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Physical Chemistry Chemical Physics :... Sep 2023The non-additive three-body interaction potential for helium was computed using the coupled-cluster theory and the full configuration interaction method. The obtained...
The non-additive three-body interaction potential for helium was computed using the coupled-cluster theory and the full configuration interaction method. The obtained potential comprises an improved nonrelativistic Born-Oppenheimer energy and the leading relativistic and nuclear-motion corrections. The mean absolute uncertainty of our calculations due to the incompleteness of the orbital basis set was determined employing complete-basis-set extrapolation techniques and was found to be 1.2%. For three helium atoms forming an equilateral triangle with the side length of 5.6 bohr - a geometry close to the minimum of the total potential energy surface - our three-body potential amounts to -90.6 mK, with an estimated uncertainty of 0.5 mK. An analytic function, developed to accurately fit the computed three-body interaction energies, was chosen to correctly describe the asymptotic behavior of the three-body potential for trimer configurations corresponding to both the three-atomic and the atom-diatom fragmentation channels. For large triangles with sides , , and , the potential takes correctly into account all angular terms decaying as -l12 -m23 -n21 with + + ≤ 14 for the nonrelativistic Born-Oppenheimer energy and + + ≤ 9 for the post-Born-Oppenheimer corrections. We also developed a short-range analytic function describing the local behavior of the total uncertainty of the computed three-body interaction energies. Using both fits we calculated the third pressure and acoustic virial coefficients for helium and their uncertainties for a wide range of temperatures. The results of these calculations were compared with available experimental data and with previous theoretical determinations. The estimated uncertainties of present calculations are 3-5 times smaller than those reported in the best previous works.
PubMed: 37548243
DOI: 10.1039/d3cp01794j -
European Journal of Pharmaceutical... Aug 2024Bioequivalence determinations for locally acting dermatology drug products rely on assessing product sameness thru physicochemical composition and structure comparison,...
Bioequivalence determinations for locally acting dermatology drug products rely on assessing product sameness thru physicochemical composition and structure comparison, comparing the concentration of the active ingredient at the putative site of action, or comparing the clinical performance of the test (would-be generic) and reference products. Topical product action on cutaneous disease may be confounded by the action of excipients and are also subject to the inherent variability of how product may interact with the skin, including thermodynamic factors such as evaporation, spreadability, and interaction with the local environment such as heat and light and skin moisture.
Topics: Humans; Administration, Cutaneous; Dermatologic Agents; Excipients; Skin; Skin Diseases; Therapeutic Equivalency
PubMed: 38797441
DOI: 10.1016/j.ejps.2024.106815 -
Physical Chemistry Chemical Physics :... Jan 2024An analytic theory based on the concept of "effective-fields" is proposed to explain the mechanism of polarization transfer from spin = 1/2 to spin = 1 in non-rotating...
An analytic theory based on the concept of "effective-fields" is proposed to explain the mechanism of polarization transfer from spin = 1/2 to spin = 1 in non-rotating (static) solids. Employing an isolated two-spin model system, the matching conditions responsible for polarization transfer in cross-polarization (CP) experiments are identified and described in terms of the single-transition operators. In contrast to other existing treatments, the polarization transfer among spins is quantified through analytic expressions highlighting the individual contributions emerging from all plausible CP matching conditions. The interplay between the CP matching conditions observed in experiments is outlined in both isotropic and anisotropic systems and verified through comparison between simulations based on analytic and exact numerical methods. The predictions emerging from the analytic theory are verified over a wide range of experimentally relevant parameters and could be beneficial in the optimization of the CP experiments.
PubMed: 38179672
DOI: 10.1039/d3cp05921a -
PloS One 2023The material study of ancient Egyptian paintings began with the advent of Egyptology during the 19th century. By the 1930s, a lot had already been sampled and described....
The material study of ancient Egyptian paintings began with the advent of Egyptology during the 19th century. By the 1930s, a lot had already been sampled and described. The limited palette for example has been analysed from actual painted surfaces but also from pigments and painting tools retrieved on site. However, most of these studies took place in museums while the painted surfaces, preserved in funerary chapels and temples, remained somewhat estranged from this primary physical understanding. The artistic process has been also reconstructed, mainly from the information presented by unfinished monuments, showing surfaces at different stages of completion. A lot of this modern and theoretical reconstruction is, however, based on the usual archaeological guessing game that aims at filling the remaining blanks. Our interdisciplinary project has decided to experiment on-site with state-of-the-art portable analysis tools, avoiding any physical sampling, to see if our knowledge of the work of the ancient Egyptian painters and draughtsmen could be taken at a further stage, while based on physical quantification that could be seen as a stronger and more reliable foundation for a redefined scientific hypothesis. The use of XRF mapping has, for instance, been applied to a known case of correction by surface repaint, something that is supposedly rare in the ancient Egyptian formal artistic process, while another fully unexpected one was discovered during the analytic exploration of a royal representation. In both cases, the precise and readable imaging of the physical composition of the painted surface offers a renewed visual approach based of chemistry, that can be shared through a multi- and interdisciplinary approach. However, this also leads to a more complex description of pigment mixtures that could have multiple meanings, where the practical often leads towards the symbolic, and from there hopefully to a renewed definition of the use of colours in complex sets of ancient Egyptian representations. At this stage, though the progress in this on-site material assessment of ancient works of art definitely means astonishing progress, one humbly has to face the fact that these ancient treasures shall still retain part of their defining mysteries.
Topics: Paintings; Egypt; Paint; Archaeology; Head
PubMed: 37437004
DOI: 10.1371/journal.pone.0287647 -
Discover Nano Sep 2023Although porphyry systems like metallo-phthalocynine are recognized as promising molecular models for electrocatalytic oxygen reduction reaction (ORR), their poor...
Although porphyry systems like metallo-phthalocynine are recognized as promising molecular models for electrocatalytic oxygen reduction reaction (ORR), their poor durability and methanol tolerance are still challenges and need improvement before being considered for practical applications. Herein, we successfully designed and constructed a Fe-phthalocyanine-derived highly conjugated 2D covalent organic framework (2D FePc-COF), using octa-amino-Fe-phthalocyanine (OA-FePc) and cyclohexanone as precursors. The prepared 2D FePc-COF was characterized via multiple analytic techniques. The electrochemical studies indicated that prepared 2D FePc-COF was far more superior to OA-FePc and 20% Pt/C, displaying anodic shift of 100 and 50 mV (vs RHE) in formal potential, respectively. Moreover, this catalyst also demonstrated excellent methanol tolerance and durability (over 10,000 CV cycles). Theoretical investigations revealed that due to extended conjugation and elimination of electron donating groups (-NH), the shifting of dz-orbital (Fe) energy took nearer to π*-orbital (O), allowing optimum coupling of both the orbitals, thereby enhancing 4e ORR. This work demonstrates the art of molecular design, aiming at improving catalytic activity of macrocyclic molecular systems towards ORR.
PubMed: 37665422
DOI: 10.1186/s11671-023-03890-w -
Journal of Food Science Mar 2024C-phycocyanin (C-PC) is a natural high-value blue phycobiliprotein from Spirulina platensis, which has wide biological applications in food, pharmaceutical, and...
C-phycocyanin (C-PC) is a natural high-value blue phycobiliprotein from Spirulina platensis, which has wide biological applications in food, pharmaceutical, and cosmetics. However, the freshness of S. platensis powder (SPP) materials and C-PC purification play critical roles in evaluating the stability and bioactivities of C-PC, which severely affect its commercial application. This study investigated the effect of spray-dried SPP freshness on the biofunctional activities of analytical grade C-PC (AGC-PC). The yield of AGC-PC extracted from spray-dried SPP could reach 101.88 mg/g (75% recovery ratio) after purification by reversed phase high-performance liquid chromatography (RP-HPLC) system. The half-life period (t ) of AGC-PC stability at 60°C and 8000 lux light could remain 171.70 min and 176.11 h within 6 months storage of spray-dried SPP. The emulsifying activity index (EAI) and foaming capacity (FC) of AGC-PC from fresh-dried SPP showed maximum values of 68.64 m /g and 252.9%, respectively. The EC of AGC-PC from fresh spray-dried SPP on 2,2-diphenyl-1-picrylhydrazyl (DPPH) and 2,2'-azinobis(3-ethylbenzothiazoline -6-sulfonic acid (ABTS+·) scavenging activity could reach 63.76 and 92.93 mg/L, respectively. The EC of AGC-PC from fresh spray-dried SPP on proteinase inhibition and anti-lipoxygenase activity were 302.96 and 178.8 mg/L, respectively. The stability and biofunctional activities of AGC-PC remained stable within 6 months storage of SPP, and then rapidly decreased after 9 months storage due to the disintegration of the trimeric (αβ) and hexameric (αβ) forms of C-PC. It is concluded that the optimal storage period of SPP for preparation of AGC-PC in commercial use should be less than 6 months. PRACTICAL APPLICATION: The C-phycocyanin (C-PC) from dried Spirulina platensis powder (SPP) has been widely applied in food nutritional, florescent markers, pharmaceuticals, cosmetics, etc, due to its blue color, fluorescence, and antioxidant properties. However, the effect of dried SPP freshness on the stability and functional activity of C-PC has been rarely reported. This study found that the thermostability, photostability, emulsifying, antioxidant, and anti-inflammatory activities of analytical grade C-PC (AGC-PC) significantly decreased after 6 months storage of SPP. Based on investigations, we have proposed that the suitable storage time of dried SPP for preparation of AGC-PC in commercial application should be within 6 months.
Topics: Phycocyanin; Antioxidants; Powders; Spirulina
PubMed: 38258911
DOI: 10.1111/1750-3841.16931 -
Antioxidants & Redox Signaling May 2024Fundamental to the application of tissue redox status to human health is the quantification and localization of tissue redox abnormalities and oxidative stress and...
Fundamental to the application of tissue redox status to human health is the quantification and localization of tissue redox abnormalities and oxidative stress and their correlation with the severity and local extent of disease to inform therapy. The centrality of the low-molecular-weight thiol, glutathione, in physiological redox balance has long been appreciated, but direct measurement of tissue thiol status has not been possible hitherto. Recent advances in instrumentation and molecular probes suggest the feasibility of real-time redox assessment in humans. Recent studies have demonstrated the feasibility of using low-frequency electron paramagnetic resonance (EPR) techniques for quantitative imaging of redox status in mammalian tissues . Rapid-scan (RS) EPR spectroscopy and imaging, new disulfide-dinitroxide spin probes, and novel analytic techniques have led to significant advances in direct, quantitative imaging of thiol redox status. While novel RS EPR imaging coupled with first-generation molecular probes has demonstrated the feasibility of imaging thiol redox status , further technical advancements are desirable and ongoing. These include developing spin probes that are tailored for specific tissues with response kinetics tuned to the physiological environment. Equally critical are RS instrumentation with higher signal-to-noise ratio and minimal signal distortion, as well as optimized imaging protocols for image acquisition with sparsity adapted to image information content. Quantitative images of tissue glutathione promise to enable acquisition of a general image of mammalian and potentially human tissue health.
Topics: Animals; Humans; Electron Spin Resonance Spectroscopy; Glutathione; Oxidation-Reduction; Oxidative Stress; Spin Labels; Sulfhydryl Compounds
PubMed: 36680741
DOI: 10.1089/ars.2022.0216 -
The Journal of Chemical Physics Nov 2023The quantum chemistry community has developed analytic forces for approximate electronic excited states to enable walking on excited state potential energy surfaces...
The quantum chemistry community has developed analytic forces for approximate electronic excited states to enable walking on excited state potential energy surfaces (PES). One can thereby computationally characterize excited state minima and saddle points. Always implicit in using this machinery is the fact that an excited state PES only exists within the realm of the Born-Oppenheimer approximation, where the nuclear and electronic degrees of freedom separate. This work demonstrates through ab initio calculations and simple nonadiabatic dynamics that some excited state minimum structures are fantastical: they appear to exist as stable configurations only as a consequence of the PES construct, rather than being physically observable. Each fantastical structure exhibits an unphysically high predicted harmonic frequency and associated force constant. This fact can serve as a valuable diagnostic of when an optimized excited state structure is non-observable. The origin of this phenomenon can be attributed to the coupling between different electronic states. As PESs approach one another, the upper surface can form a minimum that is very close to a near-touching point. The force constant, evaluated at this minimum, relates to the strength of the electronic coupling rather than to any characteristic excited state vibration. Nonadiabatic dynamics results using a Landau-Zener model illustrate that fantastical excited state structures have extremely short lifetimes on the order of a few femtoseconds. Their appearance in a calculation signals the presence of a nearby conical intersection through which the system will rapidly cross to a lower surface.
PubMed: 37916588
DOI: 10.1063/5.0172015 -
Scientific Reports Dec 2023The procedures currently used for hepatitis B (HB) detection are not suitable for screening, clinical diagnosis, and point-of-care testing (POCT). Therefore, we...
The procedures currently used for hepatitis B (HB) detection are not suitable for screening, clinical diagnosis, and point-of-care testing (POCT). Therefore, we developed and tested a QCM-based immunosensor by surface modification with AuNP-PEIs to amplify the signal and provide an oriented-immobilization surface. The AuNP-PEIs were characterized by ICP-Mass, UV/Vis, DLS, FE-SEM, and ATR-FTIR. After coating AuNP-PEIs on the gold electrode surface, anti-HBsAg antibodies were immobilized using NHS/EDC chemistry based on response surface methodology (RSM) optimization. The efficiency of the immunosensor was assessed by human sera and data were compared to gold-standard ELISA using receiver-operating-characteristic (ROC) analysis. FE-SEM, AFM, EDS, and EDS mapping confirmed AuNP-PEIs are homogeneously distributed on the surface with a high density and purity. After antibody immobilization, the immunosensor exhibited good recognition of HBsAg with a calibration curve of ∆F = - 6.910ex + 10(R = 0.9905), a LOD of 1.49 ng/mL, and a LOQ of 4.52 ng/mL. The immunosensor yielded reliable and accurate results with a specificity of 100% (95% CI 47.8-100.0) and sensitivity of 100% (95% CI 96.2-100.0). In conclusion, the fabricated immunosensor has the potential as an analytic tool with high sensitivity and specificity. However, further investigations are needed to convert it to a tiny lab-on-chip for HB diagnosis in clinical samples.
Topics: Humans; Biosensing Techniques; Metal Nanoparticles; Polyethyleneimine; Gold; Quartz Crystal Microbalance Techniques; Immunoassay; Hepatitis B; Limit of Detection
PubMed: 38071203
DOI: 10.1038/s41598-023-48766-2 -
Environmental Research Dec 2023A high-quality substrate layer is the cornerstone of supporting that green roofs (GRs) can become an efficient and sustainable nature-based solution to urban...
A high-quality substrate layer is the cornerstone of supporting that green roofs (GRs) can become an efficient and sustainable nature-based solution to urban environmental problems. In the present study, three lightweight substrate materials commonly used in GRs of peat soil, vermiculite and pumice with four appropriate proportions of the nutrient substrate and the mineral substrates were selected to install twelve substrate modules. The lightweight property, water-holding, nutrient retention and rainwater reduction performance of the substrate modules were investigated by the laboratory determination methods and the simulated rainfall experiment. An assessment model based on the multifunctional performance established by analytic hierarchy process (AHP) was used for the component design optimization of GR substrate layer. The results showed that the substrate modules based on peat soil and vermiculite (PV) as the mineral substrate, which the dry volumetric weights and the average water content were 1.40-1.70 kN m and 47.80%-49.06%, always exhibited better lightweight properties and water-holding performance compared to those composed of pumice. PV-40 had the highest value of the multifunction index even while none of its functional performance was optimal among all the substrate modules. The present study emphasizes the necessity of optimizing the GR substrate layer component based on the assessment of multifunctional performance to better promote the sustainable development of GRs in urban areas.
Topics: Rain; Soil; Aluminum Silicates; Water; Conservation of Natural Resources; Water Movements
PubMed: 37742754
DOI: 10.1016/j.envres.2023.117190