Continuous separation of maslinic and oleanolic acids from olive pulp by high‐speed countercurrent chromatography with elution‐extrusion mode

In this work, a continuous high‐speed countercurrent chromatography method has been developed on the basis of elution‐extrusion mode and this method was successfully applied to the separation of maslinic and oleanolic acid from the extract of olive pulp. In the process of ‘elution’, the sample solution was continuously loaded into the column and the maslinic acid was steadily eluted out in this step while highly retained oleanlic acid always stayed in the column. In the process of ‘extrusion’, the oleanlic acid was pushed out of the column with the stationary phase. In this way, we achieved a large sample loading. A total of 120 mL sample solution (about 89.55% of the column volume) which contains 600 mg olive pulp extract was pumped in the apparatus by a constant‐flow pump and the maslinic and oleanolic acids were largely separated within 120 min. Both of these two compounds presented high yields and high purities (271.6 mg for maslinic acid with 86.7% and 83.9 mg oleanolic acids with 83.4%).     

A simple two‐stage column chromatographic separation scheme for strontium,lead, neodymium and hafnium isotope analyses in geological samples by thermal ionization mass spectrometry or multi‐collector inductively coupled plasma mass spectrometry

Here, a two‐stage column separation scheme is developed for the concomitant isolation of Sr, Pb, Nd, and Hf from geological samples. The first column, which consists of three resin layers (AG50W‐X8 ion exchange resin + Ln specific resin + Sr specific resin), separates the high field strength element + rare earth element, Sr and Pb from the matrices. Subsequently, Nd and Hf are further separated from the high field strength element + rare earth element fraction on the second column using 1 mL of Ln specific resin. The two‐stage column process can be completed within about seven and a half hours for a batch of samples (20–30). The separated Sr fraction was ready for isotope ratio measurements by thermal ionization mass spectrometry. The Pb, Nd, and Hf fractions were converted to nitrate prior to isotopic analyses by multi‐collector inductively coupled plasma mass spectrometry. The feasibility of this new procedure is confirmed by the analyses of four international rock standards (BCR‐2, AGV‐2, BHVO‐2, and JB‐3), which yielded isotope ratios that were in good agreement with other published data.     

Validation of a HPLC/MS method for simultaneous quantification of clonidine,morphine and its metabolites in human plasma

A high‐performance liquid chromatography–tandem mass spectrometry method was developed and validated for the simultaneous quantification of morphine, morphine's major metabolites morphine‐3‐glucuronide and morphine‐6‐glucuronide, and clonidine, to support the pharmacokinetic analysis of an ongoing double‐blinded randomized clinical trial that compares the use of morphine and clonidine in infants diagnosed with neonatal abstinence syndrome. Plasma samples were processed by solid‐phase extraction and separated on an Inertsil ODS‐3 (4 μm) column using an 0.1% formic acid in water–0.1% formic acid in methanol gradient. Detection of the analytes was conducted in the positive multiple reaction monitoring mode. The range of quantitation was 1–1000 ng/mL for morphine, morphine‐3‐glucuronide and morphine‐6‐glucuronide, and 0.25–100 ng/mL for clonidine. Intra‐day and inter‐day accuracy and precision were ≤15% for all analytes across the quantitation range. Extraction recovery rates were ≥94% for morphine, ≥90% for M3G, ≥87% for M6G and ≥ 79% for clonidine. Matrix effect ranged from 85–94% for clonidine to 101–106% for M3G. The method fulfilled all predetermined acceptance criteria and required only 100 μL of starting plasma volume. Furthermore, it was successfully applied to 30 clinical trial plasma samples.     

Brush‐First ROMP of poly(ethylene oxide) macromonomers of varied length: impact of polymer architecture on thermal behavior and Li+ conductivity

The properties of polymeric materials are dictated not only by their composition but also by their molecular architecture. Here, by employing brush‐first ring‐opening metathesis polymerization (ROMP), norbornene‐terminated poly(ethylene oxide) (PEO) macromonomers ( MM‐n , linear architecture), bottlebrush polymers ( Brush‐n , comb architecture), and brush‐arm star polymers ( BASP‐n , star architecture), where n indicates the average degree of polymerization (DP) of PEO, are synthesized. The impact of architecture on the thermal properties and Li⁺ conductivities for this series of PEO architectures is investigated. Notably, in polymers bearing PEO with the highest degree of polymerization, irrespective of differences in architecture and molecular weight (~100‐fold differences), electrolytes with lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) as an Li⁺ source exhibit normalized ionic conductivities (σ_n) within only 4.9 times difference (σ_n = 29.8 × 10^?5 S cm^?1 for MM‐45 and σ_n = 6.07 × 10^?5 S cm^?1 for BASP‐45 ) at a concentration of Li⁺ r = [Li⁺]/[EO] = 1/12 at 50 °C. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 448–455     

含芳香基团的梳状聚合物型降凝剂与沥青质协同改善合成蜡油的流变性

采用流变学实验、 差示扫描量热(DSC)分析、 显微观察及沥青质沉淀实验研究了聚丙烯酸十八酯-马来酸酐(POM)、 聚丙烯酸十八酯-马来酸酐-苯胺(POMA)及聚丙烯酸十八酯-马来酸酐-萘胺(POMN)梳状聚合物对合成蜡油的流变性能的影响规律. 实验结果表明, 这3种梳状聚合物降凝剂均能在一定程度上改善不含沥青质合成蜡油(MO-1)的低温流变性, 其中POM对MO-1蜡油的流变性改善效果最佳. 添加500 mg/kg POM后, MO-1的凝点从29 ℃降至23 ℃, 屈服值从627.20 Pa降至83.35 Pa. 而POM, POMA和POMN可以显著改善含0.3%(质量分数)沥青质的合成蜡油(MO-2)的低温流变性, 且添加500 mg/kg POMA后MO-2蜡油的流变改善效果最佳: 凝点降至3 ℃, 屈服值降至1.27 Pa. 可见, 本文制备的梳状聚合物降凝剂均能与沥青质协同改善MO-2蜡油的流变性, 并且向POM中引入芳香基团能进一步促进沥青质与降凝剂分子的相互作用, 进而增强梳状聚合物降凝剂与沥青质的协同作用.     

Organocatalytic Asymmetric One‐Step Desymmetrizing Dearomatization Reaction of Indoles: Development and Bioactivity Evaluation

An organocatalytic one‐step desymmetrizing dearomatization reaction of indoles with in situ formed vinylidene ortho‐quinone methides is reported. A set of [6‐6‐5] and/or [5‐6‐5] fused indoline heterocycles were obtained in excellent yields with excellent diastereoselectivities (>20:1 d.r.) and enantioselectivities (up to 99 % ee). Moreover, some of the obtained products were screened against a panel of cancer cell lines, and one was identified to inhibit the proliferation of all the tested cancer cells, but showed marginal effects against non‐cancerous cells. The methodology provides a platform for the synthesis of new leading compounds with antitumor activity.     

A Metal–Organic Supramolecular Box as a Universal Reservoir of UV,WL, and NIR Light for Long‐Persistent Luminescence

Long persistent luminescence (LPL) materials have a unique photophysical mechanism to store light radiation energy for subsequent release. However, in comparison to the common UV source, white‐light (WL) and near‐infrared (NIR) excited LPL is scarce. Herein we report a metal–organic supramolecular box based on a D–π–A‐type ligand. Owing to the integrated one‐photon absorption (OPA) and two‐photon absorption (TPA) attributes of the ligand, the heavy‐atom effect of the metal center, as well as π‐stacking and J‐aggregation states in the supramolecular assembly, LPL can be triggered by all wavebands from the UV to the NIR region. This novel designed supramolecular kit to afford LPL by both OPA and TPA pathways provides potential applications in anti‐counterfeiting, camouflaging, decorating, and displaying, among others.     

Nanozyme‐Catalyzed Cascade Reactions for Mitochondria‐Mimicking Oxidative Phosphorylation

Multiple‐enzyme‐involving cascade reactions that yield bioenergy are necessary in natural oxidative phosphorylation. However, in vitro applications are hampered by the sensitivity of catalytic activity to environmental adaptation. Herein, we explore nanozyme‐catalyzed cascade reactions in an assembled hybrid architecture for mitochondria‐mimicking oxidative phosphorylation. Hollow silica microspheres containing trapped gold nanoparticles were synthesized to promote two enzyme‐like catalytic reactions that transform glucose into gluconic acid in the presence of oxygen. The resulting transmembrane proton gradient drives natural ATP synthase reconstituted on the surface to convert ADP and inorganic phosphate into ATP. The assembled architecture possesses high activity for oxidative phosphorylation, comparable to that of natural mitochondria. This study provides a new natural–artificial hybrid prototype for exploring bioenergy supply systems and holds great promise for ATP‐powered bioapplications.     

Silver Nanostructures on Graphene Oxide as the Substrate for Surface-Enhanced Raman Scattering (SERS)

Nanosized surface-enhanced Raman scattering (SERS) substrates fabricated by the controlled growth of metal nanostructures on water-dispersed two-dimensional nanomaterials can open a new avenue for SERS analysis of liquid samples in biological fields. In this work, regular and uniform Ag nanostructures were grown on the surface of graphene oxide (GO) through a microwave-assisted hydrothermal method. Polyamidoamine (PAMAM) dendrimers were assembled on the surface of GO to form GO/PAMAM templates for growing Ag nanostructures, which are primarily comprised of Ag dimers and trimers. The prepared Ag/GO nanocomposites are highly dispersed and stable in aqueous solution and may be used as substrates for enhanced Raman detection of rhodamine 6?G (R6G) in aqueous solution. This special substrate provides high-performance SERS and suppresses R6G fluorescence in aqueous solution and is promising as a nanosized material for the enhanced Raman detection of liquid samples in biological diagnostics.     

Facile synthesis of 1-(arylimino)naphthalen-2(1H)-ones from anilines and 2-naphthols promoted by NaBr/K2S2O8/CAN

An efficient method has been developed for the synthesis of 1-(arylimino)naphthalen-2(1H)-ones through the cascade reaction of anilines and 2-naphthols promoted by NaBr/K₂S₂O₈/Ce(NH₄)₂(NO₃)₆. Using this protocol, a series of 1-(arylimino)naphthalen-2(1H)-ones was obtained in good to excellent yields (17 examples, 70–92% yields). The reactions may proceed through the following steps: bromination of 2-naphthols by in-situ-generated bromine from NaBr and K₂S₂O₈ to afford 1-bromonaphthalen-2-ols, coupling of 1-bromonaphthalen-2-ols with anilines to afford the corresponding amines, and subsequent oxidation of the amines into the products by Ce(NH₄)₂(NO₃)_6. These newly obtained α-imine ketones have great potentials for synthesis of special optical materials bearing naphthalene moiety.