Changes In Molecular Structure Research Articles

Solubility of NaCl in water vapor at 400–700 °C

Water significantly impacts the chemical evolution of the Earth’s crust, affecting environments from volcanic settings to hydrothermal systems. These fluids transport elements essential for geological processes, such as metal ore deposit formation. At high temperatures, as water transitions from liquid to vapor, its molecular structure changes, drastically reducing its capacity to dissolve solids and solvate ions. Here, we report experimental results of halite (NaCl(s)) solubility in water vapor at 400–700 °C and 30–300 bar using a novel U-tube flow-through reactor system. The results show that halite solubility is low (xNaCl,tot = 3.2 × 10−9 to 2.9 × 10−4 mol/mol) and increases with temperature and pressure, attributed to the dissolution of NaCl followed by its hydration according to the reaction:NaCl(s)+nH2O(g)⇋NaCl·H2On(g)Thermodynamic modeling of the experimental results indicates a preference for specific hydrated species, including NaClg, NaCl·H2O4g, NaCl·H2O6g and NaCl·H2O8g. The less hydrated gaseous NaCl species become more prevalent with increasing temperature and decreasing pressure. At temperatures below 600 °C and pressures above 50 bar, halite solubility is close to stoichiometric, whereas at higher temperatures and lower pressures, the hydrolysis of NaCl(s) to form NaOH(lq,s) or a NaClxOH(1-x)(lq,s) (x < 1) solid solution is evident, resulting in the formation of HCl(g). The logarithm of the halite equilibrium solubility constant (logKn) ranges from −10.18 to −4.19 for NaCl(g), and from −13.12 to −11.94, −15.90 to −17.28, and −19.67 to –22.73 for NaCl·H2O4(g), NaCl·H2O6(g) and NaCl·H2O8(g), respectively. Standard thermodynamic properties derived from this data reveal a temperature-independent enthalpy (ΔHn,ro), entropy (ΔSn,ro) and heat capacity (ΔCp,n,ro) of reaction for each NaCl species. While the enthalpy of reaction is nearly constant, the entropy and heat capacity decrease with an increasing degree of hydration, indicating the decreasing stability of these species with increasing temperature. Our thermodynamic model results and gas species stoichiometries are in excellent agreement with previous density functional theory (DFT) calculations (Suleimenov et al., 2006). The halite solubility data obtained here compare well with prior studies and thermodynamic models for the NaCl-H2O system.

Molecular docking and spectroscopic exploration (FT‐IR, FT‐Raman) with HOMO–LUMO, ADMET, and 5,7‐dihydroxy‐2‐(4‐hydroxyphenyl) chroman‐4‐one against lung cancer: A potential uptake B‐RAF inhibitor

AbstractNaringenin has been proven to inhibit cell proliferation, which has anticancer properties. The role of Naringenin molecule in lung cancer and its processes are yet unknown. Naringenin is chemically called as 5,7‐dihydroxy‐2‐(4‐hydroxyphenyl) chroman‐4‐one, which was optimized geometrical parameters analysis such as bond length, bond angle and torsion angle were analyzed from Naringenin by utilizing Gaussian 09 W program. Characterizations of Naringenin analyzed by B3LYP density functional theory with basis set 6–311G (d,p). The energy value of Naringenin molecules are analyzed with (ground state) HOMO value −4.616, LUMO value for −0.169 (first excited state) energies and also predicted by energy cap value is 4.446. ADMET and drug likeness of the title compound was predicted, it's qualified with the Lipinski's rule of five. Naringenin molecular structural changes, distribution and also its reactive site investigated with MEP (Molecular Electrostatic Potential) analyses spans from −0.118eO to 0.118eO. The density of state (DOS) used to know molecular orbital contribution for selected compound. It was determined that Naringenin molecule in the active site of B‐RAF inhibitor (PDB code: 4MNF) has a binding energy of −8.9 based on a docking analysis and conformational changes. From this study, this drug will be expected to undergo essential future chemotherapy agent for lung cancer patient.

Synergistic Effect of Polyurethane on Pore-Sealing and Lubrication of Microarc Oxidation Coating.

Microarc oxidation (MAO) is a widely used surface treatment technology. However, its processing inevitably leads to the presence of micropores, microcracks, and other defects in the MAO coating. These defects lead to suboptimal tribological performance and diminished corrosion resistance of the MAO coating. Thus, this study proposed a new pore-sealing method with environmental protection and high efficiency. Polyurethane reactive (PUR) composite coating was prepared on the surface of MAO coating. The sealing effect of the PUR sample was analyzed using scanning electron microscopy (SEM). The molecular structure and elemental changes of the coating were analyzed using X-ray photoelectron spectroscopy (XPS). The tribological properties were analyzed using a tribological testing machine, and the corrosion resistance was tested using an electrochemical workstation. The test results show that the lubricity and corrosion resistance of PUR sample are improved significantly compared with MAO coating. When the mass fraction of PUR is 3 wt %, the PUR sample shows the best lubrication performance, and the coefficient of friction decreases by 70.8%. Compared with the traditional sealing technology, this experimental method is simple and low-cost and has a wide application prospect, which promotes the development of MAO technology.

Charge transfer behavior of triboelectric polymers and triboelectric sensors operated under ultrahigh pressure

AbstractThe energy generation performance of triboelectric materials under ultrahigh pressure remains to be investigated. Here, the variations in molecular structure and built‐in electric field of triboelectric polymers under ultrahigh pressure have been thoroughly studied. The attenuation of built‐in electric field and the escaping of triboelectric charges under ultrahigh pressure are observed in different triboelectric polymers, whereas the existence of deep traps allows the built‐in electric field to be recoverable with the release of pressure. Moreover, the macromolecular conformational changes, including twisting molecular chains and crystal structure changes, can also induce the redistribution of deep traps, leading to a sudden increase in built‐in electric field under specific pressure. Finally, a triboelectric sensor for ultrahigh pressure condition is fabricated with excellent cycle repeatability and a total thickness of 2 mm, which has a sensitivity of 0.07 V MPa−1 within a linear region of 1–100 MPa. This study offers in‐depth insight into the physical understanding of charge behavior both on interface and in bulk of triboelectric materials, whereas the proposed ultrahigh pressure sensors can promote various potential applications of triboelectric sensor in extreme environments.

Chitosan-mediated copper nanohybrid attenuates the virulence of a necrotrophic fungal pathogen Macrophomina phaseolina.

This study reported the synthesis and characterization of chitosan-copper nanoparticles (Ch-CuNPs) using a 1% copper sulfate solution in 0.2% w/v chitosan. The Ch-CuNPs, displaying a stable brick-red hue, showed an absorption peak at 572nm, indicative of monodisperse nanoparticle formation and surface plasmon resonance. X-ray diffraction confirmed the face-centered cubic structure with peaks at 36.78°, 43.38°, 50.56°, and 74.26°, and an average particle size of 87-89nm. FTIR analysis showed interactions between chitosan and copper, particularly around 3370 -3226cm⁻¹, 1633cm⁻¹, and 680cm⁻¹. In vitro assays revealed that Ch-CuNPs inhibited Macrophomina phaseolina growth by 18-71% at 0.03-0.09% concentrations, achieving complete inhibition at 0.12-0.15%, with PCA analysis confirming that growth peaked at lower concentrations and sharply declined at higher levels. Ch-CuNPs also altered fungal morphology and enzyme activity, with notable degradation at higher concentrations. The Cu uptake by the fungus peaked at 29.9% with 0.03% Ch-CuNPs and decreased at higher concentrations. FTIR analysis showed shifts and disappearance of peaks in fungal biomass treated with Ch-CuNPs, indicating molecular interactions and potential structural changes. This study underscores the potential of Ch-CuNPs as an effective antifungal agent and elucidates their interaction mechanisms.

Collagen denaturation in post-run Achilles tendons and Achilles tendinopathy: In vivo mechanophysiology and magnetic resonance imaging.

Achilles tendinopathy is often attributed to overuse, but its pathophysiology remains poorly understood. Disruption to the molecular structure of collagen is fundamental for the onset and progression of tendinopathy but has mostly been investigated in vitro. Here, we interrogated the in vivo molecular structure changes of collagen in rat Achilles tendons following treadmill running. Unexpectedly, the tendons' collagen molecules were not mechanically unfolded by running but denatured through proteolysis during physiological post-run remodeling. We further revealed that running induces inflammatory gene expressions in Achilles tendons and that long-term running causes prolonged, elevated collagen degradation, leading to the accumulation of denatured collagen and tendinopathy development. For applications, we demonstrated magnetic resonance imaging of collagenase-induced Achilles tendon injury in vivo using a denatured collagen targeting contrast agent. Our findings may help close the knowledge gaps in the mechanobiology and pathogenesis of Achilles tendinopathy and initiate new strategies for its imaging-based diagnosis.

The effect of carbon black on degradation of pipe grade black polyethylene in high concentration chlorine dioxide solutions

In this research, the impact of carbon black on the accelerated degradation of pipe grade polyethylene (PE100) exposed to high levels of chlorine dioxide (150 ppm) is examined. Tensile testing reveals a faster degradation rate in black samples compared to neat samples, indicating a detrimental effect of carbon black aggregates on the polymer's aging process. Rheological analysis shows changes in molecular weight and structure due to chemical degradation and chain scission and can be a reliable method for detecting slight changes in molecular structure. Isothermal crystallization shows a slowdown in crystallization kinetics at first, explained by gel-formation due to crosslinking which hinder the crystallization, and then an increase in the kinetics as apparently the chain scission gets dominant again. Neat samples exhibit a higher density of tie molecules, indirectly revealed by much more fibrils in crack wall observed in FESEM images, suggesting better resistance to chemical degradation while the black sample shows a much less fibrillar crack wake and becomes almost completely devoid of any fibrils at later stages of aging. The fibrils, which essentially offer a load-bearing role against the widening and growth of the crack play a key role in resistance to slow crack growth (SCG). Therefore, the higher SCG resistance is expected for neat grade compared to black samples. The study proposes a dual-layer pipe design with a UV-resistant black outer layer and an oxidation-resistant neat inner layer to prolong the lifespan of PE100 pipes by protecting against UV radiation and chemical reactions. This solution offers increased durability, lower maintenance costs, and environmental sustainability benefits.

Comprehensive analysis of polyethylene glycol – lauric acid as a promising phase change material: Spectroscopic, thermal, and quantum insights

The increasing need for effective and environmentally sustainable energy storage technologies has delineated phase change materials (PCMs) as prospective candidates for thermal energy storage applications. In this study, we thoroughly analyzed polyethylene glycol (PEG 400) and lauric acid (LA) as promising PCMs by applying spectroscopic study, thermal, and quantum approaches. The thermal stability and chemical compatibility of PEG – LA were investigated using FTIR and Raman spectroscopy, revealing that optimal molecular interactions and structural changes occur at temperatures ranging from −10 °C to 30 °C, especially at higher LA volume fraction (VLA ≥ 60 %), as evidenced by marked blue shifts in the Raman spectra. TGA demonstrated the 2-step degradation of the PEG – LA (6:4), representing good material stability and high thermal conductivity enhancement of 32.24 % due to synergistic interactions among PEG and LA. DSC analysis established a high capacitive energy storage of 181.5 J/g and a phase transition of solid–liquid at room temperature (30–40 °C), which better crystallization properties based on higher LHR and supercooling degree compared with pristine LA. The thermal cycling reliability and FTIR spectra demonstrated the thermal and chemical stability of PEG – LA even after 1000 cycles. Quantum DFT analysis verified the experimental results, exhibiting robust hydrogen bonding interactions that contribute to the thermal stability, phase transition processes, higher energy storage capacity, and reactivity of PEG – LA. These results highlight PEG – LA as a promising and effective PCM for various thermal energy storage applications.

Exploring the potential of epoxy nanocomposites infused with Alq3 for UV sensing applications

This research explores the morphological, molecular, and photoluminescent properties of epoxy-based nanocomposite sheets containing Alq3, as well as their response to UV irradiation. By analyzing the surface morphology via SEM, it is observed that the pristine epoxy sheets exhibit uniformity, while the nanocomposites display dispersed nanoparticles, influenced by the concentrations of dopants. Raman spectroscopy reveals changes in molecular structures and vibrational modes, with broadened peaks indicating potential interactions between the additives and epoxy matrix. The photoluminescence (PL) emission spectra show enhancements in intensity and shifts in peak wavelengths toward the green emission region, significantly influenced by the dopants. UV irradiation causes changes in both Raman and PL signals, with varying effects on different nanocomposite configurations. Linear regression analysis demonstrates strong correlations between signal changes and irradiation time, particularly pronounced in epoxy/Alq3 nanocomposite sheets, with marginal errors from Raman and PL signal-induced changes of 5% and 2%, respectively. Additionally, stability and reproducibility assessments reveal consistent signal trends over prolonged UV exposure and high reproducibility with minimal error of less than 5%. Overall, these epoxy nanocomposite sheets display promising results for UV sensing applications due to their sensitivity, linearity, stability, and reproducibility.

Structural insights into the molecular recognition of integrin αVβ3 by RGD-containing ligands: The role of the specificity-determining loop (SDL).

Integrin αVβ3 is a prominent member of the "RGD-recognizing" integrin family of cell surface receptors. αVβ3 binds to various extracellular matrix (ECM) proteins and oxysterols such as 25-hydroxycholesterol, is implicated in several diseases, including cancer metastasis, lung fibrosis, inflammation, and autoimmune diseases, and is pursued as a valuable therapeutic target. Despite enormous efforts to seek a pure antagonist, to date, no single drug candidate has successfully reached clinics due to associated partial agonism and toxicity issues. Developing effective and safe inhibitors require a thorough understanding of the molecular interactions and structural changes related to the receptor's activation and inhibition mechanisms. This study offers a comprehensive residue-residue contact and network analyses of the ligand-binding β-propeller βI domains (headpiece) based on all available experimental structures of integrin αVβ3 in unliganded, agonist-, antagonist-, and antibody-bound states. The analyses reveal many critical interactions that were not reported before and show that specific orientation and interactions of residues from the specificity-determining loop (SDL) are critical in molecular recognition and regulation. Also, the network analysis reveals that residues from the nearby allosteric site (site II) connect to the primary RGD-binding site via SDL, which likely acts as an interface between the two sites. Our results provide valuable insights into molecular interactions, structural changes, distinct features of the active and inactive headpiece conformations, the role of SDL in ligand recognition, and SDL-mediated allostery. Thus, the insights from this study may facilitate the designing of pure antagonists or site II-mediated allosteric modulators to integrin αVβ3 to treat various diseases.

Storage-induced changes in β-strand interactions within bovine lactoferrin powder analyzed through X-ray diffraction

Bovine lactoferrin (bLF) is a multifunctional protein used in the food and pharmaceutical industries. Various commercially available bLF powders (bLFPs) have different ratios of protein monomers to aggregates, which affects the aggregation rate. However, the changes in molecular structure and interactions during aggregation are unclear. This study investigated changes in the structure and interactions of stored bLFPs during aggregation. Five commercially available bLFPs with different molecular weight distributions were analyzed before and after storage using size-exclusion chromatography and X-ray diffraction (XRD) to monitor aggregation and β-strand interaction, respectively. These bLFPs were stored for four weeks under high temperature and humidity conditions as a stress test. The XRD results revealed changes in peak II (around 2θ = 20°), corresponding to β-strand interactions. The peak II change rate suggested that the aggregation occurs due to partial structural fluctuations and interaction changes. Furthermore, time-course analysis of peak II and correlations with the pre-storage monomer ratio and aggregation phase index demonstrated that β-strand interactions decreased during the transformation of monomers to low-molecular-weight (LMW) aggregates, while it increased during the LMW-to-high-molecular-weight aggregate phase. These results provide novel insights into the conformational changes and molecular interactions of bLFPs during aggregation.

The Development of Poly(lactic acid) (PLA)-Based Blends and Modification Strategies: Methods of Improving Key Properties towards Technical Applications-Review.

The widespread use of poly(lactic acid) (PLA) from packaging to engineering applications seems to follow the current global trend. The development of high-performance PLA-based blends has led to the commercial introduction of various PLA-based resins with excellent thermomechanical properties. The reason for this is the progress in the field of major PLA limitations such as low thermal resistance and poor impact strength. The main purpose of using biobased polymers in polymer blends is to increase the share of renewable raw materials in the final product rather than its possible biodegradation. However, in the case of engineering applications, the focus is on achieving the required properties rather than maximizing the percentage of biopolymer. The presented review article discusses the current strategies to optimize the balance of the key features such as stiffness, toughness, and heat resistance of PLA-based blends. Improving of these properties requires molecular structural changes, which together with morphology, crystallinity, and the influence of the processing conditions are the main subjects of this article. The latest research in this field clearly indicates the high potential of using PLA-based materials in highly demanding applications. In the case of impact strength modification, it is possible to obtain values close to 800 J/m, which is a value comparable to polycarbonate. Significant improvement can also be confirmed for thermal resistance results, where heat deflection temperatures for selected types of PLA blends can reach even 130 °C after modification. The modification strategies discussed in this article confirm that a properly conducted process of selecting the blend components and the conditions of the processing technique allows for revealing the potential of PLA as an engineering plastic.

The interaction between sludge and microplastics during thermal hydrolysis of sludge

In municipal wastewater treatment plants (WWTPs), large number of microplastics (MPs) accumulated in wastewater migrated into sludge. Thermal hydrolysis of sludge (THS) was one of the most promising processes for promoting changes in molecular structure of MPs. The physicochemical properties and degradative pathways of polyethylene (PE) and polyethylene terephthalate (PET) in THS under different temperatures were studied in this paper. It was found that there was a mutual promotion relationship between sludge degradation and MPs aging. The presence of PE and PET MPs not only increased organics and nitrogen concentrations of sludge filtrate, but also enhanced the transformation of organics like proteins. Sludge accelerated the aging of PE and PET MPs. The friability of PE and PET MPs was increased with more surface fragmentation and breakage under the temperature of 120 ℃−180 ℃. Moreover, PE and PET MPs occurred thermal oxidation and reduction reactions with significant chemical structure changes at 160 °C and 140 °C, respectively. Pristine PE and PET had multiple carbon and oxygen active sites. During THS reaction, not only PE and PET reacted hydrolysis/decomposition to produce short-chain hydroxyl-terminated compounds, but also hydrothermal shear broke the polymer molecules and formed carboxyl-terminated and olefin-terminated low-carbon chains. This study provided some promising sign for in situ microplastic removal during sludge treatments.

Conformational control over proton-coupled electron transfer in metalloenzymes.

From the reduction of dinitrogen to the oxidation of water, thechemical transformations catalysed by metalloenzymes underlie global geochemical and biochemical cycles. These reactions represent some of the most kinetically and thermodynamically challenging processes knownand require the complex choreography of the fundamental building blocks of nature, electrons and protons, to be carried out with utmost precision and accuracy. The rate-determining step of catalysis in many metalloenzymes consists of aprotein structural rearrangement, suggestingthat nature has evolved to leverage macroscopic changes in protein molecularstructure to control subatomicchanges in metallocofactor electronicstructure. The proton-coupled electron transfermechanisms operative in nitrogenase, photosystem II and ribonucleotide reductase exemplify this interplay between molecular and electronic structural control. We present the culmination of decades of study on each of these systems and clarify what is known regarding the interplay between structural changesand functional outcomes in these metalloenzyme linchpins.

Molecular origin of viscoelasticity and influence of methylation in mesophase pitch

The viscoelastic and thermomechanical properties of pitches are responsible for their melt-spinning behavior, a critical step for manufacturing high-performance pitch-based carbon fibers. Here, we systematically explore the impact of methyl group modifications on the viscoelastic and thermal properties of mesophase pitches. We employ a range of atomistic modeling approaches, including Density Functional Theory (DFT), Density Functional Tight Binding (DFTB), and Classical Molecular Mechanics (MM), to provide detailed insights into the molecular interactions and structural changes. Our results revealed the molecular mechanisms that promote layered structures leading to the anisotropic nature of the viscoelastic behavior of mesophase pitch. Furthermore, we propose a modified molecular representation of naphthalene-based mesophase pitch based on the analysis of x-ray diffraction measurements. This study provides fundamental insights into the molecular structures of mesophase pitch and the role of methyl groups controlling its viscosity, which offer valuable insights into mesophase-based carbon fiber production.

Basic Theory of Ice Crystallization Based on Water Molecular Structure and Ice Structure.

Freezing storage is the most common method of food preservation and the formation of ice crystals during freezing has an important impact on food quality. The water molecular structure, mechanism of ice crystal formation, and ice crystal structure are elaborated in the present review. Meanwhile the methods of ice crystal characterization are outlined. It is concluded that the distribution of the water molecule cluster structure during the crystallization process directly affects the formed ice crystals' structure, but the intrinsic relationship needs to be further investigated. The morphology and distribution of ice crystals can be observed by experimental methods while simulation methods provide the possibility to study the molecular structure changes in water and ice crystals. It is hoped that this review will provide more information about ice crystallization and promote the control of ice crystals in frozen foods.

Extrusion can ameliorate negative effects of molecular structures of brewer's spent grain on energy contents and amino acid digestibility in growing pigs.

The objectives of this study were to investigate the effects of extrusion on the chemical compositions, surface structure, and molecular structure of brewer's spent grain (BSG), as well as to determine the digestible energy (DE), metabolizable energy (ME), apparent total tract digestibility (ATTD) of nutrients and energy, and amino acid (AA) digestibility of extruded BSG when fed to growing pigs. Firstly, we determined the changes in chemical compositions and molecular structure of both non-extruded and extruded BSG. In Exp. 1, eighteen growing pigs were fed three different diets including one corn-soybean meal basal diet and two experimental diets containing 20% BSG with or without extrusion. Feces and urine were collected to determine the ATTD of nutrients and energy, DE, and ME of extruded or non-extruded BSG. In Exp. 2, eighteen growing pigs were fed three different diets including 30% BSG with or without extrusion, and an N-free diet. Ileal digesta was collected through the slaughter method to determine the apparent ileal digestibility (AID) and standardized ileal digestibility (SID) of AA of extruded or non-extruded BSG. The results showed that extrusion reduced the neutral detergent fiber, hemicellulose and cellulose contents in BSG, and increased the Arg, Asp, Glu, Ser, Tyr, total indispensable AA and total AA contents of BSG, altered the surface structure of BSG, increased the peak absorbance in amide I and amide II height, amide II and amide (I+II) area, α-helix height, decreased β-sheet height, and weakened band intensities in cellulosic compounds (CELC) area, structural carbohydrates (SCHO) area, carbohydrates area (CHO) peak 2 and 3 height, the area ratio of CELC: CHO and CELC: SCHO. Moreover, DE and ME values and ATTD of energy, dry matter, crude protein, acid detergent fiber, neutral detergent fiber, cellulose and hemicellulose increased (P < 0.05) when pigs were fed extruded BSG diets. The AID and SID of Arg, His, Lys, Val and Gly increased, whereas the AID and SID of Ile and Leu decreased when pigs were fed extrusion diets (P < 0.05). Our study found that the ATTD of nutrients and AA digestibility in pigs were positively correlated with the molecular structure of proteins, and negatively correlated with the molecular structure of carbohydrates (P < 0.05). These findings suggested that extrusion had the potential to improve the nutrient digestibility of BSG by altering its chemical compositions, surface structure, and molecular structure.

(Invited) Multiscale Modeling and Machine Learning Investigation of Battery Interphase Dynamics

In recent years, the solid electrolyte interphase (SEI) has emerged as a critical component in the development of efficient and durable electrochemical storage systems. Understanding the dynamics and properties of SEI is paramount for the enhancement of battery performance and longevity. This study presents a novel multi-scale simulation approach, incorporating Hybrid Ab Initio Reactive Molecular Dynamics (HAIR), to elucidate the intricate mechanisms governing SEI formation and evolution. Our methodology involves simulation under operando conditions, closely mimicking real-world scenarios, to provide insights into the molecular interactions and structural changes within the SEI layer. By leveraging HAIR, we bridge the gap between quantum mechanical precision and the expansive temporal-spatial scales of molecular dynamics, facilitating a more comprehensive understanding of SEI behavior [1,2]. Furthermore, we integrate machine learning (ML) techniques to refine our predictive models. These ML algorithms are trained on a rich dataset derived from HAIR simulations, enabling the prediction of key electrochemical properties, including chemical composition and electronic structure. The application of machine learning significantly enhances our ability to forecast SEI evolution under various operational conditions. A critical aspect of our research is the prediction of X-ray photoelectron spectroscopy (XPS) and Coulombic Efficiency (CE) outcomes [3]. By simulating these properties, we provide valuable predictions that align closely with experimental data, thereby validating our simulation framework. In summary, our study offers a groundbreaking perspective on SEI analysis, merging the fidelity of HAIR with the predictive power of machine learning. This approach not only deepens our fundamental understanding of SEI properties but also paves the way for the development of more efficient and durable electrochemical storage systems. Our findings hold significant implications for the future of battery technology and underscore the importance of advanced simulation techniques in electrochemical research. Reference 1. Liu Y; Yu PP; Sun QT; Wu Y; Xie M; Yang H; Cheng T*; Goddard WA; ACS Energy Lett. 2021, 6, 2320.2. Liu Y; Sun QT; Yue BT; Zhang YY; Cheng T*; J. Mater. Chem. A 2023, 11, 14640.3. Sun QT; Xiang Y; Liu Y; Xu L; Leng TL; Ye YF; Fortunelli A*; Goddard WA*; Cheng T*; J. Phys. Chem. Lett. 2022, 13, 8047. Figure 1

Do Molecular Geometries Change Under Vibrational Strong Coupling?

As pioneering experiments have shown, strong coupling between molecular vibrations and light modes in an optical cavity can significantly alter molecular properties and even affect chemical reactivity. However, the current theoretical description is limited and far from complete. To explore the origin of this exciting observation, we investigate how the molecular structure changes under strong light-matter coupling using an ab initio method based on the cavity Born-Oppenheimer Hartree-Fock ansatz. By optimizing H2O and H2O2 resonantly coupled to cavity modes, we study the importance of reorientation and geometric relaxation. In addition, we show that the inclusion of one or two cavity modes can change the observed results. On the basis of our findings, we derive a simple concept to estimate the effect of the cavity interaction on the molecular geometry using the molecular polarizability and the dipole moments.

Molecular interaction between three novel amino acid based deep eutectic solvents with surface active ionic liquid: A comparative study

Interaction between a surface active ionic liquid (IL) viz. 1-decyl-3-methylimidazolium chloride [Dmim][Cl] with three novel amino acid-based deep eutectic solvents (DES, consisting of choline chloride and l-methionine (DES1), l-phenylalanine (DES2), and l-glutamine (DES3) in a 1: 2 mol ratio) is studied. Several techniques, including surface tension, fluorescence, UV–visible spectroscopy, and Fourier transform infrared (FTIR), were used to investigate the key micellar properties and intermolecular interactions between the IL and DESs. All the DESs studied here facilitate the micellization process successfully lowering the critical micelle concentrations (CMC) of [Dmim][Cl] with addition of 5 wt% and 10 wt% of DESs. In decreasing order of DES2 > DES1 > DES3, the affinity to promote IL [Dmim][Cl] aggregation within aqueous DES solutions. Additionally, the CMC values as well as the surface tension at CMC are both noticeably reduced significantly by DES2. The surface tension method determines how three amino acid-based DESs affect the CMC, Гmax, πCMC, Amin and pC20 of micellization. When IL [Dmim][Cl] forms micelles within DES solutions, the solvophobic effect predominates, and the intermolecular hydrogen-bond interaction helps to form micelles. FTIR was used to examine the molecular interactions and structural changes of the ionic liquid self-assemblies in aqueous DESs. The results show that the presence of DESs greatly aids in the micellization of [Dmim][Cl], and to a greater extent for DES2 than for DES1/DES3. The colloidal properties of DES and their mixtures are advantageous for the solubility, micellization, and other features of ionic liquids; further details on this positive observation are provided in the results and discussion. In the areas of micellization, CMC, synthesis, catalysis, and environmental, biological, and pharmaceutical applications, among others, DESs are extremely useful.