Extraction behaviors of caffeine and chlorophylls in supercritical decaffeination of green tea leaves

The decaffeination of green tea using supercritical carbon dioxide (SC-CO₂) was optimized by response surface methodology (RSM) for the maximal removal of caffeine, and the coextration of chlorophylls was also monitored during decaffeination. The experimental conditions for the SC-CO₂ extraction of caffeine were set up according to the Box-Behnken design of RSM. The relationships between the extraction yield of caffeine and various parameters used for the SC-CO₂ extraction such as pressure, temperature and concentration of ethanol were studied at a fixed CO₂ flow rate. The extraction yields of caffeine and total chlorophyll were significantly influenced by extraction pressure, temperature and concentration of cosolvent, and their extraction yields behaved almost in parallel at different extraction conditions that were obtained by varying pressure, temperature and ethanol cosolvent concentration. At the optimal decaffeination conditions such as 3.0 g of 95% (v/v) ethanol cosolvent per 100 g of CO₂, 23 MPa, 63 °C and an extraction duration of 120 min for 10 g of green tea leaves, the extraction yields for caffeine and catechins were 96.60% (w/w) and 40.61% (w/w), respectively, and the substantial coextraction of total chlorophyll (43.09% of the total amount) was also observed during the decaffeination process.     

Microwave-assisted extraction,chemical characterization of polysaccharides from Lilium davidii var. unicolor Salisb and its antioxidant activities evaluation

Microwave-assisted extraction (MAE) of polysaccharides from Lilium davidii var. unicolor Salisb (LP_MAE) was studied. The four parameters, extraction time, microwave power, extraction temperature, extraction temperature and the ratio of solid to water, were optimized using the Box–Behnken design (BBD) with a quadratic regression model built by using response surface methodology (RSM). The optimal extraction conditions for LP_MAE were determined as follows: microwave power 597 W, extraction time 60 min, ratio of raw material to liquid 1:65, extraction temperature 50 °C, where the highest yield of LP_MAE 36.55 ± 1.1% was achieved. The resulted LP_MAE was characterized by FT-IR. The peaks at 3406 cm⁻¹, 2930 cm⁻¹, 1250 cm⁻¹, 1060, 812 cm⁻¹ indicated that LP_MAE possesses typical absorption peak of polysaccharides. Monosaccharide composition was determined by GC–MS method. LP_MAE was mainly composed of glucose and mannose with the molar ratio of 5.17:4.82. The weight average molar mass (Mw) determined by SEC-LLS was1.193 × 10⁵. In addition, the antioxidative activity of LP_MAE was investigated by measuring its scavenging ability on DPPH, hydroxyl radicals and superoxide radical, Chelating activity on ferrous ion and reducing power in vitro. The results indicated that LP_MAE has good antioxidant activity.     

FT-NIR spectroscopy for caffeine estimation in instant green tea powder and granules

The feasibility of measuring caffeine content in instant green tea and granules was investigated by Fourier Transform Near-Infrared (FT-NIR) spectroscopic technique. A calibration model was developed using pure caffeine standards of varying concentrations in the near-infrared region (4000-12000 cm⁻¹). The developed model was validated using test validation technique. FT-NIR spectroscopy with chemometrics, using the PLS-first derivative plus straight line subtraction method could predict the caffeine content in tea samples accurately up to an R² value greater than 0.98 and a standard error of prediction (SEP) value less than 2.0 with 6 factors in the prediction model. The developed model was applied to predict caffeine content in tea samples within 2-5 min. The developed procedure was further validated by recovery studies by comparing with UV spectroscopic method of caffeine determination.     

Decaffeination of fresh green tea leaf (Camellia sinensis) by hot water treatment

Hot water treatment was used to decaffeinate fresh tea leaf in the present study. Water temperature, extraction time and ratio of leaf to water had a statistically significant effect on the decaffeination. When fresh tea leaf was decaffeinated with a ratio of tea leaf to water of 1:20 (w/v) at 100 °C for 3 min, caffeine concentration was decreased from 23.7 to 4.0 mg g⁻¹, while total tea catechins decreased from 134.5 to 127.6 mg g⁻¹; 83% of caffeine was removed and 95% of total catechins was retained in the decaffeinated leaf. It is considered that the hot water treatment is a safe and inexpensive method for decaffeinating green tea. However, a large percentage of tea catechins was lost if rolled leaf and dry tea were decaffeinated by the hot water treatment and so the process is not suitable for processing black tea.     

Evaluation of hot and cold extraction of bioactive compounds in teas

This study evaluated the bioactive compounds of different types of tea by comparing hot and cold infusions. A multivariate data analysis was carried out, where the principal components analysis (PCA) and hierarchical cluster analysis (HCA) were used. Phenolic compounds varied between 267.27–2896.00 mg GAE L^?1 and 215.10–7351.33 mg GAE L^?1 for hot (80 °C) and cold extraction (20–25 °C), respectively. In the case of their antioxidant activity, results with DPPH were 43.10‐73.67% for hot extraction and 46.80‐77.13% for cold extraction. The average values for the ABTS˙⁺ method ranged between 2535.43 and 33 300.17 μmol TE L^?1 and between 1110.34 and 38 300.67 μmol TE L^?1, respectively, for hot and cold extraction. Different compounds were identified by liquid chromatography in the samples evaluated, where caffeine presented the higher concentrations in the teas. Samples of green and black tea (hot extraction) and white tea (cold extraction) showed bacteriostatic activity for S. aureus and E. coli. No extract had any bactericide activity. The current study revealed that cold infusion was more efficient in the extraction of bioactive compounds.     

Effects of cosolvents on the decaffeination of green tea by supercritical carbon dioxide

Due to the adverse effects of the caffeine in a variety of plant products, many methods have been explored for decaffeination, in efforts to remove or reduce the caffeine contained in plant materials. In this study, in order to remove caffeine from green tea (Camellia sinensis) leaves, we have employed supercritical carbon dioxide (SC–CO₂), which is known to be an ideal solvent, coupled with a cosolvent, such as ethanol or water. By varying the extraction conditions, changes not only in the amount of caffeine, but also in the quantities of the principal bioactive components of green tea, including catechins, such as epigallocatechin gallate (EGCG), epigallocatechin (EGC), epicatechin gallate (ECG) and epicatechin (EC), were determined. The extraction conditions, including temperature, pressure and the cosolvent used, were determined to affect the efficacy of caffeine and catechin extraction. In particular, the type and concentration of a cosolvent used constituted critical factors for the caffeine removal, combined with minimal loss of catechins, especially EGCG. When the dry green tea leaves were extracted with SC–CO₂ modified with 95% (v/v) ethanol at 7.0 g per 100 g of CO₂ at 300 bar and 70 °C for 120 min, the caffeine content in the decaffeinated green tea leaves was reduced to 2.6% of the initial content. However, after the SC–CO₂ extraction, a substantial loss of EGCG, as much as 37.8% of original content, proved unavoidable.     

A new method based on electrospray ionisation ion mobility spectrometry (ESI-IMS) for simultaneous determination of caffeine and theophylline

In this work for the first time, simultaneous analysis of caffeine and theophylline was done by ion mobility spectrometry (IMS) only, without a powerful separation technique (e.g., HPLC). Ion mobility spectrometry with low cost, inexpensive maintenance and very fast analysis makes an attractive technique for the simultaneous determination of the caffeine and theophylline in foodstuff samples and biological matrices. In this study, the extraction protocol using molecular imprinted polymer-solid phase extraction (MIP-SPE) was successfully used to directly extract caffeine and theophylline from real samples. The results obtained provided the detection limits of 0.2 and 0.3 μg mL⁻¹ for caffeine and theophylline, respectively. The linear dynamic range of about two orders of magnitude was obtained for these compounds. Also, the proposed method was used to analyse various real samples of green tea and spiked human plasma, and the obtained results confirmed the capability of ESI-IMS for simultaneous detection of caffeine and theophylline.     

Use of tea extracts for inhibition of polyphenoloxidase and retardation of quality loss of Pacific white shrimp during iced storage

Green tea and mulberry tea powder with and without prior chlorophyll removal were extracted with water and ethanol (800 mL L⁻¹). Extraction yield and total phenolic content of green tea extract were higher than those of mulberry tea extract, regardless of extraction media (P < 0.05). Extracts from green tea with and without prior chlorophyll removal showed the higher polyphenoloxidase (PPO) inhibitory activity, compared with mulberry tea extract, at the concentration used (0.1, 0.5 or 1 g L⁻¹). Additionally, green tea extracts had the higher reducing power, 2,2-diphenyl-1-picryl hydrazyl (DPPH) radical scavenging activities and copper chelating activity, compared with mulberry tea extract (P < 0.05). Ethanolic green tea extract with prior chlorophyll removal contained (+)-catechin (C), (−)-epicatechin (EC), (−)-epigallocatechin (EGC), (−)-epigallocatechin gallate (EGCg) and (−)-epicatechin gallate (ECG) at the levels of 242, 33.4, 125.6, 140.6 and 25.2 g kg⁻¹ dry extract, respectively. Whole white shrimp (Litopenaeus vannamei) treated with ethanolic green tea extract with prior chlorophyll removal at concentrations of 5 and 10 g L⁻¹ and stored in ice for up to 12 days had the lower psychrophilic bacterial count and lipid oxidation, compared with the control and shrimp treated with 12.5 g L⁻¹ sodium metabisulfite (SMS) (P < 0.05). Shrimp treated with 5 g L⁻¹ ethanolic green tea extract with prior chlorophyll removal possessed the lower melanosis, compared with the control, and showed similar score to those treated with SMS (P > 0.05). Furthermore, ethanolic green tea extract with prior chlorophyll removal had no adverse impact on sensory attributes of treated shrimp.     

Multicommuted fluorescence based optosensor for the screening of bitertanol residues in banana samples

A multicommuted flow through optosensor is developed in order to determine bitertanol in banana samples, by measuring the pesticide native fluorescence at 261/326 nm. The solid support used in the flow-through cell, C₁₈, allows both high selectivity and sensitivity necessary for the screening of the pesticide at residue levels. These characteristics of optosensing are implemented with low sample consumption and automation intrinsic properties of multicommutation, providing a useful tool for pesticide residue routine determination in foods. An acetonitrile extraction/partitioning and dispersive solid-phase extraction clean-up procedure proved to be useful; an additional cleaning step with C₁₈ solid phase extraction (SPE) cartridges was carried out, eliminating all matrix limitations. Recovery experiments performed on banana samples at different concentrations provided recoveries between 81% and 115%. A detection limit of 0.014 mg kg⁻¹ was obtained. This makes the method suitable for screening bitertanol in banana samples, fulfilling the maximum residue levels of 3 mg kg⁻¹ established by the European Union.     

微波辅助萃取(MAE)绿茶的浸提动态过程研究

以绿茶作为材料,采用微波辅助萃取(MAE)技术,变化微波功率、浸提时间、浸提溶剂量、浸提溶剂4个变量因子,对浸提过程中茶汤的有效成分——茶多酚、氨基酸和咖啡碱等动态变化进行研究。比较绿茶中不同有效成分在不同条件下进行MAE过程的萃取效率,并利用SPSS软件把动态过程归结为各种模型,得到的模型分别是:Y=-10.877 0.40055×X-0.00196×X2 3.324×10-6×X3(360W);Y=-2.472 0.27910×X-0.001167×X2 1.4345×10-6×X3(540W);Y=-16.492 0.72497×X-0.00463×X2 9.061×10-6×X3(720W)。     

Quantitative analysis of acrylamide in tea by liquid chromatography coupled with electrospray ionization tandem mass spectrometry

An effective sample preparation procedure was optimized and a liquid chromatography–tandem mass spectrometry (LC–MS/MS) was developed for the quantitative analysis of acrylamide in tea. [¹³C₃]-acrylamide was used as internal standard. Acrylamide was extracted at 25 °C for 20 min by 10 ml water followed by 10 ml acetonitrile, and then 4 g of magnesium sulfate and 0.5 g of sodium chloride were added to the above mixture under stirring thoroughly. In order to increase the response of acrylamide, 9 ml acetonitrile layer was taken and concentrated to 0.5 ml. Solid-phase extraction with an Oasis MCX cartridge was carried out for clean-up. The limit of detection (LOD) and limit of quantification (LOQ) were 1 and 5 ng/ml, respectively. The recovery efficiency of the extraction procedure ranged between 74% and 79%. The levels of acrylamide in 30 tea samples were less than 100 ng/g. Black, oolong, white and yellow tea samples had quite low acrylamide contents (<20 ng/g). Higher acrylamide levels occurred in baked, roasted, and one sun-dried green tea samples (46–94 ng/g).     

Supramolecular solvent-based microextraction of Sudan dyes in chilli-containing foodstuffs prior to their liquid chromatography-photodiode array determination

A supramolecular solvent made up of reverse micelles of decanoic acid was proposed for the simple and rapid extraction of Sudan I, II, III and IV from chilli-containing foodstuffs. The procedure involved the extraction of minute quantities (0.5–1 g) of homogenised food sample with an aqueous solution containing 10% THF and 200 mg of decanoic acid, conditions under which the supramolecular solvent (around 330 μL) formed in situ and instantaneously. The overall sample treatment took about 30 min and several samples could be simultaneously treated using conventional lab equipment. No clean-up or solvent evaporation were required before determination of Sudan dyes by liquid chromatography and photometric detection. Extractions were independent of salt addition (up to 1 M), the temperature (up to 60 °C) and the pH (below 4) rendering the method robust. The detection limits of the method were 4.2, 2.7, 6.5 and 7.4 μg kg⁻¹ for Sudan I, II, III and IV, respectively. Recoveries obtained by applying this approach to the analysis of six chilli-containing sauces fortified with Sudan dyes at the μg kg⁻¹ level were in the interval 86–108% with relative standard deviations between 2% and 7%.     

Analysis of some selected catechins and caffeine in green tea by high performance liquid chromatography

Green tea seems to have a positive impact on health due to the catechins-found as flavanols. Thus, the present study was aimed to develop a low cost reversed phase high performance liquid chromatographic (HPLC) method for simultaneous determination of flavanol contents, namely catechin (C), epicatechin (EC), epigallocatechin (EGC), epicatechin 3-gallate (ECG) and epigallocatechin 3-gallate (EGCG) and caffeine in 29 commercial green tea samples available in a Saudi Arabian local market. A C-18 reversed-phase column, acetonitrile–trifluoroacetic acid as a mobile phase, coupled with UV detector at 205 nm, was successfully used for precise analysis of the tested analytes in boiled water of digested tea leaves. The average values of N (No. of theoretical plates), HETP (height equivalent of theoretical plates) and R_s (separation factor) (at 10 μg ml⁻¹ of the catechins EC, EGC, EGCG and ECG) were 2.6 × 10³ ± 1.2 × 10³, 1.7 × 10⁻³ ± 4.7 × 10⁻⁴ cm and 1.7 ± 5.53 × 10⁻², respectively. The developed HPLC method demonstrated excellent performance, with low limits of detection (LOD) and quantification (LOQ) of the tested catechins of 0.004–0.05 μg ml⁻¹ and 0.01–0.17 μg ml⁻¹, respectively, and recovery percentages of 96–101%. The influence of infusion time (5–30 min) and temperature on the content of the flavanols was investigated by HPLC. After a 5 min infusion of the tea leaves, the average concentrations of caffeine, catechin, EC, EGC, ECG and EGCG were found to be in the ranges 0.086–2.23, 0.113–2.94, 0.58–10.22, 0.19–24.9, 0.22–13.9 and 1.01–43.3 mg g⁻¹, respectively. The contents of caffeine and catechins followed the sequence: EGCG > EGC > ECG > EC > C > caffeine. The method was applied satisfactorily for the analysis of (+)-catechin, even at trace and ultra trace concentrations of catechins. The method was rapid, accurate, reproducible and ideal for routine analysis.     

A validated matrix solid-phase dispersion method for the extraction of organophosphorus pesticides from bovine samples

A method based on matrix solid-phase dispersion (MSPD) was developed for the quantitative extraction of five organophosphorus (OPPs) pesticides from bovine samples. The determination was carried out by high performance liquid chromatography (HPLC) with diode array spectrophotometric UV detection. The MSPD extraction with octadecylsilyl (C18) sorbent combined with a silica gel clean-up and acetonitrile elution was optimised for chlorpyrifos, chlorfenvinphos, diazinon, fenitrothion, and parathion-methyl. The method was validated, yielding recovery values higher than 94%, except for chlorfenvinphos in liver (55%), and precision values, expressed as relative standard deviations (RSDs), which were less than or equal to 15% in liver and 11.5% in muscle at spiking levels of 0.25, 2.5 and 5 μg g⁻¹. Linearity was studied from 0.5 to 15 μg g⁻¹, and the limits of detection (LODs) were found to be lower than 0.1 μg g⁻¹_. This method was applied to the analysis of real samples with confirmative analyses performed using gas chromatography–mass spectrometry (GC–MS) in selected ion monitoring mode (SIM).     

Study the effect of sun, oven and microwave drying on quality of onion slices

Sun, oven (50 and 70 °C) and microwave oven (210 and 700 W) drying of onion slices were carried out to monitor the drying kinetics and quality degradation of the product. Page, “Modified Page” and “Midilli and Küçük” models exhibited high coefficient of determination (R²) values, ranging between 0.994 and 0.999. The calculated effective diffusivity (D_eff) values (m²/s) of onion slices for the sun, oven 50 °C and oven 70 °C, microwave 210 W and microwave 700 W drying process were 8.339 × 10⁻¹⁰, 7.468 × 10⁻¹⁰, 1.554 × 10⁻⁹, 4.009 × 10⁻⁸ and 4.869 × 10⁻⁸, respectively. Fresh and dried onion slices had high amounts of K (696.82-16357.55 mg/kg), Ca (69.64-340.03 mg/kg), Na (37.72-1895.43 mg/kg), Mg (3.31-964.77 mg/kg) and P (46.47-3384.07 mg/kg) minerals. The highest mineral values were determined in oven dried samples. Sun (L^∗ 58.00 ± 4.83, a^∗ 0.27 ± 0.10, b^∗ 14.36 ± 2.40) and microwave oven drying (210 W) (L^∗ 54.78 ± 7.54, a^∗ −0.71 ± 0.09, b^∗ 13.17 ± 1.05) revealed better colour values in the dried products. The phenolic contents of microwave oven dried samples (1664.39 ± 134.12 and 1623.59 ± 140.02 for 210 W and 700 W, respectively) were higher than those of the other dried onion slices.     

Determination of caffeine content in tea based on poly(safranine T) electroactive film modified electrode

Safranine T was electropolymerised on a glassy carbon electrode and then characterised by scanning electron microscope (SEM), X-ray diffraction (XRD) and electrochemical impedance spectroscopy (EIS). This uniform electropolymerised film was crystallisable and showed a high electrocatalytic ability towards the oxidation of caffeine. To avoid the interferences of the anions, Nafion was covered on the surface of poly(safranine T) film modified glassy carbon electrode. As a new voltammetric sensor, this modified electrode is sensitive, selective and stable to determine caffeine content in tea. The peak current increased linearly with the concentration of caffeine in the range of 3 × 10⁻⁷–1 × 10⁻⁴ M, with a detection limit of 1 × 10⁻⁷ M. All of these make it a useful tool for determining caffeine content in tea. What’s more, it produces much less organic waste compared with other analytical techniques.     

Modelling of solid-phase tea waste extraction for the removal of manganese from food samples by using artificial neural network approach

In this study, a three-layer artificial neural network (ANN) model was employed to develop prediction model for removal of manganese from food samples using tea waste as a low cost adsorbent. After removal of manganese from food samples with acetic acid (5 mol L⁻¹), manganese was adsorbed to a small amount of tea waste, desorbed with nitric acid as a eluent solvent, and determined by flame atomic absorption spectrometry. The input parameters chosen of the model was pH, amount of tea waste, extraction time and eluent concentration. After backpropagation (BP) training, the ANN model was able to predict extraction efficiency of manganese with a tangent sigmoid transfer function at hidden layer and a linear transfer function at output layer. Under the optimum conditions, the detection limit was 0.6 ng g⁻¹. The method was applied to the separation, pre-concentration and determination of manganese in food samples and one reference material.     

Rapidly colorimetric detection of caffeine in beverages by silver nanoparticle sensors coupled with magnetic molecularly imprinted polymeric microspheres

Excessively intaking caffeine can harm human health, and it is imperative to develop a rapid method to identify caffeine for food safety. The magnetic molecularly imprinted polymeric microspheres (MMIPs) were prepared to pretreat samples before silver nanoparticles (AgNPs) colorimetric detection of caffeine. Using Fe₃O₄ as supporting core, mesoporous SiO₂ as intermediate shell, α-methylacrylic acid as functional monomer and caffeine as template, the prepared MMIPs were characterised by transmission electron microscopy, Fourier transform infrared spectroscopy and vibrating sample magnetometer. Adsorption process followed Langmuir adsorption isotherm with maximum adsorption capacity at 38.8 mg g⁻¹ under 298 K. The MMIPs extract caffeine from beverages, then the AgNPs colorimetric method rapidly screened and semi-quantified caffeine ≥5 mg L⁻¹ by naked eye, and accurately quantified caffeine ranging 0.1–5 mg L⁻¹ by UV-vis spectroscopy at 393 nm, which were consistent with HPLC analytical results. Thus, this method might be used to rapidly enrich and analyse caffeine in beverages.     

Comparative evaluation of microwave‐assisted extraction and preheated solvent extraction of bioactive compounds from a plant material: a case study with cabbages

Preheated solvent extraction (PSE) was evaluated via the analysis of the extraction kinetics, microstructure of extracted samples and energy consumption as alternative to microwave‐assisted extraction (MAE). Cabbage outer leaves and ethanol were used as test material and extraction solvent, respectively. MAE was first optimised in terms of glucosinolates and phenolics yields; total antioxidant activity of the extracts was also assessed. MAE at a specific absorbed power of 0.37 W g^?1 for 9 min was selected as optimum condition to extract glucosinolates and phenolics, while PSE was optimised at 6 min of the extraction. The highest normalised total glucosinolates and phenolic contents as well as antioxidant activities of the extracts obtained via MAE were not significantly different from those obtained via PSE. Confocal laser scanning microscopy revealed no significant differences in cabbage cell damages rendered by MAE and PSE. PSE nevertheless exhibited slightly higher specific energy consumption than MAE.