Total Energy Difference Research Articles

Parametric Optimization Approach to Evaluate Dynamic Shading Within Double-Skin Insulated Glazed Units for Multi-Criteria Daylighting Performance in Tropics

This research aims to support the choice of an appropriate dynamic louver shading system (DL-SS) within double-skin facade insulated glazed units (DSF-IGUs) as a high-performance integrated window system (DSF-IGUs/DL-SS) that meets both thermal and energy performance via daylight availability under a tropical climate. The research framework has developed a multi-objective optimization method to achieve research objectives via optimizing two different scenarios of the proposed system. The first scenario was optimized for daylighting availability, meanwhile, the second scenario was optimized for energy and thermal performance. For each scenario, the best solutions are selected from respective Pareto fronts according to energy efficiency criteria, thermal comfort via enhancing daylighting availability. Based on the best options resulting from both optimizations, the final step involved comparing the results of all performance indicators in the best cases to select the best solution. Overall, based on the optimizing objectives, the ranking of the best cases varied based on giving priority to the improvement objective in the optimization process. For each scenario, the best solutions are selected from the respective Pareto fronts. Overall, ranking of the best cases varied based on giving priority to the improvement objectives. Optimizing DL-SS within DSF-IGUs while giving priority to improving energy and thermal comfort while maintaining daylighting at acceptable levels is more reasonable. Thus, the DSF-IGUs/DL-SS best-case resulting from the second optimization scenario was overcome all best cases and ranked first in energy and thermal comfort. Compared to the base case, the differences of total Predicted mean vote and percentage of dissatisfied for better thermal comfort achieved were -0.35% and -1.48% with an average decreased by 22.99% and 28.72%, respectively. The differences of total energy and cooling load for better energy performance reduced by -96.84 kwh/m2. and -86.88 kwh with an average decreased by 25.33% and 26.20%, respectively. Meanwhile, the total satisfied of spatial Daylight Autonomy for better daylighting distribution and better daylighting availability of useful daylighting illuminance improvement were improved by -5.54% and +24.76% with an average percentage variation increased by 6.25% and 36.87%, respectively.

DFT molecular modeling investigation and optical properties characterization of CR-39 films

Abstract In this study, the structural and optical characteristics of CR-39 films were investigated both theoretically and experimentally. A number of parameters for the CR-39 structure were theoretically computed by the density functional theory (DFT) method at B3LYP/6–311 G (p, d) level of theory. FTIR and UV/Vis spectroscopy were used to determine the structure compositions and the optical parameters of the CR39 film, respectively. The computed and experimental findings show good concordance. It was found that the CR-39 compound’s total energy, dipole moment, and energy difference between the LUMO and HOMO were, respectively, −994.575 a.u., 2.772 Debye, and 7.045 eV. The MEP showed a progressive change in color, with blue signifying a low electron density and red denoting a high electron density linked to nucleophilic reactivity and electrophilic reactivity. Further, the positive charges on all hydrogen atoms, which range from 0.16506 to 0.22032 a.u., imply that they are acceptors. The positive H34 is strongly produced when electrons from the negatively charged C17 are taken up. Because they are donor atoms, part of the carbon atoms in the structure is negative, while the other atoms are positive. The highest electronegative atoms H23 and H24 were substituted, resulting in the extremely negative carbon atom C7 (−0.32436). According to the experimentally determined absorption coefficient and energy gap values, CR-39 films may find application in optoelectronic devices.

Determination of mometasone furoate solubility, using deep eutectic systems, and topical formulation- experimental and computational studies

The low solubility of some drugs in aqueous medium, is currently a challenge for the pharmaceutical industry, affecting drug bioavailability and treatment efficacy, so there is the need to find new solutions for this challenge. In this work, the solubility of a glucocorticoid drug, mometasone furoate (MF), in different deep eutectic systems (DES) is studied. DES present the advantage of being sustainable solvents, which can be used directly in the final formulation, and establish a synergistic effect with the drug. The solubility of MF in different DES is increased, when compared to the solubility of this drug in an aqueous medium, particularly in DES composed by levulinic acid and terpenes such as menthol and thymol, where the solubility of MF was of 24.1 and 103.3 mgMF/gDES, respectively. Solubility was also assessed using the computational determination of the Hansen solubility parameters of MF in these DES, in particular the total solubility parameter (δT) and Relative Energy Difference (RED). The obtained results correlate well with the MF measured experimentally, showing that this computational tool can be further used to predict MF solubility in DES. Furthermore, oil-in-water emulsions containing DES with MF were developed, allowing more versatility compared to the drug in powdered form, and were prepared containing 1 and 5 % of DES with MF. This work highlights that DES can have an important role in drug solubilization and in the development of new formulation strategies for the pharmaceutical industries.

Investigation of thermodynamical stability and generation of large half-metallic gap along with optical properties in N-doped YHfO3 (YHO) (Y = Ca, Sr, and Ba) perovskite materials by first principle calculations

Considerable energy gap (Eg) in insulating channel, high spin-filtering, significant mean free path, and high magnetic transition temperature (TC) escalate half-metallic (HM) ferromagnetic (FM) materials very enticing for spintronic applications. Herein, ab-initio calculations have been executed comprehensively to inquest the structural, thermodynamical, electronic, magnetic, and optical properties of pure as well as nitrogen (N)-doped YHfO3 (YHO) (Y = Ca/Sr/Ba) materials with one N atom added at one of the oxygen (O) site. First, the thermodynamical stability of both bulk and doped YHO systems has been examined by estimating the formation enthalpies (ΔHf) by Convex Hull analysis, which confirms the practical realization of these materials on experimental grounds. Moreover, mechanical stability of these systems is affirmed by estimating the necessary elastic constants and respective parameters. Strikingly, all doped systems possess complete (100%) splitting in spin↑ and spin↓ channels at Fermi level and depict HM FM character with significant Eg of 3.31, 3.49, and 3.24 eV in spin↓ channels for CaHO (CHO), SrHO (SHO), and BaHO (BHO) systems, respectively. It is also found that N 2p orbitals are totally responsible for the emergence of metatallicity and magnetic character in all these doped structures. Moreover, the ground state long range FM stability between two added N atoms in doped systems is affirmed by computing the difference of total energies of FM and anti-ferromagnetic (AFM) spin ordering (ΔE) along with estimated TC at different distances. Lastly, it is found that N-doped systems have a lower optical energy loss than pristine YHO systems in the incident photon energy range of 0-50 eV. Hence, the present study proposes that an unconventional doping approach with intrinsically non-magnetic element in a variety of YHO perovskite systems could be a useful method to alter their various physical properties and forecast their potential applications in the development of novel spintronic and optoelectronic devices.

An in-depth look at the stability, electronic structure, mechanical properties, and thermodynamics characteristic of Ir3TM (TM: Sc, Ti, V) compounds

In this paper, the structural, mechanical, electronic, and thermodynamic properties of Ir3TM (TM = Sc, Ti, and V) intermetallic compounds in the cubic (L12) and hexagonal (D019 and D024) phases are presented. The outcomes of the simulation rely on density functional theory (DFT) within the Perdew-Burke-Ernzerhof (PBE) generalized gradient approximation (GGA) based on the full-potential linearized augmented plane wave (FP-LAPW) approach. The existing study was performed on the L12 cubic phase. in addition to hexagonal D024 and D019 phases, which may be relative but differ in the way that the atomic layers are stacked. The calculated total, cohesive energy, and heat formation suggest that the Ir3Sc compound can be stable in the D024 phase because of an overlap between the L12 and D024 phases with a total energy difference of around 0.026 eV/atom. Ir3Ti and Ir3V are more stable in L12 and D019, respectively. From elastic constants calculations, it reveals that the studied compounds are mechanically stable and harder in the cubic phase than hexagonal phase. However, Ir3Sc has the lowest hardness due to its relative ductility. Inversely, Ir3V has the maximum hardness with a lack of ductility. It was observed that these compounds have an elastic anisotropy based on the three-dimensional Young's modulus surface, and Ir3Sc has the strongest anisotropy, while Ir3V has the weakest in the L12 phase. The total density of state (TDOS) calculations shows that Ir3Ti and Ir3V are stable in the L12 and D019 phases, respectively, except for the Ir3Sc compound which might undergo a martensitic transition. Also, the pseudogap for Ir3V moves quite close to the Fermi level, indicating that the covalent bonding in this compound is sharper than the other compounds. Moreover, via the quasi-harmonic Debye model within the Gibbs computational code, thermodynamic properties are calculated and analyzed with temperature and pressure.

A computational investigation of XnK(X = Mn, Fe, co; n = 1–8) clusters by density functional theory

The properties of XnK(X = Mn, Fe, Co; n = 1–8) clusters have been systematically investigated using quantum calculations of LANL2DZ basis sets at the PBE1PBE level. By optimizing different structural isomers, we determined the ground state structure of XnK clusters, which tends to be compact as the cluster size increases. In order to study the stability of clusters, the average binding energies, dissociation energies and second-order difference of total energies of XnK clusters are calculated. The results show that the stability of FenK clusters is comparable to that of ConK clusters, and both are higher than that of MnnK clusters. Finally, the chemical activity and magnetic properties of the clusters are discussed. The dissociation energies, second-order difference of total energies, HOMO-LUMO energy gaps, and magnetic moments of the ground-state clusters show an irregular oscillatory behavior with atomic number. Fundamental insights obtained in this study can be useful in the design of Mn-K/Fe-K/Co-K catalysts.

Spin wave excitations in low dimensional systems with large magnetic anisotropy

The low-energy excitation spectrum of a two-dimensional ferromagnetic material is dominated by single-magnon excitations that show a gapless parabolic dispersion relation with the spin wave vector. This occurs as long as magnetic anisotropy and anisotropic exchange are negligible compared to isotropic exchange. However, to maintain magnetic order at finite temperatures in extended systems, it is necessary to have sizable anisotropy to open a gap in the spin wave excitation spectrum. We consider four real two-dimensional systems for which ferromagnetic order at finite temperature has been observed or predicted. Density functional theory calculations of the total energy differences for different spin configurations permit us to extract the relevant parameters and connect them with a spin Hamiltonian. The corresponding values of the Curie temperature are estimated using a simple model and found to be mostly determined by the value of the isotropic exchange. The exchange and anisotropy parameters are used in a toy model of finite-size periodic chains to study the low-energy excitation spectrum, including single-magnon and two-magnon excitations. At low energies, we find that single-magnon excitations appear in the spectrum together with two-magnon excitations. These excitations present a gap that grows particularly for large values of the magnetic anisotropy or anisotropic exchange, relative to the isotropic exchange.

Effect of MnO2 Nanoparticles Stabilized with Cocamidopropyl Betaine on Germination and Development of Pea (Pisum sativum L.) Seedlings.

This study aimed to synthesize, characterize, and evaluate the effect of cocamidopropyl betaine-stabilized MnO2 nanoparticles (NPs) on the germination and development of pea seedlings. The synthesized NPs manifested as aggregates ranging from 50-600 nm, comprising spherical particles sized between 19 to 50 nm. These particles exhibited partial crystallization, indicated by peaks at 2θ = 25.37, 37.62, 41.18, 49.41, 61.45, and 65.79°, characteristic of MnO2 with a tetragonal crystal lattice with a I4/m spatial group. Quantum chemical modelling showed that the stabilization process of MnO2 NPs with cocamidopropyl betaine is energetically advantageous (∆E > 1299.000 kcal/mol) and chemically stable, as confirmed by the positive chemical hardness values (0.023 ≤ η ≤ 0.053 eV). It was revealed that the interaction between the MnO2 molecule and cocamidopropyl betaine, facilitated by a secondary amino group (NH), is the most probable scenario. This ascertain is supported by the values of the difference in total energy (∆E = 1299.519 kcal/mol) and chemical hardness (η = 0.053 eV). These findings were further confirmed using FTIR spectroscopy. The effect of MnO2 NPs at various concentrations on the germination of pea seeds was found to be nonlinear and ambiguous. The investigation revealed that MnO2 NPs at a concentration of 0.1 mg/L resulted in the highest germination energy (91.25%), germinability (95.60%), and lengths of roots and seedlings among all experimental samples. However, an increase in the concentration of preparation led to a slight growth suppression (1-10 mg/L) and the pronounced inhibition of seedling and root development (100 mg/L). The analysis of antioxidant indicators and phytochemicals in pea seedlings indicated that only 100 mg/L MnO2 NPs have a negative effect on the content of soluble sugars, chlorophyll a/b, carotenoids, and phenols. Conversely, lower concentrations showed a stimulating effect on photosynthesis indicators. Nevertheless, MnO2 NPs at all concentrations generally decreased the antioxidant potential of pea seedlings, except for the ABTS parameter. Pea seedlings showed a notable capacity to absorb Mn, reaching levels of 586.5 μg/L at 10 mg/L and 892.6 μg/L at 100 mg/L MnO2 NPs, surpassing the toxic level for peas according to scientific literature. However, the most important result was the observed growth-stimulating activity at 0.1 mg/L MnO2 NPs stabilized with cocamidopropyl betaine, suggesting a promising avenue for further research.

Equivalent Enthalpy Model and Log-Mean Enthalpy Difference Method for Heat-Mass Transfer in Cooling Towers

Abstract In industrial processes involving both heat and mass transfer, the enthalpy or total energy difference, not the temperature difference, is a more comprehensive driving-force potential for heat exchanger systems, such as a cooling tower. However, the common practice of current enthalpy methods based on Merkel integral requires numerical integration with implied linear distributions of air enthalpy and water temperature. If the cooling range is relatively small, the outcome of the integration may carry little error. But for a large cooling range and a substantially increased temperature, the error involved may be significant. Like log-mean temperature difference, a log-mean enthalpy difference method may require only the inlet and outlet conditions without prior knowledge of the enthalpy distributions of the fluids within the heat exchanger. The known Berman's enthalpy difference method requires correction factors, which was derived based on the linearization of the interfacial enthalpy and the enthalpy difference between the interfacial moist-air enthalpy and the bulk air enthalpy without underlying interpretation to demonstrate that the method could be broadly used. In this paper, an equivalent enthalpy model is proposed, and the log-mean enthalpy difference is derived without any constraints for broad uses. The derived method is compared with the results of Merkel's method from literature with excellent agreement. Thus, the work in this paper would open the possibility for broad uses of the log-mean enthalpy difference method for many industrial processes involving mass transfer.

Energy characteristics of saturated Jurassic sandstone in western China under different stress paths

AbstractTo study the energy evolution and failure characteristics of saturated sandstone under unloading conditions, rock unloading tests under different stress paths were conducted. The energy evolution mechanism of the unloading failure of saturated sandstone was systematically explored from the perspectives of the stress path, the initial confining pressure, and the energy conversion rate. The results show that (1) before the peak stress, the elastic energy increases with an increase in deviatoric stress, while the dissipated energy slowly increases first. After the peak stress, the elastic energy decreases with the decrease of deviatoric stress, and the dissipated energy suddenly increases. The energy release intensity during rock failure is positively correlated with the axial stress. (2) When the initial confining pressure is below a certain threshold, the stress path is the main factor influencing the total energy difference. When the axial stress remains constant and the confining pressure is unloading, the total energy is more sensitive to changes in the confining pressure. When the axial stress remains constant, the compressive deformation ability of the rock cannot be significantly improved by the increase in the initial confining pressure. The initial confining pressure is positively correlated with the rock's energy storage limit. (3) The initial confining pressure increases the energy conversion rate of the rock; the initial confining pressure is positively correlated with the energy conversion rate; and the energy conversion rate has a high confining pressure effect. The increase in the axial stress has a much greater impact on the elastic energy than the confining pressure. (4) When the deviatoric stress is small, the confining pressure mainly plays a protective role. Compared with the case of triaxial compression paths, the rock damage is more severe under unloading paths, and compared with the case of constant axial stress, the rock damage is more severe under increasing axial stress.

An innovative form of the essential trace element copper for fortification of dairy products

Microelementosis is a disease associated with a deficiency of certain vital microelements. Today, there are ways to combat the lack of essential micronutrients. In this article, the mechanochemical synthesis of a triple copper-containing complex with ascorbic acid and L-isoleucine, an essential amino acid, was carried out. Examination of the sample by X-ray diffractometry showed that the sample has a trigonal crystal structure with space group P31c. As a result of computer quantum chemical modeling, the values of the difference in total energy, chemical hardness, energy of the highest occupied molecular orbital and the lowest unoccupied molecular orbital were determined. We determined the optimal option for the interaction of copper with vitamin C and L-isoleucine, where the binding occurs through hydroxyl groups attached to the C2 and C3 atoms of ascorbic acid, and through the carboxyl group and α-amino group of isoleucine. The sample was examined by IR spectroscopy and confirmed by computer modeling data. The stability of the resulting complex was studied depending on the technological parameters — pH, temperature and exposure time. Using the Greco-Latin square method, a matrix for planning a multifactorial experiment was compiled. An analysis of the dependence of the change in optical density (∆ D) on pH, temperature and exposure time showed that the pH of the medium and the temperature of the solution have a significant effect on ∆ D: an increase in the pH of the medium and the temperature of the solution leads to an increase in ∆ D. Exposure time does not have a significant effect to change the optical density value (∆ D). The parameters at which sample stability is observed correspond to the lowest values of ∆ D: pH = 3–8, t = 25–70, τ = 5–15. The effect of the concentration of a copper-containing complex on the physicochemical parameters of milk was studied. It has been established that the optimal concentration of copper ascorbate isoleucinate for fortifying dairy products is 0.005 mol/l or less. Next, an organoleptic assessment of the indicators of milk enriched with copper ascorbate isoleucinate was carried out. The analysis of the results showed that the organoleptic parameters (smell and taste) of milk enriched with ascorbate-isoleucinate of copper are 0.1 points higher than those of milk enriched with the inorganic form of the essential trace element copper and 0.3 points lower than that of the control milk sample.

Effect of atmospheric clarity on spatial differences in total solar energy in the Kurdistan Region of Iraq

الهدف من هذا البحث هو عرض الفروق في الاشعاع الشمسي الكلى في اقليم كوردستان وخاصة بين المحطات الجبلية مثل (العمادية - حاج عمران - سوران - السليماني) والمحطات الواقعة في مناطق السهل مثل (كلار - كركوك - أربيل - الموصل) ، تبين العلاقة بين شفافية الغلاف الجوي (الغطاء السحابي ، الضباب ، ظاهرة الغبار) مع هذا الاختلاف من خلال ارتباط بيرسون ، وجدت دراسة أن كمية الإشعاع الشمسي الكلي تختلف من مكان إلى آخر ، خاصة بين المناطق الجبلية والسهول ، تم الكشف أن شفافية الغلاف الجوي له علاقة قوية بهذا الاختلاف ، بحيث يكون للغطاء السحابي علاقة عكسية قوية ، يصل إلى (0.92) ، وللضباب علاقة عكسية قوية ، ويصل إلى ( 0.75) ، وظاهرة الغبار لها علاقة إيجابية ، فهي تصل فى العاصفة الترابية الى (0.65) ، والغبار المعلق (0.83) ، والغبار المتصاعد (0.91). پوختە ئامانج له‌م توێژینه‌وه‌یه‌ خۆی ده‌بینێته‌وه‌ له‌ خستنه‌ڕووی جیاوازی شوێنجێی له‌ووزه‌ی تیشكی خۆری گشتی گه‌یشتوو له‌هه‌رێمی كوردستان، به‌تایبه‌ت له‌نێوان وێستگه‌ شاخاویه‌كانی وه‌ك (ئامێدی- حاجی ئۆمه‌ران- سۆران- سلێمانی) له‌گه‌ڵ ئه‌و وێستگانه‌ی ده‌كه‌ونه‌ ناوچه‌ ده‌شتیه‌كانه‌وه‌ وه‌ك (موسڵ- هه‌ولێر- كه‌ركوك- كه‌لار)،وه‌ خستتنه‌ڕووی په‌یوه‌ندی ڕوونی به‌رگه‌ هه‌وا (ڕووپۆشی هه‌ور،ته‌م،دیارده‌ی خۆڵبارین) به‌ ئه‌م جیاوازیه‌وه‌ له‌ڕێگه‌ی هاوكۆڵكه‌ی په‌یوه‌ندی پیرسۆن (Pearson correlation)، له‌م توێژینه‌وه‌دا ڕێبازی شیكاری به‌راوردكاری به‌كارهاتوه‌،توێژینه‌وه‌كه‌ گه‌یشته‌ ئه‌وه‌ی, بڕی ووزه‌ی تیشكی خۆری گشتی گه‌یشتوو, جیاوازی تێدایه‌ له‌شوێنێكه‌وه‌ بۆ شوێنێكی تر, به‌تایبه‌ت له‌نێوان ناوچه‌ شاخاویی و ده‌شتیه‌كاندا,ده‌ركه‌وت په‌یوه‌ندی ڕوونی به‌رگه‌ هه‌وا به‌م جیاوازیه‌وه‌ په‌یوه‌ندیه‌كی به‌هێزه‌، به‌جۆرێك په‌یوه‌ندی ڕووپۆشی هه‌وری په‌یوه‌ندیه‌كی پێچه‌وانه‌ی به‌هێزه‌و ده‌گاته‌ (0.92)، وه‌ په‌یوه‌ندی ته‌م په‌یوه‌ندیه‌كی پێچه‌وانه‌ی به‌هێزه‌و ده‌گاته‌(0.75)،له‌كاتێكدا بۆ دیارده‌ی خۆڵبارین په‌یوه‌ندیه‌كی ڕاسته‌وانه‌یه‌و ده‌گاته‌ گه‌رده‌لولی خۆڵین (0.65)،تۆزی به‌رزه‌وه‌بوو(0.83)،تۆزی هه‌ڵواسراو(0.91).

First-principles study of electronic and magnetic properties in site dependent Fe-doped chalcopyrite ZnSnAs2semiconductors: Comparison with those of Mn- and Cr-doped ZnSnAs2

The electronic and magnetic properties of Fe-doped ZnSnAs2 within chalcopyrite structures have been studied by first-principles calculations using the density functional theory (DFT) full-potential linearized augmented-plane-wave method and the plane-wave pseudopotential methods. The band gap of ZnSnAs2 was determined to be 0.816 eV using the modified Beck-Jonson (mBJ) exchange potential. When Fe dopants substitutionally replace Sn atoms, half-metallic ferromagnetism is observed in ZnSnAs2 where in the spin-down band at the Fermi level is entirely unoccupied. The magnetic exchange interaction between two Fe atoms substituting Zn and Sn sites in the supercell with different geometries has been studied. The total energy difference (ΔE) between the antiferromagnetic (AFM) and ferromagnetic (FM) configurations suggests that Fe atom occupation of Zn sites in ZnSnAs2 leads to a predominantly AFM state, while the Fe atom occupation of Sn sites prefers the FM state.

Resonant electron capture by polycyclic aromatic hydrocarbon molecules: Effects of aza-substitution.

Resonant electron capture by aza and diaza derivatives of phenanthrene (7,8-benzoquinoline and 1,10-phenanthroline) and anthracene (acridine and phenazine) at incident free electron energies (Ee) in the range of 0-15eV was studied. All compounds except 7,8-benzoquinoline form long-lived molecular ions (M-) at thermal electron energies (Ee ∼ 0eV). Acridine and phenazine also form such ions at epithermal electron energies up to Ee = 1.5-2.5eV. The lifetimes (τa) of M- with respect to electron autodetachment are proportional to the extent of aza-substitution and increase on going from molecules with bent geometry of the fused rings (azaphenanthrenes) to linear isomers (azaanthracenes). These regularities are due to an increase in the adiabatic electron affinities (EAa) of the molecules. The EAa values of the molecules under study were comprehensively assessed based on a comparative analysis of the measured τa values using the Rice-Ramsperger-Kassel-Marcus theory, the electronic structure analysis using the molecular orbital approach, as well as the density functional calculations of the total energy differences between the molecules and anions. The only fragmentation channel of M- ions from the compounds studied is abstraction of hydrogen atoms. When studying [M-H]- ions, electron autodetachment processes were observed, the τa values were measured, and the appearance energies were determined. A comparative analysis of the gas-phase acidity of the molecules and the EAa values of the [M-H]· radicals revealed their proportionality to the EAa values of the parent molecules.

Analysis of cholesterol-recognition motifs of the plasma membrane Ca2+-ATPase

The plasma membrane Ca2+-ATPase (PMCA) is crucial for the fine tuning of intracellular calcium levels in eukaryotic cells. In this study, we show the presence of CARC sequences in all human and rat PMCA isoforms and we performed further analysis by molecular dynamics simulations. This analysis focuses on PMCA1, containing three CARC motifs, and PMCA4, with four CARC domains. In PMCA1, two CARC motifs reside within transmembrane domains, while the third is situated at the intracellular interface. The simulations depict more stable RMSD values and lower RMSF fluctuations in the presence of cholesterol, emphasizing its potential stabilizing effect. In PMCA4, a distinct dynamic was found. Notably, the total energy differences between simulations with cholesterol and phospholipids are pronounced in PMCA4 compared to PMCA1. RMSD values for PMCA4 indicate a more energetically favorable conformation in the presence of cholesterol, suggesting a robust interaction between CARCs and this lipid in the membranes. Furthermore, RMSF analysis for CARCs in both PMCA isoforms exhibit lower values in the presence of cholesterol compared to POPC alone. The analysis of H-bond occupancy and total energy values strongly suggests the potential interaction of CARCs with cholesterol. Given the crucial role of PMCAs in physiological calcium regulation and their involvement in diverse pathological processes, this study underscores the significance of CARC motifs and their interaction with cholesterol in elucidating PMCA function. These insights into the energetic preferences associated with CARC-cholesterol interactions offer valuable implications for understanding PMCA function in maintaining calcium homeostasis and addressing potential associated pathologies.

Evaluation of reanalysis data and dynamical downscaling for surface energy balance modeling at mountain glaciers in western Canada

Abstract. Regional-scale surface energy balance (SEB) models of glacier melt require forcing by coarse-gridded data from reanalysis or global climate models that need to be downscaled to glacier scale. As on-glacier meteorological observations are rare, it generally remains unknown how exact the reanalysis and downscaled data are for local-scale SEB modeling. We address this question by evaluating the performance of reanalysis from the European Centre for Medium-Range Weather Forecasts (ERA5 and ERA5-Land reanalysis), with and without downscaling, at four glaciers in western Canada with available on-glacier meteorological measurements collected over different summer seasons. We dynamically downscale ERA5 with the Weather Research and Forecasting (WRF) model at 3.3 and 1.1 km grid spacing. We find that our SEB model, forced separately with the observations and the two reanalyses, yields less than 10 % difference in simulated total melt energy and shows strong correlations (0.86) in simulated time series of daily melt energy at each site. The good performance of the reanalysis-derived melt energy is partly due to cancellation of biases between overestimated incoming shortwave radiation and substantially underestimated wind speed and subsequently turbulent heat fluxes. Downscaling with WRF improves the simulation of wind speed, while other meteorological variables show similar performance to ERA5 without downscaling. The choice of WRF physics parameterization schemes is shown to have a relatively large impact on the simulations of SEB components but a smaller impact on the modeled total melt energy. The results increase our confidence in dynamical downscaling with WRF for long-term glacier melt modeling in this region.

Unravelling the complex speciation of halozincate ionic liquids using X-ray spectroscopies and calculations.

Using a combination of liquid-phase X-ray spectroscopy experiments and small-scale calculations we have gained new insights into the speciation of halozincate anions in ionic liquids (ILs). Both core and valence X-ray photoelectron spectroscopy (XPS) experiments were performed directly on the liquid-phase ILs, supplemented by Zn 1s X-ray absorption near edge structure (XANES) spectroscopy. Density functional theory (DFT) calculations were carried out on both 1- and 2- halozincate anions, in both a generalised solvation model SMD (Solvation Model based on Density) and the gas phase, to give XP spectra and total energy differences; time-dependent DFT was used to calculate XANES spectra. Speciation judgements were made using a combination of the shape and width of the experimental spectra, and visual matches to the calculated spectra. For 2- halozincate anions, excellent matches were found between the experimental and calculated XP spectra, clearly showing that only 2- halozincate anions were present at all zinc halide mole fractions, x, studied. At specific values of x (0.33, 0.50, 0.60) only one halozincate anion was present; equilibria of different halozincate anions at those values of x were not observed. All findings show that chlorozincate anion and bromozincate anion speciation matched at the same x. Based on the results, predictions are made of the halozincate anion speciation for all values of x up to 0.67. Caution is advised when using differences in calculated total energies obtained from DFT to judge halozincate anion speciation, even when the SMD was employed, as predictions based on total energy differences did not always match the findings from the experimental and calculated spectra. Our findings clearly establish that the combination of high-quality experimental data from multiple spectroscopies and a wide range of calculated structures are essential to have high confidence in halozincate anion speciation identification.

ADME profiling, molecular docking, DFT, and MEP analysis reveal cissamaline, cissamanine, and cissamdine from Cissampelos capensis L.f. as potential anti-Alzheimer's agents.

The current pharmacotherapies for Alzheimer's disease (AD) demonstrate limited efficacy and are associated with various side effects, highlighting the need for novel therapeutic agents. Natural products, particularly from medicinal plants, have emerged as a significant source of potential neuroprotective compounds. In this context, Cissampelos capensis L.f., renowned for its medicinal properties, has recently yielded three new proaporphine alkaloids; cissamaline, cissamanine, and cissamdine. Despite their promising bioactive profiles, the biological targets of these alkaloids in the context of AD have remained unexplored. This study undertakes a comprehensive in silico examination of the binding affinity and molecular interactions of these alkaloids with human protein targets implicated in AD. The drug likeness and ADME analyses indicate favorable pharmacokinetic profiles for these compounds, suggesting their potential efficacy in targeting the central nervous system. Molecular docking studies indicate that cissamaline, cissamanine, and cissamdine interact with key AD-associated proteins. These interactions are comparable to, or in some aspects slightly less potent than, those observed with established AD drugs, highlighting their potential as novel therapeutic agents for Alzheimer's disease. Crucially, Density Functional Theory (DFT) calculations offer deep insights into the electronic and energetic characteristics of these alkaloids. These calculations reveal distinct electronic properties, with differences in total energy, binding energy, HOMO-LUMO gaps, dipole moments, and electrophilicity indices. Such variations suggest unique reactivity profiles and molecular stability, pertinent to their pharmacological potential. Moreover, Molecular Electrostatic Potential (MEP) analyses provide visual representations of the electrostatic characteristics of these alkaloids. The analyses highlight areas prone to electrophilic and nucleophilic attacks, indicating their potential for specific biochemical interactions. This combination of DFT and MEP results elucidates the intricate electronic, energetic, and electrostatic properties of these compounds, underpinning their promise as AD therapeutic agents. The in silico findings of this study shed light on the promising potential of cissamaline, cissamanine, and cissamdine as agents for AD treatment. However, further in vitro and in vivo studies are necessary to validate these theoretical predictions and to understand the precise mechanisms through which these alkaloids may exert their therapeutic effects.

Understanding 2p core-level excitons of late transition metals by analysis of mixed-valence copper in a metal-organic framework.

The L2,3-edge X-ray absorption spectra of late transition metals such as Cu, Ag, and Au exhibit absorption onsets lower in energy for higher oxidation states, which is at odds with the measured spectra of earlier transition metals. Time-dependent density functional theory calculations for Cu2+/Cu+ reveal a larger 2p core-exciton binding energy for Cu2+, overshadowing shifts in single-particle excitation energies with respect to Cu+. We explore this phenomenon in a Cu+ metal-organic framework with ∼12% Cu2+ defects and find that corrections with self-consistent excited-state total energy differences provide accurate XAS peak alignment.

New-Generation Electron-Propagator Methods for Calculations of Electron Affinities and Ionization Energies: Tests on Organic Photovoltaic Molecules.

A new generation of ab initio electron-propagator self-energies recently superseded its antecedents' accuracy and computational efficiency in calculating vertical ionization energies (VIEs) of closed-shell molecules. (See J. Chem. Phys. 2021, 155, 204107, J. Chem. Theory Comput. 2022, 18, 4927, J. Chem. Phys. 2023, 159, 124109.) No adjustable parameters were introduced in the generation of reference orbitals or in the construction of self-energies. The same approach has been extended in this work to vertical electron affinities (VEAs). Calculations were performed on 24 conjugated, organic photovoltaic molecules with diverse functional groups. These molecules are considerably larger than those studied in previous tests on VIEs. Several new-generation self-energies produce mean absolute errors (MAEs) below 0.1 eV versus ΔCCSD(T) (i.e., total energy differences from the coupled-cluster singles, doubles, and perturbative triples method) VIEs and VEAs obtained with identical basis sets. A composite model employs cubically and quintically scaling algorithms and power-law basis-set extrapolations based on augmented double-triple or triple-quadruple ζ data. Its MAEs are near 0.05 eV versus benchmark values, with 0.03 eV error bars for the lowest VIE and the highest VEA of each molecule. A more efficient and equally accurate composite model for calculating VIEs avoids full transformations of electron repulsion integrals to the molecular orbital basis. High probability factors support the diagonal self-energy approximation, wherein Dyson orbitals are proportional to canonical, Hartree-Fock orbitals.