Use of green alternative solvents in dispersive liquid-liquid microextraction: A review

Dispersive liquid-liquid microextraction is one of the most widely used microextraction techniques currently in the analytical chemistry field, mainly due to its simplicity and rapidity. The operational mode of this approach has been constantly changing since its introduction, adapting to new trends and applications. Most of these changes are related to the nature of the solvent employed for the microextraction. From the classical halogenated solvents (e.g., chloroform or dichloromethane), different alternatives have been proposed in order to obtain safer and non-pollutants microextraction applications. In this sense, low-density solvents, such as alkanols, switchable hydrophobicity solvents, and ionic liquids were the first and most popular replacements for halogenated solvents, which provided similar or better results than these classical dispersive liquid-liquid microextraction solvents. However, despite the good performances obtained with low-density solvents and ionic liquids, researchers have continued investigating in order to obtain even greener solvents for dispersive liquid-liquid microextraction. For that reason, in this review, the evolution over the last five years of the three types of solvents already mentioned and two of the most promising solvent alternatives (i.e., deep eutectic solvents and supramolecular solvents), have been studied in detail with the purpose of discussing which one provides the greenest alternative.     

Solvent terminated natural deep eutectic solvent microextraction for concentration of curcuminoids in Curcumae Longae Rhizoma and turmeric tea

A novel solvent terminated microextraction method based on a natural deep eutectic solvent (L-menthol and lactic acid at a molar ratio of 1:2) coupled with high-performance liquid chromatography was proposed, which was utilized for the separation and enrichment of bisdemethoxycurcumin, demethoxycurcumin and curcumin in Curcumae Longae Rhizoma and turmeric tea. The effects of independent parameters on extraction efficiency were optimized by single-factor analysis. Subsequently, four predominated parameters affecting the extraction procedure, including extractant volume, salt concentration, demulsifier consumption, and demulsification time, were further evaluated by a central composite design. Under the optimized conditions, the linear ranges of calibration curves were 0.005–0.5 μg/mL for bisdemethoxycurcumin, 0.004–0.4 μg/mL for demethoxycurcumin, and 0.0045–0.45 μg/mL for curcumin, respectively. In addition, the developed method provided low detection limits (0.1–0.4 ng/mL) and high enrichment factors (279–350). Its intra-day and inter-day precision were carried out by relative standard deviation ranging from 2.2 to 9.2%. Finally, the applicability of this method was assessed by the analysis of Curcumae Longae Rhizoma and turmeric tea samples. The results showed that these samples were detected successfully and the spiked recoveries over the range of 85.3-108.9% with relative standard deviations of 1.6-8.9% were attained, indicating its high relative recoveries with good precision in real sample analysis.     

Analysis of tamoxifen and its main metabolites in plasma samples of breast cancer survivor female athletes: Multivariate and chemometric optimization

A sensitive method based on liquid chromatography combined with a diode array detector was developed and validated to simultaneously determine tamoxifen, and its active metabolites N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen in human plasma samples. The green and sustainable vortex-assisted dispersive liquid-phase microextraction technique based on the natural hydrophobic deep eutectic solvent was used for the extraction and preconcentration of the analytes. Chemometrics and multivariate analysis were used to optimize the independent variables including the type and volume of deep eutectic solvent, extraction time, and ionic strength. Under optimal conditions, calibration curves were linear in a suitable range with the lower limits of quantification (0.8–10.0 μg/L), which covered the relevant concentrations of the analytes in plasma samples for a clinical study. Intra- and interday precision evaluated at three concentrations for the analytes were lower than 8.2 and 12.1%, respectively. Accuracy was in the range of 94.9–104.7%. The applicability of the developed method on human plasma samples illustrated the range 45.1–72.8, 98.4–128.3, 0.9–1.2, and 2.7–6.1 μg/L for tamoxifen, N-desmethyltamoxifen, 4-hydroxytamoxifen, and endoxifen, respectively. The validated method can be effective for the pharmacokinetics, pharmacodynamics, and therapeutic drug monitoring studies of tamoxifen and its main metabolites in biological fluids.     

Solubility and Stability of Some Pharmaceuticals in Natural Deep Eutectic Solvents-Based Formulations

Some medicines are poorly soluble in water. For tube feeding and parenteral administration, liquid formulations are required. The discovery of natural deep eutectic solvents (NADES) opened the way to potential applications for liquid drug formulations. NADES consists of a mixture of two or more simple natural products such as sugars, amino acids, organic acids, choline/betaine, and poly-alcohols in certain molar ratios. A series of NADES with a water content of 0–30% (w/w) was screened for the ability to solubilize (in a stable way) some poorly water-soluble pharmaceuticals at a concentration of 5 mg/mL. The results showed that NADES selectively dissolved the tested drugs. Some mixtures of choline-based NADES, acid-neutral or sugars-based NADES could dissolve chloral hydrate (dissociated in water), ranitidine·HCl (polymorphism), and methylphenidate (water insoluble), at a concentration of up to 250 mg/mL, the highest concentration tested. Whereas a mixture of lactic-acid–propyleneglycol could dissolve spironolacton and trimethoprim at a concentration up to 50 and 100 mg/mL, respectively. The results showed that NADES are promising solvents for formulation of poorly water-soluble medicines for the development of parenteral and tube feeding administration of non-water-soluble medicines. The chemical stability and bioavailability of these drug in NADES needs further studies.     

Microwave-Assisted One-Pot Lipid Extraction and Glycolipid Production from Oleaginous Yeast Saitozyma podzolica in Sugar Alcohol-Based Media

Glycolipids are non-ionic surfactants occurring in numerous products of daily life. Due to their surface-activity, emulsifying properties, and foaming abilities, they can be applied in food, cosmetics, and pharmaceuticals. Enzymatic synthesis of glycolipids based on carbohydrates and free fatty acids or esters is often catalyzed using certain acyltransferases in reaction media of low water activity, e.g., organic solvents or notably Deep Eutectic Systems (DESs). Existing reports describing integrated processes for glycolipid production from renewables use many reaction steps, therefore this study aims at simplifying the procedure. By using microwave dielectric heating, DESs preparation was first accelerated considerably. A comparative study revealed a preparation time on average 16-fold faster than the conventional heating method in an incubator. Furthermore, lipids from robust oleaginous yeast biomass were successfully extracted up to 70% without using the pre-treatment method for cell disruption, limiting logically the energy input necessary for such process. Acidified DESs consisting of either xylitol or sorbitol and choline chloride mediated the one-pot process, allowing subsequent conversion of the lipids into mono-acylated palmitate, oleate, linoleate, and stearate sugar alcohol esters. Thus, we show strong evidence that addition of immobilized Candida antarctica Lipase B (Novozym 435^®), in acidified DES mixture, enables a simplified and fast glycolipid synthesis using directly oleaginous yeast biomass.     

Hybrid process for texturization of diamond wire sawn multicrystalline silicon solar cell

Acid texture is difficult for diamond wire sawn (DWS) multicrystalline silicon (mc‐Si) wafer owing to the inhomogeneous distribution of damage layer on the surface. In this article, metal‐assisted chemical etching (MACE) has been selected for introducing a porous seeding layer to induce acid texturing etching. SEM results show that the oval pit structures coverage get obvious improvement even on the smooth areas. Owing to the further improved light absorption ability by second MACE and nanostructure rebuilding (NSR) process, nanostructured DWS mc‐Si solar cell has exhibited a conversion efficiency of 17.96%, which is 0.45% higher than that of DWS wafer with simple acid texture process. (© 2016 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)     

Multi‐crystalline silicon solar cells with metal‐assisted nano‐texturing using HNO3 as hole injection agent

In this study, metal‐assisted etching (MAE) with nitric acid (HNO₃) as a hole injecting agent has been employed to texture multi‐crystalline silicon wafers. It was previously proven that addition of HNO₃ enabled control of surface texturing so as to form nano‐cone shaped structures rather than nanowires. The process parameters optimized for optically efficient texturing have been applied to multi‐crystalline wafers. Fabrication of p‐type Al:BSF cells have been carried out on textured samples with thermal SiO₂/PECVD‐SiN_x stack passivation and screen printed metallization. Firing process has been optimized in order to obtain the best contact formation. Finally, j_sc enhancement of 0.9 mA/cm² and 0.6% absolute increase in the efficiency have been achieved. This proves that the optimized MAE texture process can be successfully used in multi‐crystalline wafer texturing with standard passivation methods.

J –V curves and SEM images of the nano and iso‐textured samples. j_sc enhancement of 0.9 mA/cm² together with 0.6% absolute efficiency gain was observed on nano‐textured samples.     

One-pot rapid synthesis of 4H-1-benzopyran derivatives in a deep eutectic solvent

A method for introducing a biologically active heterocycle, 2-methylquinoline into the 4-position of a 2-amino-4H-1-benzopyran skeleton is described. Choline chloride/glucose (1:1 molar ratio) was used as both the solvent and catalyst in the reaction of a salicylaldehyde, methylquinoline, and cyanoacetate to obtain 2-amino-4H-1-benzopyran derivatives in 48%–80% yields after short reaction times. The effects of the deep eutectic solvent type, substrate molar ratio, cosolvent, temperature, and reaction time were examined. The method has the advantages of simple steps, environmental friendliness, mild conditions, and wide substrate applicability. This is the first attempt to synthesize methylquinoline derivatives of 4H-1-benzopyran.     

Relation between light trapping and surface topography of plasma textured crystalline silicon wafers

Currently, in the photovoltaic industry, wet chemical etching technologies are used for saw damage removal and surface texturing. Alternative to wet chemical etching is plasma etching. However, as for example, the linear microwave plasma technique, developed by Roth&Rau, has not been implemented in the photovoltaic industry for etching, because of the very low etch rate (<1 µm/min) and the high cost of ownership related to the etching process. In this study, different front surface textured crystalline silicon wafers obtained by means of the linear microwave plasma technique and the expanding thermal plasma technique are investigated in terms of weighted reflection by using reflectometry (250–1200 nm) to study the optical properties of the textures in detail. In addition, atomic force microscopy is used to measure the surface topography to determine statistical roughness parameters, as presented in this paper. Effective light trapping can be obtained by multiple reflections as well as by a graded layer, which leads to a diffuse front surface, or a combination of both. A graded layer can be described as a smooth transition with increasing refractive index from air to silicon with typical thickness of (200 ± 50) nm. We have found that the average plane tilt angle correlates to the measured weighted reflection. Moreover, we can determine from the aspect ratio whether the light trapping is effective by multiple reflections. From the roughness exponent, which is a measure for the micro roughness, we can determine whether the light trapping is effective by a graded layer. Copyright © 2013 John Wiley & Sons, Ltd.     

Excellent passivation of thin silicon wafers by HF‐free hydrogen plasma etching using an industrial ICPECVD tool

In this work, hydrogen plasma etching of surface oxides was successfully accomplished on thin (～100 µm) planar n‐type Czochralski silicon wafers prior to intrinsic hydrogenated amorphous silicon [a‐Si:H(i)] deposition for heterojunction solar cells, using an industrial inductively coupled plasma‐enhanced chemical vapour deposition (ICPECVD) platform. The plasma etching process is intended as a dry alternative to the conventional wet‐chemical hydrofluoric acid (HF) dip for solar cell processing. After symmetrical deposition of an a‐Si:H(i) passivation layer, high effective carrier lifetimes of up to 3.7 ms are obtained, which are equivalent to effective surface recombination velocities of 1.3 cm s^–1 and an implied open‐circuit voltage (V_oc) of 741 mV. The passivation quality is excellent and comparable to other high quality a‐Si:H(i) passivation. High‐resolution transmission electron microscopy shows evidence of plasma‐silicon interactions and a sub‐nanometre interfacial layer. Using electron energy‐loss spectroscopy, this layer is further investigated and confirmed to be hydrogenated suboxide layers. (© 2015 WILEY‐VCH Verlag GmbH &Co. KGaA, Weinheim)