Nonparallel Orientation Research Articles

Nonmass Lesions on Breast Ultrasound: Interreader Agreement and Associations With Malignancy.

Background: Nonmass lesions (NMLs) on breast ultrasound lack clear definition and encompass a broad range of benign and malignant entities. Given anticipated inclusion of NMLs in the BI-RADS 6th edition, thorough understanding of these lesions will be critical for optimal management. Objective: To evaluate interreader agreement for classification of lesions on breast ultrasound as NMLs and to identify imaging features associated with malignancy in these lesions. Methods: This retrospective study included 2007 patients (2005 female, 2 male; mean age, 54.0±9.6 years) who underwent ultrasound-guided biopsy of 2381 breast lesions between January 2020 and December 2020. Two radiologists independently classified lesions as masses or NMLs, using a definition of NMLs from a presentation at the 2023 Radiological Society of North America annual meeting. The radiologists attempted to reach consensus for discordant cases. Another radiologist recorded NMLs' mammographic and ultrasound characteristics. Pathological outcomes for NMLs were extracted from the EHR. Results: Interreader agreement for lesion classification (mass vs NML) was substantial (κ=0.73) A total of 216 lesions were classified as NMLs by both readers independently; an additional 101 lesions were classified as NMLs by consensus review after initial discordance. Thus, 317/2381 (13.3%) of lesions were classified as NMLs, of which 101/317 (31.9%) had initial discordance. A total of 133/317 (42.0%) NMLs were malignant, including invasive ductal carcinoma (48/133), ductal carcinoma in situ (43/133), and microinvasive ductal carcinoma (34/133). A total of 30.8% of malignant NML lacked correlative mammographic abnormalities. Ultrasound findings with highest accuracy for identifying malignancy of NMLs were calcifications (65.6%), posterior shadowing (62.8%), and non-parallel orientation (59.3%). In multivariable analysis, variables showing significant independent associations with malignancy included calcifications (OR=8.9), asymmetry (OR=4.7), and mass (OR=4.7) on mammography, and greater size (OR=1.03), non-parallel orientation (OR=8.7), and posterior shadowing (OR=6.3) on ultrasound. Conclusion: The analysis provides insights into reader variability for classifying ultrasound lesions as NML by an existing definition, as well as into imaging findings' potential utility for characterizing such lesions as malignant. Clinical Impact: These findings indicate the need for further precision and clarification regarding the definition of NMLs and for further investigation into which NMLs have greatest malignancy risk.

Application of eco-friendly material as an inexpensive adsorbent for methyl violet dye removal: experimental, response surface methodology and statistical physics

Methyl Violet (MV) removal from aqueous solutions is studied using an Algerian Bentonite sample as a low-cost adsorbent. SEM-EDX, X-ray diffraction, and chemical composition characterized the adsorbent material. The modeling and optimization study of MV adsorption using artificial neural network (ANN) and response surface methodology (RSM) were also examined. The effects of pH, contact time, dye concentration, and temperature are all considered. The adsorption kinetics results are adjusted to best fit the pseudo-second-order model. Langmuir-Freundlich and Langmuir models well describe the experimental data with an adsorption capacity of 472 mg g−1. The calculated thermodynamic data demonstrates that adsorption is spontaneous and endothermic. Desorption studies with methanol indicate that the adsorbent could successfully retain MV, even after five cycles. The statistical physics theory indicates the non-parallel orientation of the MV molecule’s adsorption. The adsorption energies varied from 13.99 to 17.60 kJ mol−1, revealing the physical adsorption systems. From these results, it can be considered that the raw Algerian bentonite sample tested herein is effective in removing MV from aqueous solutions and may be used as an alternative to high-cost commercial adsorbents.

Macroscopic and Microscopic Levels of Methylene Blue Adsorption on a Magnetic Bio-Based Adsorbent: In-Depth Study Using Experiments, Advanced Modeling, and Statistical Thermodynamic Analysis

A magnetic bio-based adsorbent derived from H2O2-activated zeolite and turmeric carbohydrate polymer was fabricated, characterized, and utilized in removing methylene blue (MB) dye at pH 8.0 and temperatures between 25 and 55 °C. To understand the molecular-scale adsorption mechanism, a range of advanced statistical physics models were employed in conjunction with conventional equilibrium models. The as-synthesized biosorbent presented high maximum capacities according to the Langmuir model, with values ranging from 268.67 to 307.73 mg/g. The double-layer equation yielded the best-fitting results to the MB experimental data among the applied statistical physics models. The number of MB molecules ranged from 1.14 to 1.97, suggesting a multi-molecular mechanism with a non-parallel orientation. The main factor affecting the effectiveness of this adsorbent was the density of its functional groups, which varied from 27.7 to 142.1 mg/g. Adsorption energies in the range of 19.22–21.69 kJ/mol were obtained, representing the existence of physical forces like hydrogen bonds and electrostatic interactions. To complete the macroscopic examination of the MB adsorption mechanism, thermodynamic parameters such as entropy, Gibbs free energy, and internal energy were considered. The adsorption/desorption outcomes up to five cycles displayed the stability of the magnetic biosorbent and its potential for decontaminating industrial effluents. Overall, this work increases our understanding of the MB adsorption mechanism onto the produced biosorbent at the molecular level.

Efficient removal of a pharmaceutical compound on organoclay: batch experiment, DFT calculation, statistical physics, and modeling

This study was performed to evaluate the adsorptive properties of bentonite. Natural bentonite was found to adsorb considerable amounts of Salicylic acid (SA) after modification by hexadecyltrimethylammonium bromide (HDTMA). Batch studies investigated the adsorptive properties of the modified natural bentonite (organobentonite). The characterization results show the increase in the d001 spacing from 1.13 to 1.53 nm for raw bentonite and organobentonite, respectively. The FTIR analysis indicates the asymmetric vs. (CH2) and symmetric vs. (CH2) stretching modes for clay loaded with surfactant molecules are 2919 and 2845 cm−1, respectively. We investigate parameters such as contact time, pH, temperature, and initial concentration. Desorption and regeneration were also studied. The kinetic analysis shows that the adsorption equilibrium of salicylic acid onto organoclay was reached after 120 min and fits well to a pseudo-second-order kinetic model with the contribution of intraparticular diffusion. In addition, the adjustment of the isothermal models indicated that the Langmuir-Freundlich model best fit the isotherms data for unmodified bentonite and the Langmuir model for modified bentonite. The maximum adsorption capacity of organobentonite is 128 mg g−1 at 25 °C. According to the statistical physics model, the SA could be adsorbed on the surface of organoclay in a non-parallel orientation. The desorption-regeneration investigation revealed that the material could be successfully reused for three cycles of SA adsorption. Mechanistic studies of SA sorption on organobentonite have highlighted several mechanisms: hydrogen bonding, electrostatic attraction, and hydrophobic interaction.

Diagnostic performance of PET-CT and technical efficacy of ultrasound-guided core needle biopsy of small and intermediate size malignant supraclavicular lymph nodes

Aim: We aimed (1) to determine optimal PET-CT SUV and ultrasound (US) features associated for malignant smallintermediate size supraclavicular lymph nodes (SCN) and (2) to evaluate technical efficacy of core needle biopsy (CNB). Materials and methods: Between 2020 and 2023, CNB of SCN with short-axis less than 15 mm were included. PET-CT was evaluated for optimal SUV cut-off value. Multivariate logistic regression was performed for US features. Technical efficacy of CNB (success rate) was calculated, and US features were compared between satisfactory CNB specimen and unsatisfactory CNB specimen.Results: Eighty-four SCN per 80 patients (age 64.0±17.2 years, 45.2% female) were included. The optimal SUV cut-off value was 1.1 with diagnostic accuracy of 89.8%. US features associated with malignancy were anteroposterior dimension ≥9 mm and absence of hilum. The overall CNB success rate was 94%, and unsatisfactory specimen demonstrated shorter transverse diameter (12 mm vs 5 mm, p<0.001), and non-parallel orientation (20.3% vs. 100%, p<0.001).Conclusion: CNB should be considered for small-intermediate size SCN with SUV exceeding 1.1, anteroposterior dimension ≥9 mm, and absence of hilum. SCN with shorter transverse diameter and non-parallel orientation may result in unsatisfactory CNB specimen.

Competitive water adsorption for low-energy desalination: Insights from statistical physics theory

In this research, the statistical physics theory has been deployed to unlock the mysteries of water molecule binding on Zeolite and Silica Gel at the microscopic level. The adopted computational procedure, based on the grand canonical partition function, provided physical insights of the docking mechanism by scrutinizing the stereographic and energetic variables. The number of receiving sites, their densities, the saturation amount and the energetic factors were assessed due to the strong consistency between the numerical and experimental results. Docking inspections revealed that H2O primarily adopted a non-parallel orientation upon interaction with the adsorbent receptor sites. The estimated attachment energies ranged from 18.25 kJ/mol to 24.55 kJ/mol indicating a physisorption process where weak forces (van der Waals) mainly govern the surface occupancy. Desalination effectiveness has been examined and according to calculations the coefficient of performance (COP) and the quantitative efficiency metric (QEM) is 2.7 times and 1.2 times respectively greater in case of Zeolite than Silica Gel. By analyzing pore size distribution (PSD) and adhesion energy distribution (AED), this study elucidates the relationship between pore size and target molecule capture, and predicts binding strength and potential for molecule capture/release under various conditions.

Adsorption ability of sugar scum as industrial waste for crystal violet elimination: Experimental and advanced statistical physics modeling

Recycling solid industrial waste into useful resources is the most critical aspect of managing waste. Herein, for detoxifying poisonous crystal violet dye (CV) in aqueous media, sugar scum (SS) as an underutilized industrial discard has been tested as a promising adsorbent.The SS was thoroughly analyzed beforehand and after the adsorption process through various characterization techniques. Several operational factors, including pH, biosorbent dosage, dye concentration, and temperature, were optimized, reaching 24 mg.g-1 at (pH 10, 2 g.L−1 of SS, 10 mg.L−1 of CV and 25 °C). The bioadsorbent's performance was assessed through a range of studies involving kinetic, equilibrium (using both conventional and statistical physics models), and thermodynamic investigations.Based on the results, the equilibrium curves best fit the Freundlich model, indicating that multilayer adsorption occurs on a heterogeneous active sites surface. The statistical physics models provided detailed physiochemical insights, the double-layer with two energies model was most accurately describing the data, with a high saturation capability of 371 mg.g−1. Most interactions occur at a single adsorption site (70 %), with the remaining 30 % at two sites, involving both parallel and non-parallel orientations. The mesoporous structure of the SS surface provides an optimum size for CV adsorption. Pore filling, Van der Waals forces, hydrogen bonding, π-π and electrostatic interactions are proposed as the possible mechanisms in the CV-SS system. Thermodynamic measurements indicate that CV adsorption is spontaneous (ΔG° < 0) and exothermic ΔH° (− 41.390 kJ mol−1).The SS recyclability was assessed, exhibiting encouraging sustainability with a slight fall in effectiveness (∼7 %) after 5 sequential usages. Altogether, this study makes a substantial contribution to the promotion of ecological water treatment strategies, which highlights the utility of using SS as an environmental alternative to water contaminant remediation.

Modeling 2,4-dichlorophenoxyacetic acid adsorption on candle bush pod-derived activated carbon: Insights from advanced statistical physics models

The widespread usage of 2,4-Dichlorophenoxyacetic acid (2,4-D) as an herbicide has led to alarming levels of environmental pollution, presenting severe risks to ecosystems and human health. This study aimed to synthesize a new adsorbent, activated carbon from candle bush pods (CBAC) via low-temperature phosphoric acid activation and investigate its ability for adsorptive elimination of 2,4-D. The setup of a new adsorption system requires the experimental determination of adsorption isotherms and their thorough modeling, which is achieved through advanced statistical physics models (ASPMs). The characterization of CBAC revealed a porous morphology with a remarkable specific surface area (415.31 m2/g). XRD revealed graphitic carbon structures, while XPS detected phosphate groups, graphitic structures, and oxygen-containing functional groups. Double layer with single energy (DLSE) model – one of the ASPMs revealed both non-parallel and parallel orientation of 2,4-D molecules on CBAC, with saturation adsorption capacity values increasing with temperature (up to 252.35 mg/g) at pH 2. The adsorption was physisorption (ΔE = 12.62–16.26 kJ/mol) and spontaneous and endothermic. Hence, the findings herein demonstrate the potential of CBAC as a sustainable and effective adsorbent for mitigating environmental pollution caused by 2,4-D.

Cross-seasonal and diurnal variation in physical contact between sub-adult pigs

Social touch is an important aspect of social relationships and has a major influence on development and health. However, in many species the occurrence and function of social touch is unknown. Pigs have frequent physical contact but this behaviour is largely unexplored. The aim of this study was to investigate the undisturbed variation in physical contact between pigs, and to assess diurnal and seasonal influences. A stable group of ten Puławska sub-adult female pigs was observed for 406 h across four seasons during the day and night, by continuous observations on an individual level (406 h / pig). They were housed indoors (112 m2 pen) on straw bedding. The ethogram distinguished the amount of surface contact between pigs when lying, the orientation to others, social nosing, other non-agonistic social behaviour and agonistic behaviours. Resting location within the pen was recorded 48 times per pig, and dominance relationships were calculated from agonistic interactions. Data were analysed with mixed models accounting for repeated observations. Pigs spent on average 40 % of their time lying in body contact, most often lying with their extremities in contact (71 %), followed by lying in partial body contact (16 %) or full body contact (13 %) and were frequently nosing the head and body of others. The duration of lying in any type of contact, as well as agonistic behaviour, was influenced by season, with the longest durations in autumn. In summer, the duration of partial body contact was lowest, but full body contact was unaffected by season. Nosing behaviour remained constant throughout the year. Pigs lay in contact more during the night, while showing more social behaviours during the day. Pigs mostly lay in nonparallel orientation or head-to-head, but clearly least in the head-to-tail orientation. Season influenced the frequency of lying head-to-head and head-to-tail, but not lying nonparallel. The coefficient of variation of the lying location was influenced by season. Allo-grooming, mounting, and nudging were shown infrequently and mostly by specific individuals. In conclusion, when at a large space allowance, pigs spend nearly half of their time in body contact, even during the higher temperatures in summer. This shows that social touch, including affiliative behaviour, has an important role in pigs’ social life, and remains largely unaffected by external influences.

Exploring diclofenac potassium adsorption on activated carbon: A comprehensive statistical physics and experimental approach

This study aims to contribute to understanding the removal processes of diclofenac potassium (DP) medicine in wastewater treatment systems, employing activated carbon (AC) as an adsorbent. To achieve this goal, a multidisciplinary approach was adopted, integrating experimental and theoretical analyses of equilibrium data regarding the adsorption of DP on AC. Five statistical physics models were applied to determine the model best for the adsorption process. The selection of the most appropriate model considered both the performance of the models and the analysis of the estimated parameters. Statistically, all models exhibited satisfactory results. However, when analyzing the estimated parameters, the double-layer model with single adsorption energy emerged as the most suitable model to describe the analyzed process. Based on the chosen model’s parameters, we observed that as the temperature increases, the number of active sites occupied during adsorption and their availability on the adsorbent also increases. However, the number of available adsorption sites decreases as the temperature rises. The half-saturation concentration, in turn, increases with increasing temperature, suggesting that the process is favored when temperatures above room temperature are used. Additionally, higher temperatures provide better removal results, indicating that DP molecules’ non-parallel and parallel orientations on the AC surface favor the adsorption process. Finally, our combined results led to the proposal of a mechanism for DP adsorption on AC, which is based on physical adsorption interactions between adsorbate-adsorbent and adsorbate–adsorbate.

Breast imaging reporting and data system for sonography: Positive and negative predictive values of sonographic features in Kumasi, Ghana

BackgroundBreast cancer is the most common female cancer globally. The method of choice for screening and diagnosing breast cancer is mammography, which is not widely available in Ghana as compared to ultrasonography. This study aimed to evaluate the sonographic features of solid breast lesions using the new sonographic Breast Imaging- Reporting and Data System (BI-RADS-US) lexicon for malignancy with histopathology as the gold standard. MethodsThis was a prospective quantitative study that sonographically scanned female patients with breast masses and consecutively selected cases recommended for core biopsy from May 2018 to May 2021. Sixty (60) solid breast masses were described using the sonographic BI-RADS lexicon features. Lesion description and biopsy results from histopathology were compared and analyzed using Pearson's Chi-square test. Odds ratios, sensitivity, specificity, and predictive values were also calculated. Statistical significance level was set at p ≤ 0.05. ResultsIrregular shape (p < 0.0001), spiculated mass margins (p < 0.0001), and not parallel mass orientation (p= 0.0007) were more commonly associated with malignant masses. The sensitivity of breast ultrasound for malignancy was 93.9 % and the specificity was 55.6 % with an overall accuracy rate of 76.6 %. The negative predictive value was 88.7 % and the positive predictive value was 72.1 %. Descriptors like irregular shape, non-parallel orientation, angular and spiculated margins, echogenic halo, and markedly hypoechoic internal content, demonstrated higher odds ratios for malignancy. ConclusionsThis study adds valuable insights to the diagnosis of breast cancer using the sonographic BI-RADS lexicon features. The results demonstrate that specific sonographic descriptors can effectively differentiate between benign and malignant breast masses.

Selective Extraction and Determination of Hydrocortisone and Dexamethasone in Skincare Cosmetics: Analytical Interpretation Using Statistical Physics Formalism

Molecularly imprinted polymers (MIPs), as magnetic extraction adsorbents, are used for the selective, rapid determination and extraction of dexamethasone and hydrocortisone in skincare products. Therefore, in this paper, magnetic molecularly imprinted polymers (MMIPs) and magnetic non-molecularly imprinted polymers (MNIPs) were utilized as adsorbents to describe the adsorption phenomena of dexamethasone and hydrocortisone. This interpretation, based on a statistical physics theory, applies the multilayer model with saturation to comprehend the adsorption of the drugs. Results obtained via numerical simulation revealed that dexamethasone and hydrocortisone adsorption happens via a non-parallel orientation on the surfaces of MMIPs and MNIPs, and they also showed that the adsorption amount of the MMIPs for the template molecule was notably greater than that of the MNIPs at the same initial concentration. The adsorption energy values retrieved from the data analysis ranged between 7.65 and 15.77 kJ/mol, indicating that the extraction and determination of dexamethasone and hydrocortisone is a physisorption process. Moreover, the distribution of a site’s energy was calculated to confirm the physical nature of the interactions between adsorbate/adsorbent and the heterogeneity of the surfaces of the MMIPs and MNIPs. Finally, the thermodynamic interpretation confirmed the exothermicity and spontaneous nature of the adsorption of these drugs on the tested adsorbents.

Quantitative investigations of Zebrafish olfactory receptor ORA1 responsiveness to three pheromones: Microscopic and macroscopic characterizations via an advanced statistical physics treatment

In this work, an adsorption phenomenon putatively involved in the olfactory sense of phenylacetic acid, 4-chlorophenylacetic acid, and 4-methoxyphenylacetic acid pheromones in the Zebrafish olfactory receptor ORA1 was a helpful mechanism in interpreting and characterizing the olfaction process at a molecular level. Hence, the experimental dose-olfactory response curves were fitted by applying the one-layer adsorption model with a single energy (1LM1E). On one hand, the different parameters introduced in the selected model were used to microscopically study the three olfactory systems. Indeed, the fitting results showed that phenylacetic acid displayed the greatest maximum olfactory response at saturation, due to the effect of functional groups at the R4 position. The three pheromones were docked via a non-parallel orientation and the adsorption process was a multi-molecular mechanism. The sizes of different binding pockets of ORA1 were determined through the estimation of the olfactory receptor site size distributions (stereographic characterization). The estimated adsorption energies, ranging from 17.340 to 21.332 kJ/mol, can be used to describe the energetic interactions between the studied pheromones and the Zebrafish ORA1 binding pockets. The spectrums of the adsorption energy distributions of phenylacetic acid, 4-chlorophenylacetic acid, and 4-methoxyphenylacetic acid, which were spread out from 10 to 32.5 kJ/mol, 5 to 30 kJ/mol, and 10 to 32.5 kJ/mol, respectively, was determined to estimate the corresponding olfactory bands (energetic characterization). On the other hand, three thermodynamic functions were estimated in order to macroscopically study the three olfactory systems.

Diclofenac sodium drug adsorption isotherm on carbon xerogels via an advanced two layers model with two energies

In this work, four carbon xerogels (XCs) adsorbents, which were prepared by the polymerization of formaldehyde (F) and resorcinol (R) using cesium carbonate (Cs) as catalyst at 4 M ratios R/Cs = XCs-100, XCs-500, XCs-1000 and XCs-2000, were utilized to interpret and understand the adsorption mechanism at a molecular level of non steroidal anti inflammatory drug (NSAID), namely diclofenac sodium (DCF). Hence, Four adsorption isotherms were utilized to present the evolution of the adsorbed quantity (Qa) as a function of drug concentration describing the DCF adsorption on the four carbons xerogels at T = 298 K and at pH = 7. In addition, two other adsorption systems, describing the adsorption of DCF on XCs-500, were plotted by varying two experimental conditions: temperature and solution pH. All these experimental data were adjusted and analyzed via the advanced two layers model with two adsorption energies (A2LM2E), which was chosen as the most adequate statistical physics model. Furthermore, stereographic and energetic parameters of A2LM2E namely: the number of DCF molecules per XCs sites (n), the adsorbed quantity at saturation (Qas) and the concentrations at half saturation (C1 and C2) were estimated by a multi-variable non-linear regression. The fitting results indicated that the DCF drug molecules were docked with mixed and non-parallel orientations on the different XCs adsorbents. The investigation of the adsorbed quantity at saturation indicated that Qas increased as follows: Qas (XCs-2000) < Qas (XCs-100) < Qas (XCs-1000) < Qas (XCs-500), showing that the XCs-500 was more efficient for the adsorption of DCF drug than the other adsorbents. The calculated molar adsorption energies ΔE1 and ΔE2 for the studied adsorption systems affirmed the exothermic and the physical characters of the adsorption mechanism since ΔE1 and ΔE2 values were positive and inferior to 40 kJ/mol. Lastly, the XCs-100, XCs-500, XCs-1000 and XCs-2000 adsorbents presented unimodal pore size distributions (PSDs) centered at a pore radius of 8.38 nm, 7.17 nm, 6.05 nm and 5 nm, respectively. Finally, the estimated thermodynamic parameters such as the adsorption entropy (Sa), the Gibbs free enthalpy (G) and the internal energy (Eint) indicated that DCF adsorption on XCs-500 was spontaneous and exothermic process.

Facile synthesis of a recyclable multifunctional magnetic adsorbent prepared from H2O2-modified carbon clay/rice flour polymer/Fe3O4 nanoparticles interface for effective removal of ibuprofen

BackgroundThe combination between magnetite nanoparticles with natural carbohydrate polymers and aluminosilicates is recommended to be a positive strategy in the design of a new type of low-cost, high–efficiency, and eco-friendly magnetic adsorbents for decontamination of toxic pharmaceutical compounds from water. In particular, ibuprofen (IBP) is found to be one of the common drugs detected in water bodies, which is a suggestively alarming state. MethodsA fresh sample of gossan (iron-bearing weathered product) was used in the fabrication of magnetite nanoparticles (MNPs) to be used in the decoration of a bio-composite prepared from H2O2-activated black clay (BC) and biodegradable rice flour (RF) interface. The as-synthesized magnetic biosorbent (BC/RF/MNPs) was characterized by FTIR, FESEM, TEM, XRD, DSC, and TGA techniques and employed in the remediation of ibuprofen at pH 7.0 and temperatures of 25, 40, and 50°C. The adsorption results were fitted to kinetics, traditional isotherms, and statistical physical models to better understand the interaction between IBP and BC/RF/MNPs adsorbent. Significant findingThe pseudo-second-order (PSO) and Freundlich equations described the IBP adsorption system. Monolayer and double-layer advanced statistical physics models were employed to analyze the geometry and interactions mechanism at the molecular scale. The double-layer model showed the best-fitting results, and thus, its steric and energetic parameters and thermodynamic functions were explained. The number of the removed IBP molecules per site (steric n parameter) ranged from 0.55 to 0.84 suggesting the involvement of parallel and non-parallel orientations in the removal process. The adsorption capacity at saturation (Qsat) increased from 45.73 to 67.90mg/g at 25 - 50 ºC signifying endothermic interactions. The adsorption energy ranged from 0.42 to 3.42kJ/mol reflecting the physical interactions between IBP and BC/RF/MNPs. Thermodynamic functions suggested the endothermic and spontaneous nature of the IBP adsorption process. Adsorption/desorption results suggested the high stability and economic benefit of BC/RF/MNPs sorbent.

Investigation of the adsorption mechanism of two nitro musk odorants on OR1A1: Advanced modeling and thermodynamic study

The experimental dose-olfactory response curves of the two nitro musk odorants, such as musk tibetene and musk ambrette, on the broadly human olfactory receptor OR1A1 have been analyzed using four statistical physics models by means of the grand canonical formalism. For such a purpose, the monolayer model with one energy level and the monolayer model with two energy levels were selected to describe the adsorption mechanism of musk tibetene and musk ambrette, respectively. Indeed, three main physicochemical parameters introduced in the selected models affecting the putative adsorption phenomenon involved in the sense of smell, namely, the olfactory response at saturation, the number of nitro musk odorants per OR1A1 binding site, and the half saturation concentration related to the molar adsorption energy. Actually, the investigation of the number of nitro musk fragrances per binding site showed that musk tibetene and musk ambrette odorants were docked on OR1A1 binding sites by a non-parallel orientation and a multi-docking mechanism since the values of this stereographic parameter were higher than unity. Moreover, the selected adsorption models were used to estimate the broadly tuned human olfactory receptor site size distributions relative to musk tibetene and musk ambrette, which were spread out from 1 to 30 nm with a maximum at 4.10 nm for musk tibetene and at 3.55 nm for musk ambrette. Energetically speaking, the magnitudes of the molar adsorption energies, which were inferior to 5 kJ/mol, indicated that the two nitro musk fragrances were physisorbed on OR1A1 binding sites. Furthermore, the adsorption energy distributions, relative to the two olfactory systems, may be estimated to deeply comprehend human olfactory perception, at a molecular level, via the determination of two approximate olfactory bands through the estimation of two adsorption energy distribution bands, which were spread out from 0 to 8.50 kJ/mol for musk tibetene and from 0 to 8 kJ/mol for musk ambrette. Lastly, macroscopically speaking, three thermodynamic potentials governing the adsorption mechanism were studied. Hence, the disorder during the putative adsorption mechanism was followed via the study of the adsorption entropy. Lastly, the adsorption process introduced in the two olfactory systems was spontaneous and exothermic as it was suggested by the Gibbs free energy and the internal energy.

Real-time time-dependent self-consistent field methods with dynamic magnetic fields.

The first finite basis set implementation of the real-time time-dependent self-consistent field method in a dynamic (time-dependent) magnetic field using London atomic orbitals (LAOs) is presented. The accuracy of the finite basis approach using LAOs is benchmarked against numerical results from the literature for the hydrogen atom and H2 in the presence of rapidly oscillating magnetic fields. This comparison is used to inform the choice of appropriate basis sets for studies under such conditions. Remarkably, relatively modest compact LAO basis sets are sufficient to obtain accurate results. Analysis of electron dynamics in the hydrogen atom shows that LAO calculations correctly capture the time evolution of orbital occupations. The Fourier transformation of the autocorrelation function yields a power spectrum exhibiting harmonics associated with coherent emission, which closely matches the literature and further confirms the accuracy of this approach. The dynamical response of the electron density in H2 for a magnetic field parallel to the internuclear axis shows similar behavior to benchmark studies. The flexibility of this implementation is then demonstrated by considering how the dynamical response changes as a function of the orientation of the molecule relative to the applied field. At non-parallel orientations, the symmetry of the system is lowered and numerical benchmark data, which exploit cylindrical symmetry, are no-longer readily available. The present study demonstrates the utility of LAO-based calculations for extreme dynamic magnetic fields, providing a stress-test on the choice of basis. Future applications of this approach for less extreme dynamic magnetic fields are briefly discussed.

Spatial variation in the crustal deformation pattern in the Koyna-Warna region, western India using shear wave splitting

SUMMARY This study investigates crustal anisotropy beneath the Koyna-Warna region (KWR) using waveforms of local earthquakes of magnitude ML ≥ 1.0, recorded at 24 surface and 6 borehole seismic stations during September 2005–February 2020. Waveforms of 1402 local earthquakes that fulfil the splitting criteria (ic &amp;lt; 45°) are used for shear wave splitting analysis, yielding 738 measurements. The study examines the spatial, temporal and depth variations in the fast polarization azimuths (FPAs) and delay times (δt). The average delay times in the Koyna and Warna regions are 0.035 and 0.050 s, respectively, which did not show any significant correlation with depth. The FPAs are predominantly oriented in the NNW–SSE direction in the KWR, commensurate with the in situ maximum horizontal stress (SHmax) obtained using data from a 3-km-deep scientific borehole and individual focal mechanism solutions. The anisotropy beneath KWR is due to the alignment of fluid-filled cracks and pore throats along the SHmax, and is attributed to stress-induced anisotropy. A considerable variation in the orientation of FPAs from NW to NNW–SSE beneath KWR could be associated with heterogeneity in the lithological properties due to variation in the fracture orientation under regional stress. The non-parallel orientation of FPAs with SHmax or faults at some stations is attributed to structure-induced anisotropy, which seems to be associated with surface topography. Measurements at stations, even near the reservoirs, did not show any significant temporal variation in the splitting parameters due to the fluctuation in the water levels.

Quantitative characterizations of mOR-EG activated by vanilla odorants using advanced statistical physics modeling.

An advanced monolayer adsorption model of an ideal gas was successfully employed to investigate the adsorption of vanillin, vanillin methyl ether, vanillin ethyl ether, and vanillin acetate odorants on mouse eugenol olfactory receptor mOR-EG. In order to understand the adsorption process putatively introduced in olfactory perception, model parameters were analyzed. Hence, fitting results showed that the studied vanilla odorants were linked in mOR-EG binding pockets with a non-parallel orientation, and their adsorption was a multi-molecular process (n>1). The adsorption energy values that ranged from 14.021 to 19.193kJ/mol suggested that the four vanilla odorants were physisorbed on mOR-EG (ΔEa<40kJ/mol) and the adsorption mechanism may be considered as an exothermic mechanism (ΔEa>0). The estimated parameters may also be utilized for the quantitative characterization of the interactions of the studied odorants with mOR-EG to determine the corresponding olfactory bands ranging from 8 to 24.5kJ/mol.

Development of a novel in-situ aluminum/carbon composite from olive mill wastewater for the selective adsorption and separation of malachite green and acid yellow 61

In this study, an aluminum/carbon composite was developed from olive mill wastewater (OMWW) and successfully applied in the removal/separation of malachite green (MG) and acid yellow 61 (AY61) and in the treatment of a real discharge from a denim dye bath. The optimized composite (0.5% Al) is microporous, has a specific surface area of 1269 m2.g−1, rich in anionic sites, has an adsorption capacity of 1063 mg.g−1 and exhibited efficient separation of AY61/MG. Thermodynamic results showed physical, endothermic and disordered adsorption. The substrates were attached to the surface by electrostatic, hydrogen and π- π interactions through the contribution of multiple sites in parallel and non-parallel orientations. The composite can be used repeatedly without significantly losing its performance. This study, presents an exploitation of agricultural liquid waste to develop carbon composites for industrial dye removal and separation, creating new economic opportunities for farmers and rural communities.