Crossover Process Research Articles

Effect of psychosocial safety climate on work-family conflict and psychological health among working couples.

The purpose of the study was to look into how work-family conflict (WFC), family-work conflict (FWC), and psychological health are affected by the psychosocial safety climate (PSC). First, the study suggested that for both husband and wife, PSC moderates the relationship between job demands and WFC. Second, the study predicted FWC mediates the relationship between WFC and depressive symptoms through the "crossover" process. The study design used a multi-source sample that involved 350 teachers and their working spouses (n = 700). The analysis of mediation and moderation among job demands, WFC, FWC, PSC, and depressive symptoms was conducted using SPSS and structural equation modeling AMOS software. For the teacher's sample, based on behavioral (β = 0.166, p < 0.05) and strain-based (β = 0.170, p < 0.05) aspects, the hierarchical regression analysis revealed that the PSC moderates the relationship between physical demand and WFC. The results also showed that the relationship between time-based WFC and emotional demand is moderated by PSC (β = 0.103, p < 0.05). Next, the analysis found that PSC moderates the association between cognitive demand and WFC of strain-based (β = 0.179, p < 0.05). For the spouse's sample, according to the analysis, PSC moderates the relationship between strain-based WFC and physical demand (β = 0.091, p < 0.05). The study also revealed that FWC serves as a mediator in the relationship between WFC and depressive symptoms in both husbands (β = 0.233, p < 0.01) and wives (β = 0.135, p < 0.001). Overall, this study contributes significant insights to the current literature by examining the impact of PSC on the psychological well-being of individuals and others through the crossover process.

A randomized trial on three different minimally invasive decompression techniques for lumbar spinal stenosis. Five years follow-up from the NORDSTEN-SST.

The short-term clinical outcome for midline-preserving posterior decompression techniques was comparable. The aim of this study was to evaluate long-term clinical results after three different midline-preserving posterior decompression techniques. In the NORDSTEN spinal stenosis trial (NORDSTEN-SST) 437 patients were randomized to three different midline-retaining posterior decompression techniques: Unilateral laminotomy with crossover (UL), bilateral laminotomy (BL) and spinous process osteotomy (SPO). Primary outcome was the mean change in Oswestry disability index (ODI) score at five-years follow-up. Secondary outcomes were the proportion of patients classified as success, mean change in EQ-5D, ZCQ-score, NRS-score for leg and low back pain, a seven-point Global Perceived Effect (GPE) Scale and proportion of subsequential spinal surgery. The number of patients that completed follow-up data after five years was 358 (82%): In the UL, BL and SPO group the numbers were 122, 119 and 117, respectively. Mean age at baseline was 66.7 (SD 8.2) years, mean BMI was 27.8 (SD 4.1), and 172/358 (48%) were female. In the UL group the mean change was -18.2 (95% CI -21.0 -5.4), in the BL group it was -19.0 (95% CI -21.9-16.1) and in the SPO it was -18.6 (95% CI -21.6-15.7) (p = 0.917). No significant differences in the secondary outcomes between the three surgical groups were found, also the subsequent spinal surgery rates were similar. There were no significant differences in patient reported outcomes and subsequent spinal surgery rates after the three different decompression techniques at five-year follow-up.

Dynamic Phosphorescence/Fluorescence Switching in Hybrid Metal Halides Toward Time‐Resolved Multi‐Level Anti‐Counterfeiting

AbstractHybrid metal halides (HMHs) with time‐resolved luminescence behavior promise to be a breakthrough in multi‐level anti‐counterfeiting, but controlling the dynamic switching between phosphorescence and fluorescence is extremely challenging. Herein, an array of 0D HMHs is constructed by screening the π‐conjugated ligand with room‐temperature phosphorescence (RTP). Compared to the organic chromophore, (ETPP)2ZrCl6 possesses a misaligned stacking and rigid structure, contributing to an improved phosphorescence quantum yield (ΦP = 27.50%) and an extended phosphorescence lifetime (τ = 0.6234 s), as the intervening of inorganic unit [ZrCl6]2− suppresses the energy losses caused by nonradiative relaxation and prompts the intersystem crossover (ISC) process. Not only that, the interplay of phosphorescence‐fluorescence dual‐mode emission can be intelligently controlled by doping the active metal Te4+, resulting in a dynamic switching between RTP phosphorescence and self‐trapped exciton (STE) fluorescence. DFT calculations reveal the governing origins of RTP‐STE from the intermolecular ISC channels and spin‐orbit coupling (SOC) coefficients. These precise images into periodic pixelated arrays enable the multi‐level anti‐counterfeiting and information encryption. This work proposes a fluorescence‐phosphorescence co‐modulating strategy under the premise of dissecting the structural origins for optimizing RTP phosphorescence, which paves the way for designing high‐security‐level anti‐counterfeiting materials.

Photoluminescence optical and thermal quenching in heavily doped Gd3(Ga,Al)5O12:Ce, Mg single crystals: Dependence on the Ga3+, Ce3+, and Mg2+ concentration

Heavily doped single crystals of Gd3GaxAl5-xO12:Ce, Mg (x = 2.46–2.95) with different concentrations of Ce (0.016–0.188 at.%) and Mg (0–0.083 at.%) are investigated by the X-ray diffraction, photoluminescence, and thermoluminescence methods. Dependences of the luminescence characteristics, as well as crystal lattice parameters and distances between the Ce3+ and Mg2+ ions, on the Ga, Ce, and Mg concentration are studied. Mechanisms of the processes, resulting in the photoluminescence optical and thermal quenching and acceleration of decay kinetics, and the influence of the crystal composition on these processes are discussed. The role of close {Ce3+ - Mg2+Ga} pairs in these processes is considered. At T > 400 K, the luminescence thermal quenching is caused by the crossover process, while in the 200–350 K temperature range, by the electron transfer from the 5d1 excited state of Ce3+ to nearby defect levels (electron traps) located between the 5d1 level and the conduction band. The latter process results also in the appearance of thermally stimulated luminescence, and its efficiency depends on the Ga3+ content and concentration of intrinsic defects. The optimum concentrations of Ga3+ and Mg2+ ions in the investigated crystals are determined.

Diastereoselective Hydrodifluoromethylation of Alkenyl N-Heterocycles via Photocatalytic Radical-Polar Crossover.

A diastereoselective hydrodifluoromethylation of N-heteroaryl alkenes was successfully established. This method was applicable to an array of N-heteroaryl substrates with both cyclic and acyclic alkenes while displaying tolerance to a variety of functional groups. The conditions were also expanded to obtain hydrotrifluoromethylated products with similar results. Initial mechanistic studies suggest that the final protonation step is accessed through a radical-polar crossover process.

Cu0-Promoted Truce-Smiles Rearrangement for Aryl-Difluoromethylenation of C═C Bonds via a Reductive Radical-Polar Crossover Process.

An efficient Cu0-promoted Truce-Smiles rearrangement for the aryl-difluoromethylenation of C═C bonds by the reaction of N-alkyl-N-(arylsulfonyl)methacrylamide and 2-bromodifluoromethyl-1,3-benzodiazole via a reductive radical-polar crossover process under mild reaction conditions is presented. The protocol enables practical access to a variety of single regioisomer α-aryl-β-difluoromethylene amides in good to excellent yields through consecutive difluoromethylenation, radical-polar crossover, 1,4-aryl migration, SO2 extrusion, and N-H bond formation cascade reaction.

An integrated optimization method for the damper placements, shape and size of truss structures

This work extends the application of the approximation concept in dynamic topology optimization for truss structures. The corresponding problem contains both continuous and discrete variables, encompassing damper placements, truss shape and cross-sectional area. First, the utilization of a branched multipoint approximation (BMA) function establishes sequential approximation problems that also involve such mixed variables, marking its innovative application in dynamic optimization. Then, a modified genetic algorithm (GA) is used to optimize discrete variables. To enhance convergence stationarity, the concept of ‘adjacent individuals’ is proposed to control the degree of difference in topology configuration between initial population members and the current optimal. Additionally, adjustments to the sequence-based crossover process ensure compliance with damper quantity constraints. Examples demonstrate that the introduction of adjacent individuals is beneficial to convergence stationarity, and the shape change of the truss increases the mode damping ratio by more than 20%. The created optimization platform can also tackle other mixed variables optimization problems.

Cobalt‐Catalyzed Intramolecular Markovnikov Hydrocarbonylation of Unactivated Alkenes via Hydrogen Atom Transfer

A cobalt‐catalyzed intramolecular Markovnikov hydroalkoxycarbonylation and hydroaminocarbonylation of unactivated alkenes has been developed, enabling highly chemo‐ and regioselective synthesis of α‐alkylated γ‐lactones and α‐alkylated γ‐lactams in good yields. The mild reaction conditions allow use of mono‐, di‐ and trisubstituted alkenes bearing a variety of functional groups. Preliminary mechanistic studies suggest the reaction proceeds through a CO‐mediated hydrogen atom transfer (HAT) and radical‐polar crossover (RPC) process, in which a cationic acylcobalt(IV) complex is proposed as the key intermediate.

Cobalt-Catalyzed Intramolecular Markovnikov Hydrocarbonylation of Unactivated Alkenes via Hydrogen Atom Transfer.

A cobalt-catalyzed intramolecular Markovnikov hydroalkoxycarbonylation and hydroaminocarbonylation of unactivated alkenes has been developed, enabling highly chemo- and regioselective synthesis of α-alkylated γ-lactones and α-alkylated γ-lactams in good yields. The mild reaction conditions allow use of mono-, di- and trisubstituted alkenes bearing a variety of functional groups. Preliminary mechanistic studies suggest the reaction proceeds through a CO-mediated hydrogen atom transfer (HAT) and radical-polar crossover (RPC) process, in which a cationic acylcobalt(IV) complex is proposed as the key intermediate.

Dichloromethane as C1 Synthon for the Photoredox Catalytic Cyclopropanation of Aromatic Olefins

AbstractDichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible‐light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3−Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non‐cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium‐labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.

A new multi-objective hyperparameter optimization algorithm for COVID-19 detection from x-ray images

The coronavirus occurred in Wuhan (China) first and it was declared a global pandemic. To detect coronavirus X-ray images can be used. Convolutional neural networks (CNNs) are used commonly to detect illness from images. There can be lots of different alternative deep CNN models or architectures. To find the best architecture, hyper-parameter optimization can be used. In this study, the problem is modeled as a multi-objective optimization (MOO) problem. Objective functions are multi-class cross entropy, error ratio, and complexity of the CNN network. For the best solutions to the objective functions, multi-objective hyper-parameter optimization is made by NSGA-III, NSGA-II, R-NSGA-II, SMS-EMOA, MOEA/D, and proposed Swarm Genetic Algorithms (SGA). SGA is a swarm-based algorithm with a cross-over process. All six algorithms are run and give Pareto optimal solution sets. When the figures obtained from the algorithms are analyzed and algorithm hypervolume values are compared, SGA outperforms the NSGA-III, NSGA-II, R-NSGA-II, SMS-EMOA, and MOEA/D algorithms. It can be concluded that SGA is better than others for multi-objective hyper-parameter optimization algorithms for COVID-19 detection from X-ray images. Also, a sensitivity analysis has been made to understand the effect of the number of the parameters of CNN on model success.

Tetrafluoroisopropylation of alkenes and alkynes enabled by photocatalytic consecutive difluoromethylation with CF2HSO2Na

Direct assembly of complex fluorinated motifs from simple fluorine sources is an attractive frontier of synthetic chemistry. Reported herein is an unconventional protocol for achieving tetrafluoroisopropylation by using commercially available CF2HSO2Na as a convenient source of the tetrafluoroisopropyl [(CF2H)2CH] group, which finds widespread applications in life science and material science. Visible-light-induced hydrotetrafluoroisopropylation of alkenes and carbotetrafluoroisopropylation of alkynes have been thus developed. Various structurally diverse α-tetrafluoroisopropyl carbonyls and cyclopentanones are selectively constructed under mild conditions. A photocatalytic triple difluoromethylation cascade, driven by consecutive reductive radical/polar crossover processes, leads to the direct assembly of a tetrafluoroisopropyl moiety from CF2HSO2Na. This C1-to-C3 fluoroalkylation protocol provides a practical strategy for the rapid construction of polyfluorinated compounds that are otherwise difficult to access, thus significantly enhancing the boundary of fluoroalkylation chemistry.

Dichloromethane as C1 Synthon for the Photoredox Catalytic Cyclopropanation of Aromatic Olefins.

Dichloromethane, as a readily available and inexpensive C1 synthon is proposed as a powerful building block for cyclopropanation of alkenes under mild conditions. Herein, we report a highly efficient and versatile dual photoredox system, involving a nickel aminopyridine coordination complex and a photocatalyst, for the cyclopropanation of aromatic olefins using dichloromethane, under visible-light irradiation. The cyclopropanation protocol has been successfully applied at gram scale. Mechanistic studies suggest a Ni(II) pyridyl radical complex as the key intermediate for the homolytic cleavage of the Csp3-Cl bond, generating a chloromethyl radical that is captured by the olefin coupling partner. Our findings also highlight the versatility of this methodology. By directing the radical/polar crossover process, we were able to selectively drive the reaction towards either the formation of cyclopropyl derivatives or the corresponding non-cyclic alkyl chloride products. The methodology also successfully apply to geminal dichloroalkanes, including the formation of spiro[2,2] compounds. Moreover, our methodology extends to the synthesis of deuterium-labelled cyclopropanes, demonstrating its utility in isotopic labelling and broadening its applicability in chemical synthesis and drug development.

The Dependence on Temperature of the Mn4+ Emission Intensity and Lifetime in Na2SiF6

We have measured the dependence of the Mn4+ lifetime and intensity on temperature of commercial Na2SiF6:Mn4+ phosphor. The data are fitted to existing physical models to extract the activation energy for thermal quenching. The parameters of our fitting are compared with those reported for laboratory synthesized Na2SiF6:Mn4+ and commercial K2SiF6:Mn4+ phosphors that is sold under the trade name, TriGain®. This comparative analysis sheds light on the mechanism of thermal quenching of the Mn4+ ion luminescence in M2SiF6 (M = K, Na) compounds. We show that the activation energy and the onset temperature of thermal quenching for the 2E→4T2→4A2 crossover process is correlated with the energy of the 4T2 level and argue that this is a robust electronic structure-property relationship in fluoride hosts with low defect density. The study provides, therefore, an understanding of the factors responsible for non-radiative relaxation processes, which is fundamental to the understanding of phosphor quantum efficiency and performance.

Visible-Light-Induced Regioselective Radical-Polar Crossover 1,4-Hydrophosphinylation of 1,3-Enynes: Access to Trisubstituted Allenes Bearing a Phosphine Oxide Group.

The radical 1,4-functionalizations of 1,3-enynes have emerged as a powerful strategy for the synthesis of multisubstituted allenes. However, the phosphorus-centered radical-initiated transformations remain largely elusive. Herein, visible-light photoredox catalytic regioselective radical hydrophosphinylation of 1,3-enynes with diaryl phosphine oxides as phosphinoyl radical precursors has been realized. This protocol features mild conditions, a wide substrate scope, and good functional group tolerance, producing a diverse range of phosphinoyl-substituted allenes in moderate to good yields with high atom economy. Detailed mechanistic experiments revealed a radical-polar crossover process in the reaction.

Probabilistic Chain-Enhanced Parallel Genetic Algorithm for UAV Reconnaissance Task Assignment

With the increasing diversity and complexity of tasks assigned to unmanned aerial vehicles (UAVs), the demands on task assignment and sequencing technologies have grown significantly, particularly for large UAV tasks such as multi-target reconnaissance area surveillance. While the current exhaustive methods offer thorough solutions, they encounter substantial challenges in addressing large-scale task assignments due to their extensive computational demands. Conversely, while heuristic algorithms are capable of delivering satisfactory solutions with limited computational resources, they frequently struggle with converging on locally optimal solutions and are characterized by low iteration rates. In response to these limitations, this paper presents a novel approach: the probabilistic chain-enhanced parallel genetic algorithm (PC-EPGA). The PC-EPGA combines probabilistic chains with genetic algorithms to significantly enhance the quality of solutions. In our approach, each UAV flight is considered a Dubins vehicle, incorporating kinematic constraints. In addition, it integrates parallel genetic algorithms to improve hardware performance and processing speed. In our study, we represent task points as chromosome nodes and construct probabilistic connection chains between these nodes. This structure is specifically designed to influence the genetic algorithm’s crossover and mutation processes by taking into account both the quantity of tasks assigned to UAVs and the associated costs of inter-task flights. In addition, we propose a fitness-based adaptive crossover operator to circumvent local optima more effectively. To optimize the parameters of the PC-EPGA, Bayesian networks are utilized, which improves the efficiency of the whole parameter search process. The experimental results show that compared to the traditional heuristic algorithms, the probabilistic chain algorithm significantly improves the quality of solutions and computational efficiency.

A Hybrid Strategy Improved SPEA2 Algorithm for Multi-Objective Web Service Composition

A Hybrid Strategy Improved SPEA2 Algorithm for Multi-Objective Web Service Composition

Weekly information communication technology availability demand and family experiences in dual‐earner couples: A perspective from the spillover–crossover model

AbstractThe prevalence of information communication technology (ICT) enables employees to conveniently communicate with coworkers and clients regardless of time and place. However, recent studies have revealed a negative side of ICT use, especially its capacity to invade the family domain. This study was developed based on the spillover–crossover model (SCM) to test how ICT availability demand shapes employees' family experiences and how this demand crosses over to spouses. A total of 961 cases nested in 101 dual‐earner couples were collected using a 10‐week experience sampling method. Multilevel structural equation modelling revealed that (1) employees' work interference with family (WIF) mediated the indirect impact of employees' ICT availability demand on their family satisfaction and family undermining; (2) employees' WIF mediated the indirect impact of employees' ICT availability demand on their spouses' family satisfaction and family undermining; and (3) employees' ICT control buffered these two indirect relationships by which employees' ICT availability demand impacted their own and their spouses' family satisfaction and family undermining. This research elaborates on the spillover and crossover process through which ICT availability demand shapes family experience, thus contributing to the literature on ICT availability demand and the SCM.

First-principles design of heavy-atom-free singlet oxygen photosensitizers for photodynamic therapy.

In photodynamic therapy (PDT) treatment, heavy-atom-free photosensitizers (PSs) are a great source of singlet oxygen photosensitizer. Reactive oxygen species (ROS) are produced by an energy transfer from the lowest energy triplet excited state to the molecular oxygen of cancer cells. To clarify the photophysical characteristics in the excited states of a few experimentally identified thionated (>C=S) molecules and their oxygenated congeners (>C=O), a quantum chemical study is conducted. This study illustrates the properties of the excited states in oxygen congeners that render them unsuitable for PDT treatment. Concurrently, a hierarchy is presented based on the utility of the lowest-energy triplet excitons of thionated compounds. Their non-radiative decay rates are calculated for reverse-ISC and inter-system crossover (ISC) processes. In addition, the vibronic importance of C=O and C=S bonds is clarified by the computation of the Huang-Rhys factor, effective vibrational mode, and reorganization energy inside the Marcus-Levich-Jörtner system. ROS generation in thionated PSs exceeds their oxygen congeners as kf ≪ kISC, where radiative decay rate is designated as kf. As a result, the current work offers a calculated strategy for analyzing the effectiveness of thionated photosensitizers in PDT.

Aerodynamic/Hydrodynamic Investigation of Water Cross-Over for a Bionic Unmanned Aquatic-Aerial Amphibious Vehicle.

An aerodynamic/hydrodynamic investigation of water cross-over is performed for a bionic unmanned aquatic-aerial amphibious vehicle (bionic UAAV). According to flying fish features and UAAV flight requirements of water cross-over, the bionic conceptual design of crossing over water is described and planned in multiple stages and modes of motion. A solution procedure for the numerical simulation method, based on a modified SST turbulence model and the VOF model, is expressed, and a verification study is presented using a typical case. Longitudinal-lateral numerical simulation analysis investigates the cruise performance underwater and in the air. The numerical simulation and principal experiment verification are conducted for crossing over water and water surface acceleration. The results indicate that the bionic UAAV has an excellent aerodynamic/hydrodynamic performance and variant configuration to adapt to water cross-over. The bionic UAAV has good water and air navigation stability, and the cruise flying lift-drag ratio is greater than 15 at a low Reynolds number. Its pitching moment has the phenomenon of a "water mound" forming and breaking at the water cross-over process. The present method and the bionic variant configuration provide a feasible water cross-over design and analysis strategy for bionic UAAVs.