Sample preparation for the analysis of key metabolites from cannabinoids biosynthesis in phytoplankton using gas chromatography–mass spectrometry

Cannabinoids biosynthesis in phytoplankton has attracted much attention due to the rapid development of genetic tools and the optimization of genetic transformation methods in microalgae. To monitor the biosynthesis process, proper sample preparation and practical instrumental methods are needed to measure the various precursors, intermediates, cannabinoids, and their degradation products. The objective of this study was to develop a sample preparation procedure for the quantification of olivetolic acid (OA), cannabigerolic acid (CBGA), cannabidiolic acid (CBDA), tetrahydrocannabinolic acid (THCA), olivetol (OL), cannabidiol (CBD), and tetrahydrocannabinol (THC) using single-quadrupole gas chromatography–mass spectrometry (GC–MS). Isochrysis galbana was used as the model matrix. After methanol extraction, samples were purified using solid phase extraction (SPE), silylated with N-methyl-N-(trimethylsilyl)trifluoroacetamide, and analyzed using GC–MS in electron ionization mode. A strong anion-exchange SPE efficiently recovered OA, CBGA, CBDA, and THCA. A graphitized carbon black SPE was necessary to purify OL, CBD, and THC. Both columns removed amino acids, sugars, polyols, and pigments from the algae extract and prepared samples that are suitable for silylation and GC–MS analysis. The total protocol, including solvent extraction, SPE, silylation, and GC–MS analysis, was validated in accordance with the ICH guidelines. Performance characteristics of our method are superior to existing protocols with similar complexity in the literature.     

A new method for the investigation of fluid/fluid mass transfer—I: Mass transfer in gas/liquid systems

A new dynamic electrochemical method is introduced to investigate gas/liquid mass transfer in mechanically agitated contactors. Current transients were recorded and evaluated with a linear regression analysis in two contactors at different rotation rates. The volumetric mass trasnfer coefficient a₁k₁ and Henry's constant can be calculated from these experiments. Reliable results are obtained over a wide range of hydrodynamic conditions.     

Measurements of the effective mass transfer areas for the gas–liquid rotating packed bed

Rotating packed bed(RPB) is one of the most effective gas–liquid mass transfer enhancement reactors, its effective specific mass transfer area(ae) is critical to understand the mass transfer process. By using the NaOH–CO₂ chemical absorption method, the aevalues of three RPB reactors with different rotor sizes were measured under different operation conditions. The results showed that the high gravity factor and liquid flow rate were major affecting factors, while the gas flow rate ex...     

Modeling of Rayleigh convection in gas–liquid interfacial mass transfer using lattice Boltzmann method

Interfacial Rayleigh convection can be generated by concentration gradient near the interface in mass transfer processes. In the present study, a 2D time-dependent lattice Boltzmann method (LBM) with a double distribution model was established for simulating the liquid-phase Rayleigh convection in the mass transfer process of CO₂ absorption into various solvents. Two random parameters P and C_D denoting respectively the possibility and the magnitude of concentration perturbation at interface were introduced to model the interfacial disturbance, which is known as one of the necessary conditions of onset of Rayleigh convection. The values of the parameters were identified (0.05 ≤ P < 0.3 and 0 < C_D ≤ 10⁻⁹ kg m⁻³) by comparing simulated critical onset times of the Rayleigh convection with the experimental result from Blair and Quinn (1969) and theoretical predictions proposed by Kim et al. (2006) and 0245 and 0250. The maximum penetration depths, maximum transient Rayleigh numbers, and critical times for the onset of Rayleigh convection were obtained by the proposed model. The simulations captured the detailed information of the onset and the temporal–spatial evolution of Rayleigh convection, and gave the concentration contours of typical plume convection patterns which were well consistent with literatures. Enhancement of mass transfer by the Rayleigh convection was also demonstrated by comparing the simulated instantaneous mass flux across the interface with that predicted by penetration theory.     

A study on the causes for the elevated n−3 fatty acids in cows' milk of alpine origin

The influence of grass-only diets either from rye-grass-dominated lowland pastures (400 m above sea level) or botanically diverse alpine pastures (2000 m) on the FA profile of milk was investigated using three groups of six Brown Swiss cows each. Two groups were fed grass-only on pasture (P) or freshly harvested in barn (B), both for two experimental periods in the lowlands and, consecutively, two periods on the alp. Group C served as the control, receiving a silage-concentrate diet and permanently staying in the lowlands. Effects of vegetation stage or pasture vs. barn feeding on milk fat composition were negligible. Compared with the control, α-linoleic acid (18∶3n−3) consumption was elevated in groups P and B (79%, P<0.001) during the lowland periods but decreased on the alp to the level of C owing to feed intake depression and lower 18∶3n−3 concentration in the alpine forage. Average 18∶3n−3 contents of milk fat were higher in groups, P and B than in C by 33% (P<0.01) at low and by 96% (P<0.001) at high altitude, indicating that 18∶3n−3 levels in milk were to some extent independent of 18∶3n−3 consumption. The cis-9,trans-11 CLA content in milk of grass-fed cows was higher compared with C but lower for the alpine vs. lowland periods whereas the trans-11, cis-13 isomer further increased with altitude. Long-chain n−3 FA and phytanic acid increased while arachidonic acid decreased with grass-only feeding, but none of them responded to altitude. Grass-only feeding increased milk α-tocopherol concentration by 86 and 134% at low and high altitude (P<0.001), respectively. Changes in the ruminal ecosystem due to energy shortage or specific secondary plant metabolites are discussed as possible causes for the high 18∶3n−3 concentrations in alpine milk.     

An optimization method for enhancement of gas–liquid mass transfer in a bubble column reactor based on the entropy generation extremum principle

In this study, an optimization method is proposed to enhance the gas–liquid mass transfer in bubble column reactor based on the entropy generation extremum principle. The mass transfer–induced entropy generation can be maximized with the increase of mass transfer rate, based on which the velocity field can be optimized. The oxygen gas–liquid mass transfer is the major rate–limiting step of the toluene emissions biodegradation process in bubble column reactor, so the entropy generation due to oxy...     

Algebraic conditions,in terms of the solvent partition constants,for the separation of chemical classes by gas–liquid chromatography

The interdependence between the solvation Gibbs energy of several functional groups and the solvent partition coefficients was studied, starting from gas chromatographic data. Single-parameter relationships were derived for the –OH, -CHO, -CO, -O-,-COO (acetate), -COO (methyl ester)-, and -CN group increments. The obtained equations were found to be temperature independent, and could be successfully used for the evaluation of 19 stationary phases with respect to certain separation questions. The selectivity problem was converted into an inequality system. The graphical solution of such a system provides an image of the separation abilities of a sorbent material with respect to a given pair of solutes, and allows an efficient comparison of a great number of stationary phases. The graphs are also illustrative for the temperature effect on the selectivity features.     

A new method for the investigation of fluid-fluid mass transfer—II. Mass transfer in liquid-liquid systems

A new dynamic electrochemical method for the determination of liquid-liquid mass-transfer coefficients in a stirred cell and in a mixer cell is described. Current transients are recorded for different flow conditions and evaluated applying a non-linear regression analysis. The resulting mass-transfer coefficients correlate linearly with the stirring rate but the mean values over a long time period are considerably low. The extent of the investigated initial time dependence of the mass-transfer coefficient decreases with increasing electrolyte concentration.     

Nanoarchitectonics of three-dimensional ZnO–BiVO4 for trace nitrogen dioxide gas detection

In the present study, several novel three-dimensional (3D) ZnO–BiVO₄ composites were prepared using the hydrothermal method, and their ability to detect nitrogen dioxide (NO₂) gas was assessed. The fabricated sensing materials were examined using X-ray diffraction, transmission electron microscopy, energy dispersive spectrometry, scanning electron microscopy, ultraviolet–visible spectrophotometry, X-ray photoelectron spectroscopy, and surface-area and porosity analysis. The sensing material assessments verified that 3D ZnO–BiVO₄ was successfully prepared; the sensing data revealed that 3D ZnO–BiVO₄ exhibited excellent sensing response (24.6) to 1-ppm NO₂ at room temperature. The composites exhibited a fast response (28 s) and short recovery time (75 s) when detecting 1-ppm NO₂; they also exhibited long-term stability (decline of approximately 7% after 30 days) and selectivity to 10-ppm NO₂ gas. A reasonable NO₂ gas sensing mechanism for 3D ZnO–BiVO₄ heterojunction was also proposed in this paper.     

Effect of ultrasonic waveforms on gas–liquid mass transfer in microreactors

This study aims to investigate the effect of ultrasonic waveforms on the gas–liquid mass transfer process. For a given load power (P), continuous rectangular wave yielded stronger bubble oscillation and higher mass transfer coefficient (k_La) than continuous triangular and sinusoidal wave. For pulsed ultrasound, the k_La decreased monotonically with decreasing duty ratio (D), resulting in weak enhancement at low D (≤33%). For a given average load power (P_A), concentrating the P for a shorter period resulted in a higher k_La due to stronger cavitation behavior. For a given P_A and D, decreasing the pulse period (T) led to an increase in k_La, which reached a constant high level when the T fell below a critical value. By optimizing the D and T, a k_La equivalent to 92% of that under continuous ultrasound was obtained under pulsed ultrasound at a D of 67%, saving 33% in power consumption.     

Hydrodynamics of gas–solid flow in the circulating fluidized bed reactor for dry flue gas desulfurization

Process design and scale-up require a fundamental understanding of the hydrodynamics of gas–solid flow in the circulating fluidized bed flue gas desulfurization (CFB-FGD) reactor although the CFB system has been widely used in flue gas desulfurization and flue gas cleaning processes. The hydrodynamics in the CFB-FGD reactor model was investigated by pressure measurements and specially designed sampling probe based on three dimensionless groups for practicable similarity of industrial CFB-FGD process. The results show that the pressure drop in the venturi section is predominant as high as 60% of the total pressure drop and the total pressure drop significantly increases with the increasing external solid circulating rates at the same superficial gas velocity. Moreover, the measurements of radial solid mass fluxes show that the flow pattern in the CFB-FGD reactor is a typical core–annulus flow and this flow structure prevails until the top of the reactor. Reflux ratios are used to quantitatively evaluate the internal solid reflux in the reactor and the values in the low section of the reactor are much higher than those in the upper section.     

Demonstration of microwave method for detection of alkali–silica reaction (ASR) gel in cement-based materials

Microwave methods have previously shown success in detecting changes in moisture content and binding (e.g., bound water vs. free water) in cement-based materials through extensive analysis of their reflection coefficient. Here, the novel use of microwave measurements is demonstrated to distinguish between mortars containing alkali–silica reactive (ASR) aggregate and non-reactive aggregate. The variations in measurements are linked to the production of ASR gel and its tendency to attract free water from its environment. This paper presents the analysis and results of the interaction of microwave signals with ASR gel-producing mortar samples and those without the ASR gel.     

Equilibrium,kinetics and thermodynamic studies for the removal of organophosphorus pesticide using Amberlyst-15 resin: Quantitative analysis by liquid chromatography–mass spectrometry

In the present paper, Amberlyst-15 resin was used for the removal of malathion. Various experimental parameters such as effect of pH, contact time, resin dose, initial malathion concentration and temperature were studied to find the optimum conditions for malathion removal. The removal rate of malathion by Amberlyst-15 was rapid and equilibrium was established within 30 min. Kinetic studies showed better applicability for pseudo-second-order model and equilibrium data was best fitted to Freundlich isotherm model. The thermodynamic parameters showed that the adsorption of malathion was feasible, endothermic and spontaneous. The concentration of malathion was determined using ultra-performance liquid chromatography–tandem mass spectrometry.     

A solution strategy for the film model for non-isothermal gas–liquid reactions

A general solution strategy for the film model for gas–liquid reaction has been proposed using the boundary element method (BEM) of discretization over subintervals in gas–liquid films. Non-isothermal effects in the film are included and the associated temperature changes near the gas–liquid interface are computed. The accuracy of the solution procedure is first established using some simple isothermal and non-isothermal benchmark problems and with semi-analytical solutions. Then illustrative results are presented for a non-isothermal series reaction system to illustrate effects of various parameters such as Arrhenius number, solubility changes with temperature, effect of volatility of the liquid phase reactant, etc. The proposed solution method provides fast and accurate values for interfacial fluxes and fluxes into the bulk liquid in addition to concentration profiles. Hence the method is extremely useful for coupling local effects of the film model with global effects based on CFD coupled compartmental model for gas–liquid reactors.     

A continuum model for gas–liquid flow in packed towers

Gas–liquid flow in packed towers is commonly encountered in the chemical and processing industry. A continuum model is developed based on the volume-and-time averaging of multiphase flows in isotropic rigid porous media/packed columns. Closures are presented for the evaluations of the extra surface/intrinsic phase integral terms. Both inertia and inter-phase interactions are retained in the volume averaged (Navier–Stokes) equations. These governing equations are solved for fully-developed axi-symmetric single and gas–liquid two phase flows in highly porous packed towers. It is found that the dispersion term is present in the continuity equation as well as the momentum equations. Numerical simulations with the models show that the volume-and-time averaged equations can predict the velocity, phase hold-up and pressure drop quite well for up to the loading point for gas–liquid counter-current flows.     

Micro-computed tomography for the investigation of stationary liquid–liquid and liquid–gas interfaces in capillaries

For better understanding and optimization of multiphase flow in miniaturized devices, micro-computed tomography (μCT) is a promising visualization tool, as it is nondestructive, three-dimensional, and offers a high spatial resolution. Today, computed tomography (CT) is a standard imaging technique. However, using CT in microfluidics is still challenging, since X-ray related artifacts, low phase contrast, and limited spatial resolution complicate the exact localization of interfaces. We apply μCT for the characterization of stationary interfaces in thin capillaries. The entire workflow for imaging stationary interfaces in capillaries, from image acquisition to the analysis of interfaces, is presented. Special emphasis is given to an in-house developed segmentation routine. For demonstration purposes, contact angles of water, liquid polydimethylsiloxane, and air in FEP, glass, and PMMA are determined and the influence of gravity on interface formation is discussed. This work comprises the first steps for a systematic 3D investigation of multiphase flows in capillaries using μCT.     

A GC–MSD method for analysis of dimethyl sulfate in palm oil-based esterquat

Dimethyl sulfate (DMS) is a quarternizing agent for esteramine used for the synthesis of esterquat. To date there is no reliable published method for quantification of DMS in palm-based esterquat. Esterquat is used in the formulation of personal care and textile cleaning. The process of quaternization is usually incomplete and there will be unreacted DMS. This work presents a new simple method involving solvent extraction of DMS followed by analysis with gas chromatography–mass spectrometry detector to quantify the unreacted DMS. This method was validated as per International Council for Harmonization requirements. This novel method showed good repeatability (relative standard deviation [RSD] < 5%) and inter-day with different analyst reproducibility (RSD < 5%). The limits of detection and quantification were 5 and 10 μg mL⁻¹, respectively. The accuracy of the method was evaluated by the analysis of spiked samples and it was found that good recovery was found at spiking levels of 20, 30, and 50 μg mL⁻¹ with % recovery falling within the 80%–120% acceptable limit. However, at 10 μg mL⁻¹, the percentage recovery was slightly below the recommended limit.