离子色谱法测定甲醇和噻吩中硫、氯含量

建立了测定工业用甲醇和噻吩中硫、氯含量的离子色谱检测方法。样品经(700±25)℃灼烧后,残留物用蒸馏水洗涤,利用离子色谱仪进行分析。甲醇和噻吩中硫、氯检测结果的相对标准偏差为1.04%~1.26%,加标回收率为99.2%~101.2%。该方法操作简单,精密度和准确度高,可用于大部分可燃性有机化合物中硫、氯含量的检测。     

Amperometric detection of nitrite based on Dawson-type vanodotungstophosphate and carbon nanotubes

A nitrite sensor based on Dawson vanodotungstophosphates α₂-K₇P₂VW₁₇O₆₂·18H₂O (P₂W₁₇V) and carbon nanotubes (CNTs) was prepared by electrostatic layer-by-layer self-assembly technique. The sensor {PEI/PSS/[PDDA/P₂W₁₇V-CNTs]_n} was characterized by UV–vis spectroscopy, atomic force microscopy (AFM), scanning electron microscopy (SEM) and X-ray photoelectron spectra (XPS). The electron transfer and sensing ability of this sensor were explored using cyclic voltammetry (CV) and electrochemical impedance spectra (EIS) technology. The results show that the incorporation of CNTs and P₂W₁₇V into the composite film endowed the modified electrode with fast transfer rate and high electrocatalytic activity towards oxidation of nitrite. This nitrite sensor with 10 bilayers has a broad linear range of 5 × 10⁻⁸ to 2.13 × 10⁻³ M, a low detection limit of 0.0367 μM (S N⁻¹ = 3), a high sensitivity of 0.35 mA mM⁻¹ NO₂⁻, an excellent anti-interference property in the presence of other potential interfering species and a good stable. It was successfully employed for determination of nitrite in real towards.     

Synthesis and comparative study of the heterocyclic rings on liquid crystalline properties of 2,5-aryl-1,3,4-oxa(thia)diazole derivatives containing furan and thiophene units

A series of heterocyclic liquid crystalline compounds containing 1,3,4-oxadiazole/thiadiazole, furan and thiophene units were synthesised and characterised by means of electrospray ionisation-mass spectrometry (ESI-MS), high-resolution mass spectroscopy (HRMS), ¹H nuclear magnetic resonance (NMR) and ¹³C NMR. The thermal behaviours were investigated by differential scanning calorimetry (DSC) and polarised optical microscopy (POM). The effect of the 1,3,4-oxadiazole, 1,3,4-thiadiazole, furan, thiophene and benzene rings on the liquid crystalline properties was discussed briefly in context with the geometrical and electronic factors. The results showed that the tendency to form mesophases follows the sequence: 1,4-disustituted benzene >2,5-disubstituted thiophene >2,5-disustituted furan and 1,3,4-thiadiazole >1,3,4-oxadiazole.     

Synthesis and liquid crystalline properties of substituted 2,5‐diaryl 1,3,4‐oxadiazole derivatives without flexible chains

A series of new compounds based on aromatically 2,5‐disubstituted 1,3,4‐oxadiazoles without flexible chains, formulated as p‐R–C₆H₄–(OC₂N₂)–(p‐C₆H₄)₂–R′ with (i) R = CH₃O, R′ = CH₃O, CH₃S, F, H (Ia–Id), (ii) R = CH₃S, R′ = CH₃O, CH₃S, F, H (IIa–IId) and (iii) R = F, R′ = CH₃O, CH₃S, F, H (IIIa–IIId) (p‐C₆H₄ and OC₂N₂ represent a p‐phenylene spacer and a 1,3,4‐oxadiazole ring, respectively), were synthesised and characterised by ¹H and ¹³C NMR, MS and HRMS techniques. Mesomorphic properties were investigated using differential scanning calorimetry and polarizing optical microscopy. All of the target compounds (except Id, IId, IIIc and IIId) exhibited an enantiotropic nematic mesophase with high melting temperatures. The liquid crystalline properties of these compounds were influenced greatly by polarity, steric factors and positions of the terminal groups. The effect of the terminal groups on the liquid crystal properties is discussed.     

Evaluation of measurement uncertainty in EA–IRMS: for determination of δ 13C value and C-4 plant sugar content in adulterated honey

In this study, the method for determining the stable carbon isotope ratio value was validated. Measurement uncertainty of stable carbon isotope ratio value of whole honey and its extracted protein derived from repeatability, reference gas, reference standards and calibration curve was calculated by applying the “bottom-up” approach according to Eurachem/CITAC guide. The expanded uncertainties for all results ranged from 0.14 to 0.19 ‰, with most of them between 0.15 and 0.16 ‰ (the coverage factor k = 2, the level of confidence p is approximately 95 %). The percentage contribution of each source to the relative combined uncertainty was calculated. The data indicated that calibration curves have more contribution to the relative combined uncertainty than repeatability and reference standards. On the other hand, the measurement uncertainty of C-4 sugar content in honey was estimated. Based on these results, 58 honey samples, such as acacia, chaste, Northeast China black bee, flowers and jujube honey, have been gathered to determine the C-4 plant sugar content adulteration in honey by elemental analyzer with an isotope ratio mass spectrometer. It can be found that all honey samples were not adulterated by C-4 plant sugar.     

A green strategy for lithium isotopes separation by using mesoporous silica materials doped with ionic liquids and benzo-15-crown-5

Three new mesoporous silica materials IL15SGs (HF15SG, TF15SG and DF15SG) doped with benzo-15-crown-5 and imidazolium based ionic liquids (C₈mim⁺PF₆ ^?, C₈mim⁺BF₄ ^? or C₈mim⁺NTf ₂ ^? ) have been prepared by a simple approach to separating lithium isotopes. The formed mesoporous structures of silica gels have been confirmed by transmission electron microscopy image and N₂ gas adsorption–desorption isotherm. Imidazolium ionic liquids acted as templates to prepare mesoporous materials, additives to stabilize extractant within silica gel, and synergetic agents to separate the lithium isotopes. Factors such as lithium salt concentration, initial pH, counter anion of lithium salt, extraction time, and temperature on the lithium isotopes separation were examined. Under optimized conditions, the extraction efficiency of HF15SG, TF15SG and DF15SG were found to be 11.43, 10.59 and 13.07 %, respectively. The heavier isotope ⁷Li was concentrated in the solution phase while the lighter isotope ⁶Li was enriched in the gel phase. The solid–liquid extraction maximum single-stage isotopes separation factor of ⁶Li–⁷Li in the solid–liquid extraction was up to 1.046 ± 0.002. X-ray crystal structure analysis indicated that the lithium salt was extracted into the solid phase with crown ether forming [(Li_0.5)₂(B15)₂(H₂O)]⁺ complexes. IL15SGs were also easily regenerated by stripping with 20 mmol L^?1 HCl and reused in the consecutive removal of lithium ion in five cycles.     

Metabolism of synthetic cannabinoids PB-22 and its 5-fluoro analog, 5F-PB-22, by human hepatocyte incubation and high-resolution mass spectrometry

Background

PB-22 (1-pentyl-8-quinolinyl ester-1H-indole-3-carboxylic acid) and 5F-PB-22 (1-(5-fluoropentyl)-8-quinolinyl ester-1H-indole-3-carboxylic acid) are new synthetic cannabinoids with a quinoline substructure and the first marketed substances with an ester bond linkage. No human metabolism data are currently available, making it difficult to document PB-22 and 5F-PB-22 intake from urine analysis, and complicating assessment of the drugs’ pharmacodynamic and toxicological properties.

Methods

We incubated 10 μmol/l PB-22 and 5F-PB-22 with pooled cryopreserved human hepatocytes up to 3 h and analyzed samples on a TripleTOF 5600+ high-resolution mass spectrometer. Data were acquired via TOF scan, followed by information-dependent acquisition triggered product ion scans with mass defect filtering (MDF). The accurate mass full scan MS and MS/MS metabolite datasets were analyzed with multiple data processing techniques, including MDF, neutral loss and product ion filtering.

Results

The predominant metabolic pathway for PB-22 and 5F-PB-22 was ester hydrolysis yielding a wide variety of (5-fluoro)pentylindole-3-carboxylic acid metabolites. Twenty metabolites for PB-22 and 22 metabolites for 5F-PB-22 were identified, with the majority generated by oxidation with or without glucuronidation. For 5F-PB-22, oxidative defluorination occurred forming PB-22 metabolites. Both compounds underwent epoxide formation followed by internal hydrolysis and also produced a cysteine conjugate.

Conclusion

Human hepatic metabolic profiles were generated for PB-22 and 5F-PB-22. Pentylindole-3-carboxylic acid, hydroxypentyl-PB-22 and PB-22 pentanoic acid for PB-22, and 5′-fluoropentylindole-3-carboxylic acid, PB-22 pentanoic acid and the hydroxy-5F-PB-22 metabolite with oxidation at the quinoline system for 5F-PB-22 are likely the best targets to incorporate into analytical methods for urine to document PB-22 and 5F-PB-22 intake.

GPCR A2A AR腺苷受体蛋白的激动剂结合及其诱导的蛋白活性开关构象变化

运用分子动力学模拟,研究了腺苷酸（激动剂）与A2AAR腺苷受体蛋白的相互作用和配体结合诱导的蛋白动力学变化．识别了与腺苷酸结合力强于0．5kcal／mol的关键基团：A63^2．61,I66^2．64,V84^3.32,L85^3.33,T88^3.36,F168^5.29,M177^5.38,L249^6.51,H250^6.52和N253^6.55,观察到腺苷酸没有与L167^5.28相互作用,这一结果支持了L167^5.28是抑制剂特异性结合位点,不与激动剂结合．未结合配体（激动剂或抑制剂）的单体A2AAR和腺苷酸结合后的A2AAR在构象上有三个不同功能性开关．腺苷酸结合可以诱导A2AAR腺苷受体蛋白的构象调整,使得三个功能性开关器件的构象与单体A2AAR不同．     

Energetic Salts Based on an Oxygen‐Containing Cation: 2,4‐Diamino‐1,3,5‐triazine‐6‐one

A family of energetic salts with high thermal stability and low impact sensitivity based on an oxygen‐containing cation, 2,4‐diamino‐1,3,5‐triazine‐6‐one, were synthesized and fully characterized by IR and multinuclear (¹H, ¹³C) NMR spectroscopy, elemental analysis, and differential scanning calorimetry. Insights into their sensitivities towards impact, friction, and electrostatics were gained by submitting the materials to standard tests. The structures of 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate, 2,4‐diamino‐1,3,5‐triazine‐6‐one sulfate, 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, 2,4‐diamino‐1,3,5‐triazine‐6‐one 5‐nitrotetrazolate were determined by single‐crystal X‐ray diffraction; their densities are 1.691, 1.776, 1.854, and 1.636 g cm^?3, respectively. Most of the salts decompose at temperatures over 180 °C; in particular, the salts 2,4‐diamino‐1,3,5‐triazine‐6‐one nitrate and 2,4‐diamino‐1,3,5‐triazine‐6‐one perchlorate, which decompose at 303.3 and 336.4 °C, respectively, are fairly stable. Furthermore, most of the salts exhibit excellent impact sensitivities (>40 J), friction sensitivities (>360 N), and are insensitive to electrostatics. The measured densities of these energetic salts range from 1.64 to 2.01 g cm^?3. The detonation pressure values calculated for these salts range from 14.6 to 29.2 GPa, and the detonation velocities range from 6536 to 8275 m s^?1; these values make the salts potential candidates for thermally stable and insensitive energetic materials.