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Over the past six decades, acetonitrile (ACN) has been the most employed organic modifier in reversed-phase high-performance liquid chromatography (RP-HPLC), followed by methanol (MeOH). However, from the growing environmental awareness that leads to the emergence of “green analytical chemistry,” new research has emerged that includes finding replacements to problematic ACN because of its low sustainability. Deep eutectic solvents (DES) can be produced from an almost infinite possible combinations of compounds, while being a “greener” alternative to organic solvents in HPLC, especially those prepared from natural compounds called natural DES (NADES). In this work, the use of three NADES as the main organic component in RP-HPLC, rather than simply an additive, was explored and compared to the common organic solvents ACN and MeOH but additionally to the greener ethanol for separating two different mixtures of compounds, one demonstrating the elution of compounds with increasing hydrophobicity and the other comparing molecules of different functionality and molar mass. To utilize NADES as an organic modifier and overcome their high viscosity monolithic columns, temperatures at 50 °C and 5% ethanol in the mobile phase were used. NADES are shown to give chromatographic performances in between those observed for ACN and MeOH when eluotropic strength, resolution, and peak capacity were taken into consideration, while being less environmentally impactful as shown by the HPLC-Environmental Assessment Tool (HPLC-EAT) metric. With the development of proper technologies, DES could open a new class of mobile phases increasing the possibilities of new separation selectivities while reducing the environmental impact of HPLC analyses.

Green chemistry has a beneficial influence on the environment and the pharmaceutical enterprises’ economy. Research and quality control laboratories worldwide conduct millions of analyses daily, employing liquid chromatography as the primary analytical technique. Furthermore, advancements in stationary phase technologies aimed at achieving faster and more efficient separations have introduced a new objective for chromatographers. This objective is to supersede conventional methodologies that rely heavily on substantial quantities of organic solvents, pose environmental hazards and incur considerable economic costs. The aim of this work is to provide a brief comparison between monolithic, core-shell and traditional fully porous stationary phases. This could help analysts by offering options for high-speed versus high-resolution separation when choosing the best packing materials. The analytes used in the study are two essential drugs used in the treatment of hepatitis C virus: Sofosbuvir and Ledipasvir, which are co-formulated in tablet dosage forms. The monolithic column enabled the fastest analysis, whereas the core-shell provided the highest efficiency. Validation was conducted in accordance with ICH guidelines using the RP-C18 monolithic column, a mobile phase consisting of 0.1% acetic acid and ethanol (60:40), a flow rate of 1 mL.min − 1 , and detection at 210 nm. The total analysis time did not exceed 3 min, achieving high accuracy and sensitivity while minimizing the use of hazardous solvents. It achieved a very good score on different green analytical chemistry assessment metrics; 0.7 on AGREE, 76 on MoGAPI, 80 on BAGI, and 73 on CACI.

Crocin-I, a valuable natural compound found in saffron (Crocus sativus L.), is the most abundant among the various crocin structures. Developing a cost-effective and scalable purification process to produce high-purity crocin-I is of great interest for future investigations into its biological properties and its potential applications in the treatment of neurological disorders. However purifying crocin-I through single-column preparative chromatography (batch) poses a yield-purity trade-off due to structural similarities among crocins, meaning that the choice of the collection window sacrifices either yield in benefit of higher purity or vice versa. This study demonstrates how the continuous countercurrent operating mode resolves this dilemma. Herein, a twin-column MCSGP (multicolumn countercurrent solvent gradient purification) process was employed to purify crocin-I. This study involved an environmentally friendly ethanolic extraction of saffron stigma, followed by an investigation into the stability of the crocin-I within the feed under varying storage conditions to ensure a stable feed composition during the purification. Then, the batch purification process was initially designed, optimized, and subsequently followed by the scale-up to the MCSGP process. To ensure a fair comparison, both processes were evaluated under similar conditions (e.g., similar total column volume). The results showed that, at a purity grade of 99.7%, the MCSGP technique demonstrated significant results, namely + 334% increase in recovery + 307% increase in productivity, and − 92% reduction in solvent consumption. To make the purification process even greener, the only organic solvent employed was ethanol, without the addition of any additive. In conclusion, this study presents the MCSGP as a reliable, simple, and economical technique for purifying crocin-I from saffron extract, demonstrating for the first time that it can be effectively applied as a powerful approach for process intensification in the purification of natural products from complex matrices.

The greening of analytical methods has gained increasing interest in the field of pharmaceutical analysis to reduce environmental impacts and improve the health safety of analysts. Reversed-phase high-performance liquid chromatography (RP-HPLC) is the most widely used analytical technique involved in pharmaceutical drug development and manufacturing, such as the quality control of bulk drugs and pharmaceutical formulations, as well as the analysis of drugs in biological samples. However, RP-HPLC methods commonly use large amounts of organic solvents and generate high quantities of waste to be disposed, leading to some issues in terms of ecological impact and operator safety. In this context, greening HPLC methods is becoming highly desirable. One strategy to reduce the impact of hazardous solvents is to replace classically used organic solvents (i.e., acetonitrile and methanol) with greener ones. So far, ethanol has been the most often used alternative organic solvent. Others strategies have followed, such as the use of totally aqueous mobile phases, micellar liquid chromatography, and ionic liquids. These approaches have been well developed, as they do not require equipment investments and are rather economical. This review describes and critically discusses the recent advances in greening RP-HPLC methods dedicated to pharmaceutical analysis based on the use of alternative solvents.

Two LC methods were developed for the achiral and chiral reversed-phase (RP) analysis of an amino acid (AA) pool in a food supplement, in compliance with the main paradigms of Green Chromatography. A direct achiral ion-pairing RP-HPLC method was optimized under gradient conditions with a water-ethanol (EtOH) eluent containing heptafluorobutyric acid (0.1%, v/v), to quantify the eight essential AAs (Ile, Leu, Lys, Met, Phe, Thr, Trp, and Val) contained in the food supplement. Thus, the usually employed acetonitrile was profitably substituted with the less toxic and more benign EtOH. The method was validated for Leu and Phe. The chiral LC method performed with a teicoplanin chiral stationary phase was developed with a water-EtOH (60:40, v/v) eluent with 0.1%, v/v acetic acid. The enantioselective analysis was carried out without any prior derivatization step. Both developed methods performed highly for all eight AAs and revealed that: (i) the content of six out of eight AAs was consistent with the manufacturer declaration; (ii) only L-AAs were present. Furthermore, it was demonstrated that a two-dimensional achiral–chiral configuration is possible in practice, making it even more environmentally sustainable. A molecular modelling investigation revealed interesting insights into the enantiorecognition mechanism of Lys.

A green liquid chromatographic method is considered in this work to minimize the environmental impact of waste solvents. One important principle is to replace or eliminate the use of hazardous organic solvents. Organic impurities in any active pharmaceutical ingredient could arise either during the process of its synthesis, or as degradation products developed throughout the shelf-life. Remdesivir (RDS) is an antiviral drug, approved by the US Food and Drug Adminstration (-FDA), to treat SARS-Cov-2 virus during its pandemic crisis. We studied the stability of remdesivir against several degradation pathways using the organic solvent-free liquid chromatographic technique. Separation was performed on RP-C18 stationary phase using mixed-micellar mobile phase composed of a mixture of 0.025 M Brij-35, 0.1 M sodium lauryl sulfate (SLS), and 0.02 M disodium hydrogen phosphate, adjusted to pH 6.0. The mobile phase flow rate was 1 mL min−1, and detection was carried out at a wavelength of 244 nm. We profiled the impurities that originated in mild to drastic degradation conditions. The method was then validated according to International Conference of Harmonization (ICH) guidelines within a linearity range of 5–100 μg mL−1 and applied successfully for the determination of the drug in its marketed dosage form. A brief comparison was established with reported chromatographic methods, including a greenness assessment on two new metrics (GAPI and AGREE). This study is the first to be reported as eco-friendly, solvent-free, and stability indicating LC methodology for RDS determination and impurity profiling.

A multiple heart-cutting (mLC-LC) two-dimensional HPLC-UV achiral–chiral method for the direct analysis of branched-chain amino acids (BCAAs) in food supplements under environmentally friendly conditions was developed to cope with the very well-known limited chemoselectivity of chromatographic media for enantioselective analysis. Both achiral and chiral methods were developed in compliance with the main principles of green chromatography. The achiral analysis was performed isocratically with an optimized ion-pair reversed-phase (IP-RP) method based on a water/EtOH (95:5, v/v) mobile phase containing heptafluorobutyric acid (7 mM) as the IP agent. The achiral method was characterized by a very appreciable performance and was validated before the analysis of the real sample. High recovery values for all compounds (from 97% to 101%) were found in the interday evaluation. Additionally, low RSD% values in the long-term period were measured, in the range between 1.1% and 4.8%. Still, an LOQ value of 0.06 mg/mL was established for all compounds. The quantitative analysis of a commercial food supplement revealed that BCAAs were present in amounts very close to those declared by the producer. The enantioselective analysis was carried out through the application of the chiral ligand-exchange chromatography (CLEC) approach, using O-benzyl-(S)-serine ((S)-OBS, 0.5 mM) as the chiral selector and Cu(II) nitrate (0.25 mM) as the metal source in the eluent. Resolution and separation factor values up to 2.31 and 1.43, respectively, were obtained. The two chromatographic systems were connected through a six-port switching valve, and the developed two-dimensional mLC-LC method confirmed the absence of D-enantiomers of BCAAs in the food supplement, as reported in the manufacturer’s label.

It was found experimentally that the replacement of acetonitrile with ethanol upon the acidification of the mobile phase with phosphoric acid is an effective version for replacing acetonitrile. At that, the order of elution of glycosides of the same type of the five main anthocyanidins (delphinidin, cyanidin, petunidin, peonidin, and malvidin) does not change in eluents convenient for analysis, and the range of retention times for a complete set of such anthocyanins becomes noticeably narrower in going from acetonitrile to ethanol. To determine the effect of aglycone structure on the retention of derivatives of the same anthocyanidin (cyanidin), a mixture of six glycosides was used: one monoglycoside (3-glucoside), two 3-diglycosides (sophoroside and sambubioside), and two 3-triglycosides (2\"-glucosylrutinoside and 2\"-xylosylrutinoside). This mixture is a real set of anthocyanins, requiring the careful selection of the mobile phase for separating all components. In this work, based on an analysis of separation maps, the composition of a mobile phase based on ethanol is determined that ensures the achievement of the effective separation of these anthocyanins.

This study presents an innovative method for caffeine determination in tea, employing ethanol as the sole organic solvent for both SPE sample preparation and chromatographic analysis. This approach aligns with green chemistry principles, as confirmed by a comparative study highlighting ethanol’s safety and eco-friendliness compared to traditional solvents. The experiments validate ethanol’s efficacy in caffeine extraction and chromatographic analysis, minimizing environmental impact and eliminating toxicity risks. Utilizing a reduced chromatography column enhances the method’s efficiency and sustainability, resulting in a low limit of quantitation (0.125 μg/mL) and good reproducibility (RSD < 2.5%). Based on tea from the Polish market, the findings reveal the caffeine content (19.29–37.69 mg/g) and endorse ethanol’s role in enhancing sustainable chemical analysis in food science.

This review focuses on the fundamentals of stimuli-responsive materials and their applications to three common separation techniques, namely extraction, chromatography, and electrophoresis. Although still little investigated, materials that switch their affinity for the analyte on and off as a function of tiny changes in physical and biochemical variables offer relevant advantages for analyte extraction, concentration, and separation. Temperature and/or pH-responsive polymers in the form of chains or networks, which are dispersed in the sample as free entities or after being grafted onto beads (which may incorporate magnetic cores), enable quantitative capture and/or elution of the analyte under mild conditions and without needing organic solvents. Regarding liquid-chromatography separation, responsive stationary phases enable the implementation of “all-in-water” procedures in which retention times are modulated by means of temperature or pH gradients. Other stimuli that can be externally applied, for example light or magnetic fields, can also be used for efficient extraction or separation of the target substance without altering the composition of the sample matrix. Moreover, stimuli-responsiveness enables straightforward recycling of solid and/or stationary phases for a prolonged lifetime. Improved understanding of the phase transitions of stimuli-responsive materials and design of suitable formats for analytical applications should enable wider and more successful application of stimuli-responsive materials in analytical separations.