Gradient Model Research Articles

Nonlinear Analysis of the Multi-Layered Nanoplates

This text investigates the bending/buckling behavior of multi-layer asymmetric/symmetric annular and circular graphene plates through the application of the nonlocal strain gradient model. Additionally, the static analysis of multi-sector nanoplates is addressed. By considering the van der Waals interactions among the layers, the higher-order shear deformation theory (HSDT), and the nonlocal strain gradient theory, the equilibrium equations are formulated in terms of generalized displacements and rotations. The mathematical nonlinear equations are solved utilizing either the semi-analytical polynomial method (SAPM) and the differential quadrature method (DQM). Also, the available references are used to validate the results. Investigations are conducted to examine the effect of small-scale factors, the van der Waals interaction value among the layers, boundary conditions, and geometric factors.

Tailor-Designed Models for the Turbulent Velocity Gradient through Normalizing Flow.

Small-scale turbulence can be comprehensively described in terms of velocity gradients, which makes them an appealing starting point for low-dimensional modeling. Typical models consist of stochastic equations based on closures for nonlocal pressure and viscous contributions. The fidelity of the resulting models depends on the accuracy of the underlying modeling assumptions. Here, we discuss an alternative data-driven approach leveraging machine learning to derive a velocity gradient model which captures its statistics by construction. We use a normalizing flow to learn the velocity gradient probability density function (PDF) from direct numerical simulation (DNS) of incompressible turbulence. Then, by using the equation for the single-time PDF of the velocity gradient, we construct a deterministic, yet chaotic, dynamical system featuring the learned steady-state PDF by design. Finally, utilizing gauge terms for the velocity gradient single-time statistics, we optimize the time correlations as obtained from our model against the DNS data. As a result, the model time realizations resemble the time series from DNS statistically closely.

Research and prediction of early-age loads in double-block ballastless track structure

Considering the hydration reaction of cement, a finite element model(FEM) of the coupling of temperature and humidity field and chemical field in the early age of the double-block ballastless track structure was established, and a field monitoring test on the early age of track slab was carried out with the newly constructed Fuzhou-Xiamen high-speed railway line as a case to verify the correctness of the FEM. Based on the official meteorological data from China Meteorological Administration (CMA) and the FEM, the dataset of vertical temperature and humidity gradients in the early age of the track slab was constructed, and five machine learning training models, namely, machine learning (MLR), multivariate polynomial regression (MPR), support vector regression (SVR), random forest (RF), and gradient boosted regression (GBR), were adopted to train the temperature gradient model and humidity gradient model for the early age of the track slab. The research results show that: (1) under the combined effect of solar radiation, convective heat transfer, radiative heat exchange and the cement hydration reaction, the temperature loading leads to the susceptibility of the sleepers to diagonal cracking; the humidity loading leads to transverse cracking in the center region of the surface of the track slab; (2) the finite element model with a higher accuracy provided the training dataset for the machine learning model. According to the Spearman correlation coefficient, the input features of the temperature gradient model and the humidity gradient model are determined, respectively; (3) Five ML methods were used to train the temperature gradient model and humidity gradient model, both of which demonstrated good generalization ability with a coefficient of determination(R2) greater than 0.85. Among these methods, GBR and SVR exhibited the best performance; From the perspective of MAPE value, the prediction effect of the temperature gradient training model was better than that of the humidity gradient training model; (4) The curing method and the average value of the relative humidity were the important input features influencing the training models for the temperature and humidity gradient loads, respectively. This finding provided an important guideline for the construction of ballastless track structures.

Copper‐Catalyzed Asymmetric Hydrogenation of Unsymmetrical ortho‐Br Substituted Benzophenones

AbstractThe asymmetric hydrogenation of benzophenones, catalyzed by low‐activity earth‐abundant metal copper, has hitherto remained a challenge due to the substrates equipped with two indistinguishably similar aryl groups. In this study, we demonstrated that the prochiral carbon of the ortho‐bromine substrate exhibits the highest electrophilicity and high reactivity among the ortho‐halogen substituted benzophenones, as determined by the Fukui function (f+) analysis and hydrogenation reaction. Considering that the enantiodirecting functional bromine group can be easily derivatized and removed in the products, we successfully achieved a green copper‐catalyzed asymmetric hydrogenation of ortho‐bromine substituted benzophenones. This method yielded a series of chiral benzhydrols with excellent results. The utility of this protocol has been validated through a gram‐scale reaction and subsequent product transformations. Independent gradient model based on Hirshfeld partition (IGMH) and energy decomposition analysis (EDA) indicate that the CH⋅⋅⋅HC multiple attractive dispersion interactions (MADI) effect between the catalyst and substrate enhances the catalyst's activity.

Evaluating functional ability in older adults’ object retrieval behavior from kitchen furniture using OpenPose and REBA

The purpose of this study is to evaluate, through analysis, the ability of older persons to retrieve items from kitchen cabinets. To achieve this goal, data were collected from 128 valid questionnaires and supplemented with field research and user interviews. The study revealed that the elderly’s behavior in retrieving items from kitchen spaces is characterized by both high frequency and difficulty. For this experiment, a total of 42 participants, comprising 21 males and 21 females from the self-care elderly population in the Yangtze River Delta region, were recruited. Two different experimental settings were arranged: one with kitchen utensils arranged in a straight line and another with a purpose-made chest of drawers with varying heights. Video recordings using the Logitech C930C were utilized to capture the gestures and behaviors of the elderly while retrieving objects from the kitchen cupboards (cabinets). By employing a combination of the OpenPose model and the Rapid Entire Body Assessment (REBA) method, which involves calculating human posture angles, REBA scores, and determining the risk level of Work-Related Musculoskeletal Disorders (WMSDs), a risk assessment framework for manual operations associated with WMSDs was developed. Using the angle data acquired from the user operation experiment as parameters, a gradient model of the elderly user’s operational capability was established. The findings indicated a significant impact of neck, trunk, and knee movements on the subjects (P < 0.001). The participants were able to distinguish between different levels of exertion, categorizing movements as ‘easy’, ‘moderate,’ or ‘strenuous.’ These results form the basis for a comfort gradient model for leaning over and retrieving items. Given the prevalent conditions of bone and joint degeneration and osteoporosis among the elderly population, it is evident that they face challenges when accessing items in the kitchen. Therefore, investigating the elderly’s execution abilities during the retrieval process becomes crucial. Understanding how different cabinet heights impact the joint angles of the elderly can be instrumental in optimizing cabinet designs for elderly users, thereby reducing their physical exertion in the kitchen and enhancing their comfort levels. This research holds significant value in improving the quality of life for the elderly population at home and fostering the advancement of elderly-friendly design principles.

Significantly enhancing enzymatic saccharification of poplar waste through the effective removal of lignin and hemicellulose by 1-butanol-Na3PO4-water treatment

Na3PO4-H2O-assisted 1-butanol pretreatment was established for changing the structure of poplar waste and improving its enzymatic efficiency. After poplar waste was pretreated at 180 °C for 60 min, 51.3 % of xylan and 52.5 % of lignin were eliminated. After the enzymatic saccharification of treated poplar waste, the yield of reducing sugars reached 75.3 %. A series of characterizations demonstrated that Na3PO4-H2O-assisted 1-butanol pretreatment altered the poplar composition with improved cellulose accessibility from 231.2 to 459.5 mg/g and reduced surface area of lignin from 384.2 to 255.3 m2/g. Molecular simulations, quantum chemical calculations and independent gradient model analysis were performed on the poplar model, and the 1-butanol-Na3PO4-H2O pretreatment resulted in the increase of electrostatic and van der Waals repulsion forces in lignin and xylan, explaining the efficient lignin and xylan removal. A comprehensive interpretation of mass balance and energy flow was applied to assess the entire pretreatment process. This eco-friendly 1-butanol-Na3PO4-H2O pretreatment effectively broken the encapsulation of cellulose by enzyme inhibitors and improve biomass pretreatment effect.

Melt embayments record multi-stage magma decompression histories

Over the last decade, the melt embayment has proven its merit as a robust petrological tool capable of recording magma decompression rates for explosive eruptions. However, the models developed and applied to extract this information from embayments have not accounted for the complexity and nonlinearity of magma flow in the conduit. We present Embayment Decompression in Two Stages (EDiTS): a numerical model for extracting magma decompression rates from measured volatile diffusion profiles preserved in crystal-hosted embayments, approximating magma acceleration using two constant-rate decompression paths. This model solves for three unknown parameters: initial (deeper) and final (shallower) decompression rates, as well as the pressure where a transition occurs. We successfully benchmark EDiTS against existing numerical diffusion models, and use controlled multi-stage decompression experiments on natural quartz-hosted embayments to test the ability of our model to recover known decompression paths. We find that EDiTS is able to closely approximate the known two-stage path in the mixed-volatile (H2O + CO2) experiment, while a constant-rate modeling approach is unable to simultaneously fit H2O and CO2 gradients. However, in the H2O-saturated experiment, there is no unique solution to the resulting gradient, with both constant-rate and two-stage models reproducing the measured profile, and EDiTS notably overestimating the known total ascent time by several hours. Using decompression experiments, we show that constant-rate models can provide misleadingly good fits to embayment H2O gradients produced by more complex decompression histories, and thus the measurement and modeling of multiple diffusing species, when available, can provide crucial constraints. We then apply EDiTS to re-evaluate mixed-volatile embayment datasets from explosive silicic arc and caldera-forming eruptions from five volcanic centers (Yellowstone, WY, USA; Valles, NM, USA; Long Valley, CA, USA; Taupo, NZ; Mount St. Helens, WA, USA). In contrast to the minutes to hours of total ascent time extracted from embayment volatile profiles using constant-rate models, our two-stage model resolves slower initial ascent times that span 3.5–11 h. Final ascent rates are 1–2 orders of magnitude faster than the initial extracted rates, in agreement with theoretical conduit flow model predictions. Reassessment of embayments from the May 18th, 1980 eruption of Mount St. Helens results in an initial stage of ascent consistent with the timing of magma arrival at the surface from the seismically-inferred storage region (7–9 km) ∼3.5 h after the initial blast, and a final stage of ascent (<1–5 min) in close agreement with time-integrated bubble number densities. Our combined numerical and experimental results, and reevaluation of natural datasets, suggest that, with the application of advanced models, the melt embayment can provide a more nuanced picture of magma decompression timescales from the deep conduit to the surface.

Impacts of Digital Elevation Model Elevation Error on Terrain Gravity Field Calculations: A Case Study in the Wudalianchi Airborne Gravity Gradiometer Test Site, China

Accurate Digital Elevation Models (DEMs) are essential for precise terrain gravity field calculations, which are critical in gravity field modeling, airborne gravimeter and gradiometer calibration, and geophysical inversion. This study evaluates the accuracy of various satellite DEMs by comparing them with a LiDAR DEM at the Wudalianchi test site, a location requiring ultra-accurate terrain gravity fields. Major DEM error sources, particularly those related to vegetation, were identified and corrected using a least squares method that integrates canopy height, vegetation cover, NDVI, and airborne LiDAR DEM data. The impact of DEM vegetation errors on terrain gravity anomalies and gravity gradients was quantified using a partitioned adaptive gravity forward-modeling method at different measurement heights. The results indicate that the TanDEM-X DEM and AW3D30 DEM exhibit the highest vertical accuracy among the satellite DEMs evaluated in the Wudalianchi area. Vegetation significantly affects DEM accuracy, with vegetation-related errors causing an impact of approximately 0.17 mGal (RMS) on surface gravity anomalies. This effect is more pronounced in densely vegetated and volcanic regions. At 100 m above the surface and at an altitude of 1 km, vegetation height affects gravity anomalies by approximately 0.12 mGal and 0.07 mGal, respectively. Additionally, vegetation height impacts the vertical gravity gradient at 100 m above the surface by approximately 4.20 E (RMS), with errors up to 48.84 E over vegetation covered areas. The findings underscore the critical importance of using DEMs with vegetation errors removed for high-precision terrain gravity and gravity gradient modeling, particularly in applications such as airborne gravimeter and gradiometer calibration.

Ethyl levulinate regulates traditional sulfolane biphasic absorbent for energy-efficient CO2 capture

Traditional CO2 biphasic absorbents currently suffer from problems such as high initial phase separation loading, poor product distribution selectivity, and weak dynamic phase separation ability, which limit their potential for industrial applications. This study developed a biphasic absorbent regulated by dual physical solvents by introducing partial ethyl levulinate (EL) into a sulfolane biphasic system. The optimal composition of this system was 30 wt% 1-amino-2-propanol (MIPA), 20 wt% sulfolane and 30 wt% EL. Under dual physical solvent conditions, strong electrostatic attraction between MIPA and CO2 promoted generation of MIPA zwitterions and carbamate. Analysis of the interactions between different product components through electrostatic potentials and with an independent gradient model based on Hirshfeld's partitioning revealed only extremely weak van der Waals force-driven interactions between the reaction products and EL. These interactions substantially reduced the initial phase separation loading and offered precise control over phase transition behavior. Compared with MIPA/sulfolane system, the MIPA/sulfolane/EL system achieved a 48.9 % lower initial phase separation loading, an 11.6 % lower proportion of saturated rich phase volume, a 10.1 % higher CO2-rich phase loading, and a 6.7 % lower viscosity. The excellent dynamic phase separation performance was verified using a customized device and the energy consumption for CO2 regeneration decreased to 2.2 GJ/t CO2.

An innovative guanidinium-based ionic covalent organic frameworks with abundant aromatic rings for high-efficiency naproxen removal: Adsorption behavior, mechanisms, and density functional theory calculations

In recent years, naproxen (NPX) has raised significant environmental concerns requiring urgent attention. This study presents an innovative guanidinium-based ionic covalent organic framework (TFPB-TgCl), containing abundant aromatic rings, which was successfully synthesized via Schiff base reaction for the efficient and selective removal of NPX. Remarkably, TFPB-TgCl manifested a maximal NPX adsorption capacity of 308 mg/g at pH = 5. The adsorption on the active site (AOAS) model highlighted the simultaneous occurrence of both physical and chemical adsorption during the NPX uptake. The coefficients of the physical adsorption rates (5.6479, 1.9224, and 1.9224 min−1 for NPX concentrations of 20, 50, and 100 mg/L, respectively) were significantly higher than those of the chemical adsorption rates (0.1759, 0.0681, and 0.0567 g·mg−1·min−1 for the same concentrations), indicating the predominance of physical adsorption. Furthermore, the multilayer adsorption (MLA) model suggested that an adsorption site can interact with more NPX molecules, benefiting from various electrostatic and π-π interactions. The negative values of enthalpy change (ΔH° = −11.956 kJ/mol) and Gibbs free energy (ΔG < 0) confirmed the exothermic and spontaneous nature of the adsorption process. Additionally, in the optimal adsorption configuration (−131.57 kcal/mol), the Independent Gradient Model based on Hirshfeld partition (IGMH) was utilized to identify interaction sites between the guanidinium group of TFPB-TgCl and the carboxyl group of NPX, with subsequent electrostatic potential (ESP) analysis emphasizing their crucial role in electrostatic adsorption. Overall, the adsorption mechanism of electrostatic and π-π interactions in TFPB-TgCl highlights the significant contribution of its guanidinium and aromatic rings in facilitating NPX adsorption.

Subgrid-scale model considering the inverse energy cascade using an artificial neural network

For the closure of the subgrid-scale (SGS) stress tensor, an artificial neural network (ANN)-based SGS model that takes account of the inverse energy cascade in isotropic turbulence is developed. The data required for training this ANN-based SGS model are provided by direct numerical simulation of isotropic turbulence with an inverse energy cascade. Two input features, the root mean square of the rate-of-strain tensor and the product of the eigenvalues of the rate-of-strain tensor, are employed to characterize the inverse energy cascade. An a priori test reveals that the ANN-based model adequately predicts the SGS stress tensor in the backward energy transfer process, and the predictive capability of the gradient model is found to be slightly poorer than that of the ANN-based model, while that of the Smagorinsky model is not satisfactory. In comparison with the gradient model, the ANN-based model even predicts a few backward energy transfer events in the stage of excessive energy dissipation. In addition, the off-diagonal component of the SGS stress tensor, rather than the diagonal component, may be intimately associated with the inverse energy cascade. The ANN-based SGS model presented here is expected to provide inspiration for future investigations of the construction of SGS models that take account of the inverse energy cascade.

Linear pressure waves in mono- and poly-disperse bubbly liquids: Attenuation and propagation speed in slow and fast and evanescent modes

Using volumetric averaged equations from a two-fluid model, this study theoretically investigates linear pressure wave propagation in a quiescent liquid with many spherical gas bubbles. The speed and attenuation of sound are evaluated using the derived linear dispersion. Mono- and poly-disperse bubbly liquids are treated. To precisely describe the attenuation effect, some forms of bubble dynamics equations and temperature gradient models are employed. Focusing on the dissipative effect, we analyze the stop band that occurs in the linear dispersion relation. In the two-fluid model, even if the dissipation effect is considered, the inconvenience that the wavenumber diverges to infinity in the resonance frequency cannot be resolved. Additionally, the validity of terminating that wavenumber value in the middle of the frequency is demonstrated. To determine a linear dispersion relation that can exactly predict thermal conduction and acoustic radiation, wave propagation velocities and attenuation coefficients are compared with some experimental data and existing models. The results show that thermal conduction and acoustic radiation should be set appropriately to accurately predict the propagation velocity and attenuation except in the high frequency range, the phase velocity in the resonance frequency range, or the attenuation in the high frequency range.

Assessing the Noncovalent Interaction of Deucravacitinib and Ethanol with Special Reference to an Independent Gradient Model Based on Hirshfeld Partition.

The current study begins by optimizing the deucravacitinib molecule in the gas phase at the ωB97XD/cc-pVDZ level of theory using density functional theory and proceeds to study its intramolecular interactions. Further, a molecule of EtOH was introduced at different locations on the deucravacitinib molecule, and the noncovalent interactions arising from them were also investigated using several computational tools. In this way, eight deucravacitinib-EtOH systems (1-8) were identified and their electronic environment was studied after evaluating their binding energy. Using natural bond orbital analysis, the localization of charges between the donor and acceptor fragments in these interacting systems was examined. The nature of interactions was analyzed using the reduced gradient approach (NCI analysis), and few hydrogen bonding interactions (intermolecular and intramolecular) were found in each system. The strength of these hydrogen bonding interactions was further investigated by using theoretical tools such as atoms in molecules analysis and independent gradient model based on Hirshfeld partition analysis. The binding energy of deucravacitinib with EtOH was decomposed into energy components based on the domain-based local pair natural orbital coupled cluster technique using LED analysis. The results from the hydrogen bonding interaction analysis using different computational tools were found to be consistent with the calculated order of binding energy of systems 1-8 and they also pointed toward the higher stability of system 3.

Effective Hard Negative Mining for Contrastive Learning-based Code Search

Background. Code search aims to find the most relevant code snippet in a large codebase based on a given natural language query. An accurate code search engine can increase code reuse and improve programming efficiency. The focus of code search is how to represent the semantic similarity of code and query. With the development of code pre-trained models, the pattern of using numeric feature vectors (embeddings) to represent code semantics and using vector distance to represent semantic similarity has replaced traditional string matching methods. The quality of semantic representations is critical to the effectiveness of downstream tasks such as code search. Currently, the state-of-the-art (SOTA) learning method uses the contrastive learning paradigm. The objective of contrastive learning is to maximize the similarity between matching code and query (positive samples) and minimize the similarity between mismatched pairs (negative samples). To increase the reusing of negative samples, prior contrastive learning approaches use a large queue (memory bank) to store embeddings. Problem. However, there is still a lot of room for improvement in using negative examples for code search: ① Due to the random selection of negative samples, semantic representations learned by existing models cannot distinguish similar codes well. ② Since semantic vectors in the memory bank are reused from previous inference results and then directly used for loss function calculation without gradient descent, the model cannot effectively learn the negative sample semantic information. Method. To solve the above problems, we propose a contrastive learning code search model with hard negative mining called CoCoHaNeRe: ❶ To enable the model to distinguish similar codes, we introduce hard negative examples into contrastive training, which are negative examples in the codebase that are most similar to positive examples. As a result, hard negative examples are most likely to make the model make mistakes. ❷ To improve the learning efficiency of negative samples during training, we add all hard negative examples to the model's gradient descent process. Result. To verify the effectiveness of CoCoHaNeRe, we conducted experiments on large code search datasets with six programming languages, as well as similar retrieval tasks code clone detection and code question answering. Experimental results show that our model achieves SOTA performance. In the code search task, the average MRR score of CoCoHaNeRe exceeds CodeBERT, GraphCodeBERT, and UniXcoder by 11.25%, 8.13%, and 7.38%, respectively. It has also made great progress in code clone detection and code question answering. In addition, our method performs well in different programming languages and code pre-training models. Furthermore, qualitative analysis shows that our model effectively distinguishes high-order semantic differences between similar codes.

Unveiling the adsorption mechanism of propanehydrazine derivatives on magnesium oxide surface: Insights from computational approach

The use of green and effective inhibitors for preventing metal oxide (MgO) corrosion in industrial applications is highly significant in promoting environmental protection and sustainable development. This study delves into the adsorption behavior and interfacial mechanism of environmentally friendly inhibitor derived from propane hydrazine (PH) on MgO surface. Specifically, PH1, PH2, PH3, and PH4 were explored for their effectiveness in preventing corrosion by using advanced theoretical simulations-based density functional theory (DFT) for assessing the reactivity and adsorption characteristics. The study considered a detailed exploration of local and global reactivity descriptors, providing insights into the inhibitors’ reactivity and adsorption abilities in both isolated and adsorbed states. These findings focus more in the mechanisms underlying organic-inorganic interactions and present promising prospects for further development and application. Using first-principles DFT calculations alongside quantitative molecular surface analyses, we examined the adsorption patterns of PHs on the MgO(100) surface. These investigations are boosted by the application of independent gradient model (IGM) framework, providing robust verification of PHs' adsorption behavior on MgO(100) surface. Our calculations reveal a substantial decrease in the energy gap following complex formation, suggesting that charge density changes occur upon interaction with MgO surfaces, thereby facilitating direct electron transfer in all the studied systems. Noreover, the results highlight the crucial role of intermolecular interactions in boosting the interaction between PHs and the [Mg(H2O)6]2+ cation. First-principles DFT calculations show that all PH molecules consistently display parallel adsorption on the MgO surface, where the oxygen atoms form bonds with adjacent magnesium atoms. The bond lengths vary from 2.18 to 2.35 Å when PHs bind to the Mg atoms in parallel orientations through the oxygen atom, suggesting a stable parallel arrangement for PH molecules on the MgO surface. The calculated adsorption energy (Eads) varies in the following order: MgO-PH3 (−815.14 Kcal mol−1) > MgO-PH2 (−803.85 Kcal mol−1)) > MgO-PH4 (−695.38 Kcal mol−1) > MgO-PH1 (−125.77 Kcal mol−1). This trend indicates that parallel interactions enhance the adsorption behavior and binding of PH compounds through inter- and intra-molecular interactions, resulting in the PHs being centered at specific sites on the MgO surface. The potential enhancement in electrochemical properties is believed to stem from the synergistic interaction between the PHs and the MgO surface, which theoretically allows for a precise adjustment of their adsorption and interaction within the composite structure. This understanding provides a fundamental framework for examining the complex interfacial dynamics between inhibitor structures and elucidating how these molecular interactions influence the selection of corrosion inhibitors and their adsorption behaviors on the corrosion layer's surface, rather than on metallic Mg.

Physical conditions in Centaurus A’s northern filaments

We present the first observations of HCO+(1–0) and HCN(1–0) emission in the northern filaments of Centaurus A with ALMA. HCO+(1–0) is detected in nine clumps of the Horseshoe complex, with similar velocities as the CO(1–0) emission. Conversely, HCN(1–0) is not detected, and we derive upper limits on the flux. At a resolution of ∼40 pc, the line ratio of the velocity-integrated intensities IHCO+/ICO varies between 0.03 and 0.08, while IHCO+/IHCN is higher than unity, with an average lower limit of 1.51. These ratios are significantly higher than what is observed in nearby star-forming galaxies. Moreover, the ratio IHCO+/ICO decreases with increasing CO-integrated intensity, contrary to what is observed in the star-forming galaxies. This indicates that the HCO+ emission is enhanced and may not arise from dense gas within the Horseshoe complex. This hypothesis is strengthened by the average line ratio IHCN/ICO &lt; 0.03, which suggests that the gas density is rather low. Using non-local thermal equilibrium, large velocity gradient modelling with RADEX, we explored two possible phases of the gas, which we call ‘diffuse’ and ‘dense’ and are characterised by a significant difference in the HCO+ abundance relative to CO, respectively NHCO+/NCO = 10−3 and NHCO+/NCO = 3 × 10−5. The average CO(1–0) and HCO+(1–0) integrated intensities and the upper limit on HCN(1–0) are compatible with both diffuse (nH = 103 cm−3, Tkin = 15 − 165 K) and dense gas (nH = 104 cm−3, Tkin &gt; 65 K). The spectral setup of the present observations also covers SiO(2–1). While undetected, the upper limit on SiO(2–1) is not compatible with the RADEX predictions for the dense gas. We conclude that the nine molecular clouds detected in HCO+(1–0) are likely dominated by diffuse molecular gas. While the exact origin of the HCO+(1–0) emission remains to be investigated, it is likely related to the energy injection within the molecular gas that prevents gravitational collapse and star formation.

C-H amination chemistry mediated by trinuclear Cu(I) sites supported by a ligand scaffold featuring an arene platform and tetramethylguanidinyl residues.

Tripodal ligands that can encapsulate single or multiple metal sites in C3-symmetric geometric configurations constitute valuable targets for novel catalysts. Of particular interest in ligand development are efforts toward incorporating apical elements that exhibit little if any electron donicity, to enhance the electrophilic nature of a trans positioned active oxidant (e.g., metal-oxo, -nitrene). The tripodal ligand TMG3trphen-Arene has been synthesized, featuring an arene platform 1,3,5-substituted with phenylene arms possessing tetramethylguanidinyl (TMG) residues. Compound [(TMG3trphen-Arene)Cu3(μ-Cl)3] has been subsequently synthesized by extracting a Cu3(μ-Cl)3 cluster from anhydrous CuCl and shown to encapsulate a crown-shaped Cu3(μ-Cl)3 fragment, supported by Cu-NTMG bonds and modest Cu3⋯arene long-range contacts. Energy decomposition analysis (EDA) indicates that electrostatic contributions to the total interaction energy far exceed those due to orbital interactions. The latter involve orbital pairings largely associated with the NTMG stabilization of the Cu3(μ-Cl)3 cluster. The independent gradient model based on the Hirshfeld partition (IGMH) corroborates that contacts between the arene platform and the Cu3 triangle are noncovalent in nature. Catalyst [(TMG3trphen-Arene)Cu3(μ-Cl)3] enables amination of sec-benzylic and tert-C-H bonds of a panel of substrates by pre-synthesized PhINTces in solvent matrices that incorporate small amounts of HFIP. The involvement of an electrophilic aminating agent is evidenced by the better yields obtained for electron-rich benzylic sites and is further supported by Hammett analysis that reveals the development of a small positive charge during C-H bond activation. A rather modest KIE effect (2.1) is obtained from intramolecular H(D) competition in the amination of ethylbenzene, at the borderline of reported values for concerted and stepwise C-H amination systems. DFT analysis of the putative copper-nitrene oxidant indicates that the nitrene N atom is bridging between two copper sites in closely spaced triplet (ground state) and broken-symmetry singlet electronic configurations.

Investigating the interaction mechanisms between arachin and resveratrol: Utilizing multi-spectroscopy and computational chemistry

Arachin (ARA) and resveratrol (RES) are the primary protein and bioactive compound in peanuts and their processed products. However, the mechanism of interaction between these two substances remained unclear. To investigate protein structural changes, conformational variations, and molecular mechanisms in the interaction between them, multispectral analysis and computational chemistry methods were employed. Experimental results confirmed that RES quenched ARA's intrinsic fluorescence through static quenching, indicating their interaction. Thermodynamic analysis revealed the interaction between them was endothermic, spontaneous, and primarily hydrophobic. Molecular dynamics (MD) simulations highlighted strong affinity between RES and ARA, with key amino acids (His425, Val426, Phe405, and Phe464) facilitating their interaction. RES binding increased stability without significant protein conformational changes. The independent gradient model based on Hirshfeld partition (IGMH) validated their interaction, emphasizing van der Waals (VDW) interactions and hydrogen bonds (H-bonds) as crucial for stable binding. This research lays a theoretical foundation for potential applications of ARA-RES complex products in the food industry.

Mapping the Interaction Landscape of Adenosine and Minoxidil Sulfate Using an Independent Gradient Model Based on Hirshfeld Partition and Interaction Region Indicator.

Using theoretical techniques, the interactions between adenosine (AD) and minoxidil sulfate (MS) were studied using the DFT/M06-2X/aug-cc-pVDZ level of theory. The formation of the complex was thermodynamically favorable, so we carried out further studies. Frontier molecular orbital analysis shows that the HOMO-LUMO- gap is high (6.81 eV), which means that the complex is kinetically stable. The global reactivity parameters were also calculated to get insight about the chemical reactivity of the complex. Molecular electrostatic potential and charge analyses were carried out for the optimized complex. To study the charge transfer and inter- and intramolecular interactions present in the complex molecule, we employed natural bond orbital analysis. Noncovalent interaction (NCI) analysis along with IGMH and IRI analyses further helped us find the weak interactions. The presence of hydrogen bonds between the N atom (N27) of MS and H atom (H66) of AD and O atom (O32) of MS and H atom (H46) of AD was the main finding of these analyses. QTAIM investigation also supports this finding. EDA analysis was carried out to further study the intermolecular interactions present within the complex. Thus, the present investigation unveils the existence of weak NCIs in the complex.

Interaction of fullerenes C60 with pristine and substituted buckybowls: A theoretical study

Non-covalent interactions between experimentally available buckybowls (coronene, corannulene, sumanene, triazasumanene, pentachlorocorannulene, decachlorocorannulene) and fullerenes C60 were systematically studied by using several theoretical methods. Peculiarities of these interactions were determined using electrostatic potential maps, independent gradient model, and symmetry adapted perturbation theory (SAPT0). SAPT0 calculations confirmed that dispersion (contribute 63–70 % in attraction) and electrostatic interactions (23–28 %) play the major role for C60 binding, whereas induction forces contribute to Eint only moderately (5–7%) for all structures studied herein. Cl-substituted corannulenes were calculated to be the most favorable structures for C60 binding. Ab initio molecular dynamics (AIMD) simulations confirmed stability of the studied complexes at different temperatures. Our investigations established the high potential of the studied buckybowls for usage in molecular tweezers.