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Antibiotics are cornerstone drugs of modern medicine. However, their effectiveness is declining rapidly due to the emergence and spread of antimicrobial resistance. It is therefore critical that new antibiotics are developed that evade current resistance mechanisms and are additionally challenging for bacteria to become resistant to. Few candidate antibiotics have been discovered over the recent decades, and therefore we must make the most out of what we have. Unfortunately, the further development of key antimicrobial candidates is severely hampered by the lack of knowledge of the finer atomic-level details of how they work. Investigating these details is particularly troublesome for antibiotics that target the bacterial membrane (the fatty layer that separates the in- and outside of the bacterium) because membranes are poorly amendable to the most used analytical techniques that can provide atomic resolution information. In this thesis, we apply so-called solid-state nuclear magnetic resonance spectroscopy (ssNMR spectroscopy) towards solving this problem. We develop general methodology to produce isotopically enriched phospholipids (the major component of bacterial membranes) and demonstrate their use by investigating the interaction between antibiotic Cinnamycin and the phospholipid PE. Next, we investigate the mode of action of plectasin, a fungal antibiotic that binds to Lipid II, a crucial intermediate in the synthesis of the bacterial cell wall. By integrating the structural information from ssNMR with biochemical assays and other analytical techniques, we uncover how plectasin binds to Lipid II in membranes and that upon binding the complex further self-assembles on the membrane, forming a network, stabilized by calcium, that tightly sequesters Lipid II, making it inaccessible for the bacterium.

Background: Spinal manipulation (SM) has been claimed to change anatomy, either in structure or position, and that these changes may be the cause of clinical improvements. The aim of this systematic review was to evaluate and synthesise the peer-reviewed literature on the current evidence of anatomical changes in response to SM. Methods: The review was registered with PROSPERO (CRD42022304971) and reporting was guided by the standards of the PRISMA Statement. We searched Medline, Embase, CINAHL, AMED, Cochrane Library all databases, PEDro, and the Index to Chiropractic Literature from inception to 11 March 2022 and updated on 06 June 2023. Search terms included manipulation, adjustment, chiropractic, osteopathy, spine and spine-related structures. We included primary research studies that compared outcomes with and without SM regardless of study design. Manipulation was defined as high-velocity, low-amplitude thrust delivered by hand to the spine or directly related joints. Included studies objectively measured a potential change in an anatomical structure or in position. We developed a novel list of methodological quality items in addition to a short, customized list of risk of bias (RoB) items. We used quality and RoB items together to determine whether an article was credible or not credible. We sought differences in outcomes between SM and control groups for randomised controlled trials and crossover studies, and between pre- and post-SM outcomes for other study designs. We reported, in narrative form, whether there was a change or not. Results: The search retrieved 19,572 articles and 20 of those were included for review. Study topics included vertebral position (n = 3) facet joint space (n = 5), spinal stiffness (n = 3), resting muscle thickness (n = 6), intervertebral disc pressure (n = 1), myofascial hysteresis (n = 1), and further damage to already damaged arteries (n = 1). Eight articles were considered credible. The credible articles indicated that lumbar

It is proved that real estate is an essential element affecting the functioning of regions, as its use forms the material basis of regional development. In recent years, there has been a decrease in the efficiency of real estate use at the regional level. In this context, we should note the negative impact of external and internal factors and the consequences of Russian aggression. Therefore, theoretical provisions regarding the definition of real estate need further improvement, considering international experience. In addition, the approach to applying the method and models for forming a quantitative basis for real estate use to develop relevant scientifically based recommendations needs reconsideration. The research has achieved the goal of developing scientifically based recommendations for increasing the efficiency of real estate use at the regional level. We have solved the following tasks in the article: substantiating theoretical provisions regarding the definition of regional real estate, forming directions for improving the efficiency of real estate use at the regional level, and proposing a mechanism for using real estate. Real estate is defined as a set of land plots and other objects located on it, forming spatial support from above and below, the use of which has a long-term nature and the movement of which leads to a violation of their functional characteristics. Spatial, functional, investment, and environmental factors influence the formation and use of real estate. Their interaction and definition allow building a multi-level system of assessment indicators to form a quantitative basis for making informed decisions. To increase the level of real estate use in the regions, we have further developed methodological approaches, as recommendations, to the assessment of real estate use based on methods and models that characterise the directions and features of the use of spatial, functional, investment, and environmental support, which provide the oppor

The article is devoted to the study of the processes of adaptive management of the development of health care facilities in the conditions of digitalization. The main technological trends in the context of digital transformation in the field of healthcare are analyzed, among which the following are highlighted: artificial intelligence (AI), Internet of Medical Things (IoMT), remote monitoring of patients, virtual and augmented reality, nanotechnology, 3D bioprinting and implants, clinical automation, geolocation technologies. It has been proven that in the conditions of modern organization and digitization of the health care system in Ukraine, electronic systems become an integral component that ensures effective management and provision of medical services. The key roles of the main subjects of the electronic health care system in Ukraine have been studied. The management structure of the electronic healthcare system in Ukraine is presented. The directions of adaptive management of the development of health care institutions in the conditions of digitalization are proposed.It is proven that in the modern conditions of digitalization, modern health care is undergoing a transformation, which creates unique challenges and opportunities for health care institutions.It is noted that adaptive management becomes a key success factor in this process, as it requires not only the introduction of the latest technologies, but also a flexible approach to changes in the environment. It is argued that the implementation of the adaptive management mechanism impliesan active role of management in ensuring a strategic vision and the ability of institutions to respond to changes in the digital landscape of health care, which means not only the introduction of technical innovations, but also changes in culture and organizational processes. According to the authors, one of the important aspects of adaptive management is increasing the digital literacy of the staff of health care instit

Background: Atopic dermatitis (AD) is a chronic recurrent skin disease that is very complex due to impaired skin barrier function in the form of xerosis, chronic eczematous lesions, and itching, commonly found in infants and children. Pathogenesis is thought to be the interaction of genetic factors, immune dysfunction, epidermal barrier dysfunction, and the role of the environment and infectious agents. Approach the disease by performing etiopathogenesis algorithms, clinical manifestations, diagnosis, and treatment. Based on the 2013 Asia-Pacific consensus, AD management guidelines using the 5-pillar principle have long been used. Currently, the European consensus in 2018 has developed new guidelines for AD management. Purpose: To provide an updated treatment for AD. Review: The ethiopathogenesis of AD is influenced by genetics, skin barrier disorders, and immune response disorders. Updated management of the European consensus in 2018 includes education, avoidance of precipitating factors, psychosomatic counseling, optimization of skin barrier function with moisturizers, anti-inflammatory and antimicrobial administration, allergen-specific immunotherapy, complementary and alternative drugs, phototherapy, and controlling the itch-scratch cycle with anti-itch in pediatric and adult AD patients. AD may affect patients’ quality of self-esteem. In general, patients expect higher. Conclusion: AD affects the psychosocial aspects of patients. Updated management of AD adequately improves the quality of life.

This article presents some considerations on the mind-body relationship in Cartesian philosophy that allow us to glimpse what Descartes understands by human nature. For this, I show how the teaching of nature and the passions show us that the affections produced in the soul by the material world are undeniable and fundamental, because the information they provide helps us to preserve ourselves as individuals. Finally, I consider that the passions are closely related to the will, in such a way that some of our actions and decisions depend on this interaction., En este artículo presento algunas consideraciones sobre la relación mente-cuerpo en la filosofía cartesiana que permiten vislumbrar lo que entiende Descartes por naturaleza humana. Para esto expongo cómo la enseñanza de la naturaleza y las pasiones nos muestran que las afecciones producidas en el alma por el mundo material son innegables y fundamentales, porque la información que nos aportan nos ayuda a preservarnos como individuos. Finalmente, considero que las pasiones por darse en el alma están en estrecha relación con la voluntad, en tal sentido, algunas de nuestras acciones y decisiones dependen de dicha interacción.

It is proved that real estate is an essential element affecting the functioning of regions, as its use forms the material basis of regional development. In recent years, there has been a decrease in the efficiency of real estate use at the regional level. In this context, we should note the negative impact of external and internal factors and the consequences of Russian aggression. Therefore, theoretical provisions regarding the definition of real estate need further improvement, considering international experience. In addition, the approach to applying the method and models for forming a quantitative basis for real estate use to develop relevant scientifically based recommendations needs reconsideration. The research has achieved the goal of developing scientifically based recommendations for increasing the efficiency of real estate use at the regional level. We have solved the following tasks in the article: substantiating theoretical provisions regarding the definition of regional real estate, forming directions for improving the efficiency of real estate use at the regional level, and proposing a mechanism for using real estate. Real estate is defined as a set of land plots and other objects located on it, forming spatial support from above and below, the use of which has a long-term nature and the movement of which leads to a violation of their functional characteristics. Spatial, functional, investment, and environmental factors influence the formation and use of real estate. Their interaction and definition allow building a multi-level system of assessment indicators to form a quantitative basis for making informed decisions. To increase the level of real estate use in the regions, we have further developed methodological approaches, as recommendations, to the assessment of real estate use based on methods and models that characterise the directions and features of the use of spatial, functional, investment, and environmental support, which provide the oppor

This dissertation introduces the importance of surfactant-based organic chemical reactions and summarizes key development milestones and reaction applications by global laboratories. However, the limitations of current analytical techniques prevent understanding of these multiphasic systems. Though experiments detailed in later chapters, fluorescence microscopy emerged as a technique to examine surfactant-based reactions. A powerful feature of fluorescence microscopy is its ability to obtain subensemble information about chemical reactions and processes that are unobtainable through other analytical techniques. For example, fluorescence microscopy methods, developed by the Blum Laboratory, provide advantages over other methods due to their ability to spatiotemporally resolve effects under synthetic reaction conditions. Herein, a summary of influential studies is included, highlighting the capability of fluorescence microscopy to answer mechanistic questions in complex, multiphasic systems under many different conditions.

This thesis highlights the versatility of nickel as a transition metal that enables the activation of relatively inert chemical bonds and offers lower energy pathways to challenging bond formations. In this work, reaction development and mechanistic inquiry inform one another, enhancing our understanding of nickel catalysis.Despite major advancements in C-heteroatom cross-coupling enabled by Ni-photoredox catalysis, the mechanisms of this form of catalysis are not well understood and are highly debated. Although mild Ni-photoredox C-N cross-coupling had been reported for strong N-nucleophiles like alkylamines, such a reaction involving weak N-nucleophiles such as amides had not been reported. This work describes the development of an unprecedented Ni-photoredox-catalyzed amide arylation reaction that proceeds under mild conditions. These mild conditions enable access to a broad scope including base-sensitive functional groups and excellent preservation of epimerizable stereocenters. We hypothesized that this amide arylation reaction might proceed via an alternative mechanism to the self-sustaining Ni(I/III) cycle that is usually reported for Ni-photoredox C-N coupling. This is because our reaction utilizes a redox-inactive base and weak N-nucleophiles, whereas the prior published methods in this arena couple strong N-nucleophiles and require redox-active bases as electron shuttles. A combined approach involving stoichiometric experiments with synthesized Ni complexes and the measurement of kinetic profiles of the catalytic reaction led us to propose an unusual Ni(0/II/III) cycle, which has a profound consequence for the rate-limiting step and the overall reaction kinetics. Kinetic studies probing the effect of nickel precatalysts of various vii oxidation states revealed a marked induction period with Ni(II) precatalysts, providing insight into the photochemical process that generates the active Ni(0) species. This thesis will also discuss the optimization and mechan

Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2,2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2,2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.

Background: Spinal manipulation (SM) has been claimed to change anatomy, either in structure or position, and that these changes may be the cause of clinical improvements. The aim of this systematic review was to evaluate and synthesise the peer-reviewed literature on the current evidence of anatomical changes in response to SM. Methods: The review was registered with PROSPERO (CRD42022304971) and reporting was guided by the standards of the PRISMA Statement. We searched Medline, Embase, CINAHL, AMED, Cochrane Library all databases, PEDro, and the Index to Chiropractic Literature from inception to 11 March 2022 and updated on 06 June 2023. Search terms included manipulation, adjustment, chiropractic, osteopathy, spine and spine-related structures. We included primary research studies that compared outcomes with and without SM regardless of study design. Manipulation was defined as high-velocity, low-amplitude thrust delivered by hand to the spine or directly related joints. Included studies objectively measured a potential change in an anatomical structure or in position. We developed a novel list of methodological quality items in addition to a short, customized list of risk of bias (RoB) items. We used quality and RoB items together to determine whether an article was credible or not credible. We sought differences in outcomes between SM and control groups for randomised controlled trials and crossover studies, and between pre- and post-SM outcomes for other study designs. We reported, in narrative form, whether there was a change or not. Results: The search retrieved 19,572 articles and 20 of those were included for review. Study topics included vertebral position (n = 3) facet joint space (n = 5), spinal stiffness (n = 3), resting muscle thickness (n = 6), intervertebral disc pressure (n = 1), myofascial hysteresis (n = 1), and further damage to already damaged arteries (n = 1). Eight articles were considered credible. The credible articles indicated that lumbar

Metal nanoparticles (NPs) encapsulated within Zr-based UiO-67 metal-organic frameworks (MOFs) have increased selectivity toward methanol in CO2 reduction reactions. However, the reduction mechanism in these systems remains unclear. We built upon prior work examining the synergistic interaction between Pt nanoparticles and Zr6O4(OH)4 clusters in UiO-67 and developed five distinct models representing the possible active sites in the Pt ⊂ MOF system. Density functional theory (DFT) calculations were employed to elucidate the CO2 reduction mechanism toward methanol, methane, and CO formation. Our findings support previous evidence showing that the interface between the Zr6O4(OH)4 cluster and platinum nanoparticles plays a crucial role in the activation of CO2 to CO or formate intermediates and its further reduction to methane and methanol, respectively. Furthermore, we found different CO2 hydrogenation mechanisms for interfaces involving Pt-flat terraces and Pt-edges. On Pt terraces and interfaces near Pt terraces, the reaction goes via CO, which can be desorbed as CO(g) or be further reduced to methane. On interfaces near Pt-edges, the reaction proceeds via formate and preferably forms methanol over methane. We designed experiments to validate our computational insights involving large and small Pt nanoparticles interacting with Zr6O4(OH)4 clusters. These experiments showed that only CO and methanol were formed when smaller nanoparticles were present. Notably, methane formed with CO and methanol in the presence of larger nanoparticles, highlighting the need for flat platinum surfaces at the interfaces for methane formation. We could also associate the IR signals corresponding to CO and bidentate formate with platinum nanoparticles and Zr6O4(OH)4 clusters, respectively. Theoretical models and e

In this work, I developed and tested designs for increasing energy efficiency in threeareas: soft robotics, buildings, and jumping.In the area of soft robotics, researchers are interested in using low-boiling point fluids topower pneumatic soft robots, because they can produce large volumes of pressurized gas without the need for bulky pumps and tubing. While this approach is effective at doing work via pressurized vapor, it is highly inefficient. One way to reduce energy consumption from onboard sources (e.g., batteries) is to harvest it, and another way is to improve the energy conversion process directly. In my work, I developed soft robots that can detect heat and light sources and use ambient thermal energy to locomote up to 10 m. I also developed strategies to improve efficiency by nearly two orders of magnitude.In the area of buildings, efficient thermal regulation is a major challenge; currently, halfof US building energy usage goes towards heating and cooling. One way to increase efficiency in heating and cooling is to take advantage of the Sun and deep space, respectively, via radiative heat transfer. For my work, I designed and tested a mechanical radiative switch in the form of a roofing tile. It helps save energy by passively switching between radiative heating and cooling states. Unlike previous passive designs, my design switches over a small range of temperatures (15 °C). Tests show potential energy savings of at least 2.5× for heating and cooling compared to similar non-switching devices.In the area of jumping, engineers have built jumpers that can achieve jump heights >30m; while impressive, an estimated 50% of the energy is lost before takeoff. To reduce the energy loss, I developed and analyzed new jumper designs. Preliminary experimental results show that these new designs can improve jump height. My findings can help make future jumping robots more efficient at converting spring potential energy into vertical center of mass kinetic energy, s

Ecological and evolutionary theories have proposed that species traits should be important in mediating species responses to contemporary climate change; yet, empirical evidence has so far provided mixed evidence for the role of behavioral, life history, or ecological characteristics in facilitating or hindering species range shifts. As such, the utility of trait-based approaches to predict species redistribution under climate change has been called into question. We develop the perspective, supported by evidence, that trait variation, if used carefully can have high potential utility, but that past analyses have in many cases failed to identify an explanatory value for traits by not fully embracing the complexity of species range shifts. First, we discuss the relevant theory linking species traits to range shift processes at the leading (expansion) and trailing (contraction) edges of species distributions and highlight the need to clarify the mechanistic basis of trait-based approaches. Second, we provide a brief overview of range shift-trait studies and identify new opportunities for trait integration that consider range-specific processes and intraspecific variability. Third, we explore the circumstances under which environmental and biotic context dependencies are likely to affect our ability to identify the contribution of species traits to range shift processes. Finally, we propose that revealing the role of traits in shaping species redistribution may likely require accounting for methodological variation arising from the range shift estimation process as well as addressing existing functional, geographical, and phylogenetic biases. We provide a series of considerations for more effectively integrating traits as well as extrinsic and methodological factors into species redistribution research. Together, these analytical approaches promise stronger mechanistic and predictive understanding that can help society mitigate and adapt to the effects of climate chang

In concurrent work, we introduced a novel robotic package delivery system latching intelligent modular mobility system (LIMMS). Each LIMMS end effector requires a small, lightweight latching mechanism for pre-manufactured containers, such as cardboard boxes. In order to effectively process a high volume of packages, aligning the latching mechanism quickly and reliably is critical. Instead of depending on highly accurate controllers for alignment, we propose a novel self-aligning rotational mechanism to increase the system’s tolerance to misalignment. The radial latching design consists of evenly spaced blades that rotate into slots cut into the box. When misaligned, the blades contact the edges of the engagement slots, generating a self-correcting force that passively centers the blades with the slot pattern. This paper introduces a mathematical framework with closed form expressions to quantify error tolerance for these mechanisms. Through our mathematical and optimization analyses, it is shown that a two-blade design can tolerate a maximum misalignment of three times the radius to the blade tips, much larger than commonly used designs with three or more blade-like contacts. Our approach can be generalized for a class of rotational latching mechanisms with any number of blades. Utilizing this theory, a design process is laid out for developing an optimal self-aligning rotational latching mechanism given desired parameters and task constraints. With this methodology, we designed, manufactured, and verified the effectiveness of both two-blade and three-blade self-aligning in practical experiments.

My dissertation defends a non-mechanistic interpretation of Kant’s philosophy of nature. Inspired by the picture of nature in the Critique of Pure Reason and Metaphysical Foundations of Natural Science, most readers align Kant with Early Modern mechanists, who claim that we can know that the internally purposive form of causality characteristic of organisms has no place in nature. To these mechanistic readers, Kant banishes internal purposiveness from nature. To moderate mechanistic interpreters, because we cannot know whether there are internally purposive things in nature and we can demonstrate that mechanism applies to nature, Kant pushes us to believe that any seemingly internally purposive natural products will eventually be explained in mechanistic terms. To strong mechanistic interpreters, Kant gives us the tools to know that there is no room for the special kind of teleology organisms exhibit in nature. My non-mechanistic interpretation rejects this trend by arguing that Kant urges us to believe that the internally purposive activity characteristic of organisms exists in nature. Belief in this context is a firm, positive, and voluntary attitude that aligns with and serves a subject’s interests and ends, and that has implications for the subject’s rational action, assertion, and deliberation. Kant’s stated goal in the third Critique is to bridge the gulf between freedom and nature. My non-mechanistic interpretation offers a new account of how Kant promises to construct this bridge.

The tensile creep behavior of a vacuum arc-melted Nb45Ta25Ti15Hf15 refractory high entropy alloy was investigated over a constant true stress range of 50–300 MPa at a temperature of 1173 K. Creep tests were carried out in both high vacuum (5 × 10−6 torr) and ultrahigh purity Ar gas to examine the environmental effect. The samples tested in vacuum exhibited power law behavior with a stress exponent of 4.1 and exceptional tensile creep ductility, whereas those tested in Ar suffered significant embrittlement due to HfO2 formation at grain boundaries, which was exacerbated at low applied stresses where extended exposure to residual O2 gas resulted in more extensive brittle intergranular fracture. Phase decomposition occurred after long-term thermal exposure, where a second Hf-rich body-centered cubic phase formed predominantly at grain boundaries but did not cause embrittlement. Compared to the equiatomic TaNbHfZrTi (Senkov alloy) and face-centered cubic multiple-principal element alloys, Nb45Ta25Ti15Hf15 has superior creep resistance, especially at high applied stresses, while maintaining excellent creep ductility. Transmission electron microscopy revealed that creep deformation in Nb45Ta25Ti15Hf15 at 1173 K is controlled by cross-kink collisions from screw dislocations that results in dipole drag at lower strain rates and jog drag at higher strain rates.

The vertical jacking method has been widely used in water intake and drainage segmental tunnels. The construction method of standpipes by lifting could mainly be divided into upward shield method, vertical jacking method and vertical pipe jacking method. Comparing with the other two methods, the vertical jacking method has the advantage that its equipment is simpler. However, the vertical jacking force intensity is uncertain because it depends on many factors. The higher the pipe diameter, the higher the normal stresses, being the critical moment the starting of the jacking process. Based on numerical simulations, this paper intends to research on the structural behaviour of this method on large section standpipes and analyze the factors that controls the jacking process. The research results show: 1. The deformation of the main tunnel is a combination of two effects: the longitudinal sinking and the vertical ovalization. 2. The circumferential compressive stresses in the bottom segments of the main tunnel are greatly reduced due to the vertical force of the jack. 3. The shear of the transverse joint between two rings mainly appear in the joint between the opening ring and the contiguous one. 4. The thickness of the segment has little effect on the mechanical response of the structure for typical segment depth. 5. With the decrease of the opening area, the internal force of the open ring structure decreases, while the internal force of the contiguous rings decreases or remains basically unchanged., Postprint (published version)

Retinal pigment epithelial cell and neuroretinal damage in age-related macular degeneration (AMD) can lead to serious visual impairments and blindness. Studies have shown that mitophagy, a highly specialized cellular degradation system, is implicated in the pathogenesis of AMD. Mitophagy selectively eliminates impaired or non-functioning mitochondria via several pathways, such as the phosphatase and tensin homolog-induced kinase 1/Parkin, BCL2-interacting protein 3 and NIP3-like protein X, FUN14 domain-containing 1, and AMP-activated protein kinase pathways. This has a major impact on the maintenance of mitochondrial homeostasis. Therefore, the regulation of mitophagy could be a promising therapeutic strategy for AMD. Traditional Chinese medicine (TCM) uses natural products that could potentially prevent and treat various diseases, such as AMD. This review aims to summarize recent findings on mitophagy regulation pathways and the latest progress in AMD treatment targeting mitophagy, emphasizing methods involving TCM. Copyright © 2024 Yu, Wang, Liu and Meng.

Over the years, algae have proved to be a water pollutant due to global warming, climate change, and the unregulated addition of organic compounds in water bodies from diffused resources. Harmful algal blooms (HABs) are severely affecting the health of humans and aquatic ecosystems. Among available anti -blooming technologies, semiconductor photocatalysis has come forth as an effective alternative. In the recent past, literature has been modified extensively with a decisive knowledge regarding algal invasion, desired preparation of nanomaterials with enhanced visible light absorption capacity and mechanisms for algal cell denaturation. The motivation behind this review article was to gather algal inactivation data in a systematic way based on various research studies, including the construction of nanoparticles and purposely to test their anti -algal activities under visible irradiation. Additionally, this article mentions variety of starting materials employed for preparation of various nano -powders with focus on their synthesis routes, analytical techniques as well as proposed mechanisms for lost cellular integrity in context of reduced chlorophyll' a' level, cell rapture, cell leakage and damages to other physiological constituents; credited to oxidative damage initiated by reactive oxidation species (ROS). Various floating and recyclable composited catalysts Ag2CO3-N: GO, Ag/AgCl@ZIF-8, Ag2CrO4-g-C3N4-TiO2/ mEP proved to be game -changers owing to their enhanced VL absorption, adsorption, stability, separation and reusability. An outlook for the generalized limitations of published reports, cost estimations for practical implementation, issues and challenges faced by nano-photocatalysts and possible opportunities for future studies are also proposed. This review will be able to provide vast insights for coherent fabrication of catalysts, breakthroughs in experimental methodologies and help in elaboration of damage mechanisms.

In recent years, there has been increasing interest in utilizing time-lagged panel models to study mechanisms of change in psychotherapy. These models offer valuable insights into the dynamic relationships between variables over time and offer stronger causal inference capabilities than cross-sectional analyses. Therefore, they are wellsuited for modeling the intricate relationships between mechanisms of change and outcomes in psychotherapy studies, which are typically beyond experimental control. However, their complexity, coupled with the fact that detailed explanations are often embedded in dense statistical or econometric texts, poses challenges. This paper provides a background on cross-lagged panel models and delves deeper into explaining the issues of 1) dynamic panel bias, 2) long-run effects, and 3) testing whether different treatments work by different mechanisms. Using data from a psychotherapy study on treatment of adolescent depression, I demonstrate how these issues manifest in real data. In conclusion, I recommend using structural equation modeling to circumvent dynamic panel bias, reporting long-run effects to reveal the long-term impact of sustained therapeutic work on mechanisms of change, and carefully considering whether mediation, moderation, or a combination of both, best describes differential effects of mechanisms between treatments.

Background: Spinal manipulation (SM) has been claimed to change anatomy, either in structure or position, and that these changes may be the cause of clinical improvements. The aim of this systematic review was to evaluate and synthesise the peer-reviewed literature on the current evidence of anatomical changes in response to SM. Methods: The review was registered with PROSPERO (CRD42022304971) and reporting was guided by the standards of the PRISMA Statement. We searched Medline, Embase, CINAHL, AMED, Cochrane Library all databases, PEDro, and the Index to Chiropractic Literature from inception to 11 March 2022 and updated on 06 June 2023. Search terms included manipulation, adjustment, chiropractic, osteopathy, spine and spine-related structures. We included primary research studies that compared outcomes with and without SM regardless of study design. Manipulation was defined as high-velocity, low-amplitude thrust delivered by hand to the spine or directly related joints. Included studies objectively measured a potential change in an anatomical structure or in position. We developed a novel list of methodological quality items in addition to a short, customized list of risk of bias (RoB) items. We used quality and RoB items together to determine whether an article was credible or not credible. We sought differences in outcomes between SM and control groups for randomised controlled trials and crossover studies, and between pre- and post-SM outcomes for other study designs. We reported, in narrative form, whether there was a change or not. Results: The search retrieved 19,572 articles and 20 of those were included for review. Study topics included vertebral position (n = 3) facet joint space (n = 5), spinal stiffness (n = 3), resting muscle thickness (n = 6), intervertebral disc pressure (n = 1), myofascial hysteresis (n = 1), and further damage to already damaged arteries (n = 1). Eight articles were considered credible. The credible articles indicated that lumbar

Spray -dried niobium oxide coated with chitosan-activated carbon (NIC) was synthesized and used to remove doxorubicin hydrochloride and crystal violet from aqueous solutions under different parameters such as solution pH (2, 4, 6, and 8), contact time (1 to 9 h), initial concentration (20 to 200 mg L -1 ), and competing ions (0.1 M of CaCl 2 and NaCl). The addition of 5 % chitosan-activated carbon to the matrix of niobium oxide slightly increased the specific surface area from 26 to 30 m 2 g -1 , with the introduction of a carboxylic functional group. This led to an increase in the amount of adsorbed doxorubicin hydrochloride (DOH) from 30 to 44 mg g -1 and that of crystal violet (CV) from 15 to 32 mg g -1 from the initial respective 100 mg L -1 at pH 8. The data from the concentration study fitted into Liu isotherm having adsorption capacity of 128 and 57 mg g -1 for DOH and CV respectively, while pseudo first and second order are more suitable for adsorption kinetics. The additional functional groups on the IR spectrum of NIC after the adsorption of DOH and CV confirmed the interaction between NIC and the adsorbates' molecules. The mechanism of adsorption was supported by DFT calculations., QC 20240604

Design science often focuses on the problem and solution spaces in artifact creation, yet the alignment between these spaces is seldom explored thoroughly. This paper introduces the concept of “accommodation” to analyse the fit between a problem and its solution. Accommodation highlights the significant semantic and practical implications inherent in the relationship between problem and solution spaces beyond mere knowledge of the two. We define accommodation and demonstrate its utility in evaluating both structural and causal links between solutions and problems. This approach is exemplified through a case study in the healthcare sector.

Background: Spinal manipulation (SM) has been claimed to change anatomy, either in structure or position, and that these changes may be the cause of clinical improvements. The aim of this systematic review was to evaluate and synthesise the peer-reviewed literature on the current evidence of anatomical changes in response to SM. Methods: The review was registered with PROSPERO (CRD42022304971) and reporting was guided by the standards of the PRISMA Statement. We searched Medline, Embase, CINAHL, AMED, Cochrane Library all databases, PEDro, and the Index to Chiropractic Literature from inception to 11 March 2022 and updated on 06 June 2023. Search terms included manipulation, adjustment, chiropractic, osteopathy, spine and spine-related structures. We included primary research studies that compared outcomes with and without SM regardless of study design. Manipulation was defined as high-velocity, low-amplitude thrust delivered by hand to the spine or directly related joints. Included studies objectively measured a potential change in an anatomical structure or in position. We developed a novel list of methodological quality items in addition to a short, customized list of risk of bias (RoB) items. We used quality and RoB items together to determine whether an article was credible or not credible. We sought differences in outcomes between SM and control groups for randomised controlled trials and crossover studies, and between pre- and post-SM outcomes for other study designs. We reported, in narrative form, whether there was a change or not. Results: The search retrieved 19,572 articles and 20 of those were included for review. Study topics included vertebral position (n = 3) facet joint space (n = 5), spinal stiffness (n = 3), resting muscle thickness (n = 6), intervertebral disc pressure (n = 1), myofascial hysteresis (n = 1), and further damage to already damaged arteries (n = 1). Eight articles were considered credible. The credible articles indicated that lumbar

Inspired by the successful transfer of freestanding ultrathin films of SrTiO3 and BiFeO3 onto various substrates without any thickness limitation, in this study, using density functional theory (DFT), we assessed the structural stability of a group of two-dimensional perovskite-type materials which we call perovskenes. Specifically, we analyzed the stability of 2D SrTiO3, SrZrO3, BaTiO3, and BaZrO3 monolayers. Our simulations revealed that the 2D monolayers of SrTiO3, BaTiO3, and BaZrO3 are at least meta-stable, as confirmed by cohesive energy calculations, evaluation of elastic constants, and simulation of phonon dispersion modes. With this information, we proceeded to investigate the electronic, optical, and thermoelectric properties of these perovskenes. To gain insight into their promising applications, we investigated the electronic and optical properties of these 2D materials and found that they are wide bandgap semiconductors with significant absorption and reflection in the ultraviolet (UV) region of the electromagnetic field, suggesting them as promising materials for use in UV shielding applications. In addition, evaluating their thermoelectric factors revealed that these materials become better conductors of electricity and heat as the temperature rises. They can, hence, convert temperature gradients into electrical energy and transport electrical charges, which is beneficial for efficient power generation in thermoelectric devices. This work opens a new window for designing a novel family of 2D perovskite type materials termed perovskenes. The vast variety of different perovskite compounds and their variety of applications suggest deeper studies on the perovskenes materials for use in innovative technologies. Perovskenes: a novel family of high-stability two-dimensional perovskite-type monolayer materials with predicted electronic, optical, and thermoelectric properties predicted via first-principles calculations., National Research Council of Canada, Artificial Intelligence for Design program; Natural Sciences and Engineering Research Council of Canada, Discovery Grant [RGPIN-2019-03976]; Compute Canada (now the Digital Research Alliance of Canada); TUBITAK ULAKBIM, High Performance and Grid Computing Center, This work is supported by the National Research Council of Canada, Artificial Intelligence for Design program, by the Natural Sciences and Engineering Research Council of Canada, Discovery Grant (RGPIN-2019-03976) and by Compute Canada (now the Digital Research Alliance of Canada). The work is also supported by TUBITAK ULAKBIM, High Performance and Grid Computing Center (TR-Grid e-Infrastructure).

As avid users, university students find themselves immersed in the deluge of content being created and shared on digital platforms, which makes digital overload a significant concern. The present study examines the effects of digital overload on university students’ psychological well-being and how the use of coping mechanisms might help to mitigate some of these effects. The study developed a research model based on the S-O-R (stimulus, organism, response) framework and gathered data from undergraduate students at a major public university in the United Arab Emirates. To minimize the threat of common method bias, data collection was conducted in two rounds separated by two weeks. Hypotheses were tested using a partial least square path modeling approach. The findings show that digital overload causes psychological strains among students such as technostress and exhaustion, which subsequently encourage them to adopt coping mechanisms. The findings also show that the adoption of coping mechanisms is positively associated with student engagement. The study contributes to the literature by shifting the focus away from information overload—emphasizing digital overload instead—and investigating how students can respond to it by using coping mechanisms.

Inspired by the successful transfer of freestanding ultrathin films of SrTiO3 and BiFeO3 onto various substrates without any thickness limitation, in this study, using density functional theory (DFT), we assessed the structural stability of a group of two-dimensional perovskite-type materials which we call perovskenes. Specifically, we analyzed the stability of 2D SrTiO3, SrZrO3, BaTiO3, and BaZrO3 monolayers. Our simulations revealed that the 2D monolayers of SrTiO3, BaTiO3, and BaZrO3 are at least meta-stable, as confirmed by cohesive energy calculations, evaluation of elastic constants, and simulation of phonon dispersion modes. With this information, we proceeded to investigate the electronic, optical, and thermoelectric properties of these perovskenes. To gain insight into their promising applications, we investigated the electronic and optical properties of these 2D materials and found that they are wide bandgap semiconductors with significant absorption and reflection in the ultraviolet (UV) region of the electromagnetic field, suggesting them as promising materials for use in UV shielding applications. In addition, evaluating their thermoelectric factors revealed that these materials become better conductors of electricity and heat as the temperature rises. They can, hence, convert temperature gradients into electrical energy and transport electrical charges, which is beneficial for efficient power generation in thermoelectric devices. This work opens a new window for designing a novel family of 2D perovskite type materials termed perovskenes. The vast variety of different perovskite compounds and their variety of applications suggest deeper studies on the perovskenes materials for use in innovative technologies. Perovskenes: a novel family of high-stability two-dimensional perovskite-type monolayer materials with predicted electronic, optical, and thermoelectric properties predicted via first-principles calculations., National Research Council of Canada, Artificial Intelligence for Design program; Natural Sciences and Engineering Research Council of Canada, Discovery Grant [RGPIN-2019-03976]; Compute Canada (now the Digital Research Alliance of Canada); TUBITAK ULAKBIM, High Performance and Grid Computing Center, This work is supported by the National Research Council of Canada, Artificial Intelligence for Design program, by the Natural Sciences and Engineering Research Council of Canada, Discovery Grant (RGPIN-2019-03976) and by Compute Canada (now the Digital Research Alliance of Canada). The work is also supported by TUBITAK ULAKBIM, High Performance and Grid Computing Center (TR-Grid e-Infrastructure).

The mechanism of n-hexadecane (n-C16) hydroisomerization/hydrocracking was studied over bifunctional catalysts employing Pd and Pt as (de)hydrogenation components and large-pore zeolites and (ordered) mesoporous materials as acidic supports. Zeolite Y and Beta supports were compared to amorphous silica-alumina as well as aluminium-containing ordered mesoporous MCM-41, MCM-48 and SBA-15 materials to cover a wide range of pore sizes and topologies. Products were analyzed in terms of mono- and di-branched C16 isomers and cracked products as a function of the n-C16 conversion. All samples followed a similar mechanism in which, at low conversion, di-branched isomers with methyl groups toward the ends of the tetradecane chain were observed. At higher conversion, the products shifted to isomers with methyl groups closer to the center at higher n-C16 conversion. Consistent with these differences, the typical ‘M’ shape distribution of cracked products was obtained at low conversion, which evolved into ideal symmetric cracking patterns at higher conversion. The unusual di-branched isomer distribution at low conversion and the corresponding ‘M’ shaped cracked products distribution have earlier been associated with pore mouth catalysis induced by restricted diffusion in medium-pore zeolites. Here we show that such reaction pathways also occur in catalysts with large enough pores to exclude diffusion restrictions.

Fast disruptions of the normal heart rhythm in the main chambers of the heart (so-called ventricular tachyarrhythmias) are responsible for one out of five deaths worldwide. To better diagnose and treat these life-threatening heart-rhythm disorders, it is crucial to have an optimal understanding of the electrical characteristics of the heart, both in health and disease. In this doctorate thesis, advanced electrical and structural imaging techniques are combined to better explain normal rhythms and tachyarrhythmias of the human heart. As a main finding, the integration of combined imaging yields a more in-depth understanding than the sum of separate elements. Furthermore, the use and standardization of a new technique called “ECG-imaging” proves very valuable in explaining the electrical origins of arrhythmias. It reveals that under normal conditions, the heart’s electrical characteristics are highly personal: each heart has its own electrical “fingerprint”. This emphasizes the need for personalized approaches in the management of arrhythmias. The collective results described in this thesis improve our understanding of life-threatening arrhythmias, offer promising directions for diagnostics and treatment, and underscore the importance of a personalized approach.

Ciprofloxacin, a threat to the ecosystem, can be effectively eliminated through heterogeneous activation of peroxymonosulfate (PMS) by metallic oxide catalyst-based advanced oxidation processes (AOPs). Manganese oxide (MnOx) is one of the most promising metallic oxide catalysts and deserves in-depth research. Herein, a MnOx catalyst loaded on activated carbon (MnOx/AC) was synthesized for the PMS activation in ciprofloxacin degradation. Due to the anchoring effect of AC on MnOx, the MnOx/AC catalyst demonstrated excellent performance and good reusability in ciprofloxacin degradation. Characterizations indicated that redox circles among valence states of Mn(II, III, and IV) species on the catalyst surface triggers the generation of reactive oxygen species (ROS), including O-1(2), HO center dot and SO4-center dot. Notably, predominant species was O-1(2) (63.75%), which ascribed to the increment of Mn(II) and the consumption of lattice oxygen. Moreover, the PMS adsorption on the MnOx/AC catalyst was a crucial step in ciprofloxacin degradation, and the acidic condition was favored. Furthermore, seven intermediates were detected by liquid chromatograph mass spectrometer during the ciprofloxacin degradation, thus establishing the degradation pathway of the ciprofloxacin. This study provided insights into activation mechanism and degradation pathway for the ciprofloxacin degradation by MnOx in water treatment using PMS-AOPs reaction system.

Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2,2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2,2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.

In this article, we discuss the methodological implications of data and theory integration for Theory-Based Evaluation (TBE). TBE is a family of approaches to program evaluation that use program theories as instruments to answer questions about whether, how, and why a program works. Some of the groundwork about TBE has expressed the idea that a proper program theory should specify the intervening mechanisms underlying the program outcome. In the present article, we discuss in what way data and theory integration can help evaluators in constructing and refining mechanistic program theories. The paper argues that a mechanism is both a network of entities and activities and a network of counterfactual relations. Furthermore, we argue that although data integration typically provides information about different parts of a program, it is the integration of theory that provides the most important mechanistic insights.

Hemiacetals of cyclopropanone can be isolated and stocked, contrary to their highly reactive parent ketone. However, they are not readily converted to cyclopropanone, which limits their use as its synthetic equivalents. 2,2,2-trifluoroethoxy hemiacetals are expected to be better cyclopropanone surrogates, however, they have never been prepared, so far. We show that oxyallyl cations with a heteroatom in the -position can be intercepted with 2,2,2-trifluoroethanol, with formation of cyclopropanone trifluoroethoxy hemiacetals stable enough to be isolated, purified and characterized. These species can serve as synthetic equivalents of cyclopropanone under mild conditions.

In some parts of the Philippines, water supplies are usually short, so supplies are routinely turned down to conserve capacity. During six to eight months of the year, the weather is mostly dry, resulting in severe water shortages and people relying on potentially unsafe drinking water sources. They may also lack enough water to wash their hands to maintain basic hygiene and avoid infection. The Moringa Oleifera Seed as an Alternative Water Purifier was created as a solution to the problem of a community in water purification, and it aims to evaluate the antimicrobial activity and efficiency of a natural absorbent from Moringa Oleifera seeds in treating contaminated water.    The study results in terms of construction materials and procedures are acceptable. In contrast, the study results in terms of mechanism and presentation are moderately acceptable as assessed by the Chemical Engineers and Civil Engineers. It indicates no significant difference between the assessments of the two groups of respondents in terms of the variables above. The overall mean of the Chemical Engineers was 2.52 with a variance of 0.70. The overall weighted mean of the Civil Engineers was 2.66 with a variance of 0.62. The two groups of respondents acquired a t-computed value of 0.24, a t-critical of 2.35, =0.05, and a df =3. Therefore, the assessment of the Chemical Engineers and Civil Engineers was accepted. The ensuing discussions forwarded by the two groups of respondents are as follows: check if moringa seed will be found or produced in all seasons, try to make chambers for the water treatment process, then conduct bacterial testing and acidity testing, compare the sample with muriatic acid and chlorine-treated water, use a conventional jar test apparatus to coagulate sample of water using Moringa oleifera seeds, analyze using different parameters like pH, turbidity, TDS, TS, and Chemical Oxygen Demand (COD) and determine the colour removal percentage of wastewater using UV/Vi

The electrochemical reduction of CO2 (eCO2R) is a promising approach for converting CO2 into valuable chemicals and fuels using renewable energy sources. We investigated the mechanism of eCO2R for a small Cu8 cluster placed on SnO2 containing O vacancies using density functional theory and predicted current density and selectivity by microkinetics simulations within the computational hydrogen electrode model. Low and high H coverages were modeled by Cu8/SnO2-x and Cu8H6/SnO2-x models, using statistical methods to identify their most stable structures. Different CO2 adsorption modes on Cu8/SnO2-x and Cu8H6/SnO2-x surface models, all containing an O vacancy, resulted in distinct reaction pathways, leading to either HCOOH or CO. The preferred formation of HCOOH occurred upon CO2 adsorption on an O vacancy on the Cu8H6/SnO2-x surface, followed by sequential hydrogenation to HCOO and HCOOH. Adsorption of CO2 on Cu8/SnO2-x opened a facile pathway to CO. Electronic structure analysis revealed that differences in charge donation of Cu to the antibonding orbitals of CO2 can explain the predicted selectivity differences. The preferred adsorption mode of CO2 is bidentate at the Cu-SnO2-x interface. Our findings emphasize the role of H coverage on Cu on the selectivity of eCO2R for Cu/SnOx catalysts.

The pressure-induced (400 MPa for 15 min) gelation of blended skim milk (SMP) and pea protein concentrate (PPC) suspensions (15% w/w) at different ratios (SMP:PPC = 10:0, 8:2, 6:4, 5:5, 4:6, 2:8, 0:10) were studied. Blending milk and pea proteins reduced the gel strength markedly, indicating that milk and pea proteins do not interact with each other to the same extent. The secondary structure of the proteins was not significantly changed after HP treatment. The PPC dominating gels (0:10 and 2:8) had a large increase in surface hydrophobicity indicating higher exposure of hydrophobic clusters. Based on a differential solubility method it was established that the SMP dominating gels are govern mostly by electrostatic and hydrophobic interactions, while disulphide bonds, hydrogen bonds and electrostatic interactions contributed most to the PPC dominating gel networks. The weak 5:5 gel was established solely by hydrophobic interaction between milk and plant proteins. It is suggested that in the milk protein dominant gel (8:2), the milk proteins formed the primary gel structure likely filled with the pea protein secondary gel network and/or aggregates, whereas the inverse occurred in the pea protein dominant gel (2:8). Replacing milk proteins with pea proteins offers a great potential for produce innovative dairy products using high pressure processing, like for example dairy desserts with a neutral pH and textural properties similar to yogurt.

The biotechnological conversion of lignocellulosic biomass is an interesting option within the development and refinement of biorefinery processes. While the use of enzymes for cellulose conversion is essentially matured, enzymatic (downstream) valorisation of lignins using enzymatic processes continues to pose challenges. When thinking of lignocellulosic enzymes for such processes, the mentioned challenges derive from a lack of control of polymerisation/re-polymerisation, loss of enzymatic activity due to adverse environments generated by the compromise between enzyme needs and lignin solubility, enzyme inhibition, etc. Some of these challenges can eventually be circumvented rethinking the set-up for doing enzymatic lignin transformations. One aspect of such a rethinking could involve the use of more dynamic reaction settings, avoiding long contact times between enzyme and the products they have formed. This can be eventually facilitated going for flow chemistry principles, applied to the enzymatic lignin transformation. We present here results obtained for the use of some commercially available laccases (EC 1.10.3.2), treated in various modes to be used in a flow chemical setting for downstream lignin valorisations, including degradation and functionalisation. The presentation will highlight the challenges encountered and connected with enzyme manipulation and the incorporation of immobilised enzymes in experimental flow reactors. Scope and limitations of this approach are presented using targeted example transformation, and obtained results will also be discussed in light of process- and set-up-dependent kinetic aspects.

The pressure-induced (400 MPa for 15 min) gelation of blended skim milk (SMP) and pea protein concentrate (PPC) suspensions (15% w/w) at different ratios (SMP:PPC = 10:0, 8:2, 6:4, 5:5, 4:6, 2:8, 0:10) were studied. Blending milk and pea proteins reduced the gel strength markedly, indicating that milk and pea proteins do not interact with each other to the same extent. The secondary structure of the proteins was not significantly changed after HP treatment. The PPC dominating gels (0:10 and 2:8) had a large increase in surface hydrophobicity indicating higher exposure of hydrophobic clusters. Based on a differential solubility method it was established that the SMP dominating gels are govern mostly by electrostatic and hydrophobic interactions, while disulphide bonds, hydrogen bonds and electrostatic interactions contributed most to the PPC dominating gel networks. The weak 5:5 gel was established solely by hydrophobic interaction between milk and plant proteins. It is suggested that in the milk protein dominant gel (8:2), the milk proteins formed the primary gel structure likely filled with the pea protein secondary gel network and/or aggregates, whereas the inverse occurred in the pea protein dominant gel (2:8). Replacing milk proteins with pea proteins offers a great potential for produce innovative dairy products using high pressure processing, like for example dairy desserts with a neutral pH and textural properties similar to yogurt.

Chemical reaction engineering is closely related to data science. Masses amount of data has accumulated which people use for the design of reactions, catalysts, and reactors. The development of machine learning algorithms has attracted chemical reaction engineers as a powerful tool to tackle existing and new challenges. The ability of machine learning models to approximate highly complex functions makes them particularly suitable to predict molecular and reaction properties that are previously difficult or slow to calculate. This chapter introduces the application of machine learning in major areas of chemical reaction engineering, including catalyst design, mechanism, and kinetics prediction, and reaction condition and outcome prediction. Existing challenges and future directions, mainly related to data collection, curation, and organization, are also summarized in each area.

The electrochemical alcohol oxidation reaction (AOR) is pivotal for the development of sustainable energy. The complete oxidation of alcohols has attracted extensive attention as a vital process in fuel cells. Moreover, as an alternative reaction to the oxygen evolution reaction, the selective oxidation of alcohols emerges as an effective means to lower the energy expenditure associated with electrolytic hydrogen production while yielding high‐value products. Nonprecious metal materials have been widely applied in the selective oxidation catalysis of alcohols due to their cost‐effectiveness and excellent durability. In recent years, leveraging the advantages of nonprecious metal materials in electrocatalytic AOR, researchers have delved into catalytic mechanisms and various efficient catalysts have been fabricated and evaluated. This review provides an overview of the current advancements in the electrocatalytic selective oxidation of diverse alcohols and the catalytic systems centered around nonprecious metal materials. It systematically summarizes the shared traits and distinctions in catalytic reaction characteristics across various systems, thereby laying the theoretical foundation for developing novel catalyst systems that are efficient, stable, and highly selective. This review will facilitate the utilization of nonprecious metal catalysts further toward the electrocatalytic oxidation of alcohols.

The present paper reports a remote carbon-to-carbon boryl migration via an intramolecular 1,4-B/Cu shift, which establishes an in situ stereospecific electrophilic trap on the alkene moiety. The synthetic application is developed to prepare functionalized cyclopentenes by means of a palladium-catalyzed regioselective intramolecular coupling that completes a strategic cyclopropanation and generates valuable structural bicyclic systems. The mechanism is characterized by DFT (density functional theory) calculations which showed that the 1,4-migration proceeds through an intramolecular, nucleophilic attack of the copper-alkyl moiety on the boron atom bonded to the C(sp2), leading to a 5-membered boracycle structure. The computation of the 1,3- and 1,4-B/Cu shifts is also compared as is the impact of the endo- or exocyclic alkene on the reaction kinetics.The intramolecular 1,4-B/Cu shift justifies the observed remote carbon-to-carbon boryl migration, which makes stereoselective electrophilic trapping on the alkene moiety possible. Subsequent palladium-catalyzed regioselective intramolecular coupling enables functionalized cyclopentenes to be prepared that complete strategic cyclopropanation and deliver structurally valuable bicyclic systems. DFT mechanistic studies show that remote boryl migration occurs efficiently through 5-membered boracycle intermediates. image

A novel electrochemical cell design in a vertically stacked configuration is presented. Through a layered structure using a top macroporous working electrode, a polyelectrolyte, and a bottom metallic conductor a standalone electrochemical cell with an internal reference electrode is built. This sensor allows monitoring an electrochemical property of an external solution with only one electrode in direct contact with the sample. Using paper-based platinum electrode for the porous top electrode and Nafion as polyelectrolyte material, the self-powered detection of hydrogen peroxide is performed. The system can be operated in multiple modes. In a capacitive way, the open circuit potential is measured. Alternatively, in a self-powered current mode, the system emulates a fuel cell. Additionally, a potential-current switched mode is also demonstrated. Because of this unique design and operational features this sensor is considered as an electrochemical pixel. To further demonstrate the advantages of this device, the detection of glucose is performed by building an array of sensors using a single back (reference) electrode and multiple working electrodes. These results lay the groundwork for the development of a new generation of simple and low cost biochemical sensors and electrochemical sensing arrays.Copyright © 2023 The Authors. Published by Elsevier B.V. All rights reserved.

The article substantiates that the modeling of processes and quantitative assessment (measurement) of the quality of the economic security system of an enterprise belongs to the most complex tasks of enterprise management and is the least researched from the point of view of modeling the functioning of the economic security mechanism of an agrarian enterprise, while the relevance and practical importance of such works is quite important . The results of modeling the functioning of the mechanism of economic security of an agricultural enterprise by applying Markov processes are presented, that is, the simulation of a random system that changes its state according to the transition rule and depends on the current state was carried out, which made it possible to determine such states of the economic security system as: development and implementation of directions ensuring economic security, increasing the level of economic security, reducing the level of economic security, adjusting directions for ensuring economic security." Accordingly, conclusions were drawn regarding the need for an agricultural enterprise to monitor states of a decrease in the level of economic security and an increase in the level of economic security, since the states of the economic security system are the most significant in terms of the structure of unconditional obligations. It is argued and mathematically proven that an agricultural enterprise needs to pay attention to the study of states P2(t) - "decreasing the level of economic security" and P1(t) - "increasing the level of economic security", since, in fact, these states of the economic security system are the most essential in terms of structure unconditional obligations.