Novel Simultaneous Determination of Calcium and Magnesium Based on Flow Injection Gradient Titration

A novel approach based on flow injection gradient titration is proposed for the simultaneous spectrophotometric determination of Ca and Mg based on parameters of a single signal. Two reagents, calmagite and EDTA, are used to perform the determinations. Calmagite is introduced into a sample to form complexes with the analytes and the solutions are introduced into the holding coil of a sequential injection system in the sequence: carrier, air, sample, EDTA, and sample. In the system, EDTA replaces calmagite to form more stable complexes in turn with Ca and Mg. Next, the flow is reversed and the mixture is directed to the detector where the signal is measured at 680?nm. The signal consists of two parts: a short plateau (the signal for the sum of absorbance of complexes of Ca and Mg with calmagite) and a peak (the signal corresponding to titration of both complexes using EDTA). The absorbance values measured at the plateau and appropriately measured peak width were applied to determine analytes using two-component calibration. The method was verified for the determination of analytes in synthetic samples and in a certified reference material of surface water. Using the developed method, Mg and Ca were determined within the concentration ranges of 0.5–5.0 and 1.0–10.0?mg?L^?1, with precision better than 2.2 and 4.2% (relative standard deviation) and accuracy of 7.0 and 6.8% (relative error). The detection limits were 0.1 and 0.3?mg?L^?1 for Mg and Ca, respectively. The method was applied to analysis of mineral water samples.     

Continuous flow reaction system for the synthesis of 2,2,2-trichloroacetophenone derivatives and its application

A continuous flow reaction system was developed for the synthesis of 2,2,2-trichloroacetophenone derivatives. When aryl propiolic acids and water were mixed with trichloroisocyanuric acid in DMF at 5?°C, the 2,2,2-trichloroacetophenone derivatives were formed within 5?min with good yields. In addition, the resulting mixture was flowed to react with amines to give the corresponding benzamide. This flow reaction system provided higher yields within shorter times than the batch reaction system.     

Study on the flow of highly concentrated emulsions

An investigation was performed into the flow of highly concentrated water-in-oil emulsions. The viscosity of the low shear rate region in the downward curve was much higher than the viscosity of the upward curve due to the refining effect of the intensive shear. However, this refining effect lasted for just a short time. After that, the structure of highly concentrated emulsion (HCE) can return to its original state. The flow of HCE depends on the shear rate and droplet size of the dispersed phase. The viscosity curve of HCE, which is measured in the initial upward shearing sweep, had two platforms, whereas the region of shear rate was 10^?4?s^?1?～?10³?s^?1. The water-in-oil structure was destroyed by intensive shear and much solid ammonium nitrate (AN) was observed in the image of HCE. The small droplets can enhance the capacity of HCE to prevent the breakage of structure under shearing. The microstructure of HCE was closer to its original situation when the droplet size was small.     

Differential mobility spectrometry (DMS) reveals the elevation of urinary acetylcarnitine in non‐human primates (NHPs) exposed to radiation

Acetylcarnitine has been identified as one of several urinary biomarkers indicative of radiation exposure in adult rhesus macaque monkeys (non‐human primates, NHPs). Previous work has demonstrated an up‐regulated dose‐response profile in a balanced male/female NHP cohort. 1 As a contribution toward the development of metabolomics‐based radiation biodosimetry in human populations and other applications of acetylcarnitine screening, we have developed a quantitative, high‐throughput method for the analysis of acetylcarnitine. We employed the Sciex SelexIon DMS‐MS/MS QTRAP 5500 platform coupled to flow injection analysis (FIA), thereby allowing for fast analysis times of less than 0.5 minutes per injection with no chromatographic separation. Ethyl acetate is used as a DMS modifier to reduce matrix chemical background. We have measured NHP urinary acetylcarnitine from the male cohorts that were exposed to the following radiation levels: control, 2, 4, 6, 7, and 10 Gy. Biological variability, along with calibration accuracy of the FIA‐DMS‐MS/MS method, indicates LOQ of 20 μM, with observed biological levels on the order of 600 μM and control levels near 10 μM. There is an apparent onset of intensified response in the transition from 6 to 10 Gy. The results demonstrate that FIA‐DMS‐MS/MS is a rapid, quantitative technique that can be utilized for the analysis of urinary biomarker levels for radiation biodosimetry.     

A structure-based design approach to advance the allyltyrosine-based series of HIV integrase inhibitors

As of mid-2017, only one structure of the human immunodeficiency virus (HIV) integrase core domain co-crystallised with an active site inhibitor was reported. In this structure (1QS4), integrase is complexed with a diketo-acid based strand-transfer inhibitor (INSTI). This structure has been a preferred platform for the structure-based design of INSTIs despite concerns relating to structural irregularities arising from crystallographic packing effects. A survey of the current pool of 297 reported integrase catalytic core structures indicated that the anatomy of the active site in the complex structure 1QS4 exhibits subtle variations relative to all other structures examined. Consequently, the 1QS4 structure was employed for docking studies. From the docking of twenty-seven allyltyrosine analogues, a 3-point inhibitor binding motif required for activity was established and successfully utilised in the development of a tripeptide displaying an EC₅₀ value of 10 ± 5 μM in HIV infected human T-cells. Additional docking of “in-house” compound libraries unearthed a methyl ester based nitrile derivative displaying an IC₅₀ value of 0.5 μM in a combined 3′-processing and strand-transfer assay.     

Combining C-H functionalisation and flow photochemical heterocyclic metamorphosis (FP-HM) for the synthesis of benzo[1,3]oxazepines

C-H Activation/functionalisation and Flow Photochemical Heterocyclic Metamorphosis (FP-HM) have been combined to synthesize a library of benzo [1,3]oxazepines, a rarely described heterocyclic family. This combined protocol allows a range of arylated products to be made from simple starting materials, and the cheap flow photochemical system has proven effective for rapid synthesis of gram-quantities of benzo [1,3]oxazepines.     

Development of overlapping repeated separation of steviol glycosides with counter current chromatography and a comparison with a conventional repeated separation method

Repeated separation is a valuable method in counter current chromatography, especially on a preparative scale. It can greatly reduce the separation time and the consumption of solvent. In this study, an overlapping repeated separation method was developed. Meanwhile, this method was used to separate steviol glycosides and compared with conventional repeated separation method. The results show that both methods are effective ways for countercurrent chromatography to prepare compounds but the overlapping repeated separation method requires fewer time and solvent than the conventional repeated separation method. So this novel repeated separation method has enormous potential for a preparative separation of target compounds and is very useful for the high‐throughput purification of natural products.     

Photodecomposition of phenol in a flow reactor: Adsorption and kinetics

Summary In this study, a new air lift loop photoreactor was used for both continuous and non-continuous water photodetoxification. Also, the kinetics of phenol photodegradation were measured under flow conditions. Both the kinetics of phenol adsorption on TiO₂/SiO₂ and of the total photo-mineralization of phenol were measured in order to gain more knowledge on the photocatalytic oxidation of phenol on illuminated titania.Adsorption of phenol on TiO₂/SiO₂ proceeds even from diluted solutions. However, based on our data, it is impossible to state precisely the influence of the adsorption on the overall rate of phenol photodecomposition. The photoreaction yields stable intermediates which subsequently undergo total mineralization to CO₂ and H₂O. It is postulated that the intermediates consist mainly of polymeric compounds, difficult to determine by conventional analytical methods like GC, HPLC, or UV/Vis spectroscopy.

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Photolyse von Phenol in einem Durchflußreaktor: Adsorption und Kinetik

Zusammenfassung Ein neuartiger Photoreaktor wurde auf seine Verwendbarkeit zur kontinuierlichen und nichtkontinuierlichen Wasseraufbereitung getestet. Die Kinetik des photolytischen Abbaus von Phenol wurde unter Durchflußbedingungen untersucht. Zum besseren Verständnis der photokatalysierten Oxidation von Phenol auf belichtetem Titanoxid wurde außerdem die Kinetik sowohl der Adsorption von Phenol an TiO₂/SiO₂ als auch seiner Gesamtphotomineralisierung erforscht.Adsorption von Phenol an TiO₂/SiO₂ erfolgt bereits aus verdünnten Lösungen. Nach unseren Ergebnissen ist es allerdings unmöglich, den Einfluß der Adsorption auf die Photolyse genau zu bestimmen. Die Photoreaktion ergibt stabile Zwischenprodukte, die sich im weiteren Verlauf zu CO₂ und H₂O umsetzen. Es wird postuliert, daß es sich bei den Zwischenprodukten hauptsächlich um Polymere handelt, die mit konventionellen analytischen Techniken wie GC, HPLC oder UV/Vis-Spektroskopie schwer nachzuweisen sind.

     

The effect of ultrasound on the structure and properties of the water-soluble corn hull heteroxylan

Ultrasonic irradiation of a water-soluble corn hull xylan fraction in neutral and alkaline aqueous medium has been found to produce significant changes in its molecular properties. Degradation is first manifested by a decrease in the large molar mass component under generation of polymer chains with about the same size as those of the main molar mass component. The latter is slightly shifted to the lower molar mass region only at stronger irradiation conditions. Ultrasonication of the xylan in neutral aqueous medium at high ultrasound power and/or long irradiation caused no significant changes in its sugar composition, primary structure and viscoelastic properties.     

Picogram determination of estrogens in water using large volume injection gas chromatography–mass spectrometry

In this study, a simple and efficient large volume injection gas chromatography–mass spectrometry (GC-MS) method, via a programmable-temperature vaporizer (PTV) inlet, has been developed and applied in the determination of estrogens in environmental water samples without a prior derivatization process. Three commonly used estrogens estrone, 17 β-estradiol and 17 α-ethynylestradiol were selected as target compounds for this study. It has been demonstrated that the type of gas chromatograph liner and the initial inlet temperature can greatly affect the response intensity of estrogens. Three different types of PTV liners have been studied; the multibaffle liner generated the strongest response intensities towards the estrogen analytes. The results showed that the response intensities of estrogens reduced sharply while the initial inlet temperature increased. Various instrument conditions and sample preparation methods were studied in detail. The optimized method has been validated with good linearity, precision and accuracy. The method detection limit of each estrogen was found to be 0.041 ng/L for estrone, 0.046 ng/L for 17 β-estradiol and 0.031 ng/L for 17 α-ethynylestradiol. To the best of our knowledge, these results represent the best sensitivities achieved for estrogens analyzed in water samples via traditional GC-MS method without a derivatization process. This method has been successfully applied in the analyses of different water samples.