Spruce Bark-Extracted Lignin and Tannin-Based Bioresin-Adhesives: Effect of Curing Temperatures on the Thermal Properties of the Resins.

In this study, formaldehyde-free bioresin adhesives were synthesised from lignin and tannin, which were obtained from softwood bark. The extraction was done via organosolv treatment and hot water extraction, respectively. A non-volatile, non-toxic aldehyde, glyoxal, was used as a substitute for formaldehyde in order to modify the chemical structure of both the lignin and tannin. The glyoxal modification reaction was confirmed by ATR-FTIR spectroscopy. Three different resin formulations were prepared using modified lignin along with the modified tannin. The thermal properties of the modified lignin, tannin, and the bioresins were assessed by DSC and TGA. When the bioresins were cured at a high temperature (200 °C) by compression moulding, they exhibited higher thermal stability as well as an enhanced degree of cross-linking compared to the low temperature-cured bioresins. The thermal properties of the resins were strongly affected by the compositions of the resins as well as the curing temperatures.

Structural characterization of pectin obtained by different purification methods.

Commercial pectin production is based on vacuum evaporation and alcohol precipitation (VEAP) using large quantities of expensive and flammable alcohol. This process has high production costs that have greatly limited the commercial use of refined pectins. This study demonstrates a new technology using a diaultrafiltration (DUF) process in a pilot plant, which is a low-cost, green, and ecologically friendly way to produce pectin. In terms of the structure and quality of their products, a comparison of the two methods suggest that DUF provides significant (p < 0.05) flux enhancement, high pectin purity, and separation of the main pectin backbones, with higher molar mass (Mw) and less polydispersity (Mw/Mn) of pectin samples. An analysis of the 1D and 2D NMR spectra reveals that the DUF process removes most free impurities extracted along with the pectin macromolecules, making this method preferable to use. An analysis of power and chemical consumption demonstrates that the new process is preferable over existing methods due to lower energy consumption and higher product quality. It also possesses a flexible technical design that allows it to produce semi-products from various raw materials.

Biogenic Synthesis of Gold Nanoparticles on a Green Support as a Reusable Catalyst for the Hydrogenation of Nitroarene and Quinoline.

Direct attachment of gold nanoparticles to a green support without the use of an external reducing agent and using it for removing toxic pollutants from wastewater, i. e., reduction of nitroarene to amine, are described. A novel approach involving the reduction of gold by the jute plant (Corchorus genus) stem-based (JPS) support itself to form nanoparticles (AuNPs) to be used as a catalytic system ('dip-catalyst') and its catalytic activity for the hydrogenation of series of nitroarenes in aqueous media are presented. AuNPs/JPS catalyst was characterized using SEM, UV-Vis, FTIR, TEM, XPS, and ICP-OES. Confined area elemental mapping exhibits uniform and homogeneous distribution of AuNPs on the support surface. TEM shows multi-faceted AuNPs in the range of 20-30 nm. The reactivity of AuNPs/JPS for the transfer hydrogenation of nitroarene as well as hydrogenation of quinoline under molecular H2 pressure was evaluated. Sodium borohydride, when used as the hydrogen source, demonstrates a high catalytic efficiency in the transfer hydrogenation reduction of 4-nitrophenol (4-NP). Quinoline is quantitatively and chemoselectively hydrogenated to 1,2,3,4-tetrahydroquinoline (py-THQ) using molecular hydrogen. Reusability studies show that AuNPs are stable on the support surface and their selectivity is not affected.

Flow Biocatalysis: A Challenging Alternative for the Synthesis of APIs and Natural Compounds.

Biocatalysts represent an efficient, highly selective and greener alternative to metal catalysts in both industry and academia. In the last two decades, the interest in biocatalytic transformations has increased due to an urgent need for more sustainable industrial processes that comply with the principles of green chemistry. Thanks to the recent advances in biotechnologies, protein engineering and the Nobel prize awarded concept of direct enzymatic evolution, the synthetic enzymatic toolbox has expanded significantly. In particular, the implementation of biocatalysts in continuous flow systems has attracted much attention, especially from industry. The advantages of flow chemistry enable biosynthesis to overcome well-known limitations of "classic" enzymatic catalysis, such as time-consuming work-ups and enzyme inhibition, as well as difficult scale-up and process intensifications. Moreover, continuous flow biocatalysis provides access to practical, economical and more sustainable synthetic pathways, an important aspect for the future of pharmaceutical companies if they want to compete in the market while complying with European Medicines Agency (EMA), Food and Drug Administration (FDA) and green chemistry requirements. This review focuses on the most recent advances in the use of flow biocatalysis for the synthesis of active pharmaceutical ingredients (APIs), pharmaceuticals and natural products, and the advantages and limitations are discussed.

Green analytical assay for the quality assessment of tea by using pocket-sized NIR spectrometer.

Rapid and low-cost testing tools provide new methods for the evaluation of tea quality. In this study, a micro near-infrared (NIR) spectrometer was used for the qualitative and quantitative evaluation of tea. A total of 360 tea samples consisting of black, green, yellow, and oolong tea were collected from different countries. Chemometrics including linear partial least squares (PLS) regression, PLS discriminant analysis, and nonlinear radial basis function-support vector machine (RBF-SVM) were used. The RBF-SVM model achieved optimal discriminant performance for tea types with a correct classification rate of 98.33%. Wavelength selection of iteratively variable subset optimization (IVSO) exhibited considerable advantages in improving the predictive performance of catechin, caffeine, and theanine models. The IVSO-PLS regression models achieved satisfactory results for catechins and caffeine prediction, with Rp over 0.9, and RPD over 2.5. Thus, the study provided a portable and low-cost method for in-situ assessing tea quality.

Lignin from oil palm empty fruit bunches: Characterization, biological activities and application in green synthesis of silver nanoparticles.

Lignin was extracted from oil palm empty fruit bunches under four different conditions. The lignin samples were characterized and employed in the green synthesis of silver nanoparticles. Two-dimensional HSQC NMR analysis showed that lignins extracted under more aggressive conditions (3.5% acid, 60 min) exhibited less signals and thus, presented a more degraded chemical structure. Additionally, those lignins obtained under harsh conditions (3.5% acid, 60 min) exhibited higher antioxidant capacity than those obtained under mild conditions (1.5% acid, 20 min). Formation of lignin-mediated silver nanoparticles was confirmed by color change during their synthesis. The surface plasmon resonance peaks (423-427 nm) in UV-visible spectra also confirmed the synthesis of AgNPs. AgNPs showed spherical shape, polycrystalline nature and average size between 18 and 20 nm. AgNPs, in suspension, presented a negative Zeta potential profile. Lignin was assumed to contribute in the antioxidant capacity exhibited by AgNPs. All AgNPs presented no significant differences on the disk diffusion antimicrobial susceptibility test against E. coli. The minimum inhibitory concentration of HAL3-L AgNPs (62.5 µg·mL-1) was better than other physicochemically produced AgNPs (100 µg·mL-1).

Green and efficient removal of heavy metals from Porphyra haitanensis using natural deep eutectic solvents.

BACKGROUND: Porphyra haitanensis now faces serious heavy metal pollution problems. Natural deep eutectic solvents (NADESs) have been recognized as a novel class of sustainable solvents, which can be used for heavy metal removal. In this study, 28 kinds of NADESs were prepared and investigated as eluent in the removal of lead (Pb), cadmium (Cd), chromium (Cr), arsenic (As), and copper (Cu) from P. haitanensis for the first time, and the adsorption mechanism of NADESs was also studied. RESULTS: The removals were greatly improved by NADESs compared with control where the removal rates of Pb, Cd, Cr, As and Cu were 17.4-87.54%, 57.54-100%, 9.8-48.59%, 21.32-78.24% and 11.68-79.73%, respectively. The optimal condition was 10% water content and solid-liquid ratio of 1:20. Moreover, the addition of 20% natural surfactant arabic gum can further increase the heavy metals removal rates of NADESs. The adsorption mechanism experiments showed that the pseudo second-order model and the Freundlich adsorption model can better explain the adsorption mechanism of NADESs on heavy metals removal. CONCLUSION: Taken together, a green and efficient method for removing heavy metals from P. haitanensis was established. © 2020 Society of Chemical Industry.

Modern Flow Analysis.

A brief overview of articles published in this Special Issue of Molecules titled "Modern Flow Analysis" is provided. In addition to cross-sectional and methodological works, there are some reports on new technical and instrumental achievements. It has been shown that all these papers create a good picture of contemporary flow analysis, revealing the most current trends and problems in this branch of flow chemistry.

Parallel validation of a green-solvent extraction method and quantitative estimation of multi-mycotoxins in staple cereals using LC-MS/MS.

In this study, 15 different mycotoxins were estimated in three staple cereals from selected agro-ecological regions in Nigeria using a 'novel' green extraction method, pressurized hot water extraction (PHWE) in comparison to a conventional solvent extraction method. Discrimination of the results of PHWE and solvent extraction using principal component analysis (PCA) and orthogonal projection to latent structures discriminate analysis (OPLS-DA) did not yield any differential clustering patterns. All maize samples (n = 16), 32% (n = 38) of sorghum and 35% (n = 37) of millet samples were positive for at least one of the 15 tested mycotoxins. Contamination levels for the cereals were higher in the warm humid rain forest region and gradually decreased towards the hot and arid region in the north of the country. The results demonstrate the applicability of PHWE as a possible alternative extraction method to conventional methods of extraction, which are solvent based.

Automatic multicommuted flow-batch setup for photometric determination of mercury in drinking water at ppb level.

Herein, a multicommuted flow-batch setup and a photometric procedure for the determination of mercury at the ppb level in aqueous samples are described. The setup was designed to implement a versatile solvent extraction and pre-concentration strategy by combining flow-batch and multicommuted flow analysis approaches. The photometric method was based on Hg(II) reaction with dithizone in a chloroform medium, which was also used as the extracting organic solvent. The flow analysis system was composed of a homemade syringe pump module, a set of solenoid valves, two Aquarius mini-pumps, and a flow-batch chamber. The homemade photometer was comprised of a light emitting diode (LED), photodiode, and homemade flow cell (50 mm length). The flow system and photometer were controlled using an Arduino Due board, running custom-written software. After optimizing the operational conditions, the effectiveness of the developed system was evaluated for the determination of the mercury concentration in drinking water. For accuracy assessment, samples were analyzed using a spiking methodology and an independent method, yielding a recovery ranging from 92% to 108%. Other important characteristics of the proposed method were found as follows: linear response range, 0.5-10.0 µg L-1 (r = 0.9984); limit of detection 0.38 µg L-1 Hg(II); consumption of dithizone and chloroform, 1.85 µg L-1 and 0.8 mL per analysis, respectively; coefficient of variation, 2% (n = 10); sampling throughput, 20 determinations per h.

Green solvents and Ultrasound-Assisted Extraction of bioactive orange (Citrus sinensis) peel compounds.

Byproducts such as orange peel have potential uses because of their bioactive compounds, which are important for their potential to reduce the risk factors of diseases caused by aging. The lack of effective techniques and the high levels of pollution produced by the conventional extraction of bioactive compounds using organic solvents have highlighted the need to enhance the 'green chemistry' trend. This study evaluates the use of ultrasound to extract bioactive compounds from orange peel. The antioxidant capacity, phenolic content, ascorbic acid, total carotenoids, and HPLC profile of phenolic compounds from orange peel extracts were obtained by a physicochemical evaluation. The results demonstrate that the optimal conditions for the ultrasound-assisted extraction of bioactive orange peel compounds were a power of 400 W, a time of 30 min, and 50% ethanol in water. These conditions were used to obtain a total carotenoid concentration of 0.63 mg ß-carotene/100 g, vitamin C concentration of 53.78 mg AA/100 g, phenolic concentration of 105.96 mg GAE/100 g, and antioxidant capacity of ORAC = 27.08 mM TE and TEAC = 3.97 mM TE. The major phenolic compound identified in all orange peel extracts was hesperidin, with a maximum concentration of 113.03 ± 0.08 mg/100 g.

Cork sheet as a sorptive phase to extract hormones from water by rotating-disk sorptive extraction (RDSE).

This work reports for the first time the use of laminar cork as a sorptive phase in a microextraction technique, rotating-disk sorptive extraction (RDSE). Typical hormones (estrone, estradiol, estriol and ethinyl estradiol) were selected as analyte models and extracted from wastewater samples on laminar cork with statistically equivalent extraction efficiency to that provided by Oasis HLB. The cork characterization was performed by confocal fluorescence microscopy (CLSM), Fourier-transform infrared spectroscopy (FTIR) and scanning electron microscopy (SEM), allowing the identification of lignin, suberin and polysaccharides (cellulose and hemicellulose) as the main components of the cork. The best conditions for extraction were as follows: rotation velocity of the disk, 2000 rpm; extraction time, 45 min; and sample volume, 20 mL. The analytical features of the developed method show that calibration curves for all analytes have R2 values higher than 0.99. The absolute recoveries were higher than 63%, and the precision, expressed as relative standard deviation, ranged from 2 to 16%. The LOD and LOQ ranges were 3-19 and 10-62 ng L-1, respectively. The proposed method was applied to the analysis of wastewater, and the concentrations of hormones in a wastewater treatment plant in Santiago, Chile, ranged from

A green analytical assay for the quantitation of the total saponins in quinoa (Chenopodium quinoa Willd.) based on macro lens-coupled smartphone.

The aim of this study was to develop and validate a microtiter macro lens-coupled smartphone (MCS) assay for the quantitation of the total saponins in quinoa based on foam measurement. The 96-well micro plate with a black bottom and an inclination angle = 12.102° of macro lens-coupled smartphone allows to acquire images with a high resolution. The foam stability, a critical aspect for the MCS assay, was significantly improved by the inclusion of a chelating agent (EDTA 50 mmol L-1) and bovine serum albumin (0.5 mg mL-1). The MCS assay was linear within the range of 9.039-180.773 × 10-4 mg mL-1 of saponin (R2 = 0.9929), using the integrated density/area as a foam measurement (Y) and the logarithm of saponin concentration (X) (Y = 372.1 + 104.2LogX). The MCS assay was 50-folds more sensitive than afrosimetric assay -AA- with LOD = 3.168 × 10-4 mg mL-1 and LOQ = 4.784 × 10-4 mg mL-1. MCS assay was more reproducible (relative standard deviation (RSD) = 0.632-9.646%) than AA (RSD = 3.44-44.04%). The correlation analysis, Bland-Altman analysis and Passing-Bablok regression showed good agreement between total saponin content in quinoa as measured by the MCS assay and AA. Based on the green analytical procedure index, MCS assay can be considered as a green procedure.

Green pre-concentration techniques during pesticide analysis in food samples.

The ever-increasing demand for determining pesticides at low concentration levels in different food matrices requires a preliminary step of pre-concentration which is considered a crucial stage. Recently, the parameter of "greenness" during sample pre-concentration of pesticides in food matrices is as important as selectivity in order to avoid using harmful organic solvents during sample preparation. Developing new green pre-concentration techniques is one of the key subjects. Thus, to reduce the impact on the environment during trace analysis of pesticides in food matrices, new developments in pre-concentration have gone in three separate directions: the search for more environmentally friendly solvents, miniaturization and development of solvent-free pre-concentration techniques. Eco-friendly solvents such as supercritical fluids, ionic liquids and natural deep eutectic solvents have been developed for use as extraction solvents during pre-concentration of pesticides in food matrices. Also, miniaturized pre-concentration techniques such as QuEChERS, dispersive liquid-liquid micro-extraction and hollow-fiber liquid-phase micro-extraction have been used during trace analysis of pesticides in food samples as well as solvent-free techniques such as solid-phase micro-extraction and stir bar sorptive extraction. All these developments which are aimed at ensuring that pesticide pre-concentration in different food matrices is green are critically reviewed in this paper.

Application of Green Technology for the Acquisition of Extracts of Araçá (Psidium grandifolium Mart. ex DC.) Using Supercritical CO2 and Pressurized Ethanol: Characterization and Analysis of Activity.

Brazil is home to a wide variety of flora, including several lesser known species, such as araçá that were processed in this study using two green technologies consecutively: supercritical fluid extraction (SFE) for nonpolar fraction and pressurized liquid extraction. For polar fraction, the experiments followed a central composite design involving ethanol as solvent, with temperature and static time in each bath as independent variables. Both extracts were analyzed for antioxidant and antimicrobial activities. Total phenolics content (TPC) was determined for all ethanol extracts. In the araçá essential oil (AEO) obtained by SFE, the extraction yield was 2.33%. The three major compounds of AEO were α-pinene (20.75%), p-cymene (20.50%), and o-cymene (20.05%). In ethanol extracts, the high yield (14.49%) was obtained at 74 °C/6 min and the major TPC (136.95 mg GAE/100 g) at 60 °C/9 min. Ethanol extracts presented good antioxidant activity (EC50 = 6.37 mg/mL) at 74 °C/6 min. AEO was unable to reduce DPPH• concentration by 50%. Both extract types presented an inhibitory effect against Staphylococcus aureus, Pseudomonas aeruginosa, and Bacillus cereus, while only the ethanol extracts presented effect against Listeria monocytogenes. This work had the aim to present the innovation of the use of a whole typical Brazilian fruit that gives rise to extracts with excellent properties for employment in both the pharmaceutical and food industries.

Ultrasound-assisted emulsification liquid phase microextraction method based on deep eutectic solvent as extraction solvent for determination of five pesticides in traditional Chinese medicine.

A kind of green solvents termed deep eutectic solvent (DES) have been considered alternatives to traditional organic solvents. In this study, a method was developed for determination of five pesticide residues including triadimenol, fipronil, tebuconazole, hexaconazole and diniconazole in five different traditional Chinese medicines (TCMs). In the developed method, DES was selected as extraction solvent, ultrasound-assisted emulsification liquid phase microextraction (UA-ELPME) was used for extraction and high performance liquid chromatography (HPLC) equipped with a diode array detector (DAD) was used for quantification. In this method, DES was synthesized with choline chloride and phenol at the molar ratio 1:4 using the heating and stirring method. Meanwhile, several important parameters such as volume of DES (650 µL), volume of tetrahydrofuran (THF, 550 µL) and ultrasonic time (30 min) were optimized by using response surface methodology (RSM) based on a central composite design (CCD). Under the optimized conditions, the limits of detection and quantification of method were in the range of 0.02-0.2 µg mL-1 and 0.05-0.5 µg mL-1, respectively. The correlation coefficients (r) of five calibration curves are greater than 0.9996, relative standard deviation (RSD) of precision for this method of five pesticides were lower than 4.7%, and the mean recoveries were in the range of 81.0-92.1%. The present experiment suggests that DESs are efficiently extract solvents in UA-ELPME method for traditional herbal medicines applications.

Bio-based thin films of cellulose nanofibrils and magnetite for potential application in green electronics.

The objective of this work was to prepare bio-based thin films and evaluate the additions of magnetite and glycerol on the physico-chemical (flexibility, wettability and barrier properties) and dielectric properties of cellulose/chitosan-based films. The films were prepared by solution casting and presented a suitable dispersion of the constituents observed by SEM and FTIR. The films were thermally stable up to 150 °C and had a higher flexibility, wettability and lower barrier properties upon addition of glycerol. The calculated dielectric constant (εr) for the composite films was based on measurements of capacitance, at 100 and 1000 Hz, with the additions of magnetite and glycerol more than doubling the εr increasing the charge storage capacity. The bio-based thin films have potential to be used as insulators in capacitors on the production of green electronics thus, reducing toxic and nonrenewable e-waste generation.

Analytical Eco-Scale for Assessing the Greenness of a Developed Potentiometric Method for Lomefloxacin Hydrochloride Determination in its Different Dosage Forms, Plasma, and Dissolution Medium.

Background: Traditional methods for Lomefloxacin hydrochloride (LOM) determination involve pretreatment steps, which extend analysis time and use hazardous chemicals. Objective: The ability to provide a rapid route without sample pretreatment for quantitative determination of compounds via a low-cost instrument is a challenging task. In this work, a simple potentiometric method was developed to determine the antibacterial LOM via in-house fabricated ion selective electrodes. Methods: Different sensors were fabricated using a poly vinyl chloride-based membrane, potassium tetrakis(4-chlorophenyl) borate as a cation exchanger, and 2-Nitrophenyl octyl ether as a plasticizer (sensor 1). To increase the selectivity of sensor 1, a selective molecular recognition component 2-hydroxypropyl-ß-cyclodextrin was used as ionophore (sensor 2). Results: The proposed method was validated according to International Union of Pure and Applied Chemistry recommendations, in which the proposed sensors show a linear dynamic range from 1 × 10-5 to 1 × 10-2 mol/L, with Nernstian slopes of 55.829 and 58.229 mV/decade for sensors 1 and 2, respectively. It was applied to determine LOM in bulk powder, in different dosage forms, and in plasma with no sample pretreatment. Also, the suggested method can be used as a green, in-line bench top real-time analyzer for in-process monitoring of LOM release from its tablets, under U.S. Food and Drug Administration dissolution regulations, with clear discrimination from common excipients. Results obtained by the proposed potentiometric method were compared with those obtained by a reported HPLC method. Conclusions: The proposed method is considered as a perfect alternative to traditional reported methods for LOM determination.

Electrochemical Reduction of Carbon Dioxide to Value-Added Products: The Electrocatalyst and Microbial Electrosynthesis.

The electrochemical reduction of carbon dioxide (CO2 ) to value-added products obtains great attention and investigation worldwide in recent years. The commercialization of this green process relies on the progress of relating high-performance electrocatalysts and their feasibility with proper reactor design. The microbial electrosynthesis (MES) is an alternative route to reduce CO2 with electroactive bio-film electrode as catalyst. This review presents the research status and development of cathode catalysts, particularly focusing on the active sites and development tendency, for highly efficient electrochemical reduction CO2 from personal viewpoint. Some of our results are also presented to exhibit contributions. MES shows a similar process to the typical electrochemical reduction of CO2 . Their combination is an important trend, and the future research in this field is full of challenges and opportunities.

Green and Facile Production of Chitin from Crustacean Shells Using a Natural Deep Eutectic Solvent.

Natural deep eutectic solvents (NADESs) are sustainable, nontoxic, and biodegradable solvents, which are composed of natural primary metabolites. A green and efficient approach based on choline chloride-malic acid, a NADES, was developed for extracting chitin from crustacean shells, and its effectiveness for demineralization and deproteinization was determined. Fourier transform infrared (FT-IR) spectroscopy, thermogravimetric analysis (TGA), X-ray diffraction (XRD), and scanning electron microscopy (SEM) were used to investigate changes in the chemical composition of extracted chitin. The results revealed that most of the minerals and proteins were removed from the shrimp shells by using a NADES with the assistance of microwave irradiation. The quality of the obtained chitin was superior, and it displayed a relative crystallinity of 71%. All of these results were achieved without using harsh chemicals, which can raise environmental issues. This study provides a green and facile approach for chitin production from crustacean shells and reveals the potential of NADESs for applications in the extraction of biopolymers from natural sources.