Selective Solvent Research Articles

Green recovery of nuciferine from lotus leaf via star anise oil based two-phase solvent extraction integrated with back-extraction

In this study, we present a novel green bio-based solvent, star anise oil (SAO), which was employed to develop a two-phase solvent system incorporating both alkaline and acidic solutions for the simultaneous extraction and purification of nuciferine from waste lotus leaf. This integrative approach effectively combines two-phase solvent extraction (TPSE) with back-extraction (BE), resulting in a more streamlined extraction process that requires only vortexing (or stirring) and centrifugation, thus simplifying the overall procedure. It is important to note that this method uses very little solvent (only 2.5 times the volume of SAO relative to the weight of the lotus leaf) and takes just 4 min per extraction. After three such extractions, the recovery rate of nuciferine can reach as high as 96.9%. Unlike volatile solvents such as petroleum ether and ethyl acetate, SAO's high boiling point negates the necessity for nitrogen protection during centrifugation, thereby addressing the Pickering emulsification issues caused by particles. Only two back-extraction operations are needed to recover 96.9% of nunciferine from the TPSE extract, resulting in a nunciferine content of 45.4%. Furthermore, approximately 90% of the SAO can be directly reused for at least five cycles without additional purification. Additionally, 85.0% of the SAO remaining in the TPSE waste can be recovered through hydrodistillation (HD) within 30 min. The excellent performance in biomass and extraction solvent selection, solvent repurposing, and other factors contributed to a Path2Green score of 0.28 for this method, highlighting its suitability for the green recovery of nuciferine from lotus leaf.

Solvent-Directed Social Chiral Self-Sorting in Pd2L4 Coordination Cages.

A family of Pd2L4 cages prepared from ligands based on an axially chiral diamino-[1,1'-biazulene] motif (serving as a unique azulene-based surrogate of the ubiquitous BINOL moiety) is reported. We show that preparing a cage starting from the racemate of a shorter bis-monodentate ligand derivative, equipped with pyridine donor groups, leads to integrative ("social") chiral self-sorting, exclusively yielding the meso-trans product, but only in a selection of solvents. This phenomenon is driven by individual solvent molecules acting as hydrogen bonding tethers between the amino groups of neighboring ligands, thereby locking the final coordination cage in a single isomeric form. The experimental (solvent-dependent NMR, single-crystal X-ray diffraction) observations of this cooperative interaction could be explained by computational analyses only when explicit solvation was considered. Furthermore, we prepared a larger chiral ligand with isoquinoline donors, which, unlike the first one, does not undergo social self-sorting from its racemic mixture, further highlighting the importance of solvents bridging short distances between the amino groups. Homochiral cages formed from this larger ligand, however, furnish a cavity that can bind anionic and neutral metal complexes such as [Pt(CN)6]2- and Cr(CO)6 and discriminate between the two enantiomers of chiral guest camphor sulfonate.

Synthesis Framework for Designing PtPdCoNiMn High-Entropy Alloy: A Stable Electrocatalyst for Enhanced Alkaline Hydrogen Evolution Reaction.

High entropy alloys (HEAs) are an emerging class of advanced materials characterized by their multifunctionality and potential to replace commercial catalysts in electrocatalytic water splitting. The synergy among the various alloyed elements in HEAs makes them particularly promising for applications in electrocatalysis. However, preparation of HEA via bottom-up approaches by avoiding the formation of mono, di, and tri metallic alloys in the nanoscale is challenging. This aspect is addressed, in this study by exploring the logical selection of solvents, reducing agents, and capping agents, along with their relative fractions, in the solvothermal synthesis of the HEA comprising platinum-palladium-cobalt-nickel-manganese (PtPdCoNiMn). It is established that the reducing capabilities of both the solvent and reducing agent are crucial for the reduction of each metal to form a single-phase HEA. The synthesized HEA (20 wt.%)/functionalized carbon (FC) demonstrates excellent performance as an HER catalyst, exhibiting a low overpotential of 48.7mV at -10 mA cm-2 in an alkaline electrolyte. This performance is characterized by high reaction kinetics and stability at elevated current densities. Furthermore, the catalyst shows impressive performance in both simulated and actual seawater. This development reduces the reliance on platinum while enhancing the long-term durability and catalytic efficiency of the electrocatalyst.

Physicochemical and Antimicrobial Properties of Lactic Acid-Based Natural Deep Eutectic Solvents as a Function of Water Content

The interest in natural deep eutectic solvents (NADESs) in green technology as an alternative to organic solvents has grown over the past decades. In this work, for the first time, the effect of dilution with water on the physicochemical and antimicrobial properties of lactic acid-based NADES with choline chloride (NADES1), sorbitol (NADES2), and glucose (NADES3) was systematically studied. According to FTIR data, after the dilution of NADESs with water, the strong hydrogen bonds weakened, however, were not destroyed after dilution of up to 40% water. The dilution of NADES with water resulted in a linear decrease in density and refractive index and in a linear increase in pH. The equations for the prediction of NADES density, pH, and refractive index as a function of water content were calculated. The viscosity decreased by half after adding approximately 10% water. The initial viscosity of NADES2 and NADES3 was significantly different. However, after adding 20% of the water, the viscosity was almost the same. The most pronounced decrease in surface tension (by 46.7%) was found for NADES1. The water activity was decreased in the following order: NADES3 > NADES1 > NADES2. The dilution of NADES with water caused a gradual increase in water activity. NADES1 showed the lowest minimal inhibitory concentrations (MIC) (7.8, 3.9, and 0.98 mg/mL) and minimum bactericidal concentrations (MBC) (15.6, 7.8, and 1.95 mg/mL) for Escherichia coli, Pseudomonas aeruginosa, and Staphylococcus aureus, respectively. The antimicrobial activity was decreased by 2–8 times after the addition of 40% water. The water activity for all tested NADES together with low pH could explain the antimicrobial effect. The revealed regularity can be useful for the prediction of NADES properties and for the selection of green solvents on a laboratory and industrial scale.

Solvent Extraction of Gallium and Germanium Using a Novel Hydroxamic Acid Extractant

The rare metals gallium and germanium are key strategic metals that are widely used in emerging industries. In this work, a novel hydroxamic acid extractant, BGYW, with low toxicity, was used for the selective solvent extraction of Ga ions and Ge ions from Zn, As, Cu, and Al ions in the solution from zinc smelting. The gallium and germanium ions were extracted efficiently under optimized conditions. Gallium ions were preferentially stripped using sulfuric acid, and germanium ions were stripped using an ammonium fluoride solution. Compared with the commercial extractant YW100, the dissolution loss of BGYW was reduced by 10 times. After 15 cycles, the germanium solvent extraction efficiency of BGYW remained at 100%, and the solvent extraction efficiency of gallium was about 98.7%, while the solvent extraction efficiency of both Ga ions and Ge ions using YW100 decreased to 20% after five cycles. This novel solvent extraction system exhibits considerable promise for application in zinc smelting processes for gallium and germanium solvent extraction.

COSMO-RS prediction, experimental investigation, and mechanism analysis: A new approach to separating the n-hexane–tert-butanol azeotropic system via liquid-liquid extraction with ionic liquids

n-Hexane and tert-Butanol (TBA) are frequently utilized to refine the conditions for Grignard, Wittig, and Friedel-Crafts alkylation reactions. During the synthesis of loratadine, the formation of azeotropic mixtures n-hexane and TBA, which are challenging to separate through conventional distillation, is inevitable. This study utilizes the COSMO-RS model to identify suitable ionic liquids (ILs) for the separation of the n-hexane–TBA azeotropic system. Based on solvent capacity and selectivity, 1-ethyl-3-methylimidazolium trifluoroacetate ([EMIM][TFA]), 1-butyl-3-methylimidazolium trifluoroacetate ([BMIM][TFA]), and 1-hexyl-3-methylimidazolium trifluoroacetate ([HMIM][TFA]) were selected as extractants. The liquid–liquid equilibrium (LLE) data for the n-hexane–TBA – ILs ternary system were measured at 303.15 K and atmospheric pressure. Distribution coefficients and selectivity were calculated to evaluate the performance of the extractants, with the NRTL model used to correlate the experimental LLE data. The consistency of the NRTL model parameters was corroborated through topological analysis associated with the Gibbs tangent principle. Quantum chemical calculations, including interaction energy, ESP analysis, IGMH analysis, and QTAIM topological analysis, were performed to explore the separation mechanism at the molecular level. The results indicated that the interaction energies between the ILs and TBA were higher than those between the ILs and n-hexane, indicating a stronger attraction of ILs to TBA. Consequently, the ILs effectively separated TBA from the n-hexane–TBA azeotropic system, with extraction capacities ranked as [EMIM][TFA] > [BMIM][TFA] > [HMIM][TFA]. The quantum chemical calculations successfully explained the experimental results, aligning with COSMO-RS model predictions and confirming their reliability. IGMH and QTAIM topological analyses systematically explored the types and strengths of interactions, revealing that hydrogen bonds are predominant between the ILs and TBA, with additional contributions from van der Waals forces. Furthermore, the hydrogen bond strengths between TBA and the anions and cations of the ILs are classified as strong and moderate, respectively. This work provides valuable insights into the separation of azeotropic systems using ILs, elucidating the underlying mechanisms behind this process.

Solubility prediction and interaction mechanism of FOX-7 in ten solvents by molecular and thermodynamic modeling

Solubility is a fundamental physicochemical property of materials. Current solubility prediction models are often highly parameterized by existing data, leading to a serious issue of transferability; thus, it is still challenging to enhancing their accuracy and generalization-ability. In this study, we employ molecular dynamics (MD) simulations and some thermodynamic modeling methods (SMD, COSMO-RS, and COSMO-SAC) to predict the relative solubility of 1,1-diamino-2,2-dinitroethylene (FOX-7) in ten solvents. A meticulous comparison with experimental data reveals that the alchemical free energy approach based on MD simulations outperforms SMD, COSMO-RS and COSMO-SAC models in solubility prediction. Furthermore, we identify that the more negative solvation free energy corresponds to the higher solubility, and the stronger solute–solvent hydrogen bonding corresponds to the higher solubility for low polar solvents too. Finally, it is confirmed that the electrostatic attraction dominates the binding energy between solute and solvent molecules. This work transcends traditional solubility prediction by offering a robust theoretical framework and computational strategy, proving both economical and environmentally benign. It paves the way for the rational selection of solvents for FOX-7 crystallization and provides a versatile tool for predicting the solubility of organic compounds.

Amalgamation of Thermodynamic Screening and Process Simulation: A Promising Approach for Deep Eutectic Solvent Selection for Natural Gas Sweetening

Amalgamation of Thermodynamic Screening and Process Simulation: A Promising Approach for Deep Eutectic Solvent Selection for Natural Gas Sweetening

Sustainable Solution Processing Toward High‐Efficiency Organic Solar Cells: A Comprehensive Review of Materials, Strategies, and Applications

AbstractOrganic solar cells (OSCs) have emerged as promising candidates for renewable energy harvesting due to their lightweight, flexible, and low‐cost fabrication potential. The efficiency of OSCs is largely determined by the choice of solvents, which significantly affect the film morphology of the active layers, the intermixed donor‐acceptor domains, and overall device performance. Beginning with an introduction to the importance of solvent selection, the screening and classification of solvents, emphasizing their characteristics and classification based on sustainability, solubility, and other additional considerations are explored. Various non‐halogenated solvents, highlighting commonly used aromatic solvents, biomass‐derived solvents, and water/alcohol‐based solvents are explored. The state‐of‐the‐art donor and acceptor materials, focusing on efficient donor materials such as PM6 and D18, and high‐performing Y‐series acceptors are also presented. Strategies for developing high‐performance OSCs processed using non‐halogenated solvents are examined, including solvent engineering with additive and additive‐free approaches, ternary strategies, and layer‐by‐layer techniques. The fabrication of large‐area devices using non‐halogenated solvents is addressed, focusing on blade‐coating, slot‐coating, and other processing techniques. Finally, this review outlines future research directions in the non‐halogenated solvent processing of OSCs, emphasizing the need for continuous innovation to overcome existing limitations and propel OSC technology toward commercial viability.

Effect of Solvents on the Performance and Structure of Polymethylacrylimide Aerogels.

Solvent effects play a critical role in solution polymerization, especially in free radical polymerization, where they influence both monomer-solvent interactions and the resulting polymer structure. In this study, polymethacrylimide (PMI) aerogels were synthesized via freeze-drying using dimethylformamide (DMF), dimethylacetamide (DMAc), and dimethyl sulfoxide (DMSO) as solvents. The effects of monomer reactivity ratios, monomer distribution, and solvent-monomer interactions on the shrinkage, bulk density, pore size, and compressive properties of the aerogels were investigated. Results demonstrated that solvent choice significantly impacted the polymerization process, leading to variations in the structure and properties of the final aerogels. Notably, aerogels synthesized in DMSO, the most polar solvent, exhibited the lowest shrinkage (33.98%), highest density (0.1582 g·cm-3), and highest compressive stress (1695.48 kPa at 70% strain). These findings underscore the importance of solvent selection in controlling the microstructure and enhancing the mechanical performance of PMI aerogels.

Greenness and whiteness appraisal for bioanalysis of quetiapine, levodopa and carbidopa in spiked human plasma by high performance thin layer chromatography.

A sustainable HPTLC-densitometric method was developed for quantitative determination of Quetiapine (QUET), Levodopa (LD) and Carbidopa (CD) in presence of Dopamine (DOP) as an internal standard. This applicable technique was achieved by spiking human plasma and extraction was performed using the protein precipitation approach. The mobile phase used was acetone, dichloromethane, n-butanol, glacial acetic acid and water (3: 2.5: 2: 2: 1.75, by volume). Method validation was done according to US-FDA guidelines and was able to quantify Quetiapine, Levodopa and Carbidopa in the ranges of 100-4000, 200-8000 and 30-1300 ng/mL, respectively. Bioanalytical method validation parameters were assessed for the studied drugs. Finally, the analytical suggested methodology was evaluated using various green and white analytical chemistry metrics and other tools, such as the green solvent selection tool, analytical eco-scale, green analytical procedure index, analytical greenness metric approach and the red-green-blue algorithm tool. The results revealed that the applied analytical method had a minor impact on the environment and is a relatively greener option than other previously reported chromatographic methods.

Impact of PM2.5 filter extraction solvent on oxidative potential and chemical analysis

ABSTRACT Fine particulate matter (PM2.5) is hypothesized to induce oxidative stress, and has been linked to acute and chronic adverse health effects. To better understand the risks and underlying mechanisms following exposure, PM2.5 is collected onto filters but prior to toxicological analysis, particles must be removed from filters. There is no standard method for filter extraction, which creates the possibility that the methods of extraction selected can alter the chemical composition and ultimately the biological implications. In this study, comparisons were made between extraction solvents (methanol (MeOH), dichloromethane (DCM), 0.9% saline, and Milli-Q water) and the results of oxidative potential and elemental concentration analysis of PM2.5 collected across sites in Arkansas, USA. Significant differences were observed between solvents, with DCM having significantly different results compared to all other extraction solvents (p ≤ 0.001). Significant correlations between element, black carbon, and PM2.5 concentrations and oxidative potential were observed. The observed correlations were extraction solvent dependent. For example, in saline extracted samples, oxidative potential had significant negative correlations with: Ba, Cd, Ce, Co, Ga, Mn and significant positive correlations with: Cr, Ni, Th, U. While in MeOH extracted samples, significant positive correlations were only between oxidative potential and Ga, U and significant negative correlations with V. This indicates that PM2.5 samples extracted with different solvents will yield different conclusions about the causal components. This study highlights the importance of filter extraction methods in interpretation of oxidative potential results and comparisons between studies. Implications While there is no standard method for PM2.5 filter extraction, variation of extraction methods impact analytical results. This project identifies that extraction method variation, particularly extraction solvent selection, leads to discrepancies in chemical and toxicological analysis for PM2.5 collected on the same filter. This work highlights the need for methods standardization to support accurate comparisons between PM2.5 research studies, thus providing better understanding of PM2.5 across the globe.

Exploring Selectivity of Supercritical-CO2 for Vitamin E Extraction from Canola Seeds

AbstractThe objective of the current study was to investigate the selectivity of supercritical-CO2 for extraction and concentration of Vitamin E components from canola seeds. The selectively extracted Vitamin E in supercritical-CO2 solvent was related to pressure, temperature, and density through the developed thermodynamic modeling approach. The results suggested that increased pressure and density would enhance the selectivity of supercritical-CO2 solvent, consequently obtaining highly concentrated Vitamin E. The thermodynamic modeling equations have correlated the selectivity of supercritical-CO2 solvent for extracting Vitamin E in terms of processing conditions including pressure, temperature, and density of the supercritical-CO2 solvent fluid. The activity coefficient in thermodynamic modeling was involved with those key parameters that are important in determining selectivity, concentration, and extraction results. The supercritical-CO2 solvent can be made highly selective by precisely controlling the operating pressure and temperature. This allowed the supercritical-CO2 solvent to achieve the desired density in the supercritical phase, thereby enhancing the selectivity for targeted components. The thermodynamic mathematical modeling offered valuable insights for enhancing extraction processes in industrial settings. A high regression coefficient via linear structural modeling analysis indicated that the response equation fitted with the experimental data (R2 = 0.8737). The experimental results for the separation parameters provide optimal selectivity of supercritical-CO2 solvent for extracting and concentrating Vitamin E compounds for establishing commercial production.

PH‐sensitive size/surface charge‐adaptive quaternary ammonium salt copolymer micelles for antibiofilm activity against Staphylococcus aureus

AbstractThe low penetration of antibacterial materials within biofilms results in a 1000‐fold decrease in bactericidal efficiency, complicating the complete removal of biofilms and potentially leading to persistent and recurrent bacterial infections that significantly impact human health. In this study, we present a multifunctional pH‐responsive antibacterial material based on random copolymers poly(dimethylaminoethyl methacrylate decyl ammonium bromide‐co‐polyethylene glycol methacrylate) copolymer (PQACs10‐co‐PEGMA10). The PQACs10‐co‐PEGMA10 copolymers could self‐assemble into micelles in selective solvent water. With the stealth function of polyethylene glycol (PEG), the PQACs10‐co‐PEGMA10 micelles can rapidly penetrate biofilms in a physiological environment and exhibit excellent antibacterial activity by exposing the quaternary ammonium salt (QACs) in an acidic microenvironment to eliminate biofilm. Furthermore, PQACs10‐co‐PEGMA10 micelles were applied as coatings using a dropwise method. The PEG chain formed hydration layer and the QACs chain for sterilization can hinders bacterial adhesion and proliferation, thereby preventing biofilm formation. The results show that the minimal inhibit concentration values and minimum biofilm eradication concentrations of the PQACs10‐co‐PEGMA10 micelles against Gram‐positive Staphylococcus aureus were 64 and 128 μg/mL, respectively. The antifouling and antibacterial rates of micelle coating against S. aureus were more than 99.99%. Taken together, the pH‐responsive PQACs10‐co‐PEGMA10 micelles demonstrate a good ability to clear and prevent biofilms, holding promise for complete biofilm removal and a reduction in biofilm‐related infections.

Selection of solvent and positive control concentration for enhanced Ames test conditions for N-nitrosamine compounds

The Ames test is a widely used bacterial mutagenicity assay to evaluate the potential of chemical compounds to induce mutations. In recent years, there has been growing concern regarding the presence of N-nitrosamines in pharmaceuticals, food, and other consumer products. N-Nitrosamines are probable mutagens and carcinogens. To address the reduced sensitivity of the standard Ames test for N-nitrosamines, particularly N-nitrosodimethylamine, the European Medicines Agency (EMA) and United States Food and Drug Administration (FDA) have recently published recommendations for enhanced Ames test (EAT) conditions. However, there is a lack of clear guidance on the selection of N-nitrosamine positive control concentrations, particularly for 1-cyclopentyl-4-nitrosopiperazine, and the amount of solvent to be used in the EAT. This study aims to address the current gap in concentration and volume specifications by providing a comprehensive guide to set up enhanced Ames test conditions specifically for N-nitrosamine compounds using appropriate amounts of solvent, new solvents, and strain-specific positive control concentrations.

Enhancing the Biomimetic Mechanics of Bottlebrush Graft-Copolymers through Selective Solvent Annealing.

Self-assembled networks of bottlebrush copolymers are promising materials for biomedical applications due to a unique combination of ultra-softness and strain-adaptive stiffening, characteristic of soft biological tissues. Transitioning from ABA linear-brush-linear triblock copolymers to A-g-B bottlebrush graft copolymer architectures allows significant increasing the mechanical strength of thermoplastic elastomers. Using real-time synchrotron small-angle X-ray scattering, it is shown that annealing of A-g-B elastomers in a selective solvent for the linear A blocks allows for substantial network reconfiguration, resulting in an increase of both the A domain size and the distance between the domains. The corresponding increases in the aggregation number and extension of bottlebrush strands lead to a significant increase of the strain-stiffening parameter up to 0.7, approaching values characteristic of the brain and skin tissues. Network reconfiguration without disassembly is an efficient approach to adjusting the mechanical performance of tissue-mimetic materials to meet the needs of diverse biomedical applications.

Multidimensional Exploration of Wood Extractives: A Review of Compositional Analysis, Decay Resistance, Light Stability, and Staining Applications

Extractives, which naturally evolve as fundamental defense mechanisms in wood against environmental stresses, hold an essential place in the field of wood conservation science. Despite their low content in woody substrates, extractives are chemically complex and can be extracted accurately by solvents with different polarities, covering key components such as aliphatic, terpenoid, and phenolic compounds. The application of solvent extraction allows for the effective recovery of these extracts from forestry waste, thereby creating new opportunities for their reuse in wood modification and enhancing the economic value and potential applications of forestry waste. In the wood industry, extractives not only act as efficient preservatives and photo-stabilizers, significantly improving the decay resistance and photodegradation resistance of wood, but also serve as ideal dyes for fast-growing wood due to their abundant natural colors, which lend the product a distinct aesthetic appeal. The aim of this paper is to provide a comprehensive review of the origin and distribution characteristics of wood extractives and to examine the impact of solvent selection on extraction efficiency. At the same time, the mechanism of extractives in enhancing wood decay resistance and slowing down photodegradation is deeply analyzed. In addition, specific examples are presented to illustrate their wide utilization in the wood industry. This is intended to provide references for research and practice in related fields.

Mobile Phase Contaminants Affect Neutral Lipid Analysis in LC-MS-Based Lipidomics Studies.

Lipidomics is a well-established field, enabled by modern liquid chromatography mass spectrometry (LC-MS) technology, rapidly generating large amounts of data. Lipid extracts derived from biological samples are complex, and most spectral features in LC-MS lipidomics data sets remain unidentified. In-depth analyses of commercial triacylglycerol, diacylglycerol, and cholesterol ester standards revealed the expected ammoniated and sodiated ions as well as five additional unidentified higher mass peaks with relatively high intensities. The identities and origin of these unknown peaks were investigated by modifying the chromatographic mobile-phase components and LC-MS source parameters. Tandem MS (MS/MS) of each unknown adduct peak yielded no lipid structural information, producing only an intense ion of the adducted species. The unknown adducts were identified as low-mass contaminants originating from methanol and isopropanol in the mobile phase. Each contaminant was determined to be an alkylated amine species using their monoisotopic masses to calculate molecular formulas. Analysis of bovine liver extract identified 33 neutral lipids with an additional 73 alkyl amine adducts. Analysis of LC-MS-grade methanol and isopropanol from different vendors revealed substantial alkylated amine contamination in one out of three different brands that were tested. Substituting solvents for ones with lower levels of alkyl amine contamination increased lipid annotations by 36.5% or 27.4%, depending on the vendor, and resulted in >2.5-fold increases in peak area for neutral lipid species without affecting polar lipid analysis. These findings demonstrate the importance of solvent selection and disclosure for lipidomics protocols and highlight some of the major challenges when comparing data between experiments.

Integrating thermodynamic and kinetic approaches for the design of effective and sustainable PET chemical upcycling systems

Understanding and optimizing the individual contributions of recycling process components are critical in the development of effective and sustainable upcycling systems. Herein, each process component, i.e., alcohol, co-solvent, Lewis acid, and reaction conditions, is newly and holistically assessed for the alcohol-based conversion of postconsumer polyethylene terephthalate (PET) to terephthalic acid (TPA) and its precursors by integrating thermodynamic and kinetic considerations. First, an analysis based on the Flory-Huggins interaction parameter (χ1,2) establishes the importance of co-solvents in the depolymerization process due to reduction of thermodynamic potential. Second, a kinetic analysis of the catalyst component proves the vitality of the solubility of the Lewis acid source for efficient PET deconstruction. In addition, further validation experiments determine methanol as the most effective option in tandem alcoholysis given its reduced steric hindrance and relatively higher nucleophilicity, whereas process optimization tests suggest the existence of an optimum methanol molar ratio (XMetOH) of 0.16 and operation at 50 °C to realize TPA yields that exceed 90 % within 15 min across various pure and mixed PET feedstocks. Selection and implementation of greener solvents in the process is also found to reduce co-solvent based emissions by 96.3 % whilst retaining comparable monomer production efficiency. Overall, the implementation of thermodynamic considerations and kinetics-based understanding of roles played by each component is found to boost the overall depolymerization process, and the integration of these thermodynamic and kinetic approaches provides a unified avenue for optimizing and developing sustainable recycling processes for post-consumer plastic waste.

Liquid-Liquid Extraction Solvent Selection for Comparing Illegal Drugs in Whole Blood and Dried Blood Spot with LC-MS/MS.

This study focused on the simultaneous detection of amphetamine, 3,4-methyl enedioxy methamphetamine, morphine, benzoylecgonine, and 11-nor-9-carboxy- tetrahydrocannabinol (Δ9-THC-COOH) in whole blood and DBS. It is aimed to select a solvent mixture for liquid-liquid extraction (LLE) technique employing LC-MS/MS. The obtained DBS results were compared with the whole blood samples results. A simple, rapid, and reliable LC-MS/MS method was developed and validated for all analytes in whole blood and DBS. LC was performed on a Hypersil Gold C18 column an initial step with a gradient of 0.01 % formic acid, 5 mM ammonium format buffer in water, and acetonitrile at 0.3 ml/min with 7.5-min runtime. A methanol:acetonitrile (40:60 v/v) mixture was selected for both matrices. LOQ values were 10-25 ng/mL; linear ranges were LOQ-500 ng/ml for all analytes; correlation coefficients were greater than 0.99, and all calibrator concentrations were within 20%. Analytical recovery in blood and DBS ranged from 84.9-113.2% of the expected concentration for both intra and-inter day. Analytes were stable for 1, 10, and 30 days after three freeze/thaw cycles. It was determined that the variances of the results obtained with the two matrices in the comparison study were equal for each analyte, and the results were highly correlated (r=0.9625). A sensitive, accurate, and reliable chromatographic method was developed to determine amphetamine, MDMA, morphine, benzoylecgonine, and cannabis, by performing the same preliminary steps with whole blood and dried blood spots. It was observed that the results obtained in these two matrices were compatible and interchangeable when statistically compared.