Li-Sheng Ding

Organocatalytic enantioselective indole alkylations of α,β-unsaturated ketones

The C3-selective enantioselective Michael-type Friedel-Crafts alkylations of indoles with nonchelating alpha,beta-unsaturated alkyl ketones, catalysed by a chiral primary amine derived from natural cinchonine, were investigated. The reactions, in the presence of 30 mol% catalyst, were smoothly conducted at 0 to -20 degrees C. Moderate to good ee (47-89%) has been achieved.

Enantioselective construction of quaternary carbon centre catalysed by bifunctional organocatalyst

The bifunctional thiourea-tertiary amine derivatives of simple chiral diamines serve as highly enantioselective catalysts for the Michael addition of alpha-substituted cyanoacetates to vinyl sulfones, giving an efficient protocol for the construction of an all-carbon substituted quaternary stereocentre.

Organocatalytic asymmetric Friedel–Crafts alkylation/cascade reactions of naphthols and nitroolefins

The asymmetric Michael-type Friedel-Crafts reaction of naphthols and nitroolefins promoted by bifunctional thiourea-tertiary amine organocatalysts (up to 95% ee) was investigated; on simply extending the reaction time further cascade reactions could occur to generate enantiopure dimeric tricyclic 1,2-dihydronaphtho[2,1-b]furanyl-2-hydroxylamine derivatives.

Stimuli-induced gel–sol transition of multi-sensitive supramolecular β-cyclodextrin grafted alginate/ferrocene modified pluronic hydrogel

This paper studies a kind of biocompatible hydrogel composed of alginate-g-β-cyclodextrin (Alg-β-CD) and ferrocene-terminated pluronic F127 (F127-Fc), which showed gel–sol phase transformations in response to temperature, oxidizing agents, and glucose because of the reversible association–dissociation of Fc-β-CD inclusions and F127 micelles.

An experimental design approach using response surface techniques to obtain optimal liquid chromatography and mass spectrometry conditions to determine the alkaloids in Meconopsi species

A statistic approach using response surface methodology (RSM) for optimization of the ultra-high performance liquid chromatography (UHPLC) gradient and ionization response of electrospray ionization mass spectrometry (ESI-MS) to analyze the main alkaloids from the plant matrices of six Meconopsi species is presented. The optimization was performed with Box-Behnken designs (BBD) and the multicriteria response variables were described using global Derringers desirability. Four parameters of UHPLC and six major parameters of ESI-MS were investigated for their contribution to analytes separation and response, leading to a total of 27 and 54 experiments being performed for each instrument, respectively. Quantitative analysis of four main alkaloids in nine samples from six Meconopsis species was employed to evaluate the statistical significance of the parameters on UHPLC-QTOF/ESI-MS analytes response. The results indicated that the optimized UHPLC-QTOF-MS method is very sensitive with the limit of detections (LODs) ranging from 0.5 to 0.1 ng/ml. The overall intra-day and the inter-day variations were less than 2.45%. The recovery of the method was in the range of 94.3-104.8% with RSD less than 4.0%. This approach has important implication in sensitivity enhancement of the ultra-trace determination of alkaloids from complex matrixes in the fields of natural products, metabolomics and pharmacokinetics.

Qualitative and quantitative analysis of diterpenoids in Salvia species by liquid chromatography coupled with electrospray ionization quadrupole time-of-flight tandem mass spectrometry.

An on-line ultra-high-performance liquid chromatography (UHPLC) coupled with photodiode-array detection and quadrupole time-of-flight tandem mass spectrometry (QTOF-MS/MS) method has been optimized and established for the qualitative and quantitative analysis of the important diterpenoids in the methanol extracts of 12 Salvia species. Specific marker components were identified for the classification of the Salvia samples by principal component analysis. The accurate mass measurement within 3 ppm error for all the protonated molecules and subsequent fragment ions offers higher quality structural information for interpretation of fragmentation pathways of various groups of diterpenoids. Thus, a total of 21 diterpenoids from different Salvia species were separated within 10 min, and were unequivocally or tentatively identified via comparisons with authentic standards and literature. This UHPLC-QTOF-MS/MS method was validated to be sensitive, precise and accurate with the limit of detections at 3.0-16 ng/ml, and the overall intra-day and the inter-day variations less than 3%. The recovery of the method was in the range of 96.2-101.8%, with relative standard deviation (RSD) less than 3.0%. The results demonstrated that the qualitative and quantitative differences in diterpenoids were not only useful for chemotaxonomy in some Salvia species but also for the standardization and differentiation of large numbers of similar samples.

Conductive Elastomers with Autonomic Self-Healing Properties

Healable, electrically conductive materials are highly desirable and valuable for the development of various modern electronics. But the preparation of a material combining good mechanical elasticity, functional properties, and intrinsic self-healing ability remains a great challenge. Here, we design composites by connecting a polymer network and single-walled carbon nanotubes (SWCNTs) through host-guest interactions. The resulting materials show bulk electrical conductivity, proximity sensitivity, humidity sensitivity and are able to self-heal without external stimulus under ambient conditions rapidly. Furthermore, they also possess elasticity comparable to commercial rubbers.

Ligand fishing from Dioscorea nipponica extract using human serum albumin functionalized magnetic nanoparticles

Dioscorea nipponica and the preparations made from it have been used for long to prevent and treat coronary heart disease in traditional Chinese medicine. A group of steroidal saponins present in the plant are believed to be the active ingredients. It has been a challenge to study the individual saponins separately due to the similarities in their chemical and physical properties. In this work, human serum albumin (HSA) functionalized magnetic nanoparticles (MNPs) were used to isolate and identify saponin ligands that bind to HSA from D. nipponica extract. Electrospray ionization mass spectrometry (ESI-MS) was used for compound identification and semi-quantification. Three saponins, i.e. dioscin, gracillin, and pseudo-protodioscin showed affinity to HSA-MNPs and thus isolated effectively from the extract. The other two saponins detected in the extract (i.e. protodioscin and 26-O-β-D-glucopyranosyl-3β,20α,26-triol-25(R)-Δ(5,22)-dienofurostan-3-O-α-L-rhamnopyranosyl (1→2)-[α-L-rhamnopyranosyl (1→4)]-β-D-glucopyranoside) exhibited no affinity at all. Among the three saponins fished out, dioscin bound to HSA much stronger than gracillin and pseudo-protodioscin did. The results indicated that affinity interaction between HSA immobilized on MNPs and small molecule compounds were highly dependent on chemical structures and, potentially, medicinal usefulness. The present work demonstrates a facile and effective way to isolate and identify ligands of receptors from medicinal plants.

Semi-permeable nanocapsules of konjac glucomannan-chitosan for enzyme immobilization.

Carboxymethyl konjac glucomannan-chitosan (CKGM-CS) nanocapsules, spontaneously prepared under very mild conditions by electrostatic complexation, were used for immobilizing L-asparaginase. The matrix has semi-permeability to allow the substrate and product to pass through and to keep L-asparaginase in the matrix to prevent leaking. The cell-like hydrogel matrix was prepared in aqueous system without organic solvents and reagents. The process of the preparation does not denature the enzyme and the activity of the immobilized and native enzyme is very similar. The activity, stability, and characters of the enzyme-loaded nanocapsules were studied. The results indicated the immobilized enzyme has better stability and activity in contrast to the native enzyme. These studies may supply a new material for the immobilization of pH and temperature-sensitive enzyme.

Self-assembly hollow nanosphere for enzyme encapsulation

This paper studies a kind of self-assembled hollow nanosphere for L-asparaginase encapsulation, and it was found that the hollow spheres not only enable a high loading of enzyme, but also show semi-permeability which could prevent the enzyme from leaving while allowing substrates and products to pass through to maintain the enzyme activity, and the encapsulated L-asparaginase showed significantly higher stability.