revealing a new atomic structure.

I demonstrate that the macrocosmic gravitational interaction between two masses and the microcosmic electrostatic interaction between two charges unify in simple concepts and mathematical laws when electric charge and ordinary mass are interpreted in reciprocal terms. No previous research has ever attempted to unify charge and mass. The difficulty has been lack of an intelligible definition of charge. A three-point paradigm shift solves the problem, giving convincing evidence – for the first time – that positron and negatron are the ultimate elementary particles. That is, matter is pure positive and negative grains of electricity. Paradigm shift #1: Electron is a moving charge; a charge is static electron – ‘one entity two identities’. This implies that ordinary matter contains equal numbers of positive and negative electrons – observed in motion as ‘electrons’ and at rest as ‘charges’. In motion, a positron-negatron pair obeys the laws of electrodynamics and annihilates; at rest, the pair obeys the laws of electrostatics and neutralizes. Paradigm shift #2: Electron mass and electrostatic field are either positive or negative. Opposite masses and fields, rather than indefinable ‘charge’, make opposite electrons physically different. Paradigm shift #3: Electric charge and ordinary mass interconvert. Positive charge (e⁺) and negative charge (e^-) neutralize to neutral charge (2e⁰), which is nature’s quantum of ordinary mass. Conversely, a quantum of ordinary mass splits to opposite charges e.g. in frictional electrification. The insights systematize the search, identification and classification of ‘elementary particles’, ending decades of confusion in the ‘elementary particle zoo’. They identify a new, stable subatomic particle – a third nucleon.

In the succinic acid-producing bacterium Pseudoclostridium thermosuccinogenes the fumarate reductase (FRD) genes reside in an operon together with those encoding an electron bifurcating complex (FlxABCD-HdrABC) that shuttles electrons from NADH to ferredoxin and a disulfide bond. Based on phylogeny and genomic co-occurrence we propose two hypothetical mechanisms via which the FRD is involved in electron bifurcation: (I) A disulfide bond from a hitherto unknown cofactor is reduced by the electron-bifurcating FlxABCD-HdrABC complex, using NADH to generate two thiol groups, while facilitating the unfavourable reduction of ferredoxin by NADH. The disulfide bond is subsequently regenerated via the reduction of fumarate by the FRD using the previously formed thiol groups. (II) The FRD forms an integral part of the FlxABCD-HdrABC complex, and NADH is used to reduce ferredoxin and fumarate directly, without an intermediate disulfide-forming cofactor. Either way enables the conservation of additional energy by a soluble FRD, analogous to fumarate respiration.

Background/Aim: There is continuing interest in engineering esthetic labial archwires. The aim of this study was to coat nickel-titanium (NiTi) and beta-titanium (β-Ti), also known as titanium molybdenum (TMA), archwires by plasma electrolytic oxidation (PEO) and to analyze the characteristics of the PEO-surfaces. Materials and Methods: PEO-coatings were generated on 0.014-inch NiTi and 0.19x0.25-inch β-Ti archwires. The surfaces were analyzed by scanning electron microscopy and stereomicroscopy. Cytocombability testing was performed with ceramized and untreated samples according to EN ISO 10993-5 in XTT-, BrdU- and LDH-assays. The direct cell impact was analyzed using LIVE-/DEAD-staining. In addition, the archwires were inserted in an orthodontic model and photographs were taken before and after insertion. Results: The PEO coatings were 15 to 20 µm thick and esthetically pleasing. The cytocompatibility analysis revealed good cytocompatibility results for both ceramized NiTi and β-Ti archwires. In the direct cell tests, the ceramized samples showed improved compatibility as compared to those of uncoated samples. However, bending of the archwires resulted in loss of the PEO-surfaces. Nevertheless, it was possible to insert the β-Ti PEO-coated archwire in an orthodontic model without loss of the PEO-ceramic. Conclusion: PEO is a promising technique for the generation of esthetic orthodontic archwires. Since the PEO-coating does not resist bending, its clinical use seems to be limited so far to orthodontic techniques using straight or pre-bended archwires.

Bitumen aging is the major factor which contributes to the deterioration of the road pavement. Oxidation and volatilization are generally considered as the most important phenomena affecting aging in asphalt paving mixtures. The present study was carried to investigate whether various antioxidants provided by natural resources such as phospholipids, ascorbic acid as well as lignin from rice husk, could be used to reduce age hardening in asphalt binders. A selected bituminous material was modified by adding 2 % w/w of the anti-aging natural additives and subjected to accelerated oxidative aging regimes according to the Rolling Thin Film Oven Test (RTFOT) method. The effects of aging were evaluated based on changes in sol-gel transition temperature of modified bitumens measured through Dynamic Shear Rheology (DSR). Moreover, changes of Electron Paramagnetic Resonance (EPR) spectra were monitored on the bituminous fractions asphaltene and maltene separated by solvent extraction upon oxidative aging. The phospholipids-treated binder exhibited the highest resistance to oxidation and the lowest age-hardening effect compared to the other tested anti-oxidants. The combination of EPR and DSR techniques represents a promising method for elucidating the changes in associated complex properties of bitumen fractions promoted by addition of free radical scavengers borrowed by green resources.

X-ray crystallographic and theoretical charge density data for a series of compounds [(Co(Ts3tren))M(Co(Ts3tren))] (M = Mg, Ca, Sr and Ba) is examined. The crystal structures are isostructural and the alkaline earth metal ions have the same arrangement of donor oxygen atoms despite the large variation in ionic radii. The isomorphism of these molecules is surprising and a theoretical examination of the electronic structures, with the different metal ions along the series, provides detailed insight into their stabilities. The theoretical and experimental data are consistent and agree well. The local properties of the Co(II) ion and its donor atoms are relatively independent of the alkali earth metal.

Band-gap alignment engineering has now been extensively studied due to its high potential application. Here we demonstrate a simple route to synthesize two metal oxide layers and align them together according to their bandgaps on surface of crystalline silicon (c-Si) solar cells. The metal oxide layers can not only extend absorption spectrum to generate extra carriers but also serve to separate electron-hole pairs more efficiently. As a consequence, the photovoltaic performance of SnO₂/CdO /Si double-layer solar cell (DLSC) is highly improved compared to CdO/Si and SnO₂/Si single-layer solar cells(SLSCs) and SnO₂/CdO/Si double-layer solar cell (DLSC). By the alignment engineering, the SnO₂/CdO/Si DLSC produces a short circuit photocurrent (J_sc) of 38.20 mA/cm², an open circuit photovoltage (V_oc) of 0.575 V and a fill factor (FF) of 68.7%, corresponding to a light to electric power conversion efficiency (η) of 15.09% under AM1.5 illumination. These results suggest that with the use of metal oxide layers by band-gap alignment engineering, new avenues have been opened for developing high-efficiency and cost-effective c-Si solar cells.

The formation and propagation of cracks occurs through irreversible dislocation movements at notches, material defects and grain boundaries. Since this process is partly thermally controlled, the resistance to dislocation movements at low temperatures increases. This slows both fatigue initiation and fatigue crack propagation. From recent experimental data, it can be seen that fatigue crack growth is accelerated below the fatigue transition temperature (FTT) that correlates with the ductile-brittle transition temperature (DBTT) found by well-known fracture mechanics tests, i.e., Charpy impact, fracture toughness, and CTOD. Hence, this study investigates the relation between FTT and DBTT in S500 high-strength steel base material and welded joints at low temperatures using fatigue crack growth, fracture toughness tests as well as scanning electron microscopy. From the tests, an almost constant decrease in fatigue crack propagation rate is determined with decreasing test temperature even below the DBTT.

Self-phase modulation (SPM) broadening of laser spectra was studied in a transmission mode in natural and synthetic diamonds at variable laser wavelengths (515 and 1030 nm), pulse energies and widths (0.3 - 12 ps, positively chirped pulses), providing their filamentary propagation. Besides the monotonous SPM broadening of the laser spectra versus pulse energy, more pronounced for the (sub)picosecond pulsewiths and more doped natural diamond, periodical low-frequency modulation was observed in the spectra at the shorter laser pulsewidths, indicating dynamic Bragg filtering of the supercontinuum due to ultrafast plasma and nanoplasmonic effects. Damping of broadening and ultramodulation for the longer picosecond pulsewidths was related to thermalized electron-hole plasma regime established for the laser pulsewidths longer, than 2 ps. Unexpectedly, at higher pulse energies and corresponding longer microfilaments, the number of spectral modulation features increases, indicating dynamic variation of the periods in the longitudinal plasma Bragg gratings along the filaments due to prompt secondary laser-plasmon interactions.

Direct Energy Deposition (DED) is a versatile and efficient method in metal additive manufacturing. However, humping, caused by abnormal dynamics in the melt pool (MP), poses a significant threat to the geometric integrity of manufactured products. Current state-of-the-art (SOTA) methods primarily detect humping by analyzing late-stage spatial abnormalities, such as MP detachment. This approach is fundamentally reactive, leading to a tendency to miss early humping spatiotemporal dynamics, like cyclic elongation of the MP. This study introduces a novel, proactive indicator named VIMPS (Variability of Instantaneous MP Solidification-Front Speed), a physics-based tool designed to quantify early abnormal fluctuations in MP solidification speed. The experiments demonstrate VIMPS correlation with humping-induced geometric inaccuracies. By capturing early spatiotemporal dynamics of the MP, VIMPS reduces detection latency by 30 seconds compared to existing SOTAs that focus solely on spatial abnormalities. This significant improvement transforms detection from reactive to proactive, providing the time needed for corrective actions to enhance the overall productivity and quality of the DED process.

The main focus of the in vitro toxicity assessment methods is on the viability of the cells, which is usually based on metabolism changes. Yet, when exposed to toxic substances, the cell triggers multiple signals in response. With this in mind, we have developed a promising cell-based toxicity method that observes various cell responses when exposed to toxic substances (either death, division or remaining viable). Based on the collective cell response, we observed and predicted the dynamics of the cell population to determine the toxicity of the toxicant. The method was tested with two different conformations: In the first conformation, we exposed a monoculture model of blood macrophages to UV light, hydrogen peroxide, nutrient deprivation, tetrabromobisphenol A, fatty acids and 5-fluorouracil. In the second, we exposed a coculture liver model consisting of hepatocytes, hepatic stellate cells, Kupffer cells and liver sinusoidal endothelial cells to rifampicin, ibuprofen and 5-fluorouracil. The method showed good accuracy compared to established toxicity assessment methods. In addition, this approach provided more representative information on the toxic effects of the compounds as it considers the different cellular responses induced by toxic agents.