Confinement-Induced Biocatalytic Activity Enhancement of Light- and Thermoresponsive Polymer@Enzyme@MOF Composites.

Metal-organic frameworks (MOFs) are favorable hosting materials for fixing enzymes to construct enzyme@MOF composites and to expand the applications of biocatalysts. However, the rigid structure of MOFs without tunable hollow voids and a confinement effect often limits their catalytic activities. Taking advantage of the smart soft polymers to overcome the limitation, herein, a protection protocol to encapsulate the enzyme in zeolitic imidazolate framework-8 (ZIF-8) was developed using a glutathione-sensitive liposome (L) as a soft template. Glucose oxidase (GOx) and horseradish peroxidase (HRP) were first anchored on a light- and thermoresponsive porous poly(styrene-maleic anhydride-N,N-dimethylaminoethyl methacrylate-spiropyran) membrane (PSMDSP) to produce PSMDSP@GOx-HRP, which could provide a confinement effect by switching the UV irradiation or varying the temperature. Afterward, embedding PSMDSP@GOx-HRP in L and encapsulating PSMDSP@GOx-HRP@L into hollow ZIF-8 (HZIF-8) to form PSMDSP@GOx-HRP@HZIF-8 composites were performed, which proceeded during the crystallization of the framework following the removal of L by adding glutathione. Impressively, the biocatalytic activity of the composites was 4.45-fold higher than that of the free enzyme under UV irradiation at 47 °C, which could benefit from the confinement effect of PSMDSP and the conformational freedom of the enzyme in HZIF-8. The proposed composites contributed to the protection of the enzyme against harsh conditions and exhibited superior stability. Furthermore, a colorimetric assay based on the composites for the detection of serum glucose was established with a linearity range of 0.05-5.0 mM, and the calculated LOD value was 0.001 mM in a cascade reaction system. This work provides a universal design idea and a versatile technique to immobilize enzymes on soft polymer membranes that can be encapsulated in porous rigid MOF-hosts. It also holds potential for the development of smart polymer@enzyme@HMOFs biocatalysts with a tunable confinement effect and high catalytic performance.

Right arcuate fasciculus and left uncinate fasciculus abnormalities in young smoker.

Previous diffusion tensor imaging (DTI) studies had investigated the white matter (WM) integrity abnormalities in smokers. Exposure to nicotine disrupts neurodevelopment during adolescence, possibly by disrupting the trophic effects of acetylcholine. However, little is known about the diffusion parameters of specific fibre bundles at multiple locations in young smokers. Thirty-seven young smokers and 29 age-, education- and gender-matched healthy non-smokers participated in this study. Automated Fibre Quantification (AFQ) was employed to investigate the WM microstructure in young smokers by integrating multiple indices. Diffusion parameters, that is, fractional anisotropy (FA), axial diffusion (AD), radial diffusion (RD) and mean diffusion (MD), were calculated at 100 points along the length of 18 major brain tracts. The relationships between neuroimaging differences and smoking behaviours were explored, including Fagerström Test of Nicotine Dependence (FTND) and pack-years. Compared with non-smokers, young smokers showed significantly increased FA, AD and decreased RD in the left uncinate fasciculus (UF) and right thalamic radiation (TR), increased AD, RD and decreased FA in the right arcuate fasciculus (Arc). Correlation analyses revealed that FA values of the left UF and RD values of the right Arc were negatively correlated with FTND score in smokers and FA values of the right Arc were positively correlated with FTND scores. Positive correlation was observed between AD values of the left UF and pack-years in smokers. The findings enhanced our understanding of the potential effect of adolescent smoking on WM microstructure.

Abnormal resting-state EEG power and impaired inhibition control in young smokers.

Exposure to nicotine during adolescence may cause neurophysiological changes and increase the risks of developing nicotine dependence; it can even lead to lifelong smoking. The intake of nicotine may also lead to abnormal patterns of oscillatory brain activity and inhibition control deficits. However, little is known about the specific relationship between oscillatory brain activity during the resting state and inhibition control capacity in young smokers. In the present study, we acquired resting-state electroencephalography (EEG) data from thirty-four young smokers and 39 age-matched non-smoking controls. Inhibition control performance was measured by a Go/NoGo task. Compared with non-smoking controls, we detected reduced low-frequency delta band activity in the frontal, central and posterior cortices of young smokers. Furthermore, young smokers committed more errors in response to infrequent NoGo trials. Notably, we demonstrated that delta absolute power in the frontal region was negatively correlated with NoGo errors and that alpha power in the central region was positively correlated with NoGo errors in non-smoking controls but not in young smokers. These findings may suggest that these inhibitory control processes were associated with alterations in oscillatory brain activity during the resting state. Our findings suggest that alterations of power spectra in delta bands may act as a useful biomarker of inhibitory control performance and provide a scientific basis for the diagnosis and treatment of nicotine addiction in adolescents.

Elution-extrusion counter-current chromatography for the separation of two pairs of isomeric monoterpenes from Paeoniae Alba Radix.

In this work, a simple and efficient protocol for the rapid separation of two pairs of isomeric monoterpenes from Paeoniae Alba Radix was developed by combining macroporous resin and elution-extrusion counter-current chromatography. The crude extract was firstly subjected to a D101 macroporous resin column eluted with water and a series of different concentrations of ethanol. Then, effluents of 30 and 95% ethanol were collected as sample 1 and sample 2 for further counter-current chromatography purification. Finally, a pair of isomers, 96 mg of compound 1 and 48 mg of compound 2 with purities of 91.1 and 96.2%, respectively, was isolated from 200 mg of sample 1. The other pair of isomers, 14 mg of compound 3 and 8 mg of compound 4 with purities of 93.6 and 88.9%, respectively, was isolated from 48 mg of sample 2. Their purities were analyzed by high-performance liquid chromatography, and their chemical structures were identified by mass spectrometry and (1) H NMR spectroscopy. Compared to a normal counter-current chromatography separation, the separation time and solvent consumption of elution-extrusion counter-current chromatography were reduced while the resolutions were still good. The established protocol is promising for the separation of natural products with great disparity of content in herbal medicines.

An efficient strategy for the extraction and purification of lignans from Schisandra chinensis by a combination of supercritical fluid extraction and high-speed counter-current chromatography.

An efficient strategy for extracting and separating five lignans from Schisandra chinensis (Turcz.) Baill has been developed using supercritical fluid extraction (SFE) and high-speed counter-current chromatography (HSCCC) in the present study. First, the extraction was performed by a preparative SFE system under 15 MPa of pressure at 36°C for 4 h. Then, the SFE extract was successfully separated and purified by HSCCC with a two-phase solvent system composed of n-hexane/ethyl acetate/methanol/water (6:4:5:5, 6:4:6:4, 6:4:8:2, v/v) in a stepwise elution mode. The fractions were analyzed by HPLC, and the chemical structures of the products were identified by ESI-MS and 1H NMR spectroscopy. As a result, a total of 12.5 mg of schisandrin at 98.0% purity, 7.1 mg of gomisin A at 98.1% purity, 1.8 mg of schisantherin B at 93.3% purity, 4.4 mg of deoxyschisandrin at 92.9% purity, and 6.8 mg of γ-schisandrin at 89.1% purity were obtained from 300 mg crude extract in a one-step purification.