Chiral resolution of diphenylalanine by high-performance liquid chromatography on a crown-ether-based chiral stationary phase and by NMR spectroscopy

Summary The enantiomers of diphenylalanine (DPA) were well separated by chiral HPLC and NMR spectroscopy on the chiral stationary phase (CSP) derived from (18-crown-6)-2,3,11,12-tetracarboxylic acid (18-C-6-TA). The chromatographic parameters such as separation factors and retention times were greatly influenced by the mobile phase conditions. The (+)-18-C-6-TA used in the CSP was also employed as a chiral solvating agent for the enantiodiscrimination of the DPA enantiomers by NMR spectroscopy. The proton of the DPA analyte showing the chemical shift nonequivalences was used in determining the enantiomeric composition of the analyte.     

Influence of extractions on physicochemical characterization and bioactivity of Piper nigrum oils: Study on the non-isothermal decomposition kinetic

Black pepper oils have been investigated frequently in the recent years. However, there is a significant variation in physicochemical properties and bioactivity of oils depended on extraction techniques. In this study, the systemic investigation of four various extraction methods was performed to evaluate the physicochemical characterizations, antioxidant and antibacterial activity. The investigation of ¹H NMR, FTIR and UV–Vis spectra confirmed presence of non-volatile components in oils extracted through supercritical CO₂ and hexane-soaking extractions which induced their typical thermal properties. The isothermal behaviour of extracted oils related to evaporation was within range of 3.2–7.3% (w/w) at 27 °C. The SEM images of the black pepper confirmed different operation manners of mechanism between extractions using the solvents and heating process. The lowest MIC for both essential oils from conventional hidrodistillation and microwave-assisted hidrodistillation against two bacteria including E. coli and B. subtilis were found to be 137 µg mL⁻¹. The non-isothermal decomposition kinetics were investigated on the essential oil of microwave-assisted hydrodistillation extraction. The activation energies and pre-exponent factors of non-isothermal decomposition were found to be in range of 36.5–73.7 KJ mol⁻¹ and 4.98 × 10³–1.97 × 10⁸ s⁻¹, respectively, dependent on conversional fractions of the oil. The results revealed that chemical components, physicochemical properties and bioactivity of black pepper essential oils depended on the extraction techniques.     

合并带流动注射分光光度法研究硫羟乳酸掩蔽性能

本文运用合并带流动注射分析技术，建立了以Ｙｂ＾３＋ＸＯ显色体系为参考体系研究硫羟乳酸掩蔽性能的方法，在ｐＨ５．６硫羟乳酸能掩蔽Ｓｎ＾４＋，Ｂｉ＾３＋，Ｔｌ＾３＋，Ｈｇ＾２＋，Ｃｕ＾２＋，Ｃｒ＾３＋和Ｃｄ＾２＋测定Ｙｂ＾３＋的线性范围为１．３６×１０＾－６～２．７２×１０＾－５ｍｏｌ／Ｌ，采样频率可达１２０次／ｈ。     

Closed tube sample introduction for gas chromatography-ion mobility spectrometry analysis of water contaminated with a chemical warfare agent surrogate compound

Ion mobility spectrometry (IMS) is a proven technology for detection of vapor phase chemical warfare agents. The technology is suitable for field portable instrumentation due to its small size, high sensitivity, speed of analysis, and low power consumption. However, it suffers from a limited dynamic range and potential difficulties in identifying compounds in complex matrices. The use of gas chromatography (GC) coupled to IMS can overcome the difficulty of chemical identification in mixtures by separating the sample into individual components before detection. Using this approach, IMS technology has previously been adapted to detect biological aerosols using an open tube pyrolyzer and a short GC column (Py-GC-IMS). The open sample introduction tube of a Py-GC-IMS instrument would be a convenient configuration to accept aerosol particulates, and while viewed as needed for aerosol trapping, is not optimal for liquid chemical analyses. To examine the usefulness of an existing Py-GC-IMS system for analysis of chemicals in water, an existing open-port sample interface was replaced with a septum-equipped closed tube injector to contain analyte vapors resulting from liquid injection. Tributylphosphate (TBP) was used as a surrogate chemical warfare agent, and aqueous injections into both closed and open tube assemblies were performed. Sample introduction into the closed tube inlet was also accomplished using solid phase microextraction (SPME) preconcentration. The limit of detection for TBP using an open tube, closed tube, and closed tube configuration with SPME sample introduction was 0.980, 0.196, and 0.0098 mg/L, respectively.     

Eco-friendly synthesis of high silica zeolite Y with choline as green and innocent structure-directing agent

Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure-directing agents (OSDAs), which are chronically hazardous to humans and the environment. It is a growing trend to develop an eco-friendly and nuisanceless OSDA for zeolite synthesis. Herein, choline is employed as a non-toxic and green OSDA to synthesize high silica Y zeolite with SiO₂/Al₂O₃ ratios of 6.5–6.8. The prepared Y zeolite samples exhibited outstanding (hydro)thermal stability at ultrahigh temperature owing to the higher SiO₂/Al₂O₃ ratio. The XRF, SEM, ²⁹Si-NMR and ¹³Na+ results suggested that choline plays a structure-directing role in the synthesis of Y zeolite, while the feed molar fraction of Na⁺ is a crucial determinant for the framework SiO₂/Al₂O₃ ratio and the crystal morphology.     

Polymer blends based on the β-modification of polypropylene

iPP/sPP, iPP/rPP, iPP/PVDF and iPP/PA-6 blends, and their β-nucleated forms were prepared in the present study. The components of iPP/sPP and iPP/rPP blends are compatible in the molten state. The phase structure of the melt of iPP/PVDF and iPP/PA-6 blends is heterogeneous. The melting and crystallisation characteristics as well as the structure and polymorphic composition of these blends were studied by polarised light microscopy (PLM) and differential scanning calorimetry (DSC). When semicrystalline polymers are added to iPP, the most important factor of the formation a blend with β-crystalline phase is the α-nucleation effect of the second polymer. In the case of polymers with an α-nucleating effect, the temperature range of their crystallisation should be lower than that of β-iPP. β-nucleated iPP/PVDF and iPP/PA-6 blends are extreme examples showing that completely β-iPP matrix can not form even in the presence of a highly effective β-nucleant, because of the strong α-nucleating ability and higher crystallisation temperature range of PVDF and PA-6. We found that the β-crystallisation tendency of random propylene copolymers can be enhanced by adding an iPP homopolymer.     

Gd complexes of diethylenetriaminepentaacetic acid conjugates of low-molecular-weight chitosan oligosaccharide as a new liver-specific MRI contrast agent

This study was to describe the synthesis of complexes of gadolinium diethylenetriaminepentaacetic acid conjugates of low-molecular-weight chitosan oligosaccharide Gd-DTPA-CSn (n = 6, 8, 11) as a new class of contrast agent as well as its magnetic property in a pilot magnetic resonance imaging. The efficacy of the contrast agent was assessed by measuring the longitudinal relaxivity (r₁), FLASH imaging in phantoms in vitro and signal intensity in vivo of the rat abdominal axial imaging. The r₁ of Gd-DTPA-CS₁₁ was up to 11.65 mM^− 1·s^− 1, which was 3 times higher than that of the analogous MRI contrast agent Gd-DTPA in commercial use. In vivo MR images of rat obtained with Gd-DTPA-CS₁₁ showed strong signal enhancement in liver and the vessels of the liver parenchyma during the extended period of time. The present study suggests that the new synthesized gadolinium complexes can be used as a new class of practical liver-specific MRI contrast agent because of its superior performance compared with Gd-DTPA.