## 1 Introduction  
The development of analytical methods for quantitative analyses in environmental water, biological sample matrices, and in food or food supplements with a reduced amount of toxic solvents, and the replacing with non-toxic ones, without loss of efficacy in the extraction procedure, are important aims for contemporary researchers [1; 2]. These aspects are deeply valued during method development and validation in all fields [3].  
Often, these aspects lead to the development of new approaches for analyte extraction and clean-up involved in the development of better sorbent coating technology for solid phase microextraction and stir bar sorptive extraction. The use of novel devices, like packed sorbent (in microextraction by packed sorbent, MEPS), fabric phase sorptive extraction media (in fabric phase sorbent extraction, FPSE), and imprinted polymer (in molecularly imprinted polymer extraction), as well as the use of combined strategies with magnetic elements, can enhance the efficiency and the recovery of the target analyte.  
Liquid phase microextraction methods have demonstrated important innovations for the extraction and pre-concentration of analytes from different matrices. Dispersive liquid-liquid microextraction (DLLME) and its modifications, such as ultrasound-assisted DLLME (UA-DLLME), ionic liquid-based dispersive liquid-liquid microextraction (IL-DLLME), deep eutectic solvent-based dispersive liquid-liquid microextraction (DES-DLLME), and sugaring-out assisted liquid-liquid extraction (SULLE), can offer unique benefits, such as a high pre-concentration factor for the target analytes, low cost, simplicity and combined use with almost every analytical measurement technique [4].  
A large number of solvent microextraction techniques, including single-drop microextraction, DLLME, and liquid-phase microextraction (LPME), have been reported. Implementation of these techniques can vary widely, but common features remain the same, including the use of only a small amount of organic solvents and a high sample-to-acceptor volume ratio. The organic phase, which extracts and pre-concentrates the target analyte(s), can be used for quantification by means of different types of instrument configurations [5]. LPME is usually performed to analyze water samples or aqueous solutions. Analysis of solid samples is commonly done in two steps: the solid sample is converted to aqueous solution using a suitable pretreatment procedure, and then the LPME is applied. Direct analysis of solid samples is somewhat exceptional, rather than common. Several works have been reported for the determination of different analytes in complex matrices, such as phenolic compounds in plant materials [6] and food samples [7; 8] by using DLLME in combination with High Performance Liquid Chromatography-UltraViolet/Visible detector (HPLC-UV/Vis) [6] and Gas Chromatography-Mass Spectrometry detector (GC-MS) [7] instrument configurations.  
Replacing hazardous solvents with ionic liquids (IL) or natural deep eutectic solvents (NADES) is another important task available in DLLME, and was recently reviewed by [PERSON] and co-workers [9]. It is possible to modify the IL's properties depending on the analytical purpose, due to the cation's fine structure and the anion's identity [10], but high cost and toxicity remain as the main disadvantages [11]. Recently, NADESs have been rapidly developed as a new type of green solvents, as an alternative to ILs. NADESs are based on primary metabolites, such as organic acids, amino acids and sugars, but limited data are available for these solvents' properties.  
The aim of this review is to report the recently applied protocols and devices used in the extraction (and clean-up) procedures for quantitative analyses in complex matrices, with the main goal being the reduction of time, sample manipulation, solvent consumption and use of non-toxic solvents, in accordance with Green Analytical Chemistry (GAC) concepts.