Assessing the nucleophilic character of 2-amino-4-arylthiazoles through coupling with 4,6-dinitrobenzofuroxan: Experimental and theoretical approaches based on structure-reactivity relationships

A kinetic study of the reactions of potentially bioactive 2-amino-4-arylthiazoles with highly reactive 4,6-dinitrobenzofuroxan (DNBF) is reported herein in acetonitrile solution. The complexation reaction was followed by recording the UV–vis spectra with time at λ_max = 482 nm. Electronic effects of substituents influencing the rate of reaction have been studied using structure-reactivity relationships. It is shown that the Hammett plot relative to the reaction of DNBF with 2-amino-4-(4-chlorophenyl)thiazole exhibit positive deviation from the log k₁ versus σ correlation, while it showed excellent linear correlation in terms of Yukawa–Tsuno equation. It has be noticed that the nonlinear Hammett plot observed for 2-amino-4-(4-chlorophenyl) thiazole is not attributed to a change in rate-determining step but is due to nature of electronic effect of substituent caused by the resonance of stabilization of substrates. The second-order rate constant (k₁) relating to the bond C–C and C-N forming step of the complexation processes of DNBF with 4-substituted-aminothiazoles and 2-amino-5-methyl-4-phenylthiazole, respectively, is fit into the linear relationship log k = s_N (N + E), thereby permitting the assessment of the nucleophilicity parameter (N) of the 2-amino-4-arylthiazoles of the range (4.90 < N < 6.85). 2-amino-4-arylthiazoles is subsequently ranked by positioning its reactivity on the general nucleophilicity scale developed recently by Mayr and coworkers (2003) leading an interesting and a direct comparison over a large domain of π-, σ -, and n-nucleophiles. The global electrophilicity/nucleophilicity reactivity indexes of the 2-amino-4-arylthiazoles have been investigated by means of a density functional theory (DFT) method. .     

Surface passivation in n-type silicon and its application in silicon drift detector

Based on the surface passivation of n-type silicon in a silicon drift detector(SDD), we propose a new passivation structure of SiO2/Al2O3/SiO2 passivation stacks. Since the SiO2 formed by the nitric-acid-oxidation-of-silicon(NAOS)method has good compactness and simple process, the first layer film is formed by the NAOS method. The Al2O3 film is also introduced into the passivation stacks owing to exceptional advantages such as good interface characteristic and simple process. In addition, for requirements of thickness and deposition temperature, the third layer of the SiO2 film is deposited by plasma enhanced chemical vapor deposition(PECVD). The deposition of the SiO2 film by PECVD is a low-temperature process and has a high deposition rate, which causes little damage to the device and makes the SiO2 film very suitable for serving as the third passivation layer. The passivation approach of stacks can saturate dangling bonds at the interface between stacks and the silicon substrate, and provide positive charge to optimize the field passivation of the n-type substrate.The passivation method ultimately achieves a good combination of chemical and field passivations. Experimental results show that with the passivation structure of SiO2/Al2O3/SiO2, the final minority carrier lifetime reaches 5223 μs at injection of 5×10¹⁵ cm^-3. When it is applied to the passivation of SDD, the leakage current is reduced to the order of nA.     

Controlled synthesis of ZnO nanoparticles from a Zn(II) coordination polymer: Structural characterization,optical properties and photocatalytic activity

A zinc coordination polymer derived from pyridine-2,6-dicarboxylate (PDC), {[Zn₂(PDC)₂]}_n, was successfully prepared via conventional, sonication and microwave-irradiation methods. The composition and characteristics of the obtained coordination polymers (CPs) were investigated by elemental analysis, TGA/DTA, X-ray diffraction and spectroscopic techniques. The so obtained CPs were heat-treated in the air at 600 °C for 2 h to produce ZnO of nanosized particles (NPs). It is of interest to note that the synthesis approach of the precursor greatly affects both the nanoparticle size and the structure of the resulting ZnO NPs. Moreover, the smallest particle size was associated with the sample derived from the ultrasonically prepared precursor. TEM analysis revealed that all samples have sphere-like morphologies. Structural analysis of the prepared ZnO samples was conducted and compared using Rietveld analysis of their PXRD patterns. Optical band gap calculations based on analysis of the UV–vis spectra of ZnO samples using Tauc's power law were achieved. The highest band gap of 3.63 eV was observed for ZnO sample obtained from the ultrasonically prepared precursor. Furthermore, the photocatalytic activity of ZnO NPs for the removal of Eosin Y color was monitored. The highest removal efficiency was recorded for ZnO originated from the ultrasonically synthesized precursor. Enhancement of removal efficiency that reached 98% was attained in only a period of 8 min. Its recycling test showed that it can be reused without structural changes over four cycling experiments.     

o-Trityl phenoxy-imino vanadium (III) complexes: synthesis,characterization, and catalysis on ethylene (co)polymerization

Several phenoxy-imine ligands bearing o-trityl group in phenoxy moiety RN=CHArOH (Ar = C₆H₂(CPh₃)^tBu, R = 2,6-Me₂C₆H₃ ( L ₁ H ); 2,6-ⁱPr₂C₆H₃ ( L ₂ H ); 3,5-(CF₃)₂C₆H₃ ( L ₃ H ); 3,5-(OMe)₂C₆H₃ ( L ₄ H ); CHPh₂ ( L ₅ H ); CPh₃ ( L ₆ H )) were synthesized and characterized by¹H NMR and ¹³C NMR spectroscopy. The vanadium complexes based on these ligands LVCl₂(THF)₂ ( 1–6 ) were synthesized via conventional transmetalation reaction in moderate to high yields. Complexes 1–6 were fully characterized by FT-IR, elemental analyses and the molecular structures of 1 , 2 ·H₂O, (2 ·H₂O ) ₂ (μ-Cl) ₂ , 4 , and 5 were confirmed by X-ray crystallographic analysis in which the six-coordinated vanadium centers are in a typical octahedral geometry. Upon activation with Et₂AlCl in toluene, complexes 1–6 showed high activities in ethylene polymerization affording polymers with moderate molecular weight (5.9–11.8 × 10⁴ Da). Moreover, in hexane or CH₂Cl₂, 1–6 /Et₂AlCl exhibited enhanced activities. When activated with MAO or MMAO in toluene, these complexes showed relatively low activities but afforded polymers with ultra-high molecular weight (up to 3.30 × 10⁶ Da). 1–6 /Et₂AlCl also showed high activities in ethylene/1-hexene copolymerization at room temperature giving moderate molecular-weight polymers (6.5–11.4 × 10⁴ Da) with co-monomer incorporation being of 6.0 ~ 7.8%.     

Anti-neuraminidase activity of chemical constituents of Balanophora involucrata

Balanophora involucrata J. D. Hooker has been known to possess potential anti-inflammatory and antibacterial activities; however, its antiviral activity has not been evaluated so far. In order to find new neuraminidase inhibitors (NAIs), the neuraminidase (NA) inhibition activity of different B. involucrata extracts was evaluated. In this study, an in vitro NA inhibition assay was performed to identify which extract of B. involucrata exhibits (maximal) inhibitory activity against NA. Ultra high performance liquid chromatography/quadrupole time-of-flight–tandem mass spectroscopy (MS/MS) and molecular docking techniques were used to identify the specific compounds responsible for the anti-influenza activity of the extract, and to explore the potential natural NAIs. The ethyl acetate extract of B. involucrata exhibited significant inhibitory activity against NA with 50% inhibitory concentration (IC₅₀) value of 159.5 μg/mL. Twenty compounds were identified according to the MS/MS spectra; among them two compounds (quercitrin and phloridzin) showed obvious inhibitory activity against NA, with IC₅₀ of 311.76 and 347.32 μmol/L, respectively. This study suggested that B. involucrata can be a potential natural source of NAIs and may be useful in the fight against ferocious influenza viruses.     

Simple and Precise Quantification of Iron Catalyst Content in Carbon Nanotubes Using UV/Visible Spectroscopy

Iron catalysts have been used widely for the mass production of carbon nanotubes (CNTs) with high yield. In this study, UV/visible spectroscopy was used to determine the Fe catalyst content in CNTs using a colorimetric technique. Fe ions in solution form red–orange complexes with 1,10-phenanthroline, producing an absorption peak at λ=510 nm, the intensity of which is proportional to the solution Fe concentration. A series of standard Fe solutions were formulated to establish the relationship between optical absorbance and Fe concentration. Many Fe catalysts were microscopically observed to be encased by graphitic layers, thus preventing their extraction. Fe catalyst dissolution from CNTs was investigated with various single and mixed acids, and Fe concentration was found to be highest with CNTs being held at reflux in HClO₄/HNO₃ and H₂SO₄/HNO₃ mixtures. This novel colorimetric method to measure Fe concentrations by UV/Vis spectroscopy was validated by inductively coupled plasma optical emission spectroscopy, indicating its reliability and applicability to asses Fe content in CNTs.     

Development of an LC‐MS/MS method for determining the pharmacokinetics of clonidine following oral administration of Zhenju antihypertensive compound

Zhenju antihypertensive compound (ZJAHC) is a combined Chinese–Western medicine formula including clonidine (CLO), hydrochlorothiazide (HCT), rutin, Chrysanthemum indicum extract and pearl powder. Compared with CLO preparations, ZJAHC shows improved activities and decreased adverse effects. It is believed that the side effects of CLO are caused by its high peak plasma concentration. Hence, study of the influence of ZJAHC on the pharmacokinetic behaviors of clonidine seems essential. In present study, the plasma concentrations of CLO were determined with a liquid chromatography–tandem mass spectrometry (LC‐MS/MS) method. The MS/MS transitions monitored for clonidine and internal standard were 230.2 → 213.1 and 152.2 → 110.2, respectively. The analyte was quantified in a single run within 3 min. The pharmacokinetic study showed that the area under the plasma concentration–time curve of CLO in ZJAHC (60 µg/kg CLO) was similar to that of CLO‐HCT‐high (120 µg/kg CLO) but the peak concentration was much lower than that in CLO‐HCT‐high. ZJAHC could enhance the bioavailability without greatly increasing peak concentration of clonidine. This comprehensive effect of enhancing the bioavailability and avoiding the high peak plasma concentration for CLO might mainly result from the co‐contribution of Western medicine and traditional Chinese medicine (TCM), while the effect of TCM was stronger than that of Western medicine. Copyright © 2014 John Wiley & Sons, Ltd.     

The antidepressant effect of 4-hydroxybenzyl alcohol 2-naphthoate through monoaminergic,GABAergic system and BDNF signaling pathway

Abstract

Gastrodigenin, also known as 4-hydroxybenzyl alcohol (HBA), is one of the main components of Gastrodia elata, which is a perfect lead compound of natural products. In order to get new active compounds, we modified the structure of HBA through esterification with carboxylic acid, and got a series of derivatives in which 4-hydroxybenzyl alcohol 2-naphthoate (NHBA) showed stronger antidepressant activity than HBA. In this paper, we firstly evaluated the antidepressant activity of NHBA by tail suspension test (TST) and forced swimming test (FST). Then, we carried out the biochemical assay and western blot to determine its mechanism. The results displayed that NHBA could increase the content of serotonin, dopamine, norepinephrine, γ-aminobutyric acid, brain-derived neurotrophic factor (BDNF) and tropomyosin receptor kinase B (TrkB) in mice brain. It suggested that NHBA exhibited an antidepressant-like effect through monoaminergic system, GABAergic system and BDNF/TrkB signaling pathways.     

Studies on metabolism of total glucosides of paeony from Paeoniae Radix Alba in rats by UPLC‐Q‐TOF‐MS/MS

Total glucosides of paeony are the active constituents of Paeoniae Radix Alba. In this study, a novel strategy was proposed to find more metabolites and the differences between paeoniflorin, albiflorin and total glucosides of paeony (TGP). This strategy was characterized as follows: firstly, the animals were divided into three groups (paeoniflorin, albiflorin and TGP) to identify the source of TGP metabolites from paeoniflorin or albiflorin; secondly, a generic information‐dependent acquisition scan for the low‐level metabolites was triggered by the multiple mass defect filter and dynamic background subtraction; thirdly, the metabolites were identified with a combination of data‐processing methods including mass defect filtering, neutral loss filtering and product ion filtering; finally, a comparative study was used in the metabolism of paeoniflorin, albiflorin and TGP. Based on the strategy, 18 metabolites of TGP, 10 metabolites of paeoniflorin and 13 metabolites of albiflorin were identified respectively. The results indicated that the hydrolysis, conjugation reaction and oxidization were the major metabolic pathways, and the metabolic sites were the glycosidic linkage, the ester bond and the benzene ring. This study is first to explore the metabolism of TGP, and these findings enhance our understanding of the metabolism and the interactions of paeoniflrin and albiflorin in TGP. Copyright © 2015 John Wiley & Sons, Ltd.     

Recent trends in capillary and micro-chip electrophoretic instrumentation for field-analysis

Technical advances in the development of field-deployable capillary and microchip electrophoretic instruments and reports of their deployment between 2013 and 2017 were reviewed. Strategies and considerations in the design of the injection, separation and detection hardware, chemistry and associated infrastructure were discussed from an in-field perspective, with portability, robustness and automation/“ease of use” featuring as key requirements. Integration of functionality is important for adequate in-field performance. Progress was made towards the use of multiple channel devices for increased throughput and/or resolving power, mixing devices for on-line/in-line sample derivatization, battery operation and temperature control. The strengths and weaknesses of the various approaches described in the literature are discussed from the perspective of in-field operation. An overview of the applications of the field electrophoretic instruments is provided, including environmental science and planetary investigation.