Green Synthesis of 2-thioxothiazolidin-4-one Derivatives in Deep Eutectic Solvents via Knoevenagel Condensation

Recently, more and more researchers are resorting to green methods and techniques to avoid environmental pollution. Accordingly, many researchers have been working on the development of new green synthetic procedures trying to avoid the use of toxic organic solvents. A sustainable concept of green and environmentally friendly solvents in chemical synthesis nowadays encompasses a relatively new generation of solvents called deep eutectic solvents (DESs). DESs often have a dual role in the synthesis, acting as both, solvents and catalysts. In this study, DESs are used in the Knoevenagel synthesis of rhodanine derivatives, with no addition of conventional catalysts. A model reaction of rhodanine and salicylaldehyde was performed in 20 different DESs at 80 °C, in order to find the best solvent, which was further used for the synthesis of the series of desired compounds. A series of rhodanines was synthesized in choline chloride: acetamide (ChCl:acetamide) DES with good to excellent yields (51.4 – 99.7 %).

Adsorption of N,N,N′,N′-Tetraoctyl Diglycolamide on Hypercrosslinked Polysterene from a Supercritical Carbon Dioxide Medium

The work considers for the first time the preparation of sorbents based on hypercrosslinked polysterene (HCP) and chelating agent N,N,N′,N′-tetraoctyldiglycolamide (TODGA) by impregnation in the supercritical (SC) CO2 medium. Such sorbents can be applied for further isolation and separation of lanthanides, actinides and other metals. They are usually prepared by impregnation in toxic organic solvents (e.g., methanol, dichloromethane). Our study shows that application of SC CO2 instead of organic solvents can significantly speed up the impregnation, perfom it in one stage and make the process more eco-friendly. At the same time, the obtained sorbents are close in their parameters to the classical ones. This article presents the results of measuring the TODGA adsorption isotherms on two HCP sorbents (MN202 and MN270) on a wide range of SC fluid parameters. Adsorption measurements were carried out using on-line supercritical fluid chromatography and gravimetry. Based on the sorption capacity parameter, MN202 sorbent was selected as the better carrier for TODGA. An impregnation temperature increase within the range 313–343 K in isochoric conditions (ρ = 0.780 g/mL) reduces the maximum of TODGA adsorption from ~0.68 mmol/g to ~0.49 mmol/g.

Highly Soluble Fluorinated Polyimides Synthesized with Hydrothermal Process towards Sustainable Green Technology

Polyimides, a widely used engineering plastic, require use of large amounts of toxic and hazardous organic solvents which threaten our daily lives, calling for new and easy synthetic methods for sustainable environmentally friendly development. In this paper, highly soluble fluorinated polyimides based on 4,4′-(hexafluoroisopropylidene) diphthalic anhydride were synthesized via hydrothermal process without using any toxic organic solvents and the advantages of the newly demonstrated synthetic methods are shown by comparative analysis performed with the two conventional synthetic methods using organic solvent: thermal and chemical imidization. Lower temperature is required (~200 °C) compared to thermal imidization and functional groups for high fusibility formed more easily compared to chemical imidization. According to the comparative analysis, hydrothermally synthesized PIs showed excellent solubility and maintained high thermal stability (>500 °C) and glass transition temperature (>300 °C) compared to conventional PI. The hydrothermally synthesized polyimide is much more convenient to store and manage than other form of polyimide which is much more stable when it is exposed to humidity as it is a powder form. The hydrothermal synthetic method is verified to be a “Green” and facile method for sustainable PI synthesis.

Microencapsulation of Phenolic Extracts from Cocoa Shells to Enrich Chocolate Bars

Cocoa bean shells were subjected to green extraction technologies, based on the absence of toxic organic solvents, to recover polyphenols; the extract was then encapsulated using a spray dryer and maltodextrin as coating agent. The best conditions observed in the spray drying tests (core-to-coating ratio 1:5; inlet temperature 150 °C; flow rate 6 ml min−1) were applied to produce the microcapsules used to enrich the same cocoa mass as the shells and processed for the preparation of the chocolate bars. Sensory analysis showed no significant differences between enriched chocolate bar and the unenriched reference one, except for the appearance. Both samples were then subjected to accelerated storage tests, at the end of which the polyphenols in the control chocolate bar (0.85 g 100 g−1) were reduced by about 50% (0.42 g 100 g−1), while in the enriched chocolate (1.17 g 100 g−1) by only 22% (0.97 g 100 g−1). The proposed process significantly enriched the chocolate bars with phenolic antioxidants recovered from cocoa waste without increasing the sensations of bitterness and astringency.

Simulation of Enzymatic Production of Amoxicillin

This project report is an attempt to find better conditions and reaction parameters for the potential commercialization of the enzymatic production of amoxicillin. A kinetic model from the literature was used to describe a reaction between p-hydroxyphenylglycine methyl ester (PHPGME) and 6-aminopenicillanic acid (6-APA) that is catalyzed by penicillin G acylase immobilized onto glyoxyl-agarose gel beads. A C++ computer program was developed using the Fourth Order Runge-Kutta method to simulate higher substrate and enzyme concentration during the reaction. For model validation, simulation results were compared with experimental data from the literature and fractional errors. This simulation model predicted 24% yield of amoxicillin at high substrate concentration (50mM of 6-APA; 300mM of PHPGME). It also predicted that increasing the enzyme concentration by four fold could produce a similar amoxicillin yield four times faster. The simulation results obtained in this work could be used in the future to aid in optimization and in further modifications of the kinetic model to predict even better yields. This enzymatic process could therefore become an industrial process to substitute the existing chemical route, which contains toxic organic solvents.

Simulation of Enzymatic Production of Amoxicillin

This project report is an attempt to find better conditions and reaction parameters for the potential commercialization of the enzymatic production of amoxicillin. A kinetic model from the literature was used to describe a reaction between p-hydroxyphenylglycine methyl ester (PHPGME) and 6-aminopenicillanic acid (6-APA) that is catalyzed by penicillin G acylase immobilized onto glyoxyl-agarose gel beads. A C++ computer program was developed using the Fourth Order Runge-Kutta method to simulate higher substrate and enzyme concentration during the reaction. For model validation, simulation results were compared with experimental data from the literature and fractional errors. This simulation model predicted 24% yield of amoxicillin at high substrate concentration (50mM of 6-APA; 300mM of PHPGME). It also predicted that increasing the enzyme concentration by four fold could produce a similar amoxicillin yield four times faster. The simulation results obtained in this work could be used in the future to aid in optimization and in further modifications of the kinetic model to predict even better yields. This enzymatic process could therefore become an industrial process to substitute the existing chemical route, which contains toxic organic solvents.

DISTRIBUTION OF THORIUM (IV) IONS IN AQUEOUS EXFOLIATING SYSTEM CONTAINING ANTIPYRINE AND SULFOSALICYLIC ACID

The possibilities of an aqueous delaminating system containing antipyrine (AP) and sulfosalicylic acid (SSA) for extracting macro - and microamounts of thorium (IV) were studied. The proposed extraction system eliminates the use of toxic organic solvents. The dependences of the distribution of metal from nitrate solutions between phases on the concentration of reagents, acidity of the medium, the amount of inorganic salting-out agent (NaNO3, NH4NO3, Na2SO4) and the volume of the aqueous phase are determined, and optimal conditions for extraction are found. It is shown that in the organic phase with a volume of 1.6 ml at room temperature, macro-and microamounts of thorium (IV) are extracted by 88 and 90%, respectively. The maximum extraction of the cation is achieved at the ratio of AP: SSA = 2.0 : 1.0 and their concentration, mol/l: 0.6: 0.3, while the acidity of the medium created by nitric acid should be equal to 0.015 mol/l (pHequ. = 1.8-1.9). The extraction of thorium (IV) becomes quantitative if inorganic salts (sodium sulfate, sodium nitrate) are introduced into the AP – SSA – 0,015 mol/l HNO3 – H2O system, which, by reducing the activity of water, increase the concentration of reagents in the aqueous phase. The concentration of salting-out agents should correspond to 1.0 and 2.5 mol/l. A mechanism for the distribution of a mixed thorium (IV) complex containing AP, SSA, nitrate ions, solvated with a salt of antipyrinium sulfosalicylate is proposed. The extract is mixed in any relationship with distilled water, providing the use of various instrumental methods of analysis. A method for extraction-photometric determination of thorium (IV) with a toron indicator has been developed. The limit for the fulfillment of the Bouguer-Lambert-Beer law is established. The apparent coefficient of light absorption is calculated (ε = 1.7∙104).

Iron-Containing Hypercrosslinked Composite Prepared From Polystyrene Foam Plastic in the Sorption of Toxic and Foul-Smelling Substanc

A convenient method for obtaining an iron-containing hypercrosslinked polystyrene composite based on foam plastic waste is developed. The iron-containing composite can be used for the sorption of hydrogen sulfide, toxic organic solvents, as well as foul-smelling and toxic products of degradation of natural remains—putrescine, cadaverine, indole, and skatole.

Green Synthesis of Silver Nanoparticles Using Extract of Cilembu Sweet Potatoes (Ipomoea batatas L var. Rancing) as Potential Filler for 3D Printed Electroactive and Anti-Infection Scaffolds

Electroactive biomaterials are fascinating for tissue engineering applications because of their ability to deliver electrical stimulation directly to cells, tissue, and organs. One particularly attractive conductive filler for electroactive biomaterials is silver nanoparticles (AgNPs) because of their high conductivity, antibacterial activity, and ability to promote bone healing. However, production of AgNPs involves a toxic reducing agent which would inhibit biological scaffold performance. This work explores facile and green synthesis of AgNPs using extract of Cilembu sweet potato and studies the effect of baking and precursor concentrations (1, 10 and 100 mM) on AgNPs’ properties. Transmission electron microscope (TEM) results revealed that the smallest particle size of AgNPs (9.95 ± 3.69 nm) with nodular morphology was obtained by utilization of baked extract and ten mM AgNO3. Polycaprolactone (PCL)/AgNPs scaffolds exhibited several enhancements compared to PCL scaffolds. Compressive strength was six times greater (3.88 ± 0.42 MPa), more hydrophilic (contact angle of 76.8 ± 1.7°), conductive (2.3 ± 0.5 × 10−3 S/cm) and exhibited anti-bacterial properties against Staphylococcus aureus ATCC3658 (99.5% reduction of surviving bacteria). Despite the promising results, further investigation on biological assessment is required to obtain comprehensive study of this scaffold. This green synthesis approach together with the use of 3D printing opens a new route to manufacture AgNPs-based electroactive with improved anti-bacterial properties without utilization of any toxic organic solvents.

Mechanical Cell Disruption Technologies for the Extraction of Dyes and Pigments from Microorganisms: A Review

The production of pigments using single cell microorganisms is gaining traction as a sustainable alternative to conventional syntheses, which rely, in no negligible proportions, on petrochemicals. In addition to depending on petroleum, these syntheses involved the use of toxic organic solvents, which may be inadequately disposed of across a range of industries, thus compounding the deleterious effects of fossil fuel exploitation. Literature suggests that notable research efforts in the area of sustainable pigment production using single cell microorganisms are focused on the production of pigments coveted for their interesting qualities, which transcend their mere capacity to dye various fabrics both natural and synthetic. As interest in sustainable pigment biosynthesis grows, the need to devise effective and efficient cell disruption processes becomes more pressing given that the viability of pigment biosynthesis is not only dependent on microorganisms’ yield in terms of production, but also on researchers’ ability to recover them. This review chiefly reports findings as to mechanical cell disruption methods, used individually or in various combinations, and their aptitude to recover biosynthetic pigments.