Spontaneous Formation of Uniform Cell-Sized Microgels through Water/Water Phase Separation.

In this study, a one-step method is discussed for producing uniform cell-sized microgels using glass capillaries filled with a binary polymer blend of polyethylene glycol (PEG) and gelatin. Upon decreasing temperature, phase separation of the PEG/gelatin blends and gelation of gelatin occur, and then the polymer blend forms linearly aligned, uniformly sized gelatin microgels in the glass capillary. When DNA is added to the polymer solution, gelatin microgels entrapping DNA are spontaneously formed, and the DNA prevents the coalescence of the microdroplets even at temperatures above the melting point. This novel method to form uniform cell-sized microgels may be applicable to other biopolymers. This method is expected to contribute to diverse materials science via biopolymer microgels and biophysics and synthetic biology through cellular models containing biopolymer gels.

Development of tLyP-1 functionalized nanoliposomes with tunable internal water phase for glioma targeting.

tLyP-1 peptide is verified to recognize neuropilin (NRP) receptors overexpressed on the surface of both glioma cells and endothelial cells of angiogenic blood vessels. In the present study, tLyP-1 was conjugated with DSPE-PEG2000 to prepare tLyP-1-DSPE-PEG2000, which was further employed to prepare tLyP-1 functionalized nanoliposome (tLyP-1-Lip) to achieve enhancing target of glioblastoma. Process parameters were systematically studied to investigate the feasibility of tuning the internal water phase of nanoliposomes and encapsulating more Temozolomide (TMZ). The particle size, Zeta potential, and encapsulation efficiency of tLyP-1-Lip/TMZ were fully characterized in comparison with conventional nanoliposomes (Lip-TMZ) and PEGylated nanoliposomes (PEG-Lip/TMZ). The release behaviors of TMZ from PEG-Lip/TMZ and tLyP-1-Lip/TMZ are similar and slower than TMZ-Lip in acidic solutions. The tLyP-1-Lip/TMZ demonstrated the strongest cytotoxicity in comparison with TMZ-Lip and PEG-Lip/TMZ in both U87 and HT22 cells, and displayed the highest cellular internalization. The pharmacokinetic studies in rats revealed that tLyP-1-Lip/TMZ showed a 1.4-fold (p < 0.001) increase in AUCINF_obs and a 1.4-fold decrease (p < 0.01) in clearance compared with PEG-Lip/TMZ. We finally confirmed by in vivo imaging that tLyP-1-Lip were able to penetrate the brains and tumors of mice.

The Nature of Hydrogen Adsorption on Platinum in the Aqueous Phase.

The thermodynamic state of H2 adsorbed on Pt in the aqueous phase was determined by kinetic analysis of H2 reacting with D2 O to HDO, HD, and D2 , and by DFT-based ab initio molecular dynamics simulations of H2 adsorption on Pt(111), Pt(110), and Pt nanoparticles. Dissociative adsorption of H2 on Pt is significantly weakened in the aqueous phase compared to adsorption at gas-solid interfaces. Water destabilizes the adsorbed H atoms, decreasing the heat of adsorption by 19-22 kJ m o l H 2 - 1 while inducing an additional entropy loss of 50-70 J m o l H 2 - 1 K-1 . Upon dissociative adsorption of H2 , the average distance of water from the Pt surface increases and the liquid adopts a structure that is more ordered than before close to the Pt surface, which limits the translation mobility of the adsorbed H atoms. The presence of hydrated hydronium ions next to the Pt surface further lowers the H-Pt bond strength.

The Finite Element Analysis for a Mini-Conductance Probe in Horizontal Oil-Water Two-Phase Flow.

Oil-water two-phase flow is widespread in petroleum industry processes. The study of oil-water two-phase flow in horizontal pipes and the liquid holdup measurement of oil-water two-phase flow are of great importance for the optimization of the oil production process. This paper presents a novel sensor, i.e., a mini-conductance probe (MCP) for measuring pure-water phase conductivity of oil-water segregated flow in horizontal pipes. The MCP solves the difficult problem of obtaining the pure-water correction for water holdup measurements by using a ring-shaped conductivity water-cut meter (RSCWCM). Firstly, using the finite element method (FEM), the spatial sensitivity field of the MCP is investigated and the optimized MCP geometry structure is determined in terms of the characteristic parameters. Then, the responses of the MCP for the oil-water segregated flow are calculated, and it is found that the MCP has better stability and sensitivity to the variation of water-layer thickness in the condition of high water holdup and low flow velocity. Finally, the static experiments for the oil-water segregated flow were carried out and a novel calibration method for pure-water phase conductivity measurements was presented. The validity of the pure-water phase conductivity measurement with segregated flow in horizontal pipes was verified by experimental results.

Microstructure-dependent CO2-responsive microemulsions for deep-cleaning of oil-contaminated soils.

CO2-responsive microemulsion (ME) is considered a promising candidate for deep-cleaning and oil recovery from oil-contaminated soils. Understanding the responsive nature of different microstructures (i.e., oil-in-water (O/W), bicontinuous (B.C.) and water-in-oil (W/O)) is essential for unlocking the potential and mechanisms of CO2-responsive emulsions in complex multiphase systems and providing comprehensive guidance for remediation of oil-contaminated soils. Herein, the responsiveness of microstructures of ME to CO2 trigger was investigated using experimental designs and coarse-grained molecular dynamic simulations. MEs were formed for the first time by a weakly associated pseudo-Gemini surfactant of indigenous organic acids (naphthenic acids, NAs are a class of natural surface-active molecules in crude oil) and tetraethylenepentamine (TEPA) through fine tuning of co-solvent of dodecyl benzene sulfonic acid (DBSA) and butanol. The O/W ME exhibited an optimal CO2-responsive character due to easier proton migration in the continuous aqueous phase and more pronounced dependence of configuration on deprotonated NA ions. Conversely, the ME with W/O microstructure exhibited a weak to none responsive characteristic, most likely attributed to its high viscosity and strong oil-NA interactions. The O/W ME also showed superior cleaning efficiency and oil recovery from oil-contaminated soils. The results from this study provide insights for the design of CO2-responsive MEs with desired performance and guidance for choosing the favorable operating conditions in various industrial applications, such as oily solid waste treatment, enhanced oil recovery (EOR), and pipeline transportation. The insights from this work allow more efficient and tailored design of switchable MEs for manufacturing advanced responsive materials in various industrial sectors and formulation of household products.

Coconut shell-derived activated carbon-enhanced water phase change material for cold thermal energy storage.

In building cooling, the demand for cooling surges during specific times, stressing air-conditioner operation, and additional cooling is often wasted during low-demand periods. Water-phase change material (W-PCM)-based thermal energy storage (TES) allows for load shifting and effective management of peak demand by storing cooling energy when the demand is low. This stored energy can be deployed during peak hours, decreasing energy usage and associated CO2 emissions. However, the use of W-PCMs was hindered by phase separation, slow energy transfer, and high supercooling degree (SCD). We synthesized coconut shell (CNS)-produced activated carbon (ACC) to use as a thermal enhancer in W-PCMs for the first time. First, ACC was synthesized from CNS via steam activation. Then, transmission electron microscopy was used to confirm the pore morphology of the CNS-ACC. The synthesis of the W-PCM with various weight percentages (0.1, 0.6, and 1.2) of CNS-ACC was accomplished in two steps. Zeta potential distribution analysis revealed that the W-PCM with CNS-ACC exhibited colloidal stability. Thermal conductivity (TC) and thermogram analyses revealed that a dose of 1.2 wt% CNS-ACC enhanced liquid and solid TC by 9% and 22%, respectively, despite a 6% and 8% decrease in specific heat and latent heat. More specifically, solidification assessment in a spherical enclosure revealed 100% suppression of SCD with 1.2 wt% CNS-ACC. As a result of this and the enhanced TC, the overall solidification process was accelerated, reducing the overall duration by 18.5%. Thus, the combination of CNS-derived ACC and W-PCM for TES in building cooling could reduce energy consumption and associated CO2 emissions.

Dual-template hydrophilic imprinted resin as an adsorbent for highly selective simultaneous extraction and determination of multiple trace plant growth regulators in red wine samples.

In recent years, numerous plant growth regulators have been found in foods and have a toxicity to human health, so its simultaneous multiple monitoring is urgently. For the first time, a rapid, accurate, and high-selective method was established to extract and determine multiple plant growth regulators simultaneously in red wines using a new dual-template hydrophilic molecularly imprinted resin (DHMIR) as an adsorbent of pipette tip solid-phase extraction coupled with HPLC. The as-prepared DHMIR combined the advantages of the hydrophilicity of hydrophilic resin and multi-imprinted recognition of dual-template molecular imprinting, overcoming the poor imprinted recognition ability of traditional imprinting materials in water and low extraction efficiency to multiple targets. Under the optimized conditions, the proposed method exhibited high sensitivity (2.29-3.94 ng mL-1) and recoveries (80.9-109.0 %) using only 15 mg DHMIR. This study provides an effective strategy for rapid, accurate, low-cost, and high-selective determination of the multiple analytes in food samples.

Paddling time parameters and paddling efficiency with the increase in stroke rate in kayaking.

The paddling stroke rate (SR) is one of the key determinants of flat water kayak performance. The aim of this study was to analyse the way in which the kayak paddler changes the duration of the water and aerial phases due to the increase in stroke rate. Ten elite kayak paddlers (five males and five females) were analysed performing 200 m on-water trials in an individual kayak (K1), at four different stroke rates (60, 80, 100 strokes per minute and race pace). The duration of the water and aerial phases, SR and impulse were computed based on the data collected using the FPaddle system. Results corroborate the importance of reaching higher SR to increase kayak velocity (r = 0.904, p < 0.001). Both water and aerial phase durations correlated negatively with SR (r = -0.929, p < 0.001; R = -0.909, p < 0.001, respectively). However, with the first, the correlation was linear (r2 = 0.883), and for the second, the trend of relationship was curvilinear (r2 = 0.893). Due to differences in correlation, the results suggest that at high SR (above 120 strokes per minute) to continue increasing SR it will be more productive to reduce the duration of the water phase.

Computational Insights into the Esterification of Palmitic Acid with Methanol in Water.

This work provides quantified explanations for the thermodynamic and kinetic characteristics of esterification in aqueous phase, and how phase transfer catalysts improve water phase esterification of fatty acids in a computational-experimental way. Self-catalyzed reaction mode with or without solvation effects, water participated reaction mode, and catalytic reaction mode (catalyzed by p-dodecyl benzene sulfonic acid, DBSA) are discussed. Our results show that the initial self-catalytic reaction mode undergoes the energy barrier of 100.1 kJ/mol, and rises to 148.9 kJ/mol when water molecule is involved, which hinders the esterification reaction. With the DBSA catalyst, this energy barrier will drop to 97.5 kJ/mol and the water phase esterification is successfully promoted with the yield of 81%. The key kinetic factor of binding energy is discussed as that water molecule has a strong reactant binding competitiveness (with the binding energy of -57.9 kJ/mol, and the value for the non-aqueous phase mode is 3.0 kJ/mol) and DBSA has the binding energy with the value of -45.3 kJ/mol, so it can compete with water to form reactant complexes. This work is a successful practice of a computation-experiment combined scheme, and provides a quantitative basis for the improvement of phase transfer catalysts on water phase esterification reactions. The calculation mode and method of aqueous esterification make it possible to convert bio-based fatty acids into fatty acid esters in fermentation broth.

Meso- and Macro-Mechanical Analysis of the Frost-Heaving Effect of Void Water on Asphalt Pavement.

In cold regions, many types of structural damages are caused by the frost heaving of asphalt pavements. Hence, it is important to quantitatively determine the frost-heaving effect of asphalt pavement using a mechanical method to control frost-heaving damage. In this study, first, the internal voids of the asphalt mixture were regarded as a single void, and the water phase transition generating the freezing water in the voids was simulated using a simplified hollow sphere model to create a uniform internal pressure. Second, the prediction equation of the equivalent linear expansion coefficient was proposed by taking the phase transition of water in the saturated asphalt mixture voids into account. A step function was used during the phase transition of water to determine the sudden change in the equivalent linear expansion coefficient, heat capacity, density, and thermal conductivity. Finally, the typical cooling conditions were simulated with the water phase transition and the nonwater phase transition. The experimental results showed that the proposed model could accurately simulate the effect of frost heaving. Higher stress and strain were generated on the surface and in the interior of the pavement, and the positions of maximum stress and strain occurred on the pavement surface under the frost-heaving conditions. The compressive strength of the asphalt mixture in a uniaxial compression test is about 4.5-6 MPa with a single freeze-thaw cycle. Furthermore, when frost heaving occurs on the asphalt pavement between 5.8 and 6.5 MPa, the numerical simulation method can be used to calculate the internal stress of the structure, which found that the compressive stress under the frost-heaving condition was the same magnitude as the compressive strength under the freeze-thaw testing condition.

Spatiotemporal distribution and mass loading of organophosphate flame retardants (OPFRs) in the Yellow River of China (Henan segment).

During three sampling periods in 2014, systematic investigations were conducted into contamination profiles of ten organophosphate flame retardants (OPFRs) in both suspended particulate phase and water phase in the Yellow River (Henan Area). This research shows that OPFRs exist at lower concentrations in the suspended phase than in the water phase. The median concentration of 10 OPFRs (∑10OPFRs) in the suspended particulate phase was 62.5 ng/g (fluctuating from ND to 6.17 × 103 ng/g, dw), while their median concentration in the water phase was 109 ng/L (fluctuating from 35.6 to 469 ng/L). Among the selected 10 OPFRs, triethylphosphate (TEP), tris(1-chloro-2-propyl) phosphate (TCPP), and tris(2-chloroethyl) phosphate (TCEP) were the predominant compounds in the water phase (occupying 91.6% of the ∑10OPFRs), while TCPP, TCEP, and tri-o-tolyl phosphate (o-TCP) were the most common in the suspended particulate phase, accounting for 90.1% of the ∑10OPFRs. Across the three sampling periods, there was no significant seasonable variation for OPFRs either in the water phase or in the suspended particulate phase, except for TCEP and TCPP in the water phase. Compared with research findings relating to concentrations of OPFRs around China and abroad, the OPFRs of the Yellow River (Henan Area) in the water phase were at a moderate level. Suspended particles (SS) had a very important impact on the transportation of OPFRs in the studied area, with about 83.9% of ∑10OPFRs inflow attributed to SS inflow and about 81.7% of ∑10OPFRs outflow attributed to SS outflow. The total annual inflow and outflow of OPFRs were 7.72 × 104 kg and 6.62 × 104 kg in the studied area, respectively.

CO2-responsive O/W microemulsions prepared using a switchable superamphiphile assembled by electrostatic interactions.

A CO2-responsive superamphiphile was designed to form switchable O/W microemulsions of rapid switching responses. The linear structured superamphiphile was assembled via electrostatic interactions between anionic oleic acid and cationic Jeffamine D-230 at a mole ratio of 1:1. Addition of the CO2-responsive superamphiphile and 1-butanol as a co-surfactant led to the spontaneous formation of stable heptane-in-water microemulsions. Treating this stable microemulsion with CO2 for 20 s caused dissociation of the superamphiphile into interfacial inactive components, leading to a complete phase separation of the microemulsion into immiscible oil and water phases. Removing the CO2 from the system by N2 sparging at 60 °C for 10 min converted the phase-separated system into a transparent microemulsion as a result of the in situ formation of the superamphiphile. Compared with the results from previous studies, the O/W microemulsion formed using the current superamphiphile with the co-addition of 1-butanol featured not only a unique thermodynamical stability of nano-sized droplets, but also a desired response to CO2 to achieve a rapid and complete phase separation, and re-microemulsification as desired with N2 sparging, making this CO2-responsive O/W microemulsion a promising candidate for applications such as nanomaterial synthesis, enhanced oil recovery and soil remediation.

Distribution of bioactive factors in human milk samples.

Background: Breast milk provides nutrition for infants and also contains a variety of bioactive factors that influence the development of the newborn. Human milk is a complex biological fluid that can be separated into different layers (water phase and lipid phase with its component water and lipid fractions). It can affect the developing human body along the whole length of the gastrointestinal tract, and through the circulation, its factors may reach every organ. Methods: In the present study, we analyzed milk samples collected monthly for 6 months from 16 mothers from the 4th week postpartum between 2014 and 2016 in Baranya County, Hungary. The 96 samples provided us information about the fluctuation of certain bioactive factors during the first 6 months of lactation. We investigated with Luminex technology the concentrations of several cytokines (CD40, Flt-3L), chemokines (MCP-1, RANTES, GRO, MIP-1ß, MDC, eotaxin, fractalkine), and epidermal growth factor (EGF). Paired t-tests and one-way ANOVA followed by Bonferroni post-hoc tests were used to compare the data. Results: We detected the presence of each bioactive factor in every layer of the milk samples during the first 6 months of breastfeeding in widespread concentration ranges. In the case of GRO, MIP-1ß, MDC, Flt-3L, fractalkine, and eotaxin, the concentrations were constant during the first 6 months of lactation. The water phase of human milk contained higher factor concentrations compared to both fractions of the lipid phase for most factors (except eotaxin and MIP-1ß). The concentrations of CD40, EGF, MCP-1, and RANTES in the first 3 months were significantly different compared to the values detected between 4th and 6th months. In the water phase, the level of MCP-1 was significantly decreased, while all of the other factors increased during the 4th through 6th months. We found significantly higher EGF, GRO, and RANTES levels in the water fraction compared to the lipid fraction of the lipid phase. Conclusions: The novel findings of this investigation were the presence of Flt-3L and MDC in all layers of breast milk, and nearly all bioactive factors in the lipid phase. Due to their widespread physiological effects these factors may have an essential role in organogenesis.

Photolytic degradation of ciprofloxacin in solid and aqueous environments: kinetics, phototransformation pathways, and byproducts.

Many lipophilic pharmaceuticals may be sorbed in solid phases, leading to different photochemical behaviors. This study investigated the photochemistry of ciprofloxacin in a solid-phase system and compared it to that in a water-phase system. Kaolinite was used as the model solid matrix. The photolysis of ciprofloxacin in kaolinite fits pseudo-first-order kinetics for thicknesses less than 199 µm, and the rate constants k p decreased from 0.0154 to 0.0016 min-1 as the thickness of the layer increased. Unlike the aqueous phase, two-step degradation processes were observed for all kaolinite layer thicknesses (14-199 µm), and the pseudo-first-order constant at the surface of the kaolinite layer was smaller than that in the water phase. Comparatively , a similar photolysis rate constant of ciprofloxacin in a kaolinite suspension was also observed, and it was an order of magnitude smaller than that of the direct photodegradation (0.035 min-1) in water. The results indicate that ciprofloxacin is likely more stable when it is adsorbed on kaolinite and that the half-lives of ciprofloxacin in kaolinite and a kaolinite suspension are 2-25 times longer than that in deionized water (20 min) under simulated sunlight. Direct photolysis is proposed to be the main photodegradation mechanism for ciprofloxacin in kaolinite, and the cleavage of a piperazine ring is the main degradation pathway. However, the interaction between ciprofloxacin and kaolinite reduces the direct photolysis and leads to a higher light stability. In association with the reduction in photolysis, the yields of norfloxacin and defluorinated byproduct decreased significantly. Consequently, the interaction increases the persistence of ciprofloxacin and thus the ecological risk to the environment.

Electrokinetically assisted oil-water phase separation in oily sludge with implementing novel controller system.

Upstream and downstream petroleum industry generate of significant amounts of oily sludge per day. On the other hand, a disposal of such sludge requires expensive pre-treatments following local regulations. Conventional processes, like centrifugal separation provide sludge volume reduction and water extraction. However, water-in-oil emulsion requires extra stages for phase separation, which overall increases the costs. Therefore, electrokinetically (EK) assisted oil-water phase separation method was considered. In this study, a novel implemented controller, installed into the EK system, permitted to increase the length of exposure time to electrical field, while a significant decrease of energy consumption was observed. The controller, implemented based on Percolation Theory and applied to a linear horizontal EK system, showed enhanced sludge demulsification and improvement the quality of separated fractions. TGA analysis showed a superior quality of liquids extracted by EK with controller comparing to liquids without controller or generated by centrifuging process. A reaction rate with respect to temperature to assess the presence of water in the oil was also defined. The method, shown in this paper, advances the oil-water phase separation and permits for better oil recovery and sludge volume reduction.

MOF-Templated Fabrication of Hollow Co4N@N-Doped Carbon Porous Nanocages with Superior Catalytic Activity.

Metallic Co4N catalysts have been considered as one of the most promising non-noble materials for heterogeneous catalysis because of their high electrical conductivity, great magnetic property, and high intrinsic activity. However, the metastable properties seriously limit their applications for heterogeneous water phase catalysis. In this work, a novel Co-metal-organic framework (MOF)-derived hollow porous nanocages (PNCs) composed of metallic Co4N and N-doped carbon (NC) were synthesized for the first time. This hollow three-dimensional (3D) PNC catalyst was synthesized by taking advantage of Co-MOF as a precursor for fabricating 3D hollow Co3O4@C PNCs, along with the NH3 treatment of Co-oxide frames to promote the in situ conversion of Co-MOF to Co4N@NC PNCs, benefiting from the high intrinsic activity and electron conductivity of the metallic Co4N phase and the good permeability of the hollow porous nanostructure as well as the efficient doping of N into the carbon layer. Besides, the covalent bridge between the active Co4N surface and PNC shells also provides facile pathways for electron and mass transport. The obtained Co4N@NC PNCs exhibit excellent catalytic activity and stability for 4-nitrophenol reduction in terms of low activation energy (Ea = 23.53 kJ mol-1), high turnover frequency (52.01 × 1020 molecule g-1 min-1), and high apparent rate constant (kapp = 2.106 min-1). Furthermore, its magnetic property and stable configuration account for the excellent recyclability of the catalyst. It is hoped that our finding could pave the way for the construction of other hollow transition metal-based nitride@NC PNC catalysts for wide applications.

Characteristics of removal of waste-water marking pharmaceuticals with typical hydrophytes in the urban rivers.

The investigations on their variation and distribution of 13 called waste-water marking pharmaceuticals (WWMPs) were conducted under 4 hydrophyte conditions (without plants, with submerged aquatic plant (Myriophyllum verticillatum L.), emergent aquatic plant cattail (Typha orientalis Presl) and floating aquatic plant (Lemna minor L.)) in a simulated urban river system. By the calculation of mass balance, the quantitative distribution of WWMPs in water phase, sediment and plant tissues was identified, and the overall removal efficiencies of target pharmaceuticals in the whole system could be determined. Without plants, high persistence of atenolol (ATL) (97.7%), carbamazepine (CBM) (102.8%), clofibric acid (CLF) (101.8%) and ibuprofen (IBU) (80.9%) was detected in water phase, while triclosan (TCS) (53.5%) displayed strong adsorption affinity in sediment. The removal under the planted conditions was considerably raised, compared with no plant condition for most WWMPs. However, TCS did not show obvious differences among the hydrophyte conditions due to its strong adsorption affinity and high hydrophobicity. The relatively higher removal was found for the hydrophilic (logKow<1) or moderately hydrophobic (14.0) did not show significant differences among the whole tests in sediment. Mass balance calculation displayed the removal of CBM (5.6%-13.6%), CLF (4.0%-17.8%) and caffeine (8.4%-17.2%) through the plant uptake was relatively higher. For the rest WWMPs, only small parts (<6.0%) of the initial concentrations were found in plant tissues. The higher removal efficiencies of most WWMPs under the planted conditions indicated that aquatic plants indeed played an important role in the removal of WWMPs although the direct uptakes might not be a dominant pathway to the overall removal of WWMPs. Besides, the floating aquatic plant removed most WWMPs from the water phase efficiently. In contrast, submerged and emergent aquatic plants could effectively remove them in sediment.

Occurrence of organotins in the aquatic environment during an operating cycle of the Three Gorges Reservoir, China.

Organotins (OTs) pollution in the aquatic environment of the Three Gorges Reservoir (TGR) was assessed during the reservoir's operating cycle. Butyltins (BTs) and phenyltins (PhTs) in the water phase and suspended particulate matter (SPM) at different water levels were analysed. It was found that the distribution of OTs in the surface and bottom water phases were similar, with the dominant OTs being BTs at the low water level and PhTs at the high water level. The detection rates and concentrations of OTs in the water phase at the high water level were both higher than those at the low water level, with most OTs being monobutyltin (MBT) at the low water level and monophenyltin (MPhT) at the high water level. The concentrations of OTs in SPM at the low water level were higher than those at the high water level, and BTs, especially dibutyltin (DBT) and tributyltin (TBT), were the predominant OTs whether surface or bottom layer at each water level. The BTs and SPM concentrations had a significant positive relationship in all samples, indicating that the SPM concentration would determine the distribution of BTs in the aquatic environment of the TGR region (TGRR). The difference in the distribution of OTs at the different water levels indicated that the hydrological and hydraulic behaviour of the TGR influences OTs transport in the aquatic environment of the TGRR.

Use of hydrolytic enzymes as green and effective extraction agents for ultrasound assisted-enzyme based hydrolytic water phase microextraction of arsenic in food samples.

In order to contribute to the development and improvement of green sample preparation techniques, a new special approach combining the principles and advantages of microextraction techniques, hydrolytic enzymes and ultrasonic radiation power is presented. This new approach is called as ultrasound assisted-enzyme based hydrolytic water phase microextraction method (UA-EH-WPME). In this study, We developed and used a solvent-free UA-EH-WPME method as innovative, green and simple sample preparation method for the extraction of arsenic (As) in rice and flour samples prior to Inductively Coupled Plasma-Mass Spectrometer (ICP-MS) determination. The UA-EH-WPME method based on the extraction of total As in 10.0 mg of food samples to 300 µL of pH 7.0 aqueous phase with the help of the 3.0 mg of α-amylase in as little as 5 min. In this method, α-amylase acts as a bond breaker agent to break down certain bonds of bio-molecules in food matrix, which lead to extraction of As from food matrix to aqueous phase. 1568A Rice Flour certified reference material was used to optimize the important analytical parameters, which were type of hydrolytic enzyme, pH, volume of aqueous phase, amount of enzyme, temperature of extraction medium and time of ultrasonic radiation, for the quantitative extraction of As from food matrix to aqueous phase. This innovative solvent-free method leads to emerge new ideas in the sample preparation field, by using the benefits of microextraction techniques, hydrolytic enzymes and ultrasonic radiation power, such as elimination of the toxic solvent usage, necessity of mg level of enzyme and food samples, very short and simple extraction process. The LOD, inter-day RSD and intra-day RSD values for the developed UA-EH-WPME/ICP-MS procedure were found as 27.3 µg kg-1, 4.27% and 6.13%, respectively.