Simultaneous determination of monosaccharides and oligosaccharides in dates using liquid chromatography-electrospray ionization mass spectrometry

a b s t r a c t Ultra performance liquid chromatography coupled to mass spectrometry was used for the simultaneous separation and determination of reducing monosaccharides (fructose and glucose), a non-reducing disaccharide (sucrose) and oligosaccharides (kestose and nystose) in HILIC mode. The chromatographic separation of all saccharides was performed on a BEH amide column using an acetonitrile-water gradient elution. The detection was carried out using selected ion recording (SIR) acquisition mode. The validation of the proposed method showed that the limit of detection and limit of quantification values for the five analyzed compounds were in the range of 0.25-0.69 lg/mL and 0.82-3.58 lg/mL, respectively; while the response was linear in the range of 1-50 lg/mL. The developed method showed potential usefulness for a rapid and sensitive analysis of underivatized saccharides and was used for determination of sugars in three date samples (Sefri, Mabroom, Ghassab) which were soxhlet extracted by ethanol

PLC Virtualization and Software Defined Architectures in Industrial Control Systems

Today’s automation systems are going through a transition called Industry 4.0, referring to the Fourth Industrial Revolution. New concepts, such as cyber-physical systems, mi-croservices and Smart Factory are introduced. This brings up the question of how some of these new technologies can be utilized in Industrial Control Systems. Machines and production lines are nowadays controlled by hardware PLCs and this is considered as a state-of-the-art solution. However, the market demands are continuously increasing and pushing the industry e.g. to lower the operational costs and to develop more agile solutions. Industry 4.0 provides promising approaches to take a step forward and consider PLC virtualization. The purpose of this thesis was to evaluate PLC virtualization possibilities using different Software Defined Architectures. Requirements and benefits of different solutions were evaluated. The major objective of the case study was to compare container- and hypervisor-based virtualization solutions using Docker and KVM. The case study provides a modular and scalable IIoT solution in which a virtual PLC takes over the control instead of a hardware PLC. Node-RED was used as a runtime environment and an I/O-module was needed to set up a control loop test. Response time of the control loop was measured by capturing Modbus traffic with tcpdump. Multiple iterations were performed to show minimum, maximum, average, median and 90th pctl. latencies. The results indicate that the container-based solution has a smaller overhead than the hypervisor-based solution and it has a very little overhead in general. Peak latencies are a concern and even the average latencies show that this solution would not be suitable for any hard real-time or safety-related applications. Further investigation on the topic would be needed to estimate the actual potential of PLC virtualization on hard real-time applications. First of all, a more powerful hardware PC would be needed to perform such tests. Secondly, a faster industrial protocol than Modbus TCP/IP would be required. Perhaps another kind of approach would be needed to overcome the issues that were experienced in this case study. It would be interesting to test a direct communication between virtual PLC and I/O and use Node-RED nodes for example to trigger inputs. Anyhow, it seems that container-based solution is holding much promise as a virtualization approach

Impact of Different Storage Regimes on the Levels of Physicochemical Characteristics, Especially Free Acidity in Talh (<i>Acacia gerrardii</i> Benth.) Honey

This study investigates how storage conditions (temperature and duration) may affect the physicochemical parameters, especially free acidity (FA), of Talh honey originating from Acacia gerrardii that have naturally high FA levels. Fresh Talh honey samples were kept at 0, 25, 35, and 45 °C, and analyzed monthly over a period of eight months. The Talh honey was monofloral with 69% A. gerrardii pollen content. The free acidity (FA) of freshly harvested Talh honey samples was higher (93 ± 0.3 meq/kg) than that of standard limits (≤50 meq/kg) and remained stable at 0 °C throughout the storage period. A significantly increase in FA started to occur after storage for 6 months at 25 °C (103 ± 0.2 meq/kg), 2 months at 35 °C (108 ± 0.3 meq/kg), and 1 month at 45 °C (112 ± 0.3 meq/kg). After 8 months of storage, the highest FA level was recorded at 45 °C (159 ± 0.5 meq/kg), followed by 127 ± 0.3 meq/kg at 35 °C, 105 ± 0.2 meq/kg at 25 °C, and 94 ± 0.3 meq/kg at 0 °C. It was found that 0 °C was an appropriate temperature for storing honey for long time. The electrical conductivity (EC) of fresh Talh samples (1.46 ± 0.0 mS/cm) was above the accepted limit (≤0.8 mS/cm), which was slightly increased (non-significant) throughout the storage period under all the storage temperatures. Hydroxymethylfurfural (HMF), diastase activity (DN), and reducing sugars (RSs) showed normal levels only at 0 °C and 25 °C throughout the storage period. However, HMF exceeded the standard limits after the first month at 45 °C (127 ± 9.6 mg/kg) and after the second month at 35 °C (90 ± 23.5 mg/kg), DA decreased below standard limits after the second month (5 ± 1 DN) under 45 °C and after the seventh month under 35 °C (7 ± 2 DN, and RSs decreased below 60% after 2 months under 45 °C and after 6 months at 35 °C. The physicochemical parameters (moisture content, pH, color, and sucrose) were the least affected and were within the standard range throughout the storage period under all the storage temperatures. The levels of FA and EC in fresh Talh samples were higher than the acceptable limits. The moisture content, pH, color, and sucrose content were not affected by storage conditions and remained within the acceptable limits. HMF, DA, and RSs were significantly affected by storage conditions only at 35 and 45 °C. The storage of honey at low temperatures (0 and 25 °C) for up to eight months presented the least amount of changes in the honey, and the honey was unchanged from its fresh status. Honey storage at 35 and 45 °C resulted in significant changes. It is recommended that Talh honey, which normally has high acidity levels, should be stored at temperatures not exceeding 25 °C

Microwave Irradiation Assists the Synthesis of a Novel Series of <i>bis</i>-Arm <i>s</i>-Triazine Oxy-Schiff Base and Oxybenzylidene Barbiturate Derivatives

A novel series of s-triazines incorporating 4-hydroxybenzaldehyde and 4-hydroxy-3-methoxybenzaldehyde was prepared and fully characterized. The reaction was carried out via stepwise nucleophilic aromatic substitution of chlorine atoms in cyanuric chloride. The first chlorine was substituted by different amines (morpholine, piperidine, or diethylamine) to afford 2,4-dichloro-6-substituted-1,3,5-triazine. The second and third chlorines were substituted by benzaldehyde derivatives in the presence of Na2CO3 as a HCl scavenger to afford the target products: s-triazine oxyaldehyde derivatives (dipodal). The dipodal derivatives were reacted with acid hydrazide, hydralazine, barbituric, or thiobarbituric acid derivatives using conventional heating or microwave irradiation to afford the di-arm s-triazine oxy-Schiff base and oxybenzylidene barbiturate derivatives in good yields. Microwave irradiation done in less solvent afforded the target product in less reaction time with good yield and purity. These types of derivatives might have special interest in coordination and medicinal chemistry

Rapid and Sensitive Determination of Methylxanthines in Commercial Brands of Tea Using Ultra-High-Performance Liquid Chromatography-Mass Spectrometry

Recently, chromatographic techniques have the potential to be greener in order to reduce the environmental impact. In this work, a new simple, sensitive, efficient, and green analytical method based on UHPLC-MS has been developed for a quick determination of methylxanthines including caffeine, theobromine, and theophylline in tea. Under the optimum conditions, a baseline separation has been achieved within 30 seconds, using isocratic elution consisting of 90% water and only 10% acetonitrile at 0.5 mL/min flow rate (3 mL acetonitrile per hour). The mass spectrometer was operated with the SIR mode in ESI+. The developed method was found to be linear in the range of 0.03–5 μg/mL, with correlation coefficients greater than 0.9995 for the three compounds. The respective values of LOD were found to be 0.025, 0.015, and 0.01 μg/mL for caffeine, theobromine, and theophylline, respectively. The proposed assay was applied to 30 commercial tea samples of different brands. Both caffeine and theobromine were found in all tea samples with maximum concentration in sample no. 15, corresponding to 32.6 and 2.72 mg/g of caffeine and theobromine, respectively. On the contrary, theophylline was not detected at all in most samples. When compared with all previous studies that dealt with the same compounds in different matrices, the developed method was found to be the fastest, allowing high-throughput analyses with more than 100 samples/h. The results prove that the method is suitable for routine analysis of methylxanthines and to distinguish the quality of tea samples of various brands

Development of In-Needle SPME Devices for Microextraction Applied to the Quantification of Pesticides in Agricultural Water

The chemical industry explosion in the 20th century has led to increased environmental pollution, affecting fauna, flora, and waterways. These substances alter water’s taste, color, and smell, making it unfit for consumption or toxic. Agricultural water networks face threats from pollution before and after treatment. Some chemical contaminants, like pesticides, are embedded in natural biogeochemical cycles. In this study, we developed a simple and low-cost procedure for the fabrication of needles coated with polydimethylsiloxane (PDMS) as an efficient sorbent for the microextraction of organic pollutant traces from water. The prepared needles were used as an alternative for commercial solid-phase micro-extraction (SPME) devices in analytical chemistry. The PDMS polymeric phase was characterized by Fourier-transform infrared spectroscopy (FT-IR), thermogravimetry (TGA), and scanning electron microscopy (SEM). The PDMS-coated needles were used for extraction of thirteen pesticides by direct-immersion solid-phase microextraction (DI-SPME) from contaminated waters, followed by determination with gas chromatography-mass spectrometry (GC-MS). The developed analytical method showed limits of detection (LODs) between 0.3 and 2.5 ng mL−1 and RSDs in the range of 0.8–12.2%. The homemade needles were applied for the extraction of pesticides in surface and ground aqueous samples collected from an agricultural area. Several target pesticides were identified and quantified in the investigated water samples

Antibacterial, Antioxidant Activity of Ethanolic Plant Extracts of Some Convolvulus

Convolvulus austroaegyptiacus Abdallah & Sa’ad (CA) and Convolvulus pilosellifolius Desr. (CP) are commonly used in the Saudi Arabia folk medicine. They are potent in treating the ulcers and skin diseases. The lack of information about their biological activities led us to investigate the possible biological activities by determination of antibacterial and antioxidant activities of total ethanolic extracts and various fractions. Total flavonoid contents of the plants were determined by colorimetric method while total phenols were determined by using Folin-Ciocalteu method. In vitro antibacterial activity was studied against E. coli, P. aeruginosa, and B. subtilis, and the total antioxidant capacity was evaluated by radical scavenging method. IC50 were found to be 21.81, 17.62, and 3.31 μg/mL for CA, CP, and vitamin C, respectively, while the lowest MIC value of 0.25 mg/mL was recorded with CP extract against B. subtilis. Around 21 compounds are tentatively elucidated from both plants using rapid, simple, and high-resolution analytical technique for chemical profiling of natural compounds by direct analysis in real-time of flight-mass spectrometry, of which 17 were not isolated or reported previously

Indirect chiral separation of crystal methamphetamine seized in Saudi Arabia using GC-MS

In the last decade, worldwide illegal production and consumption of methamphetamine (MA) has dramatically increased. MA is chiral and its two enantiomers have different biological properties, the S isomer having higher stimulating and addictive effects and therefore important to determine the enantiomeric ratio in drug seizures. The chiral separation and determination of R and S-MA may be used for characterization of the seized samples and elucidation of the illicit method of preparation. The present article aims to investigate the enantiomeric distribution of R and S methamphetamine in a series of seized samples. The enantioseparation was achieved first by derivatization of MA using L-TPC followed by separation of the resulting diastereomers using GC-MS. The optimized chromatographic method allowed baseline separation of the peaks with a resolution parameter of 2.16. While the total concentration of methamphetamine in the seized samples was between 15.09 and 213.20 mg/g, all investigated samples showed the presence of both R and S enantiomers, with a higher content of S-MA. The enantiomeric excess (ee%) was calculated to characterize each sample, the obtained values were in the range 55.27–92.38%. The results demonstrated that the seized samples originated from different batches and most likely from a stereospecific synthetic route

Mercerized mesoporous date pit activated carbon—A novel adsorbent to sequester potentially toxic divalent heavy metals from water - Fig 5

<p>SEM images of DPAC before (a), and after Cu(II) (b), Zn(II) (c), Cd(II) (d), Pb(II) adsorption.</p

Mercerized mesoporous date pit activated carbon—A novel adsorbent to sequester potentially toxic divalent heavy metals from water - Fig 6

<p>TGA plot (a), FT-IR spectra of DPAC before and after heavy metals adsorption (b).</p