Energetic Relationships Research Articles

Non-invasive surrogates for right Ventricular-Pulmonary arterial coupling: a systematic review and Meta-Analysis.

Right ventricle-pulmonary artery (RV-PA) coupling describes the energetic relationship between RV contractility and its afterload. The gold standard for assessment of this relationship requires invasive pressure-volume (PV) loop measurements. Non-invasive surrogates of RV-PA coupling have been developed, such as the echocardiographic tricuspid annular plane systolic excursion to pulmonary artery systolic pressure ratio (TAPSE/PASP), but their performance has not been systematically assessed. We sought to assess performance of TAPSE/PASP ratio compared to PV loop-defined RV-PA coupling. A systematic search was conducted. Studies were included if PV loop derived RV-PA coupling metrics were compared to echocardiographic or magnetic resonance imaging surrogates. We conducted a meta-analysis of TAPSE/PASP correlation to PV loop-defined RV-PA coupling. 1452 studies were identified in the initial search, of which ten met inclusion criteria. Five studies allowed for pooled analysis of TAPSE/PASP to Ees/Ea correlation (r = 0.52, 95% confidence interval 0.36-0.65). There was moderate heterogeneity across the pooled studies. Despite the common use of Non-invasive surrogates of RV-PA coupling, there is only moderate correlation with gold standard measurements. These metrics do not inform on the individual components of RV-PA coupling, limiting their use in the management of patients with RV dysfunction.

MEDICINAL BIOMAGNETISMO IN THE TREATMENT OF PROSTATE CANCER

Prostate cancer (PC) is reported as an important neoplasm worldwide, caused by the uncontrolled multiplication of cells in the prostate. The main risk factors are age over 50 years, family history, genetic susceptibility, hormonal disorders, obesity and environmental factors. Active surveillance of low-risk PC defers aggressive treatment until disease progression and is an increasingly recommended treatment strategy. This strategy aims to reduce costs and decrease treatment-related morbidity without affecting survival. Medicinal Biomagnetism (BM) is based on the distortion of the limit of homeostasis towards hyperacidity and hyperalkalinity of two specific points for each pathogenic microorganism or glandular dysfunction. The induction of loads that are in a vibrational and energetic relationship, by means of medium intensity magnets, greater than 1000 Gauss, corrects or prevents the distortion of the pH of the organs or tissues of the human body. In this way, the neutralization of pathogenic bioenergetic distortions promotes health. The aim of this study was to evaluate the effect of BM in the treatment of prostatic adenocarcinoma, prognostic group 1. After three sessions of BM, the levels of prostate-specific antigen (PSA) decreased and the prostate adenocarcinoma regressed to discrete chronic inflammation. This study represents the first in the evaluation of BM for the treatment of CP and may stimulate further studies in this field that are likely to yield important discoveries.

The energetic relationship between ports and cities; how the role of shared values is under pressure

Worldwide, ports are subject to the same trends such as globalization, increase in scale of the modus operandi and the process of containerization. These are general dynamics that are responsible for a changing relationship between the port and the city where it is located. This paper aims to describe and explain the developments that three port regions in Europe have experienced over the last decades, i.e., Hamburg, Antwerp and Rotterdam. Special attention is paid to the relationships between the most important actors within the three port-city clusters. The complex relationships are operationalized by a set of newly developed sensitizing concepts. It is concluded that all three cases have unique shared values play that play a crucial role in the changing relationships between ports and cities. The nature and intensity of these shared values are responsible for the impact of the trends on the relationship between a certain port and its city. E.g., the bond between the port and the city is the strongest in Hamburg and based on a strong culture that strengthen the integration of between port and city in many domains of society. For Antwerp, the political constellation is responsible for a continuing presence in the development of the city and the port, but also of the surrounding smaller municipalities. In Rotterdam, a more business-oriented culture was introduced that replaced a culture of common interests. It is concluded that the three cases have in common that variations in shared values plays a crucial role in the changing relationships between port and city.

Evidence of rate-determining step variation along reactivity in acetylene hydrogenation: a systematic kinetic study on elementary steps, kinetically relevant(s) and active species

We report here that the reduction degree of the metal at the catalytic interface dominates the reactivity of acetylene hydrogenation, mainly in terms of turnover rates (TORs) and activation energies, which could certainly cause the switch of kinetically relevant steps (KRS) from “C2H3*+H*” over Ce(OH)SO4·xH2O dispersed Pd catalyst to “C2H4*+H*” elementary step over Pd/CeO2. Besides, a compact kinetic model has been established to describe the reaction process and the dissociative mechanism was confirmed by H2/D2 exchange experiment. Meanwhile, the rate-determining step (RDS) and the main adsorbed species of the reaction were confirmed by systematic kinetic studies as well as in-situ FTIR analysis. More importantly, with the aid of parity fitting and gas isothermic adsorption analysis, the energetic relationship among the steps along with the acetylene hydrogenation is quantitatively described, which provides a good support and complement for the previous research, and helps researchers build up advanced reaction systems.

Synergistic Control of Hot Exciton Relaxation and Exciton–Polaron Dispersion Using a Polaron Retarder for Long Lifetime in Thermally Activated Delayed Fluorescence Organic Light‐Emitting Diodes

AbstractThe operational stability of thermally activated delayed fluorescence (TADF) organic light‐emitting diodes (OLEDs) is an essential property to utilize their efficient triplet harvesting ability and reduce the usage of expensive metal complexes in commercial applications. In this study, a device strategy for extending the device lifetime using the synergistic effects of the hot exciton relaxation and polaron dispersion is demonstrated. By doping a polaron retarder to a conventional TADF‐emitting layer, the lifetime of the blue TADF device is enhanced by 98% at an initial luminance of 1000 cd m−2. Kinetic modeling describing the device degradation indicates that the concurrent contribution via the suppression of exciton and polaron interactions and hot exciton‐related degradation are the origin of the lifetime enhancement. It is demonstrated that the introduction of the polaron retarder finely fits to the ground and that the excited energetic relationship of the host–dopant structure simultaneously improves the operation lifetime and device efficiency without sacrificing other device characteristics.

Protometabolism as out-of-equilibrium chemistry.

It is common to compare life with machines. Both consume fuel and release waste to run. In biology, the engine that drives the living system is referred to as metabolism. However, attempts at deciphering the origins of metabolism do not focus on this energetic relationship that sustains life but rather concentrate on nonenzymatic reactions that produce all the intermediates of an extant metabolic pathway. Such an approach is akin to studying the molecules produced from the burning of coal instead of deciphering how the released energy drives the movement of pistons and ultimately the train when investigating the mechanisms behind locomotion. Theories that do explicitly invoke geological chemical gradients to drive metabolism most frequently feature hydrothermal vent conditions, but hydrothermal vents are not the only regions of the early Earth that could have provided the fuel necessary to sustain the Earth's first (proto)cells. Here, we give examples of prior reports on protometabolism and highlight how more recent investigations of out-of-equilibrium systems may point to alternative scenarios more consistent with the majority of prebiotic chemistry data accumulated thus far.This article is part of the theme issue ‘Emergent phenomena in complex physical and socio-technical systems: from cells to societies’.

Insights Into Energy Accumulation and Allocation Strategy of Reproductive Migration of Black Amur Bream (Megalobrama terminalis) in the Pearl River Basin, China

Energy allocation is an important component of the reproductive cycle, and as such, it will affect survival, migration, and reproductive success. To reduce the risk of reproductive migration failure and to optimally allocate a limited amount of energy, it is vital to first understand the trade-off between reproduction and somatic growth in migrating fish. In this study, we chose Megalobrama terminalis, an endemic species residing in the Pearl River basin with relatively high migratory potential, as a candidate to investigate energy accumulation and allocation strategy during reproductive migration. The analysis used a quantitative assessment of biochemical composition and energy density in somatic and visceral tissues of M. terminalis females during the reproductive cycle. The results indicated that stage III to stage IV of M. terminalis was the vital migration-launching period. The asynchrony of development was confirmed in energetic relationships in muscle and ovary. Specifically, there was a regulatory mechanism for allocating lipids to each tissue reasonably during the breeding migratory preparation period (stage III). The significant change in lipid content of the ovary is considered as a crucial physiological index, which reflects the readiness for breeding migration of M. terminalis. In addition, the negative energy density relationship between somatic and reproductive tissues indicated a trade-off between maximum metabolic ability and energy efficiency before migration launching in M. terminalis. The present findings provide effective information for initiating further research on the ecological adaptation of migrating fish species.

DAKWAH INKLUSIF DALAM KERANGKA MAQĀṢID AL-SHARĪ’AH: STUDI KASUS POLA INTERAKSI LINTAS AGAMA PADA MASYARAKAT KALUKKU

This study aims to elaborate and analyze the harmonization model of religious life which is integrated into the patterns of religious social interaction in Kalukku and the role of religious leaders in knitting religious social harmony. The method applied is a qualitative method using inductive data analysis. The results of this study indicate that the pattern of religious interaction in Kalukku refers to the three patterns of Hossein Nasr interaction, namely: 1) concentric interaction patterns; 2) reciprocal interaction patterns; and 3) bound interaction patterns, which are carried out in an integrated manner have succeeded in creating a dynamic, harmonious and quality model of religious interaction. The motivation that underlies the realization of an energetic relationship refers to the concept of the four pillars of maqāṣid Ibn ‘Āshūr namely Fiṭrah, Samāḥa, al-Musāwāh, and Ḥurriyah. The paradigm of religious leaders towards the existence of cross-faith parties leads to a tolerant attitude based on the concept of Cak Nur's inclusive theology. The harmony and tolerant paradigm in Kalukku is built through formal and non-formal da'wah which is woven in efforts to acculturate religion and culture.

Structure–Property–Energetics Relationship of Organosulfide Capture Using Cu(I)/Cu(II)-BTC Edited by Valence Engineering

Valence engineering of copper (Cu) within functional materials is effective to tune the performance and energetics of catalysts and sorbents. Here, by precisely controlling the Cu(II)/Cu(I) ratio e...

Kinematic and Dynamic Conditions in Metal Rolling of Porous Materials

Mathematical modeling of plastic deformations in rolling consists in a consequent combination of the general energetic relationship in plasticity and the variation inequality expressed the principle of minimum of entire deformation energy. A real deformation state in a plastic zone beneath rolls and corresponding kinematic and dynamics conditions on the contact surface are considered as a limited one for the consequent approximate deformation states and are found out by the method of approximated approach. Any realization of this method on personal computers requires a rational construction of a kinematic-possible velocity field in the spatial domain on plastic flow. Using the ordinary propositions and a new assumptions the authors have constructed a simple kinematic-possible velocity field in the plastic zone beneath rolls. On the base of the consequent approach in which the general energetic relationship and the variation inequality are interrelated the authors have been able to find out the geometric, kinematic and dynamics characteristics of plastic deformation’s states in metal rolling.

(Invited) Photocatalytic Water Splitting: Particulate Model and Reactor Engineering

Particulate photocatalysts offer a materials platform that potentially converts light energy to chemical energy at scale, water splitting being an immediate application. However, the state-of-the art solar-to-hydrogen conversion efficiency by particles is <5%, whereas photoelectrochemical cells have achieved 20%. In a holistic view, the conversion process for photocatalysts dispersed in a reactor involve coupled photophysical and electrocatalytic processes: light absorption, carrier generation, charge separation, charge transfer across the photocatalyst/co-catalyst/liquid interface, as well as mass transport of reactants and products. First, we extend the Gerischer/Lewis kinetic expression to semiconductor/liquid junctions that co-evolve hydrogen and oxygen. Because of the locally non-equilibrium environment, we carefully designed steady-state experiments to validate a mutually-dependent relationship of kinetics and energetics. On a single particle level, co-catalysts induce spatially-varying asymmetric energetics, i.e. band bending vs. flat bands; these asymmetric energetics drive electrons and holes to separate laterally along the liquid interface and accumulate at their respective sites; and it was found that redox selectivity defines local energetics thus influencing charge separation efficiency. Assembled by photocatalysts, a particulate panel or suspension produces hydrogen and oxygen which transport under pressure gradient. We will show the systematic measurement of product diffusion rates. Finally, we apply the multi-scale particulate model to implement a novel coating-stabilized water-splitting panel that is efficient and safe, delivering pressurized hydrogen under sunlight.

A improved equation of state for Xe gas bubbles in γU-Mo fuels

A monolithic fuel design based on a U–Mo alloy has been selected as the fuel type for conversion of the United States High-Performance Research Reactors (HPRRs). An issue with U–Mo monolithic fuel is the large amount of swelling that takes place during operation. The accurate prediction of fuel evolution under irradiation requires implementation of correct thermodynamic properties into mesoscale and continuum level fuel performance modeling codes. However, the thermodynamic properties of the fission gas bubbles (such as the relationship among bubble size, equilibrium Xe concentration, and bubble pressure) are not well known. This work studies Xe bubbles in γU-Mo from a diameter of 3 nm up to 8.5 nm and from 400 K up to 700 K. The energetic relationship of Xe bubbles with regard to voids and Xe substitutional atoms is described. The transition is also determined for when a bubble becomes over-pressurized. Finally, an equation of state is fit to the pressure as a function of molar volume and temperature.

Workers Participation in Management with Reference to Loganathan Interior, Chennai

The officials which understood another game plan of characteristics to work and the board. Generally the possibility of Workers' Participation in Management (WPM) implies speculation of non-managerial delegates in the fundamental administration technique of the affiliation. Workers' advantage is generally called 'work backing' or 'agent venture' in the officials. In Germany it is known as co-affirmation while in Yugoslavia it is known as self-organization. The International Labor Organization has been asking part nations to propel the arrangement of Workers' Participation in Management. [1],[ 3],[5] Workers' interest in the administrators recommends mental and energetic relationship of workers in the organization of Enterprise. It is considered as an instrument where workers have a state in the desicion

Asexual reproduction and growth rate: independent and plastic life history traits in Neurospora crassa

Trade-offs among traits influencing fitness are predicted by life history theory because resources allocated to one function are unavailable to another. Here we examine the relationship between two such traits, asexual reproduction and growth rate, in the filamentous fungus Neurospora crassa, where shared genetic and physiological factors and a source–sink energetic relationship between growth and reproduction may constrain the evolution of these traits. To test growth–reproduction relationships in this species, we independently selected on mycelial growth rate or asexual spore production in a heterogeneous lab-derived population and evaluated the response of the non-selected traits. Combined with phenotypes for the 20 wild strains used to produce the heterogeneous population and the genome-wide genotypes of 468 strains, these data show that growth and reproduction are highly plastic in N. crassa and do not trade off either among wild strains or after laboratory selection in two environments. Rather, we find no predictable growth–reproduction relationship in the environments tested, indicating an effective absence of genetic constraint between these traits. Our results suggest that growth rate and asexual reproduction may not respond predictably to environmental change and suggest that reliance on a single trait as a proxy for fitness in fungal studies may be inadvisable.

Winged-Cone Conformation in Hexa-p-tert-butylcalix[6]arene Driven by the Unusually Strong Guest Encapsulation.

Hexa-p-tert-butylcalix[6]arene (1) is believed to adopt a winged conformation in a solution, featured by four phenyl rings perpendicular to the calix basis and two others at 1,4-positions lying down. However, there is some controversy on the occurrence of this conformation because it has never been found in the solid state of calix[6]arenes, regardless of the substitution pattern at lower and upper rims. Here, we have observed the winged-cone conformation for the first time in a solvate form of 1 with dimethyl sulfoxide (DMSO), dimethylformamide, and pyridine. The DMSO molecule is strongly encapsulated into 1 through two OH···O hydrogen bonds with both flattened phenolic moieties, one lp(S)···π and four CH···π interactions with the four perpendicular phenyl rings. This host–guest complex has energy lower by 23.4 kcal mol–1 than the isolated species. In addition, another DMSO solvate form with 1,2,3-alternate conformation was also obtained in this study, and its structure is compared with that of the precedent one. A detailed density functional theory study has also been carried out to understand the energetic relationships among cone conformers, intramolecular hydrogen-bonding patterns, and DMSO encapsulation.

Effects of Wolf Presence on Daily Travel Distance of Range Cattle

The presence of gray wolves (Canis lupus) can directly and indirectly affect beef cattle (Bos taurus) production on rangelands of the Northern Rocky Mountains. While fairly extensive knowledge exists for the direct effects of wolf predation threat (e.g., cattle death and injury losses, elevated stress), our understanding of wolf-caused changes in cattle behavior and the associated cascade of potential indirect effects on cattle resource selection, diet quality, activity budgets, and energetic relationships is still largely in its infancy. We investigated whether wolf presence affected the daily travel distance of Global Positioning System (GPS)−collared cattle under a replicated, Impact-Control study conducted in western Idaho and northeastern Oregon during 2008−2012. Cattle in three Control (Oregon) study areas, where wolf presence was consistently low, traveled farther per day (13.7 ± 0.396 SE km day−1) than those in three Impact (Idaho) study areas (11.4 ± 0.396 SE km day−1) with moderate to high wolf presence. At Control study areas, cattle traveled farthest per day in July (13.2 ± 0.355 SE km day−1) and were least mobile in October (11.8 ± 0.365 SE km day−1), but daily travel distances were similar across all months for cattle in Impact study areas. This observational study provides evidence suggesting cattle in mountainous grazing areas alter their spatial behavior in response to gray wolf presence. These behavioral changes have energetic consequences that could potentially impact cattle productivity and ranch economics. Additional research into the activity budget and resource selection responses of these collared cattle is required to better understand the specific mechanisms behind these daily travel distance results.

Metal-organic frameworks for H2 and CH4 storage: insights on the pore geometry-sorption energetics relationship.

This study aims to assess the possibility of improving H2 and CH4 binding affinity to the aromatic walls of a designed new Metal-Organic Framework (MOF) through simultaneous dispersive interactions. It is suggested here that desirable H2 and CH4 storage media at low pressures require narrow uniform pores associated with large surface area, a trade-off that is challenging to achieve.

Optical Determination of Electron Transfer Dynamics and Kinetics for Asymmetrical [Mo2]–ph–[Mo2] Systems

We report the study, in terms of electronic coupling (EC) and electron transfer (ET), on three asymmetrical Mo2 dimers [Mo2(DAniF)3]2[μ-(NH)OCC6H4CO2] ([NO–ph–OO]) (DAniF = N,N′-di(p-anisyl)formamidinate), [Mo2(DAniF)3]2[μ-(NH)2CC6H4CO2] ([NN–ph–OO]), and [Mo2(DAniF)3]2[μ-(NH)2CC6H4C(NH)O] ([NN–ph–NO]), which are closely related to the three symmetrical analogues [OO–ph–OO], [NO–ph–NO], and [NN–ph–NN] reported earlier. The mixed-valence (MV) complexes [NO–ph–OO]+, [NN–ph–OO]+, and [NN–ph–NO]+ exhibit metal to ligand and ligand to metal charge transfer bands, along with an intervalence (IV) transition absorption in the Near-IR region. The free energy change (ΔG°) for ET is determined by comparing the redox potential splitting (ΔE1/2) and IV transition energy (EIT) with the data for the symmetrical species. The reorganization energy (λ) is estimated from the Hush model (Δν1/2 = [16ln(2)λRT]1/2). Significantly, electrochemical and optical analyses verify EIT = ΔG° + λ, the core energetic relationship underlying the semiclassical theories. With the electronic coupling parameters calculated from the method suggested by Creutz, Newton and Sutin (HMM′ = ∼ 500 cm–1), the adiabatic ET rate constants ket (f) are determined to be ∼1010 s–1 for [NO–ph–OO]+ and [NN–ph–NO]+, smaller than ket (r) for the backward reaction and ket for the symmetrical analogues by 1 order of magnitude, and ∼109 s–1 for [NN–ph–OO]+. This work illustrates that the redox asymmetry in D–B–A systems controls the ET rate and direction.

First principles studies on the impact of point defects on the phase stability of (AlxCr1−x)2O3 solid solutions

Density Functional Theory applying the generalised gradient approximation is used to study the phase stability of (AlxCr1−x)2O3 solid solutions in the context of physical vapour deposition (PVD). Our results show that the energy of formation for the hexagonal α phase is lower than for the metastable cubic γ and B1-like phases–independent of the Al content x. Even though this suggests higher stability of the α phase, its synthesis by physical vapour deposition is difficult for temperatures below 800 °C. Aluminium oxide and Al-rich oxides typically exhibit a multi-phased, cubic-dominated structure. Using a model system of (Al0.69Cr0.31)2O3 which experimentally yields larger fractions of the desired hexagonal α phase, we show that point defects strongly influence the energetic relationships. Since defects and in particular point defects, are unavoidably present in PVD coatings, they are important factors and can strongly influence the stability regions. We explicitly show that defects with low formation energies (e.g. metal Frenkel pairs) are strongly preferred in the cubic phases, hence a reasonable factor contributing to the observed thermodynamically anomalous phase composition.

Oxygen and sulfur heterocyclic compounds

The knowledge of the thermodynamic properties of heterocyclic compounds, particularly the corresponding enthalpies of formation in condensed and gaseous states, enables a better understanding of their chemical behavior and, consequently, leads to an important background for the future development of their practical applications. Following our particular interest along the last decade on the establishment of energetic and structural relationships for heterocycle compounds with one or two benzene rings fused to a five- or six-membered ring containing oxygen or sulfur heteroatoms, we review the thermochemical data for derivatives of the following main structures: benzoxazole/benzothiazole, dibenzofuran/dibenzothiophene, xanthene/thioxanthene, and phenoxazine/phenothiazine. The experimental results, obtained by calorimetric and effusion techniques, namely static and rotating bomb combustion calorimetry, vacuum sublimation/vaporization drop microcalorimetry, and Knudsen effusion methods, were used to derive reliable thermodynamic values for the compounds studied. A complementary analysis of computational results for these molecules is presented. The agreement between the calculated and the experimental gas-phase enthalpies of formation represents a reinforcement on the validation of the established predictive schemes, supporting their use for related compounds whose energetic study is not available.