Molecular Radius Research Articles

Molecular Simulation of CH4 Adsorption Characteristics under the Coupling of Different Temperature and Water Content

The adsorption characteristics of CH4 have an important influence on gas content prediction, gas extraction, and hazard prevention. Therefore, we explored the mechanism of CH4 adsorption under the action of water and temperature to grasp the influence of water and temperature on the adsorption characteristics of CH4. In this paper, a giant, regular-system Monte Carlo method is used to simulate the CH4 adsorption behavior at the molecular level under different temperatures, water contents, and the coupling of both. The results indicate that an empirical formula for the coupling effect of temperature and water content on CH4 adsorption was obtained. The impact of different effects on CH4 adsorption is as follows: coupling effect > single temperature effect > single water content effect. The optimal combination is at a temperature of 363 K and a water content of 8.31%. Compared with the CH4 adsorption capacity without water at room temperature, the CH4 adsorption capacity is reduced by 68.04% under the coupling effect of the optimal combination. Temperature has a negative effect on the adsorption of CH4, and temperature changes the adsorption capacity by changing the average molecular kinetic energy of CH4. The reason why the increase in H2O reduces the adsorption capacity of CH4 is that the interaction between H2O and the oxygen-containing functional groups of coal is stronger than that of CH4. As the water content increases, the adsorption heat decreases, thereby inhibiting the adsorption of CH4. In addition, H2O has a smaller molecular dynamics radius as compared to CH4; the larger the free volume and surface area in the pore structure, the more adsorption pores it occupies, resulting in a more significant reduction in the adsorption of CH4.

Probing the Roles of Temperature and Cooperative Effects in Chirality-Induced Spin Selectivity: Photoelectron Spin Polarization in Helical Tetrapyrroles.

We investigate the roles of molecular vibrations and intermolecular interactions in the mechanism underlying chirality-induced spin selectivity (CISS) in monolayers of helical tetrapyrrole (TPBT) molecules. The spin polarization of photoelectrons emitted from TPBT-functionalized Cu(111) surfaces was measured as a function of the temperature and the surface coverage. We employed DFT calculations to determine the energy and temperature-dependent population of vibrational modes which vary either the molecular pitch and/or the molecular radius. In combination, the data demonstrate that molecular vibrations do not play a significant role for CISS in the TPBT layers. Submonolayer coverages were created by gradual thermal desorption of the molecules from the surface during the spin polarization measurements. While the spin polarization scales nonlinearly with the surface coverage, this behavior can be rationalized entirely through changes of the photoelectron yield upon surface functionalization, and therefore represents no evidence for cooperative effects involved in CISS.

Heavy metals remediation using MOF5@GO composite incorporated mixed matrix ultrafiltration membrane

A polysulfone-based mixed matrix membrane (MMM) was prepared by incorporation of MOF5@GO composite in the polymer matrix. The prepared membrane was characterized by permeability, scanning electron microscopy, Fourier transform infrared spectroscopy, zeta potential, X-ray photoelectron spectroscopy, atomic force microscope, molecular weight cut-off and average pore radius. MMM exhibits enhanced permeability, pore size, surface roughness and molecular weight cut-off compared to polysulfone membrane. Pure water permeability of M−0.5 enhanced from 37.9 to 59.5 L/m2h.bar, which corroborated an increase in molecular weight cut-off from 46.9 to 74.1 kDa and pore radius from 66.9 to 75.4 Å as MOF5@GO composite was incorporated in polysulfone polymer matrix. At neutral pH, the optimized MMM (M−0.5) shows –22.7 mV zeta potential facilitating the adsorption of heavy metals. The M−0.5 membrane exhibits 95–99 % rejection of Pb, Cu, Zn and Cd at 2 bar pressure with enhanced permeate flux (∼116 L/m2h) compared to the polysulfone membrane. M−0.5 membrane shows better antifouling properties than the polysulfone membrane. Among the heavy metals studied, lead and copper showed the maximum rejection. The MMM shows 99 % rejection of lead and copper and breakthrough time of 12 and 9 h, respectively for a small membrane area (0.0012 m2). Thus, the prepared low-pressure driven mixed matrix ultrafiltration membrane was suitable and competent for heavy metal rejection. A modified convection-adsorption model based on the first principle was used to predict the long-term filtration performance of the membrane. The same model was used to generate the performance curve for scaling up the process.

Geometry, reactivity descriptors, light harvesting efficiency, molecular radii, diffusion coefficient, and oxidation potential of RE(I)(CO)3Cl(TPA-2, 2′-bipyridine) in DSSC application: DFT/TDDFT study

Dye-sensitized solar cells (DSSCs) are an excellent alternative solar cell technology that is cost-effective and environmentally friendly. The geometry, reactivity descriptors, light-harvesting efficiency, molecular radii, diffusion coefficient, and excited oxidation state potential of the proposed complex were investigated. The calculations in this study were performed using DFT/TDDFT method with B3LYP functional employed on the Gaussian 09 software package. The calculations were used the 6–311 + + G(d, p) basis set for the C, H, N, O, Cl atoms and the LANL2DZ basis set for the Re atom, with the B3LYP functional.. The balance of hole and electron in this complex has increased the efficiency and lifetime of DSSCs for photovoltaic cell applications. The investigated compound shows that the addition of the TPA substituent marginally changes the geometric structures of the 2, 2′-bipyridine ligand in the T1 state. As EDsubstituents were added to the compound, the energy gap widened and moved from ELUMO (− 2.904 eV) (substituted TPA) to ELUMO (− 3.122 eV) (unsubstituted). In the studying of solvent affects; when the polarity of the solvent decreases, red shifts appears in the lowest energy an absorption and emission band. Good light-harvesting efficiency, molecular radii, diffusion coefficient, excited state oxidation potential, emission quantum yield, and DSSC reorganization energy, the complex is well suited for use as an emitter in dye-sensitized solar cells. Among the investigated complexes mentioned in literature, the proposed complex was a suitable candidate for phosphorescent DSSC.

Particle size effect on surface/interfacial tension and Tolman length of nanomaterials: A simple experimental method combining with theoretical.

Surface tension and interfacial tension are crucial to the study of nanomaterials. Herein, we report a solubility method using magnesium oxide nanoparticles of different radii (1.8-105.0nm, MgO NPs) dissolved in pure water as a targeted model; the surface tension and interfacial tension (and their temperature coefficients) were determined by measuring electrical conductivity and combined with the principle of the electrochemical equilibrium method, and the problem of particle size dependence is discussed. Encouragingly, this method can also be used to determine the ionic (atomic or molecular) radius and Tolman length of nanomaterials. This research results disclose that surface/interfacial tension and their temperature coefficients have a significant relationship with particle size. Surface/interfacial tension decreases rapidly with a radius <10nm (while the temperature coefficients are opposite), while for a radius >10nm, the effect is minimal. Especially, it is proven that the value of Tolman length is positive, the effect of particle size on Tolman length is consistent with the surface/interfacial tension, and the Tolman length of the bulk does not change much in the temperature range. This work initiates a new era for reliable determination of surface/interfacial tension, their temperature coefficients, ionic radius, and Tolman length of nanomaterials and provides an important theoretical basis for the development and application of various nanomaterials.

Effect of Tween and CTAB surfactants on aqueous solubility of the silibinin anticancer drug studied by using physicochemical properties at 310.15 K

The silibinin (SB) is an anticancer drug exhibits partial solubility in aqueous medium due to its slightly hydrophobic nature. In this context, the aqueous solubility of SB with Tween 40 (Tw 40), Tween 60 (Tw 60), Tween 80 (Tw 80) and Cetyltrimethylammonium bromide (CTAB) surfactants at 310.15 K are reported. The physicochemical properties (PCPs) such as density (ρ, g cm−3), Apparent Molar Volume (Vϕ, cm3·mol−1), viscosity (η, mPa.s), surface tension (γ, mNm−1), friccohesity (σ, s.m−1), activation energy (Δµ2*, kJ/mol), and molecular radii (r, nm) of SB with aqueous solution of Tw 40, Tw 60, Tw 80 and CTAB surfactants separately. The PCPs reflects the state of intermolecular forces (IMF) developed between SB and aqueous solutions of Tween (40, 60, 80) and CTAB surfactants with concentration varied from 25 to 150 µM (µM). This study focused on intermolecular interacting mechanism determined by using PCPs to evaluate self-aggregation potential of SB in aqueous surfactants solution. The PCPs data furnished interaction and structure breaking behavior of SB with surfactant molecules. The development of hydrogen bond (HB), hydrophilic, hydrophobic and electrostatic interactions of SB with surfactants which revealed that the structure dependent interacting activities enhances with increasing concentration of SB in aqueous surfactants.

Label-free detection and profiling of individual solution-phase molecules.

Most chemistry and biology occurs in solution, in which conformational dynamics and complexation underlie behaviour and function. Single-molecule techniques1 are uniquely suited to resolving molecular diversity and new label-free approaches are reshaping the power of single-molecule measurements. A label-free single-molecule method2-16 capable of revealing details of molecular conformation in solution17,18 would allow a new microscopic perspective of unprecedented detail. Here we use the enhanced light-molecule interactions in high-finesse fibre-based Fabry-Pérot microcavities19-21 to detect individual biomolecules as small as 1.2 kDa, a ten-amino-acid peptide, with signal-to-noise ratios (SNRs) >100, even as the molecules are unlabelled and freely diffusing in solution. Our method delivers 2D intensity and temporal profiles, enabling the distinction of subpopulations in mixed samples. Notably, we observe a linear relationship between passage time and molecular radius, unlocking the potential to gather crucial information about diffusion and solution-phase conformation. Furthermore, mixtures of biomolecule isomers of the same molecular weight and composition but different conformation can also be resolved. Detection is based on the creation of a new molecular velocity filter window and a dynamic thermal priming mechanism that make use of the interplay between optical and thermal dynamics22,23 and Pound-Drever-Hall (PDH) cavity locking24 to reveal molecular motion even while suppressing environmental noise. New in vitro ways of revealing molecular conformation, diversity and dynamics can find broad potential for applications in the life and chemical sciences.

Nanoassembly-Mediated Exendin-4 Derivatives to Decrease Renal Retention.

An Exendin-4 analogue that was conjugated with 68Ga exhibited an excellent diagnostic effect on insulinoma in clinical practice. On account of its low molecular weight and short hydration radius, 68Ga-Exendin-4 showed high accumulation in kidney tissues. Nanoparticle-mediated strategies have attracted much attention due to polyvalent properties and the size amplification effect. In this study, Exendin-4 derivatives of radionuclide nanodevices were developed and evaluated. The Exendin-4 derivatives consisting of a ternary block recombinant protein were purified by an inverse transition cycle (ITC) and allowed to self-assemble into a nanodevice under physiological conditions. Our results showed that the nanoassemblies of Exendin-4 derivatives formed homogeneous spherical nanoparticles, exhibited outstanding affinity for insulinoma cells, and could be deposited in insulinoma tissues in vivo. The nanoassembly-mediated Exendin-4 derivatives showed fivefold reduced renal retention and exhibited an outstanding tumor-suppression effect.

Quantitative analysis of mRNA-lipid nanoparticle stability in human plasma and serum by size-exclusion chromatography coupled with dual-angle light scattering

Understanding the stability of mRNA loaded lipid nanoparticles (mRNA-LNPs) is imperative for their clinical development. Herein, we propose the use of size-exclusion chromatography coupled with dual-angle light scattering (SEC-MALS) as a new approach to assessing mRNA-LNP stability in pure human serum and plasma. By applying a dual-column configuration to attenuate interference from plasma components, SEC-MALS was able to elucidate the degradation kinetics and physical property changes of mRNA-LNPs, which have not been observed accurately by conventional dynamic light scattering techniques. Interestingly, both serum and plasma had significantly different impacts on the molecular weight and radius of gyration of mRNA-LNPs, suggesting the involvement of clotting factors in desorption of lipids from mRNA-LNPs. We also discovered that a trace impurity (~1 %) in ALC-0315, identified as its O-tert-butyloxycarbonyl-protected form, greatly diminished mRNA-LNP stability in serum. These results demonstrated the potential utility of SEC-MALS for optimization and quality control of LNP formulations.

Fractional Extended Diffusion Theory to capture anomalous relaxation from biased/accelerated molecular simulations.

Biased and accelerated molecular simulations (BAMS) are widely used tools to observe relevant molecular phenomena occurring on time scales inaccessible to standard molecular dynamics, but evaluation of the physical time scales involved in the processes is not directly possible from them. For this reason, the problem of recovering dynamics from such kinds of simulations is the object of very active research due to the relevant theoretical and practical implications of dynamics on the properties of both natural and synthetic molecular systems. In a recent paper [A. Rapallo et al., J. Comput. Chem. 42, 586-599 (2021)], it has been shown how the coupling of BAMS (which destroys the dynamics but allows to calculate average properties) with Extended Diffusion Theory (EDT) (which requires input appropriate equilibrium averages calculated over the BAMS trajectories) allows to effectively use the Smoluchowski equation to calculate the orientational time correlation function of the head-tail unit vector defined over a peptide in water solution. Orientational relaxation of this vector is the result of the coupling of internal molecular motions with overall molecular rotation, and it was very well described by correlation functions expressed in terms of weighted sums of suitable time-exponentially decaying functions, in agreement with a Brownian diffusive regime. However, situations occur where exponentially decaying functions are no longer appropriate to capture the actual dynamical behavior, which exhibits persistent long time correlations, compatible with the so called subdiffusive regimes. In this paper, a generalization of EDT will be given, exploiting a fractional Smoluchowski equation (FEDT) to capture the non-exponential character observed in the relaxation of intramolecular distances and molecular radius of gyration, whose dynamics depend on internal molecular motions only. The calculation methods, proper to EDT, are adapted to implement the generalization of the theory, and the resulting algorithm confirms FEDT as a tool of practical value in recovering dynamics from BAMS, to be used in general situations, involving both regular and anomalous diffusion regimes.

Refractive index and related properties for the mixture (1, 4-dioxane + water) at temperature T= (295.15, 298.15, 301.15, 304.15, 307.15, 310.15 and 313.15) K

ABSTRACT The refractive index n D for the mixture (1,4-dioxane (1) + water (2)) was measured over the whole composition range at different temperatures and atmospheric pressure. From measured values of the refractive indices, the molar refraction R m , reduced molar free volumes V m R m , molecular radii r and internal pressure, P int were calculated. On the other hand, some excess parameters were also deduced. The obtained results have been discussed and interpreted in terms of the type and nature of specific intermolecular interactions existed between the components. Furthermore, we have used nine mixing rules for refractive index proposed by different authors to calculate the refractive indices of the present mixture. A comparative study was carried out between the measured and calculated indices. The Redlich–Kister polynomial equation has been used to fit the presented excess parameters to derive the adjustable fitting coefficients and estimate the standard error values.

The effect of aromatic side chains on the dilational rheological properties of N-acyltaurate amphiphiles at water-decane interfaces.

To elucidate the effect of aromatic side chains on dilational rheological properties of N-acyltaurate amphiphiles at the decane-water interface, the interfacial rheological properties of sodium N-2-(2-naphthoxy)-tetradecanoyltaurinate (12+N-T) and sodium N-2-(p-butylphenoxy)-tetradecanoyltaurinate (12+4B-T) were investigated utilizing the drop shape analysis method. The effects of adsorption time, interfacial pressure, oscillating frequency, and bulk concentration on the interfacial dilational modulus and phase angle were explored. The results show that the 12+4B-T molecule with a longer hydrophobic chain shows a higher ability for reducing the interfacial tension (IFT). In addition, the interfacial films of both 12+N-T and 12+4B-T are dominated by diffusion exchange at high concentrations. The rigidity of molecules controls the diffusion exchange at low concentrations, while the molecular hydrodynamic radius determines the diffusion exchange at high concentrations. Thus, at low concentrations, the stronger intermolecular interaction between 12+4B-T molecules results in higher dilational modulus values than 12+N-T. When approaching the CMC (critical micelle concentration) value, the rapid diffusion exchange of 12+4B-T between the sublayer micelles and the interface causes a significant decrease in the dilational modulus, while the relatively rigid structure of 12+N-T enables a higher dilational modulus than 12+4B-T. What's more, the longer hydrophobic chain allows 12+4B-T molecules to escape from the interface more easily, resulting in a higher phase angle at low concentrations. However, the diffusion exchange of 12+4B-T is slower than that of 12+N-T, which results in lower phase angles for 12+4B-T than 12+N-T at high concentrations. In general, the introduction of a rigid naphthalene ring in the molecular structure gives the interfacial film greater strength at high concentration. The research results in this paper provide a new technique for the strength regulation of interfacial surfactant adsorption films.

Insights into adsorption and diffusion of CO2, CH4 and their mixture in MIL-101(Cr) via molecular simulation

An in-depth comprehension of the adsorption and diffusion properties of CH4, CO2, and their mixture in MIL-101(Cr) is crucial for its application in the highly selective separation of CO2 and CH4 mixtures in biogas. Existing studies often overlook the influence of gas molecular radius and MIL-101 topological structure on adsorption and lack quantitative analysis of the primary and secondary adsorption sites of MIL-101. Additionally, there is a significant gap in research on the adsorption mechanism of gas mixtures. To address these gaps and to provide new knowledge, this study employs Monte Carlo and molecular dynamics simulations to evaluate various factors such as CH4 and CO2 adsorption isotherms, density distribution profiles, self-diffusion coefficients, radial distribution functions (RDF), and CO2/CH4 selectivity within MIL-101 metal-organic framework (MOF). The insightful and comprehensive atomic-level study reveals several unique and new findings, include 1) the RDF analysis shows that the C = C double bond of the benzene ring within MIL-101 primarily governs the adsorption of CH4, while the open metal center (Cr) exhibits significant adsorption effects on CO2; 2) the density distribution profile analysis indicates that CH4 molecules tend to localize in the larger and medium-sized cages, whereas CO2 molecules exhibit relatively uniform distribution. 3) evaluation of self-diffusivity coefficients and diffusion activation energies demonstrated that CH4 diffuses more easily than CO2, and in the CO2 and CH4 two-component gas, the existence of CH4 can further reduce the diffusion coefficient of CO2. This investigation provides a microscopic understanding of adsorption and diffusion phenomena within MIL-101, contributing to the overall comprehension of its behavior in gas separation applications.

Revisiting Maxwell-Smoluchowski theory: Low surface roughness in straight channels

The Maxwell-Smoluchowski (MS) theory of gas diffusion is revisited here in the context of gas transport in straight channels in the Knudsen regime of large mean free path. This classical theory is based on a phenomenological model of gas-surface interaction that posits that a fraction ϑ of molecular collisions with the channel surface consists of diffuse collisions, i.e., the direction of post-collision velocities is distributed according to the Knudsen Cosine Law, and a fraction 1−ϑ undergoes specular reflection. From this assumption one obtains the value D=2−ϑϑDK for the self-diffusivity constant, where DK is a reference value corresponding to ϑ=1. In this paper we show that ϑ can be expressed in terms of micro- and macro-geometric parameters for a model consisting of hard spheres colliding elastically against a rigid surface with prescribed microgeometry.Our refinement of the MS theory is based on the observation that the classical surface scattering operator associated to the microgeometry has a canonical velocity space diffusion approximation by a generalized Legendre differential operator whose spectral theory is known explicitly. More specifically, starting from an explicit description of the effective channel surface microgeometry—a concept which incorporates both the actual surface microgeometry and the molecular radius—and using this operator approximation, we show that ϑ can be resolved into easily obtained geometric parameters, ϑ=λh/C, having the following interpretation: C is a macroscopic parameter determined by the shape of the channel cross-section; h is a parameter that precisely captures the degree of roughness of the effective microgeometry, and λ is a parameter that characterizes the overall curvature of the surface microgeometry independent of h. Thus ϑ is resolved as the quotient of microscopic (λh) over macroscopic (C) signature parameters of the channel geometry. The identity ϑ=λh/C holds up to higher order terms in the roughness parameter h, so our main result better applies to well polished, or low roughness, surfaces.

Molecular Simulation of Adsorption and Diffusion of Methane and Ethane in Kaolinite Clay under Supercritical Conditions: Effects of Water and Temperature

Grand Canonical Monte Carlo (GCMC) simulation and Molecular Dynamics (MD) simulations were used to study the effects of temperature (310 K to 400 K), pressure (≤30 MPa) and water content (0 molecule/nm3 to 9 molecule/nm3) on the adsorption and diffusion behavior of CH4 and C2H6 in 3 nm kaolinite slit under supercritical conditions. The obtained adsorption capacity, isosteric adsorption heat, concentration distribution and diffusion coefficient were analyzed and compared. The simulation results show that the adsorption capacity of C2H6 is higher under low pressure conditions, and the adsorption capacity of CH4 is higher under high pressure conditions due to the small molecular radius and increased adsorption space. The addition of water molecules and the increase in temperature will reduce the adsorption capacity and isosteric adsorption heat of the two gases. We analyzed the changes in Langmuir volume and Langmuir pressure of the two gases under different temperature and water content conditions. The addition of water molecules and the increase in temperature will reduce the saturation adsorption capacity (which has a greater effect on C2H6) and the adsorption rate of the two gases in the kaolinite slit. The water molecules occupy the adsorption site of the gas molecules (limiting the diffusion of the gas molecules), which reduces the interaction between gas molecules and the wall surface, thus altering the distribution of the two gases in the slit. The increase in temperature will accelerate the oscillation of the gas molecules, increasing diffusion, and also leads to a reduction in the peak value of the adsorption peaks of the two gases.

Synthesis of high concentration polycarboxylate superplasticizers via a photoinitiated one-pot method

Polycarboxylate superplasticizers (PCEs) are primarily liquid products (40 wt%) with narrow application range, which incur high transportation and storage costs. However, the high reaction viscosity makes it challenging to produce high concentration PCEs. In our study, high concentration PCEs are successfully synthesized by a photoinitiated one-pot method at room temperature. The results show that the reaction viscosity of photoinitiation is slightly higher than that of traditional initiation systems, but the photoinitiated reaction remains stable and controllable, with no occurrence of violent polymerization. The impact of varying reaction concentrations on the polymerization rate, molecular structure, and properties of PCEs has been studied under the photoinitiated one-pot method. The results indicate that an increase in reaction concentration leads to a rise in polymerization rate, molecular weight, and molecular gyration radius of the polymers. The conversion rate of the macromonomer exceeds 80%, while the polydispersion index (PDI) for molecular weight is below 2 with a narrow distribution. Furthermore, the monomer polymerization ratio of the product remains close to the feeding ratio at different reaction concentrations. Finally, it is observed that PCEs with a high concentration of 80 wt% exhibit favorable dispersion, rheology and adsorption properties. This study presents a new method for synthesizing high concentration PCEs using photoinitiation.

Field- and Temperature-Dependent Paramagnetic Relaxation Enhancements in Co(II) Trispyrazolylmethanes.

A comprehensive field- and temperature-dependent examination of nuclear magnetic resonance paramagnetic relaxation enhancements (PREs) for the constitutive protons of [Co(Tpm)2][BF4]2 is presented. Data for an apically substituted derivative clearly establish that bis-Tpm complexes of Co(II) undergo Jahn-Teller dynamics about the molecular threefold axis. PREs from the parent Tpm complex were used to numerically extract the electron relaxation times (T1e). The Tpm complex showed field-dependent behavior, with an approximately 40% higher activation barrier than the related trispyrazolylborate (Tp) complex, based on fits to the T1e vs T, B0 data. Analysis of the field-dependent line widths revealed a surprisingly large contribution from susceptibility (Curie) relaxation (20-35% at the highest field), and a molecular radius (9.5 Å) that is consistent with a tightly associated counterion slowing rotation in solution. Density functional theory showed a shared vibration that is consistent with the Jahn-Teller and appears proportionately higher in energy in [Co(Tpm)2]2+. Complete active-space self-consistent field calculations support ascribing electron relaxation to enhanced mixing of the two Eg orbital sets that accompanies the tetragonal distortion and the differences in electron correlation times to the higher Jahn-Teller activation barrier in [Co(Tpm)2]2+.

Data-Driven Insight into the Reductive Stability of Ion-Solvent Complexes in Lithium Battery Electrolytes.

Lithium (Li) metal batteries (LMBs) are regarded as one of the most promising energy storage systems due to their ultrahigh theoretical energy density. However, the high reactivity of the Li anodes leads to the decomposition of the electrolytes, presenting a huge impediment to the practical application of LMBs. The routine trial-and-error methods are inefficient in designing highly stable solvent molecules for the Li metal anode. Herein, a data-driven approach is proposed to probe the origin of the reductive stability of solvents and accelerate the molecular design for advanced electrolytes. A large database of potential solvent molecules is first constructed using a graph theory-based algorithm and then comprehensively investigated by both first-principles calculations and machine learning (ML) methods. The reductive stability of 99% of the electrolytes decreases under the dominance of ion-solvent complexes, according to the analysis of the lowest unoccupied molecular orbital (LUMO). The LUMO energy level is related to the binding energy, bond length, and orbital ratio factors. An interpretable ML method based on Shapley additive explanations identifies the dipole moment and molecular radius as the most critical descriptors affecting the reductive stability of coordinated solvents. This work not only affords fruitful data-driven insight into the ion-solvent chemistry but also unveils the critical molecular descriptors in regulating the solvent's reductive stability, which accelerates the rational design of advanced electrolyte molecules for next-generation Li batteries.

Thermodynamic and Kinetic Behaviors of Persulfate-Based Electron-Transfer Regime in Carbocatalysis.

A carbon-based advanced oxidation process is featured for the nonradical electron-transfer pathway (ETP) from electron-donating organic compounds to activated persulfate complexes, enabling it as a green technology for the selective oxidation of organic pollutants in complex water environments. However, the thermodynamic and kinetic behaviors of the nonradical electron-transfer regime had been ambiguous due to a neglect of the influence of pH on the mechanisms. In this study, three kinds of organic pollutants were divided in the carbon-based ETP regime: (i) physio-adsorption, (ii) adsorption-dominated ETP (oxidation rate slightly surpasses adsorption rate), and (iii) oxidation-dominated ETP (oxidation rate outpaces the adsorption rate). The differential kinetic behaviors were attributed to the physicochemical properties of the organic pollutants. For example, the hydrophobicity, molecular radius, and positive electrostatic potential controlled the mass-transfer process of the adsorption stage of the reactants (peroxydisulfate (PDS) and organics). Meanwhile, other descriptors, including the Fukui index, oxidation potential, and electron cloud density regulated the electron-transfer processes and thus the kinetics of oxidation. Most importantly, the oxidation pathways of these organic pollutants could be altered by adjusting the water chemistry. This study reveals the principles for developing efficient nonradical systems to selectively remove and recycle organic pollutants in wastewater.

Roles of the Stereochemical Code and the Entropic Index q in the Protein Folding Process: How to Map Out Folding Intermediate Conformations

Background: Here, the inverse protein folding problem is approached from the viewpoint of the entropic index q. We present a brief overview of the problem. Further, we provide general information about the three-dimensional structure of proteins and the universal characteristics of the folding process. Methods: We explain how the stereochemical model was conceived. Our main objective is to change how Monte Carlo (MC) simulations are performed. We replace the Boltzmann weight with the Tsallis weight in order to achieve better sampling. This change leads to the q Monte Carlo method (MCq). There are two main ways to employ the index q: one is to set it as a fixed parameter (MCq*), and the other is to set it as an autonomous variable associated with the instantaneous molecular radius of gyration, a feature that is allowed by the Beck-Cohen superstatistics. In addition, we propose a meaningful physical interpretation for the index q. Furthermore, we explain how to assemble amino acid sequences for the inverse problem. Results: We present several results and discuss the implications associated with the MC and MCq methods. The latter method is an efficient approach to tracking down folding intermediate conformations, which can enable us to better find and define folding pathways for successive configurations of a polymeric chain kept in solution at the same macroscale temperature, T. Conclusion: We have explained how and why protein kinetics becomes significantly more advantageous when we employ q ≠ 1. However, this is only possible if we set the correct upper value of qmax.