Volatile Organic Solvents Research Articles

Thermodynamic Properties, Activity Coefficients at Infinite Dilution and Cosmo‐SAC Modelling of Deep Eutectic Solvents at Different Temperatures

AbstractA deep understanding of the solute‐ deep eutectic solvent (DESs) interactions is required for an appropriate selection of DESs as absorption media in the extraction of binary mixtures. As a result, these studies are done to evaluate the values of the activity coefficients at infinite dilution ( ), allowing us to define and understand the nature of these intermolecular interactions comprising DES mixtures with volatile organic solvents at different temperatures using gas liquid chromatography technique to determine the for 34 solutes in DESs [zinc chloride+acetic or phosphoric acid] prepared at 1 : 2 molar ratio for the temperature range (313.15–353.15) K. The thermal stability of the prepared DESs was determined by a thermogravimetric analyser. Excess thermodynamic parameters [partial molar excess enthalpies and Gibbs free energies ] were derived from the data. The selectivity and capacity values for the industrial separations were calculated and compared with the literature values of other DESs, ionic liquids, and sulfolane to assess the suitability of the investigated DESs for possible applications as extracting solvents. The selectivity and capacity values are high and therefore, [zinc chloride+acetic or phosphoric acid] can be used as a potential solvent to replace the currently used conventional solvents in the separation of the selected azeotropes. COSMO‐SAC predictions were qualitatively in very good agreement with the experimental data.

A brief exposure to toluene vapor alters the intrinsic excitability of D2 medium spiny neurons in the rat ventral striatum.

Although volatile organic solvents such as toluene are used for commercial and industrial uses, they are often voluntarily inhaled for their intoxicating and euphoric effects. Research into the effects of inhalants such as toluene on brain function have revealed actions on a variety of ligand-gated and voltage-activated ion channels involved in regulating neuronal excitability. Previous work from this laboratory has also shown that brief exposures to toluene vapor induce changes in the intrinsic excitability and synaptic transmission of neurons within the medial prefrontal cortex and ventral tegmental area that vary depending on projection target. In the present study, we recorded current-evoked spiking of medium spiny neurons (MSNs) in the nucleus accumbens (NAc) core and shell in adolescent rats exposed to an intoxicating concentration of toluene vapor. Compared to air controls, firing of NAc core MSNs in Sprague-Dawley rats was not altered 24 h after exposure to 10,500 ppm toluene vapor while spiking of NAc shell MSNs was enhanced at low current steps but reduced at higher current steps. When the rheobase current was used to putatively identify MSN subtypes, both "D1-like" and "D2-like" MSNs within the NAc shell but not core showed toluene-induced changes in firing. As toluene may itself have altered the rheobase resulting in misclassification of neuron subtype, we conducted additional studies using adolescent D2-Cre rats infused with a Cre-dependent mCherry reporter virus. Following toluene vapor exposure, spiking of NAc shell D2+ MSNs was enhanced at low current steps but inhibited at higher currents as compared to air controls while there were no differences in the firing of NAc shell D2- MSNs. The toluene-induced change in NAc D2+ shell MSN firing was accompanied by alterations in membrane resistance, rheobase, action potential rise time and height with no changes noted in D2- MSNs. Overall, these data add to a growing literature showing that brief exposures to intoxicating concentrations of toluene vapor causes selective alterations in the excitability of neurons within the addiction neurocircuitry that vary depending on sub-region, cell-type and projection target.

Efficient and Reversible Separation of Chloroform from Chlorinated Hydrocarbons and Water Utilizing a Two-Dimensional Coordination Network.

Chloroform is a volatile organic solvent and a contaminant that is slightly soluble in water, making the reversible separation of chloroform from water a critical and challenging task within the chemical and environmental industries. In this study, we present a newly developed coordination framework, [Zn(4-pmntd)(opa)] [4-pmntd, N,N'-bis(4-pyridylmethyl)naphthalene diimide; opa, o-phthalic acid], which demonstrates a high adsorption capacity for chloroform (2.5 mmol/g) and an excellent ability to separate chloroform from water. The effectiveness of chloroform extraction by Zn(4-pmntd)(opa) was confirmed through vapor sorption, grand canonical Monte Carlo simulation, and 1H nuclear magnetic resonance spectroscopy. The porous framework was also utilized to create a filtration film using natural rubber, which successfully separated chloroform from water with a minimum test concentration of approximately 1 × 10-6 mol/L and a chloroform purity of 99.2%. [Zn(4-pmntd)(opa)] therefore has significant potential for low-energy separation and recycling of chloroform from water under ambient conditions.

Environmentally Friendly Approach to the Synthesis of 3-[Benzylideneamino]-2-methylquinazolin-4(3H)-one Derivatives and Calculation of Their Toxicity.

Application of deep eutectic solvents in synthesis of different heterocyclic compounds was proven very efficient. These solvents are a new generation of green solvents showing excellent potential for different purposes, where they are used as environmentally acceptable substitute for toxic and volatile organic solvents. This research describes their application in the synthesis of series of quinazolinone Schiff bases in combination with microwave, ultrasound-assisted and mechanochemical methods. First, a model reaction was performed in 20 different deep eutectic solvents to find the best solvent and then reaction conditions (solvent, temperature and reaction time) were optimized for each method. Afterwards, 40 different quinazolinone derivatives were synthesized in choline chloride/malonic acid (1 : 1) DES by each method and compared by their yields. Here we show that deep eutectic solvents can be very efficient in the synthesis of quinazolinone derivatives as an excellent substitution for volatile organic solvents. With green chemistry approach in mind, we have also performed a calculation on compounds' toxicity and solubility, showing that most of them possess toxic and mutagenic properties with low water solubility.

An environmentally benign protocol for the synthesis of sugar 1,2-orthoesters in poly(ethylene glycol) dimethyl ether (DMPE)

An environmentally benign procedure has been developed for the synthesis of sugar orthoesters using anhydrous sodium acetate in poly (ethylene glycol)dimethyl ether (DMPE). Various sugar orthoesers were prepared without using volatile organic solvent and quaternary ammonium salt. The sugar orthoesters were obtained in good to excellent yields.

Molecular Guide for Selecting Green Deep Eutectic Solvents with High Monosaccharide Solubility for Food Applications.

Monosaccharides play a vital role in the human diet due to their interesting biological activity and functional properties. Conventionally, sugars are extracted using volatile organic solvents (VOCs). Deep eutectic solvents (DESs) have recently emerged as a new green alternative to VOCs. Nonetheless, the selection criterion of an appropriate DES for a specific application is a very difficult task due to the designer nature of these solvents and the theoretically infinite number of combinations of their constituents and compositions. This paper presents a framework for screening a large number of DES constituents for monosaccharide extraction application using COSMO-RS. The framework employs the activity coefficients at infinite dilution (γi∞) as a measure of glucose and fructose solubility. Moreover, the toxicity analysis of the constituents is considered to ensure that selected constituents are safe to work with. Finally, the obtained viscosity predictions were used to select DESs that are not transport-limited. To provide more insights into which functional groups are responsible for more effective monosaccharide extraction, a structure-solubility analysis was carried out. Based on an analysis of 212 DES constituents, the top-performing hydrogen bond acceptors were found to be carnitine, betaine, and choline chloride, while the top-performing hydrogen bond donors were oxalic acid, ethanolamine, and citric acid. A research initiative was presented in this paper to develop robust computational frameworks for selecting optimal DESs for a given application to develop an effective DES design strategy that can aid in the development of novel processes using DESs.

Dispersive Liquid–Liquid Microextraction of Preservatives for Their Chromatographic Determination in Beverages

A method of dispersive liquid–liquid microextraction, based on the dispersion of an extractant by the gas phase formed as a result of a phase transition, i.e., the evaporation of a highly volatile nonpolar organic solvent (dispersant) upon heating the extraction,—is developed. The analytical capabilities of the method are shown in the determination of preservatives (sorbic and benzoic acids) in soft drinks for baby food by high-performance liquid chromatography with photometric detection. The extractant and the dispersant for the microextraction of preservatives are chosen a terpenoid and a highly volatile organochlorine solvent, respectively, which excluded the use of polar organic solvents for dispersing phases, with which the distribution coefficients are reduced. The limits of detection (3σ) for sorbic and benzoic acids are 0.3 mg/L. The developed method does not require centrifugation for phase separation

On Water Synthesis of 3-Aryl-1,2,4-Triazolo[4,3-a]Pyridines Using Iodobenzene Diacetate (IBD)

Abstract: An iodobenzene diacetate (IBD)-mediated simple and green method was determined for the intramolecular oxidative cyclization of 3-aryl-2-pyridiylhydrazones of different aromatic aldehydes in an aqueous medium at room temperature. This efficient strategy provides a route to the synthesis of 3-aryl-1,2,4-triazolo[4,3-a]pyridines in water which eliminates the requirement to use costly and unsafe volatile organic solvents. All reactions were carried out by just stirring the reaction components in water at room temperature. This protocol provides a wide substrate scope and good functional group tolerance.

Biodegradable waterborne polyurethane‐urea dispersion adhesives with high biocontent

AbstractNon‐biodegradable petroleum‐based plastic wastes have become a leading environmental concern, and new efforts are underway to prepare biobased and biodegradable replacements. We have explored the preparation of adhesives suitable for use in consumer products, and here we report the development of waterborne, biodegradable adhesives from biobased monomers resulting in adhesives exceeding 70% biocontent. Using water as the polymer medium, viscosity challenges and the use of volatile organic solvents are avoided. Material properties of the polyurethane dispersions, resulting films, and laminates produced showed Mw ranging between 56,000 and 124,000. Lastly, the biodegradability of films and laminates was evaluated. The resulting metrics indicate that the adhesives produced meet the desired mechanical and biodegradability targets, indicating that high renewability content solvent‐free polyurethane dispersions are a viable solution for lamination adhesives.

Unlocking the Potential of Deep Eutectic Solvents for C-H Activation and Cross-Coupling Reactions: A Review.

Green chemistry principles have underpinned the development of deep eutectic solvents (DESs). In this brief overview, we discuss the potential of DESs as a greener alternative to volatile organic solvents for cross-coupling and C-H activation reactions in organic chemistry. DESs offer numerous benefits, such as easy preparation, low toxicity, high biodegradability, and the potential to replace volatile organic compounds. The ability of DESs to recover the catalyst-solvent system enhances their sustainability. This review highlights recent advances and challenges in utilizing DESs as a reaction media, as well as the impact of physicochemical properties on the reaction process. Several types of reactions are studied to highlight their effectiveness at promoting C-C bond formation. Aside from demonstrating the success of DESs in this context, this review also discusses the limitations and future prospects of DESs in organic chemistry.

Lithium recovery and solvent reuse from electrolyte of spent lithium-ion battery

Great progresses have been made in recovering valuable metals or regenerating materials from spent lithium-ion batteries (LIBs), but how to treat the spent electrolyte and recover its valuable components economically are still a bottleneck. In this study, the volatile organic solvents (dimethyl carbonate (DMC) and diethyl carbonate (DEC)) in spent electrolyte were recycled through vacuum distillation based on thermodynamic analysis and reused for LIBs. The recovery efficiencies of DMC and DEC reach almost 100% and 79.40%, respectively, under the distillation temperature of 130 °C for 120 min. The prepared electrolyte by recovered DMC and DEC shows high discharge capacity and good cycle performance (discharge capacity retention is over 99% after 400 cycles at 1C) by Li/graphite battery. Moreover, lithium left in non-volatile components (ethylene carbonate (EC)) was recovered as lithium carbonate (purity is 92.45%) with a recovery efficiency of 86.93%. The proposed process sheds light on the comprehensive recycling of electrolyte from spent LIBs.

ECOLOGIZATION OF PRINTING PLATE PROCESSES PRODUCTION

The article analyzes the technological process of manufacturing photopolymer flexographic plates, determines the danger from the point of view of ecological impact that certain technological processes can cause, and proposes measures that minimize their dangerous impact on the environment. A comparison of the properties of solvents and their advantages and at the same time harmfulness was carried out with the establishment of the reasons for the subsequent development of alternative organic solvents and the operation of washout flexographic photopolymer printing plates with water or waters solutions. General strategic directions for solving the problem of using volatile organic solvents have been established. The following classification of ways to solve this problem is proposed: use of less toxic solvents or water; elimination of the washing operation from the technological process of manufacturing flexographic photopolymer plates; development of new technological processes for the production of flexographic plates. Based on the results of a comparative analysis of mold manufacturing technologies, a change in the anthropogenic factor was established as a result of improving processes and their environmentalization. It is shown that by introducing information and laser technologies into the technological processes of manufacturing printing forms due to the reduction of the influence of the anthropogenic factor, a significant improvement in the environmental safety of production is achieved, although the introduction of such technology requires large capital investments. According to the results of a comparative analysis of printing plate manufacturing technologies, the so-called ecological factor is shown as a result of improving processes and their ecologization. If we talk about spent photopolymer plates, then the problem of their disposal is still open. Taking into account the current negative effects on the economy of Ukraine, the use of more environmentally friendly technologies and materials in the flexographic sector of printing depends to a greater extent on the economic situation at specific enterprises, and not on the purposeful environmental policy of the state.

Measurement of Activity Coefficients at Infinite Dilution for Various Organic Solutes in Deep Eutectic Solvent (1-Butyl-2,3-dimethylimidazolium Chloride + Ethylene Glycol) at Different Temperatures

Activity coefficients at infinite dilution (γ13∞) for organic solutes in deep eutectic solvent (DES) prepared by {1-butyl-2,3-dimethylimidazolium chloride (BDMIM Cl) + ethylene glycol (EG)} at a molar ratio of 1:3 have been measured using the gas–liquid chromatographic method (GLC). The thermal stability of the entrainer was determined by the thermogravimetric analyzer. The measurements were carried out in the temperature range of T = (313.15 to 343.15) K and at atmospheric pressure. The values of the partial molar excess enthalpies at infinite dilution (H1E,∞) were derived from the temperature dependence of the γ13∞∞ values. The entropies (Tref ΔS1E,∞) and Gibbs energies (ΔG1E,∞) of organic solutes at a reference temperature Tref = 323.15 K were also calculated from the γ13∞ values. These excess thermodynamic functions were calculated to further explain the intermolecular interactions occurring between the volatile organic solvents and the prepared deep eutectic solvent. Important separation parameters such as selectivities (Sij∞) and capacities (Kj∞) at infinite dilution were computed from the activity coefficients at infinite dilution data at T = 313.15 K. Selectivity and capacity data were calculated for the industrial mixtures such as cyclohexane/benzene, hexane/thiophene, cyclohexane/ethanol. There results were compared to the literature data comprising deep eutectic solvents and ILs with the cation of 1-butyl-3-methylimidazolium. The investigated solvent was found suitable to separate azeotropes formed by alkanes/alcohols.

Room-temperature ionic liquids as candidate materials for produced water desalination: Experiments and molecular dynamic analysis

Room-temperature ionic liquids (RTILs) have been promoted as “green” chemicals that can be used as alternatives to conventional volatile organic solvents. In addition to low volatilities, hydrophobicity for organic liquids and hydrophilicity for ions in RTILs lead to a wide spectrum of applications. ILs have recently been considered as alternative solvents to carboxylic acids and amines used for solvent extraction desalination (SED). RTILs are used in pairs of cations and anions that can significantly influence SED potentials. This study aimed to find an optimal combination of cationic and anionic RTIL as a desalination solvent through theoretical, experimental, and computational approaches. SED potentials in terms of water absorption and salt rejection were investigated for ten pairs of RTILs using different combinations of imidazolium and phosphonium cations with various anions. SED potentials were highly dependent on the anion type, with Tf2N showing the most promising SED potential. Imidazolium based RTILs exhibited better SED performances than phosphonium based RTILs in experiments. [BMIM][Tf2N] was recommended as a candidate SED-IL material, showing a water absorption and salt rejection of 1.73 % and 93.7 %, respectively. Molecular dynamics (MDs) simulation was implemented in parallel in order to examine and analyze intermolecular interactions that led to particular experimental observations.

The High‐Strength, Flexible Organic Solvent Driven Reversible “Deformation‐Recovery‐Reverse Deformation” Responsive g‐PLA/PPC/PVA Film for Contactless Actuation

AbstractThe non‐contact deformation response driven by organic solvent has potential applications in the fields of intelligent devices, soft robots, sensing detection, and biomedical micro‐devices. The modified polyactic acid (g‐PLA)/polypropyl carbonate (PPC)/polyvinyl alcohol (PVA) sandwich with deformation response film is prepared by the asymmetric swelling response mechanism. Specially, the flexible sandwich film achieves the non‐contact driving response of “deformation‐recovery‐reverse deformation”, showing excellent deformation performance. The curvature of sandwich film reaches 13.79 cm−1 within 15 s, and the film recovers to its initial state within 3 s, then the curvature of the reverse coil reaches 18.18 cm−1 within 15 s and finally achieves a stable state. This special phenomenon is caused by the different adsorption swelling and desorption rates of volatile organic solvents in g‐PLA, PPC, and PVA layers. Additionally, the flexible film has high strength, reversible circulation, and stable actuation performance. The application scenarios of the bionic flower actuator, artificial octopus, intelligent protective cover, and transportable objects are successfully implemented. This work will significantly provide substantial guidance for the development of intelligent driving technology in the future.

Innovative three-phase partitioning based on deep-eutectic solvents and sugars (sugaring-out effect) for cucumber peroxidase purification

Traditional three-phase partitioning (TPP) systems used for extracting and purifying bioactive substances typically consist of t-butanol and ammonium sulfate. However, the use of volatile and flammable organic solvents and high-concentration inorganic salts results in environmental pollution. Therefore, an innovative TPP based on deep eutectic solvents (DESs) and sugars (sugaring-out effect) was used to extract and preliminarily purify cucumber peroxidase (POD). Various factors affecting the extraction were optimized using response surface methodology (RSM). DES-8 (menthol: octanoic acid = 1:1) and sucrose were selected as the optimal constituents of TPP. Under these conditions, the sucrose concentration was 36% (w/v), DES: crude extract (v/v) was 1.4:1, system pH was not adjusted, extraction time was 6 min, and extraction temperature was 31 °C; the enzyme recovery and purification fold reached 84.53% and 5.28, respectively. Recycling experiments demonstrated that the DESs can be well recycled and reused after five recycles. Sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) was used to analyze cucumber POD, which showed that the TPP system achieved primary purification of cucumber POD. This TPP is much greener and more efficient than traditional TPP systems and shows great application potential in the enzymes and proteins separation field.

Residues of pesticide co-formulants in lettuce and parsley: Identification of decline processes using field trials in different cropping systems.

Although co-formulants constitute a substantial portion of the total plant protection product (PPP) mass applied to crops, data on residue formation and the behaviour of these substances on plants are scarce. In an earlier study we demonstrated that co-formulants commonly used in PPPs can form considerable residues, i.e., in the low to medium mg/kg range, but normally decline rapidly within few days. In the field trial reported here, we aimed to identify the major decline processes of co-formulants. Residues of co-formulants were therefore monitored in parsley and lettuce grown in an open field as well as under foil tunnels equipped with either an overhead or a drip irrigation system. Dissipation of three anionic surfactants was markedly faster when crops (parsley and lettuce) were exposed to natural rainfall or irrigation from above compared to drip irrigation. In contrast, the decline of three volatile organic solvents was not affected by rain or irrigation, but was dependent on the crop, with much shorter half-lives in lettuce than in parsley. Furthermore, dilution through plant growth contributed significantly to the reduction of residues over time. In this work we substantiate earlier findings on the magnitude and dissipation of residues of anionic surfactants and solvents representing the most important co-formulant classes. The chosen experimental setup allowed differentiation between decline processes and we confirm that foliar wash-off is a major dissipation process for anionic surfactants. For volatile organic solvents, dissipation appears to depend on the properties not only of the substance but also of the plant (surface). © 2023 The Authors. Pest Management Science published by John Wiley & Sons Ltd on behalf of Society of Chemical Industry.

Organic Solvent Free Synthesis and Processing of Semiconducting Polymers for Field Effect Transistors in Waterborne Dispersions

AbstractConjugated semiconducting polymers are key active materials for printable electronics, sensors and biosensors, organic photovoltaics, organic light emitting devices, and more. The research in the field developed very efficient materials and sound structure property relationships, thus making a case for a transition from laboratory to industrial environment. At this critical juncture, sustainability, and ease of scaling up are at least as important as performances, to the point that efficient materials on a lab scale could become unpractical for the industry. The development of more efficient synthetic protocols and the complete removal of all organic solvents from both the synthesis and the processing of semiconducting polymers can help tremendously to improve sustainability and reduce costs. It is shown that the use of an aqueous dispersion of the food grade surfactant lecithin as the medium, enables the synthesis and processing of the representative semiconducting alternating copolymer poly (9,9‐dioctylfluorene‐alt‐bithiophene) (PF8T2) in high yield and high quality and with transistor performances comparable with those obtained with reference materials synthetized and processed from volatile organic solvents.

Drug Release from Carrier Systems Comprising Meloxicam Crystals Formed by Impregnation-Evaporation

The impregnation of poorly water-soluble drug onto the surface of a suitable pharmaceutical excipient, used as a hydrophilic carrier, can lead to the preparation of systems with improved dissolution properties due to the separation of drug crystal particles on the carrier surface. For this purpose, a method based on impregnation of hydrophilic matrix by the hydrophobic poorly water-soluble drug Meloxicam (MX) solution in volatile organic solvent was used. After the evaporation of the solvent, the method resulted in coverage of the carrier surface by drug crystals. The influence of the amount and concentration of the impregnating solution on the formed MX crystal size and the dissolution rate was evaluated. Firstly, the impregnation forming crystals on the planar surface was studied and the MX maximum dissolution flux from that surface was determined. The optimum preparation method was further used to produce a volume of impregnated granules. The dissolution performance of the granules was evaluated, and the dissolution kinetics was described by mathematical models. The polymorphic modification of impregnated API and influence of impregnated drug amount on the hydrophilic carrier surface coverage were considered. From the results of this work, it is clear that the impregnated drug amount and the number of impregnations cycles can be optimized to achieve maximum drug release rate.

Investigation of reactive extraction of monocarboxylic acids with menthol-based hydrophobic deep eutectic solvent by response surface methodology

ABSTRACT The growing demand for producing organic acids by fermentative techniques has increased the significance of separating carboxylic acids from their fermentation broth with the reactive extraction process. Considering the environmental impacts, deep eutectic solvents can be considered as a potential green alternative for the replacement of volatile organic solvents commonly used in the extraction process. In this study, a new type of green solvent named hydrophobic deep eutectic solvent (HDES) based on decanoic acid as a hydrogen bond acceptor and menthol as a hydrogen bond donor was utilized for the reactive extraction of formic, acetic, and propionic acids from their aqueous solutions. The effect of initial acid concentration, HDES molar ratio, and tri-n-octyl amine (TOA) concentration on extraction efficiency was investigated. Modeling of the reactive extraction process was performed via a response surface methodology with a central composite design. Herein, the effect of the parameters of TOA concentration, HDES molar ratio, and initial acid concentration on the distribution coefficient was investigated. According to the results, it was reported that the most effective parameter on the extraction efficiency (%E) was the amount of extractant. The results of the experimental studies showed that the highest separation efficiency was obtained for 5% initial concentrations of formic, acetic, and propionic acids by using a mixture of 0.5 HDES molar ratio solvent and 1.9 mol/L TOA. The extraction efficiencies of these acids were found to be 88.71, 92.52, and 95.90 with ±0.1 standard deviation, respectively.