Neutral Organic Compounds Research Articles

Emerging Rare Earth Element Separation Technologies

Rare earth elements are essential for numerous clean energy applications, yet their mining, separation, and processing pose significant environmental challenges. Traditional separation processes often result in ecological damage, highlighting the critical need for innovative techniques that reduce environmental impacts. This article reviews recent advancements in rare earth separation technologies, with a particular focus on the role of neutral organic compounds. It explores how these compounds change selectivity across the rare earth series, offering promising strategies for designing more effective rare earth element separation systems. Furthermore, the article points out research areas requiring additional investigation to improve the sustainability of these critical processes.

Polyparameter Linear Free Energy Relationships for Partitioning of Neutral Organic Compounds to Storage Lipids.

Storage lipids are an important compartment in the bioaccumulation of neutral organic compounds. Reliable models for predicting storage lipid-water and storage lipid-air partition coefficients (Kislip/w and Kislip/a), as well as their temperature dependence, are considered useful. Polyparameter linear free energy relationships (PP-LFERs) are accurate, general, and mechanistically clear models for predicting partitioning-related physicochemical quantities. About a decade ago, PP-LFERs were calibrated for Kislip/w at the physiological temperature of 37 °C. However, to date, a comprehensive collection and sufficiently reliable PP-LFERs for Kislip/w and Kislip/a at the most common standard temperature of 25 °C are still lacking. In this study, experimentally based Kislip/w and/or Kislip/a values at 25 °C for 278 compounds were extensively collected or converted from the literature. Subsequently, PP-LFERs were calibrated for Kislip/w and Kislip/a at 25 °C, performing well over 10 orders of magnitude with root-mean-square errors of 0.17-0.21 log units for compounds with reliable descriptors. Furthermore, standard internal energy changes of transfer from water or air to storage lipids for 158 compounds were derived and used to calibrate PP-LFERs for estimating the temperature dependence of Kislip/w or Kislip/a. Additionally, using PP-LFERs, low-density polyethylene was confirmed to be a better storage lipid analogue than silicone and polyoxymethylene in the equilibrium passive sampling of nonpolar and H-bond acceptor polar compounds.

Effects of Membrane Degradation due to Chlorine Exposure on the Removal of Neutral Organic Compounds by Reverse Osmosis for Potable Reuse

Effects of Membrane Degradation due to Chlorine Exposure on the Removal of Neutral Organic Compounds by Reverse Osmosis for Potable Reuse

Novel Models for Accurate Estimation of Air-Blood Partitioning: Applications to Individual Compounds and Complex Mixtures of Neutral Organic Compounds.

The air-blood partition coefficient (Kab) is extensively employed in human health risk assessment for chemical exposure. However, current Kab estimation approaches either require an extensive number of parameters or lack precision. In this study, we present two novel and parsimonious models to accurately estimate Kab values for individual neutral organic compounds, as well as their complex mixtures. The first model, termed the GC×GC model, was developed based on the retention times of nonpolar chemical analytes on comprehensive two-dimensional gas chromatography (GC×GC). This model is unique in its ability to estimate the Kab values for complex mixtures of nonpolar organic chemicals. The GC×GC model successfully accounted for the Kab variance (R2 = 0.97) and demonstrated strong prediction power (RMSE = 0.31 log unit) for an independent set of nonpolar chemical analytes. Overall, the GC×GC model can be used to estimate Kab values for complex mixtures of neutral organic compounds. The second model, termed the partition model (PM), is based on two types of partition coefficients: octanol to water (Kow) and air to water (Kaw). The PM was able to effectively account for the variability in Kab data (n = 344), yielding an R2 value of 0.93 and root-mean-square error (RMSE) of 0.34 log unit. The predictive power and explanatory performance of the PM were found to be comparable to those of the parameter-intensive Abraham solvation models (ASMs). Additionally, the PM can be integrated into the software EPI Suite, which is widely used in chemical risk assessment for initial screening. The PM provides quick and reliable estimation of Kab compared to ASMs, while the GC×GC model is uniquely suited for estimating Kab values for complex mixtures of neutral organic compounds. In summary, our study introduces two novel and parsimonious models for the accurate estimation of Kab values for both individual compounds and complex mixtures.

Predicting pesticide residues in pod fruits with a modified peel-like uptake model: A green pea demonstration

Peas are among the most popular leguminous plants, consumed by both humans and animals in large quantities. Pesticides are widely used globally to increase pea yield, and as a result, pesticide residues can be taken up by pea plants and bioaccumulate in their fruits, including peas and pods. However, there is a lack of modeling approaches available to predict residue concentrations in peas. To address this issue, a pod fruit model (specifically designed for neutral organic compounds) was proposed to simulate the bioaccumulation process of pesticide residues in pea plants, which was developed by modifying a peel-like uptake model. The simulation results, based on green pea as the modeling demonstration, reveal that moderately-lipophilic pesticides (i.e., log KOW around 3) have higher simulated concentrations in peas at harvest compared to hydrophilic (i.e., log KOW less than 0) or highly-lipophilic (i.e., log KOW over 5) pesticides, which is due to the enhanced uptake process of moderately-lipophilic compounds in the pod-pea system, such as their ability to penetrate the pod cuticle and be transported via phloem sap. The sensitivity test and variability analysis conducted in this study revealed that the degradation kinetics, including metabolism, hydrolysis, and photolysis, had a significant impact on moderately-lipophilic pesticides due to their high simulated concentrations in the pea plant. This can result in substantial loss of residue mass via degradation. The validation of the model demonstrated that the simulation results, specifically residue concentrations in the fruit, were consistent with the harvested data. However, some inconsistency was observed immediately after pesticide application, which could be attributed to plant growth dynamics and initial surface mass distributions. The proposed pod fruit model provides new insights into the bioaccumulation process of pesticide residues in pea plants and enables high-throughput simulations of residue concentrations at harvest. To enhance the performance of the pod fruit model, future research should consider plant growth dynamics, plant uptake of ionizable compounds, and initial mass distribution functions.

Visible light photocatalysis alleviates ceramic membrane fouling caused by intracellular organic matter of Microcystis aeruginosa

Ultrafiltration (UF) is an effective technology for treating algae-containing water. The algal intracellular organic matter (IOM) released by dead algae during an excessive algae growth phase causes more serious membrane fouling than viable algal cells and algal extracellular organic matter (EOM), which seriously restricts stable operation of UF. This paper studied the removal of IOM by a Bi2O3–TiO2/PAC (Bi-doped TiO2 nano-composites supported by powdered activated carbon) photocatalytic oxidation-ceramic ultrafiltration membrane, the inhibitory effect of membrane fouling at different photocatalytic oxidation times, and the fouling mechanism. The results show that both the adsorption and photocatalytic oxidation of Bi2O3–TiO2/PAC can significantly remove proteinoids and humic acid-like fluorescent components present in IOM, with removals of UV254 and DOC reaching up to 81.8% and 44.0%. The generated superoxide radicals and hydroxyl radicals positively affect the degradation of organic compounds of various molecular weights, and holes mainly degrade acidic low-molecular weight organic compounds. When the photocatalytic oxidation time was extended to 60 min, the membrane flux increased by 70.7% and the reversible resistance and irreversible resistance decreased by 83.4% and 90.1%, respectively. Under these conditions, the fouling mechanism changed from complete blockage to intermediate blockage. In the late stage of photocatalytic oxidation (90–120min), part of the high and medium molecular weight organic components were oxidized to produce low-molecular weight organic compounds (LMW acidic and neutral organic compounds), and blockage of filter cake became the main fouling mechanism. After photocatalysis, the zeta potential decreases significantly and the interaction forces between pollutants and pollutants are transformed into repulsive forces. Application of an appropriate photocatalytic oxidation time can alleviate the ultrafiltration membrane fouling caused by algal-derived organics.

Generic Model for Plant Uptake of Ionizable Pharmaceuticals and Personal Care Products.

Plant uptake of pharmaceuticals and personal care products (PPCPs) has been recognized as a potential path to human exposure. Most existing regressions and uptake models are limited to neutral organic compounds, but 80% of pharmaceuticals and an unknown number of personal care products ionize under environmentally relevant conditions. A widely used generic plant uptake model was expanded step-by-step with processes relevant for weak and strong acids and bases, such as ionization, membrane permeability, ion trap, phloem transport, and sorption to proteins. The differential equation system was solved analytically, and the equations were implemented in a spreadsheet version. The changes in predicted plant uptake of neutral substances, acids, and bases were found for a range of key input data (log KOW , pKa , pH, sorption to proteins). For neutral compounds, sorption to proteins and phloem transport are of relevance only for the more polar compounds (low log KOW , ≤2). Weak acids (pKa ≤6) are trapped in phloem due to pH-related effects, and in roots when pH in soil is low (pH 4-5). Cations sorb stronger and hence show less bioavailability and less translocation than anions. Sorption to proteins reduces translocation to leaves and fruits for all substances, but this is more evident for polar and ionic compounds that have negligible sorption to lipids. The new generic model considers additional processes that are of relevance for polar and ionizable substances. It might be used instead of existing standard approaches for chemical risk assessment and assessment of the environmental fate of PPCPs. Environ Toxicol Chem 2023;42:793-804. © 2023 The Authors. Environmental Toxicology and Chemistry published by Wiley Periodicals LLC on behalf of SETAC.

Gas phase H+, H3O+ and NH4+ affinities of oxygen-bearing volatile organic compounds; DFT calculations for soft chemical ionisation mass spectrometry.

Quantum chemistry calculations were performed using the density functional theory, DFT, to understand the structures and energetics of organic ions relevant to gas phase ion chemistry in soft chemical ionisation mass spectrometry analytical methods. Geometries of a range of neutral volatile organic compound molecules and ions resulting from protonation, the addition of H3O+ and the addition of NH4+ were optimised using the B3LYP hybrid DFT method. Then, the total energies and the normal mode vibrational frequencies were determined, and the total enthalpies of the neutral molecules and ions were calculated for the standard temperature and pressure. The calculations were performed for several feasible structures of each of the ions. The proton affinities of several benchmark molecules agree with the accepted values within ±4 kJ mol-1, indicating that B3LYP/6-311++G(d,p) provides chemical accuracy for oxygen-containing volatile organic compounds. It was also found that the binding energies of H3O+ and NH4+ to molecules correlate with their proton affinities. The results contribute to the understanding of ligand switching ion-molecule reactions important for secondary electrospray ionisation, SESI, and selected ion flow tube, SIFT, mass spectrometries.

PIPs from Fragaria vesca: A structural analysis of native and mutated protein

Aquaporins are an ancient family of membrane channel proteins present in all eukaryotes and most prokaryotes, and apart from water, allow the transport of neutral solutes and organic compounds through the pore. These proteins are essential role differentially expressed during ripening in Fragaria vesca fruits. Fv PIP2-1a is intensively expressed in fruits, inclusive several other proteins member are differentially expressed in fruit but also in other plant tissues. Phylogenetic analysis shows that Fv PIP2-1a grouped with other Fragaria proteins and far apart from other F. vesca PIP proteins. A structural model for Fv PIP2-1a protein was built by comparative modelling methodology, which was validated and refined by molecular dynamics simulation. Fv PIP2-1a structure consists of 6 transmembrane regions and two NPA domains. The mobilization of water was analyzed by molecular docking simulations in wildtype and two mutants. Interestingly, the mutant FvPIP2-1a_H214G allowed the prediction of an increment in the flux of water molecules. On contrary, structural analysis predicted that H214E mutation blocked passage of water associated to constriction of the pore.

Accurate determination of solvation free energies of neutral organic compounds from first principles

The main goal of molecular simulation is to accurately predict experimental observables of molecular systems. Another long-standing goal is to devise models for arbitrary neutral organic molecules with little or no reliance on experimental data. While separately these goals have been met to various degrees, for an arbitrary system of molecules they have not been achieved simultaneously. For biophysical ensembles that exist at room temperature and pressure, and where the entropic contributions are on par with interaction strengths, it is the free energies that are both most important and most difficult to predict. We compute the free energies of solvation for a diverse set of neutral organic compounds using a polarizable force field fitted entirely to ab initio calculations. The mean absolute errors (MAE) of hydration, cyclohexane solvation, and corresponding partition coefficients are 0.2 kcal/mol, 0.3 kcal/mol and 0.22 log units, i.e. within chemical accuracy. The model (ARROW FF) is multipolar, polarizable, and its accompanying simulation stack includes nuclear quantum effects (NQE). The simulation tools’ computational efficiency is on a par with current state-of-the-art packages. The construction of a wide-coverage molecular modelling toolset from first principles, together with its excellent predictive ability in the liquid phase is a major advance in biomolecular simulation.

The Changing of Dissolved Organic Matter Based on Its Molecular Weight Through Alum Coagulation and Adsorption Activated Carbon

Surface water may contain dissolved organic matter (DOM), which is derived from microbial activities in water and discharged from the watershed. Source water is mainly used as raw water for clean and drinking water, and DOM in water could affect the treated water quality. Therefore, it is necessary to remove DOM in water. This study aims to know the efficiency of removal of DOM by using alum coagulation followed by adsorption with activated carbon. In addition, this study applied the chromatograms method to identify the changing of DOM based on its molecular weight. The results show that raw water was composed of two main organic fractions: humic substances and low molecular weight acids and neutral.The humic substances organic fractions have been removed through alum coagulation up to 48%, and removal increased up to 85% through adsorption with activated carbon. The low molecular weight acids and neutral organic compounds have been removed about 85% and 40% in alum coagulation and adsorption,respectively.

Reliable Prediction of Sensory Irritation Threshold Values of Neutral Organic Compounds in Pure and Complex Mixtures Using New Models Based on Linear Free Energy Relationships and Gc×Gc Retention Parameters

Reliable Prediction of Sensory Irritation Threshold Values of Neutral Organic Compounds in Pure and Complex Mixtures Using New Models Based on Linear Free Energy Relationships and Gc×Gc Retention Parameters

Predicting Leachables Solubilization in Polysorbate 80 Solutions by a Linear Solvation Energy Relationship (LSER).

A linear solvation energy relationship (LSER) was developed to predict the partitioning of neutral chemicals from polysorbate 80 (PS 80) micelles to water. Predicted partition coefficients were converted to a concentration dependent solubilization strength of aqueous PS 80 solutions. This solubilization strength represents a key parameter to project equilibrium levels of leaching from pharmaceutical plastic materials. To construct the LSER model equation, partition coefficients between PS 80 micelles and water were measured via a reference phase method or collected from the literature. Multiple linear regression of partition coefficients against five publicly available solute parameters was used to obtain the LSER system parameters. 112 chemically diverse compounds were incorporated for LSER model regression. The model equation shows a very good fit (R2 = 0.969, SD = 0.219) for the entire dataset. The accuracy of the multi-parameter LSER model was proven to be substantially better in comparison to a single-parameter log-linear model based on the octanol-water partition coefficient. PS 80 solubilization strength in water can expediently and accurately be calculated for neutral organic compounds with the proposed LSER model. LSER system parameters provide insightful chemical information with respect to solubilization in aqueous solutions of PS 80.

Design of Novel Uncharged Organic Superbases: Merging Basicity and Functionality.

ConspectusOne of the constant challenges of synthetic chemistry is the molecular design and synthesis of nonionic, metal-free superbases as chemically stable neutral organic compounds of moderate molecular weight, intrinsically high thermodynamic basicity, adaptable kinetic basicity, and weak or tunable nucleophilicity at their nitrogen, phosphorus, or carbon basicity centers. Such superbases can catalyze numerous reactions, ranging from C-C bond formation to cycloadditions and polymerization, to name just a few. Additional benefits of organic superbases, as opposed to their inorganic counterparts, are their solubility in organic reaction media, mild reaction conditions, and higher selectivity. Approaching such superbasic compounds remains a continuous challenge. However, recent advances in synthetic methodology and theoretical understanding have resulted in new design principles and synthetic strategies toward superbases. Our computational contributions have demonstrated that the gas-phase basicity region of 350 kcal mol-1 and even beyond is easily reachable by organosuperbases. However, despite record-high basicities, the physical limitations of many of these compounds become quickly evident. The typically large molecular weight of these molecules and their sensitivity to ordinary reaction conditions prevent them from being practical, even though their preparation is often not too difficult. Thus, obviously structural limitations with respect to molecular weight and structural complexity must be imposed on the design of new synthetically useful organic superbases, but strategies for increasing their basicity remain important.The contemporary design of novel organic superbases is illustrated by phosphazenyl phosphanes displaying gas-phase basicities (GB) above 300 kcal mol-1 but having molecular weights well below 1000 g·mol-1. This approach is based on a reconsideration of phosphorus(III) compounds, which goes along with increasing their stability in solution. Another example is the preparation of carbodiphosphoranes incorporating pyrrolidine, tetramethylguanidine, or hexamethylphosphazene as a substituent. With gas-phase proton affinities of up to 300 kcal mol-1, they are among the top nonionic carbon bases on the basicity scale. Remarkably, the high basicity of these compounds is achieved at molecular weights of around 600 g·mol-1. Another approach to achieving high basicity through the cooperative effect of multiple intramolecular hydrogen bonding, which increases the stabilization of conjugate acids, has recently been confirmed.This Account focuses on our efforts to produce superbasic molecules that embody many desirable traits, but other groups' approaches will also be discussed. We reveal the crucial structural features of superbases and place them on known basicity scales. We discuss the emerging potential and current limits of their application and give a general outlook into the future.

Per- and polyfluoroalkyl substances (PFASs) in the soil-plant system: Sorption, root uptake, and translocation.

Per- and polyfluoroalkyl substances (PFASs) are ubiquitous in the environment but pose potential risks to ecosystems and human health. The soil-plant system plays an important role in the bioaccumulation of PFASs. Because most PFASs in the natural environment are anionic and amphiphilic (both lipophilic and hydrophilic), their sorption and accumulation behaviors differ from those of neutral organic and common ionic compounds. In this review, we discuss processes affecting the availability of PFASs in soil after analyzing the potential mechanisms underlying the sorption and uptake of PFASs in the soil-plant system. We also summarize the current knowledge on root uptake and translocation of PFASs in plants. We found that the root concentration factor of PFASs for plants grown in soil was not significantly correlated with hydrophobicity, whereas the translocation factor was significantly and negatively correlated with PFAS hydrophobicity regardless of whether plants were grown hydroponically or in soil. Further research on the cationic, neutral, and zwitterionic forms of diverse PFASs is urgently needed to comprehensively understand the environmental fates of PFASs in the soil-plant system. Additional research directions are suggested, including the development of more accurate models and techniques to evaluate the bioavailability of PFASs, the effects of root exudates and rhizosphere microbiota on the bioavailability and plant uptake of PFASs, and the roles of different plant organelles, lipids, and proteins in the accumulation of PFASs by plants.

Translation of Chemical Structure into Dissipative Particle Dynamics Parameters for Simulation of Surfactant Self-Assembly.

Dissipative particle dynamics (DPD) can be used to simulate the self-assembly properties of surfactants in aqueous solutions, but in order to simulate a new compound, a large number of new parameters are required. New methods for the calculation of reliable DPD parameters directly from chemical structure are described, allowing the DPD approach to be applied to a much wider range of organic compounds. The parameters required to describe the bonded interactions between DPD beads were calculated from molecular mechanics structures. The parameters required to describe the nonbonded interactions were calculated from surface site interaction point (SSIP) descriptions of molecular fragments that represent individual beads. The SSIPs were obtained from molecular electrostatic potential surfaces calculated using density functional theory and used in the SSIMPLE algorithm to calculate transfer free energies between different bead liquids. This approach was used to calculate DPD parameters for a range of different types of surfactants, which include ester, amide, and sugar moieties. The parameters were used to simulate the self-assembly properties in aqueous solutions, and comparison of the results for 27 surfactants with the available experimental data shows that these DPD simulations accurately predict critical micelle concentrations, aggregation numbers, and the shapes of the supramolecular assemblies formed. The methods described here provide a general approach to determining DPD parameters for neutral organic compounds of arbitrary structure.

PFAS Exposure Pathways for Humans and Wildlife: A Synthesis of Current Knowledge and Key Gaps in Understanding.

We synthesize current understanding of the magnitudes and methods for assessing human and wildlife exposures to poly- and perfluoroalkyl substances (PFAS). Most human exposure assessments have focused on 2 to 5 legacy PFAS, and wildlife assessments are typically limited to targeted PFAS (up to ~30 substances). However, shifts in chemical production are occurring rapidly, and targeted methods for detecting PFAS have not kept pace with these changes. Total fluorine measurements complemented by suspect screening using high-resolution mass spectrometry are thus emerging as essential tools for PFAS exposure assessment. Such methods enable researchers to better understand contributions from precursor compounds that degrade into terminal perfluoroalkyl acids. Available data suggest that diet is the major human exposure pathway for some PFAS, but there is large variability across populations and PFAS compounds. Additional data on total fluorine in exposure media and the fraction of unidentified organofluorine are needed. Drinking water has been established as the major exposure source in contaminated communities. As water supplies are remediated, for the general population, exposures from dust, personal care products, indoor environments, and other sources may be more important. A major challenge for exposure assessments is the lack of statistically representative population surveys. For wildlife, bioaccumulation processes differ substantially between PFAS and neutral lipophilic organic compounds, prompting a reevaluation of traditional bioaccumulation metrics. There is evidence that both phospholipids and proteins are important for the tissue partitioning and accumulation of PFAS. New mechanistic models for PFAS bioaccumulation are being developed that will assist in wildlife risk evaluations. Environ Toxicol Chem 2021;40:631-657. © 2020 SETAC.

Adsorption of neutral organic compounds on polar and nonpolar microplastics: Prediction and insight into mechanisms based on pp-LFERs

Adsorption of 18 neutral organic compounds (OCs) on polar (polybutylene succinate (PBS) and polycaprolactone (PCL)) and nonpolar (low-density polyethylene (LDPE) and polystyrene (PS)) microplastics (MPs) were investigated. The adsorption coefficients (Kd) varied with ranges of 130–42,002, 124–27,768, 6.40–10,713, and 1.52–10,332 L kg−1 for adsorption on PCL, PBS, LDPE, and PS MPs, respectively. The polar MPs showed greater adsorption capacities than nonpolar MPs. Non-specific interaction, i.e. hydrophobic partition played a crucial role in the adsorption of OCs on all MPs, while polar interactions also contributed significantly to the greater adsorption on polar MPs. Poly-parameter linear free energy relationships (pp-LFERs) with multiple linear regression (MLR) and feedforward network (FN) were then employed to model the adsorption of OCs on MPs so as to obtain deep insights into adsorption mechanisms. The MLR models achieved Radj2 of 0.90–0.97 and root mean square error (RMSE) of 0.13–0.38 log units, while the FN models achieved Radj2 of 0.85–0.90 and RMSE of 0.21–0.60 log units. The MLR models are more accurate under selected equilibrium concentrations while FN models are capable of making predictions under varying equilibrium concentrations. Lastly, both MLR and FN models showed good prediction on literature adsorption data on nonpolar MPs.

A Reduced Model for Bioconcentration and Biotransformation of Neutral Organic Compounds in Midge.

A bioconcentration factor (BCF) database and a toxicokinetic model considering only biota-water partitioning and biotransformation were constructed for neutral organic chemicals in midge. The database contained quality-reviewed BCF and toxicokinetic data with variability constrained to within 0.5 to 1 log unit. Diverse conditions in exposure duration, flow set-up, substrate presence, temperature, and taxonomic classification did not translate into substantial variability in BCF, uptake rate constant (k1 ), or depuration rate constant (kT ), and no systematic bias was observed in BCFs derived in unlabeled versus radiolabeled studies. Substance-specific biotransformation rate constants kM were derived by difference between the calculated biota-water partitioning coefficient (KBW ) and experimental BCF for developing a midge biotransformation model. Experimental midge BCF was modeled as BCF = KBW /(1 + kM/ k2 ) with log kM (kM in h-1 ) = -0.37 log KOW - 0.06T (in K) + 18.87 (root mean square error [RMSE] = 0.60), log k1 (k1 in L kgwet.wt-1 h-1 ) = -0.0747 W (body weight in mgwet.wt ) + 2.35 (RMSE = 0.48). The KBW value was estimated using midge biochemical composition and established polyparameter linear free energy relationships, and the diffusive elimination rate constant (k2 ) was computed as k2 = k1 /KBW. The BCF model predicted >85% of BCFs that associated with neutral organic compounds (log KOW = 1.46 - 7.75) to within 1 log-unit error margin and had comparable accuracy similar to amphipod or fish models. A number of outliers and critical limitations of the kM model were identified and examined, and they largely reflected the inherent limitation of difference-derived kM , the lack of chemical diversity, and inadequate temperature variation in existing data. Future modeling efforts can benefit from more BCF and toxicokinetic observations of BCF on structurally diverse chemicals for model training, validation, and diagnosis. Environ Toxicol Chem 2021;40:57-71. © 2020 SETAC.

Recent advances for assessment of the condensed phase heat of formation of high-energy content organic compounds and ionic liquids (or salts) to introduce a new computer code for design of desirable compounds

The condensed phase heat of formation of organic compounds as well as ionic liquids or salts is an important thermodynamic parameter for the evaluation of their energy contents, performances, and sensitivities. For using these materials as components of fuels, propellants or explosives, chemical industries should produce the compounds with high positive heat of formation because they can provide high heat of combustion or detonation performance. In contrast, their thermodynamic stability may decrease with higher positive values in their heats of formation. Experimental values of the condensed phase heats of formation for high energy content-neutral and ionic compounds are scarce in the literature. This work reviews reliable models for prediction of the condensed phase heat of formation of important classes of organic and ionic liquid energetic compounds. A novel easy to handle and user-friendly computer code is introduced for prediction of the condensed phase heat of formation using suitable and reliable predictive methods. The reliability of the new computer code is checked for organic compounds containing energetic groups -O-O-, –N3, –ON=O, –NO2, -ONO2 and –NNO2 as well as high nitrogen content materials and imidazolium- or triazolium-based ionic liquids (or salts). The values of the root mean square (rms) deviations of the condensed phase heat of formation by the new computer code/ quantum mechanical approaches for 11 neutral energetic organic compounds, 14 high-N content compounds, and 72 imidazolium- and triazolium-based energetic ionic liquids or salts are 45.8/78.0, 79.4/105.3, and 39.8/318.7 kJ/mol, respectively. Thus, the reliability of the outputs the new computer code is higher than the computed results from complex quantum mechanical methods, especially for imidazolium- and triazolium-based energetic ionic liquids or salts, wherein they need high-speed computers, specific computer codes and expert users.