Simultaneous determination of 11 related impurities in propofol by gas chromatography/tandem mass spectrometry coupled with pulsed splitless injection technique

A variety of related impurities, including starting materials, process impurities, and degradation products, can be detected in propofol. In this article, a sensitive and selective GC‐MS/MS method using pulsed splitless injection technique for the determination of 11 main related impurities in propofol in one chromatogram is investigated. This method is extensively validated for its linearity, recovery, precision, LOD, and LOQ, and is able to detect trace‐level related impurities (LOD = 0.2–5.6 μg/g) in propofol bulk drug. Stressed tests proposed that oxidative degradation, photolytic degradation, and heat are the main causes for the formation of degradation products in propofol.     

Comparison of different sample pre‐treatments for multi‐residue analysis of organochlorine and pyrethroid pesticides in chrysanthemum by gas chromatography with electron capture detection

The widespread use of insecticides in Chinese herbal medicines has created a compelling need for the development of a multiresidue analytical method to help assure herbs safety. The operating variables affecting the performance of the multiresidue analysis of 34 organochlorine and 12 pyrethroid pesticides in chrysanthemum, a widely used kind of Chinese herbal medicines, were evaluated. Three different extraction solvents including n‐hexane and its mixtures with acetone and petroleum ether were compared, and n‐hexane was found to be an appropriate option. A combination of gel permeation chromatography and SPE was selected as the optimum cleanup, in comparison with dispersive SPE, or the two former methods alone. The determination of the 46 pesticide residues in the spiked chrysanthemum samples was performed by GC with electron capture detection. The average recoveries ranged from 71.3 to 102.6% with RSDs of 1.4–15.7% for all of the pesticides. The LOQs were in the range of 0.0015–0.2 mg/kg, while the LODs were between 0.0005 and 0.1 mg/kg. The satisfactory accuracy, and precision, in combination with a good separation and few interferences, have demonstrated the strong potential of this technique for its application in chrysanthemum analysis.     

Oxidation of Aliphatic α,β-Unsaturated Aldimines to Amides Specifically by Oxone with AlCl3

α,β-Unsaturated aldimines were specifically oxidized to amides with Oxone in the presence of AlCl₃ as a Lewis acid in CH₂Cl₂. No migration of aryl group occurred in the rearrangement reaction.     

Synthesis of β,β′-edge fused, π-extended porphyrins and their applications in the dye-sensitized solar cells

Four π-extended, β,β′ aromatic ring fused porphyrins including mono- and opp-dibenzoporphyrins bearing two carboxyl groups at only one fused benzo group were synthesized. The optical results by UV–vis spectroscopy indicate that when compared with the absorption spectra of monobenzoporphyrins, greater light-harvesting capabilities can be realized for opp-dibenzoporphyrins with two benzo group at the opposite β,β′ positions of the porphyrin. The photovoltaic properties of these π-extended porphyrins were examined for the first time and the highest conversion efficiency of 1.62% was realized for opp-dibenzoporphyrin 8a-sensitized solar cell, which is ∼60% higher than that of monobenzoporphyrin 4a based solar cell indicating the effect of an extra aromatic π conjugation on the light-harvesting capabilities of π-extended porphyrins. Subsequent DFT calculation results supported our results obtained in the optical and photovoltaic studies.     

Synthesis of poly(l-lactic acid) with improved thermal stability by sulfonic acid-catalyzed melt/solid polycondensation

Melt/solid polycondensation (MP/SSP) is deemed as an alternative synthetic route besides ring-opening polymerization (ROP) in synthesizing poly(l-lactic acid) (PLLA). However, it is found that PLLA synthesized by MP/SSP has much poorer thermal stability than that by ROP due to more residual Sn(II) metallic catalyst in the former, but sulfonic acids does not show any detrimental effect on the thermal stability of PLLA. To synthesizing PLLA with good thermal stability by MP/SSP, a variety of commercially available sulfonic acids were screened as catalysts in MP/SSP of PLLA. Among these nonmetallic catalysts, it was found that 1,3-propanedisulfonic acid (PSA) and 1,5-naphthalene disulfonic acid (NSA) exhibited satisfactory catalytic reactivity and PLLAs with excellent thermal stability, high molecular weight, little coloration and good optical purity were successfully synthesized by MP/SSP. The decomposition temperature was increased by 80–100 °C in comparison to SnCl₂-catalyzed PLLA, and the thermal stability is comparable to commercial PLLA produced by ROP.     

Direct Blue 71 staining as a destaining‐free alternative loading control method for Western blotting

In Western blotting, a suitable loading control is indispensable for correcting errors in the total amount of loaded protein. Immunodetection of housekeeping proteins and total protein staining have traditionally been used as loading control methods. Direct Blue 71 (DB71) staining—a novel, sensitive, dye‐binding staining method compatible with immunodetection—may offer advantages over these traditional loading control methods. Three common neuroscientific samples (human plasma, human oligodendrocytes, and rat brain) were employed to assess DB71 staining as a loading control method for Western blotting. DB71, CBB, one traditional housekeeping protein, and one protein of interest were comparatively assessed for reliability and repeatability and linear dynamic range over 2.5–40 μg of protein loaded. DB71's effect on the reliability and repeatability and linear dynamic range of immunoreaction were also assessed. Across all three sample types, DB71 was either equivalent or superior to CBB and housekeeping protein‐based methods in terms of reliability and repeatability and linear dynamic range. Across all three sample types, DB71 staining did not impair the reliability and repeatability or linear dynamic range of immunoreaction. Our results demonstrate that the DB71 staining can be used as a destaining‐free alternative loading control method for Western blotting.     

Synthesis of aromatic diamine-based benzoxazines and effect of their backbone structure on thermal and flammability properties of polymers

Three kinds of novel aromatic diamine-based benzoxazines containing naphthalene, propane-2,2-diyldibenzene and neopentyl groups in the backbone, respectively (designated as BAPNCP, BAPBACP and BAPNPGCP, respectively), were synthesized and characterized. In addition, the effects of backbone structures on curing behaviors of the monomers and thermal and flammability properties of the resulting polymers were systematically studied. The results indicated that BAPNPGCP displayed the highest enthalpy of the curing reaction associated with the ring-opening of benzoxazine, which was due to the effect of benzoxazine ring content per unit mass. Interestingly, the 5 wt% weight loss temperature and char residue after thermogravimetric test for poly(BAPNPGCP) were 8 °C and 7% higher than those of poly(BAPBACP). Meanwhile, the total heat release of poly(BAPNPGCP) was less than half of that for poly(BAPBACP), indicating the substantial effect of benzoxazine ring content on flammability and char formation. Furthermore, it was found that poly(BAPNCP) gave the best thermal stability and flame retardancy, which was due to the synergistic effect between naphthalene group and benzoxazine ring content. This study provides new insight into the curing behavior of benzoxazine and further understanding on the high performance of polybenzoxazine.     

Surface Performance and Cytocompatibility Evaluation of Acrylic Acid-Mediated Carboxymethyl Chitosan Coating on Poly(tetrafluoroethylene-co-hexafluoropropylene)

To improve the biocompatibility of poly(tetrafluoroethylene-co-hexafluoropropylene) (FEP) film, a technique based on Ar plasma pretreatment and UV-induced grafting polymerization was used to immobilize carboxymethyl chitosan (CMCS) on the FEP film surfaces. Initially Ar plasma was used to treat FEP film. Then, plasma treated FEP film was modified via UV-induced grafting polymerization with hydrophilic acrylic acid (AAc) monomer. The following immobilization of CMCS on the FEP-pAAc surface was carried out via an amidation reaction. The change of chemical composition and surface morphology of FEP film were characterized by attenuated total reflectance Fourier transform infrared (ATR-FTIR), X-ray photoelectron spectroscopy (XPS), scanning electronic microscopy (SEM) and atomic force microscopy (AFM). Results of water contact angles measurement showed that the hydrophilicity of the surface has improved significantly after surface modification. Furthermore, methyl thiazolyl tetrazolium (MTT) assay and cell morphology analysis confirmed that mouse fibroblasts (L929 cells) attachment and proliferation were improved remarkably on the modified FEP surface. These results suggest that CMCS were successfully employed to surface engineering FEP film, and enhanced its cell biocompatibility. The approach presented here may be exploited for surface modification of biomaterials.     

双功能配体促进的钯催化不对称醚化和胺化反应（英文）

研究双亚砜膦配体(BiSO-P)亚砜基团的Bronsted碱性在协同催化反应中的作用.1H NMR研究表明双亚砜膦与醇和胺等质子试剂形成氢键;并将此类配体应用于钯催化的不对称醚化和胺化反应,最高获得99%ee.研究发现氢键的存在能有效提高反应的ee值,配体亚砜基团在反应过程中同时起着Lewis和Bronsted碱的作用.