RSC Advances

Tang, Yang-Hua; Wu, Jing; Fan, Ting-Ting; Zhang, Hui-Hui; Gong, Xiao-Xia; Cao, Zheng-Yu; Zhang, Jian; Lin, Hou-Wen; Han, Bing-Nan

doi: 10.1039/c9ra00965epmid: 35521179

Three new aplysiatoxins, neo-debromoaplysiatoxin D (1), oscillatoxin E (2) and oscillatoxin F (3), accompanied by four known analogues (4–7), were identified from the marine cyanobacterium Lyngbya sp. Structural frames differ amongst these metabolites, and therefore we classified compounds 1 and 4–6 as aplysiatoxins as they possess 6/12/6 and 6/10/6 tricyclic ring systems featuring a macrolactone ring, and compounds 2, 3 and 7 as oscillatoxins that feature a hexane-tetrahydropyran in a spirobicyclic system. Bioactivity experiments showed that compounds 1 and 4–6 presented significant expression of phosphor-PKCδ whereas compounds 2, 5 and 7 showed the most potent blocking activity against potassium channel Kv1.5 with IC50 values of 0.79 ± 0.032 μM, 1.28 ± 0.080 μM and 1.47 ± 0.138 μM, respectively. Molecular docking analysis supplementing the binding interaction of oscillatoxin E (2) and oscillatoxin F (3) with Kv1.5 showed oscillatoxin E (2) with a strong binding affinity of −37.645 kcal mol−1 and oscillatoxin F (3) with a weaker affinity of −32.217 kcal mol−1, further supporting the experimental data.

Machado, Noelia D.; Fernández, Mariana A.; Häring, Marleen; Saldías, César; Díaz, David Díaz

doi: 10.1039/c8ra09655dpmid: 35521173

A series of biohydrogels based on mixtures of kappa-carrageenan (κ-carrageenan, κ-C) and gelatin were evaluated as potential soft delivery vehicles for the encapsulation and subsequent release of non-ionic surfactant vesicles (niosomes) loaded with resveratrol (RSV). The niosomes were prepared using a mixture of amphiphilic lipids Tween 80 and Span 80 in water. The results showed that RSV-niosomes did not significantly affect the hydrogelation properties of the biopolymer mixture. Moreover, in vitro drug release experiments from biohydrogels containing RSV-niosomes were successfully carried out under simulated gastrointestinal conditions. The RSV-niosomal liberation profiles from hydrogels were fitted using first order kinetics, Higuchi, Korsmeyer–Peppas and Weibull drug release models, showing the prevalence of diffusion mechanisms in each case. In addition, the RSV release was easily tuned by adjusting the total concentration of κ-C : gelatin. Interestingly, the niosomal-hydrogel system was also found to prevent the trans-to-cis photoisomerization of RSV.

Walko, Martin; Hewitt, Eric; Radford, Sheena E.; Wilson, Andrew J.

doi: 10.1039/c8ra10436kpmid: 35521201

Chemical cross-linking mass-spectrometry (XL-MS) represents a powerful methodology to map ligand/biomacromolecule interactions, particularly where conventional methods such as X-ray crystallography, nuclear magnetic resonance (NMR) spectroscopy or cryo-electron microscopy (EM) are not feasible. In this manuscript, we describe the design and synthesis of two new photo-crosslinking reagents that can be used to specifically label free thiols through either maleimido or methanethiosulfonate groups and facilitate PXL-MS workflows. Both crosslinkers are based on light sensitive diazirines – precursors of highly reactive carbenes which offer additional advantages over alternative crosslinking groups such as benzophenones and aryl nitrenes given the controlled rapid and more indiscriminate reactivity.

Dennison, Genevieve H.; Curty, Christophe; Metherell, Alexander J.; Micich, Eva; Zaugg, Andreas; Ward, Michael D.

doi: 10.1039/c9ra00824apmid: 35521155

The addition of G- and V-series organophosphorus chemical warfare agents and simulants to a paper-based assay of a dual-luminescent Ir(iii)/Eu(iii) dyad generated different emissive responses between the classes and compound types. The emission responses are complex and based not only on altering the balance between red Eu(iii)-based and blue Ir(iii)-based luminescent components, but also incorporate other factors such as analyte volatility, concentration and UV absorption. The extent of this emission colour change was analysed colorimetrically and related to the change in RGB output over time.

Fan, Shuo; Yuan, Ruchao; Wu, Dequn; Wang, Xueli; Yu, Jianyong; Li, Faxue

doi: 10.1039/c8ra10325apmid: 35521176

A facile route of ‘copolymerization/blending’ was proposed to fabricate silicon/nitrogen synergistically reinforced flame-retardant PA6 nanocomposites with simultaneously improved anti-dripping and mechanical properties. Firstly, a persistently inherent flame-retardant PA6 (FR-PA6), with 1,3-bis(3-aminopropyl)tetramethyl disiloxane (MSDS), was synthesized via controllable amidation and a polycondensation reaction. Melamine cyanurate (MCA) nanoparticles as a ‘gas phase’ synergistic agent were then added into FR-PA6 to further improve its flame retardancy. The primarily obtained FR-PA6 could be extinguished after a few melt droplets dropped as ignited, and passed the V-2 rating with enhanced mechanical properties, while PA6 had no rating (NR). The prepared FR-PA6/MCA nanocomposites could attain a limiting oxygen index (LOI) value of 32.7%, and passed the V-0 level with only 1 melting droplet with similar mechanical properties to PA6. Accordingly, the special ‘condensed-gas phase’ synergistic flame-retardant mechanism of FR-PA6/MCA nanocomposites was proposed through studying the residues and pyrolysis volatiles. This work provided a facile route as a model for developing functional PA6 for diverse engineering applications.

Duan, Zheng; Luo, Yufeng; Luo, Zhiling; Yu, Wei; Liu, Changhong; Fan, Shoushan

doi: 10.1039/c9ra00151dpmid: 35521203

In recent years, carbon nanotube/polyaniline (CNT/PANI) nanocomposites have aroused much interest because of their broad application prospects as electrodes in supercapacitors and batteries. However, a great deal of heat can be generated during fast charging and discharging processes and this can influence the efficiency of devices. In this paper, we measured the thermal properties of CNT/PANI in different oxidation states. The results indicate that within an electric potential range from −0.4 V to +0.4 V, both the thermal diffusivity and the thermal conductivity decrease obviously with potential due to the successive loss of electrons from PANI. Losing protons at higher voltages leads to a reduction in thermal conductivity but a jump in thermal diffusivity. The composite material provides an example for studying the influence of the loss or gain of electrons and protons on the thermal properties of a polymer. It also provides a superb system for thermal management through electric potential.

Li, Yan; Zhang, Zhiqiang

doi: 10.1039/c8ra10262gpmid: 35521168

To understand the mechanism and origin of the stereoselectivity of the [3 + 2] annulation reaction between a carboxylic ester and an isatin generating spirooxindole lactone catalyzed by N-heterocyclic carbene (NHC), density functional theory (DFT) calculations have been carried out. DFT results indicate that the catalytic cycle begins with the coupling of the catalyst with benzotriazole ester, followed by α-deprotonation to produce the enolate intermediate. The subsequent 1,4-proton transfer affords the homoenolate intermediate. The next crucial step is the stereoselective C–C bond formation. Then proton transfer takes place leading to the formation of the lactone intermediate. Finally, the elimination of the catalyst furnishes the final product. The presence of 1-hydroxybenzotriazole (HOBt) dramatically accelerates the proton transfer step. More importantly, HOBt has a non-negligible impact on stereoselective C–C bond formation, and the SR-configured product is the major stereoisomer of the annulation product, which is in good agreement with the experimental observations. The differential π⋯π stacking, C–H⋯π, lone pair (LP)⋯π and repulsion interactions are found to be responsible for the stereoselectivity. The obtained mechanistic insights should provide valuable information for understanding the important roles of the NHC catalyst and HOBt additive and be helpful for designing better NHC catalysts for this kind of reaction.

Wang, Xin; Xue, Min; Liu, Songbai; Jiang, Kuo; Zhang, Zhuli

doi: 10.1039/c8ra09501apmid: 35521192

Herein, powders composed of La2Zr2O7 (LZ) and ZrO2 phases were synthesized by an in situ reaction using a sol-spray pyrolysis method; moreover, 24 mol% LaO1.5–ZrO2 (volume ratio = 1 : 1) powders were characterized by XRD, Raman spectroscopy, SEM, and TEM. XRD and Raman results showed that the samples maintained a tetragonal ZrO2 and a pyrochlore LZ phase from 900 to 1100 °C. The addition of LZ could be helpful in the stabilization of t-ZrO2 and decreasing the grain size of ZrO2. The SEM results revealed that the LZ and ZrO2 phases were homogeneously distributed in the sintered bulk. The HRTEM results suggested that the crystal orientations of the nano-LZ and nano-ZrO2 phases were accordant; this was in agreement with the characteristics of the coherent boundaries. The fracture toughness of LZ–ZrO2 was markedly improved by the transformation toughening of the ZrO2 phase, and a value that was 2.2-fold that of the LZ prepared by a similar technique was achieved.

Al Otaibi, Ahmed; Deane, Fiona M.; Russell, Cecilia C.; Hizartzidis, Lacey; McCluskey, Siobhann N.; Sakoff, Jennette A.; McCluskey, Adam

doi: 10.1039/c9ra00118bpmid: 35521167

The Ugi four component reaction of an aldehyde, amine, isocyanide and an ethanoic acid was effected smoothly in protic ionic liquids ethylammonium nitrate (EAN) and propylammonium nitrate (PAN) to afford analogues of α-phenylacetamido amides in good to excellent isolated yields. The corresponding reactions in [BMIM][PF6] and the protic ionic liquid ethanolammonium nitrate (ETAN) failed. Microwave irradiation in EAN facilitated rapid access to three focused libraries, based on the parent isocyanide: cyclohexyl isocyanide, benzyl isocyanide and ethyl isocyanoacetate. Analysis of the structure activity relationship data suggested the presence of a bulky moiety originating from the isocyanide (cyclohexyl and benzyl) enhanced cytotoxicity. Removal of the acetylenic H-atom from the ethanoic acid moiety was detrimental to cytotoxicity. The most active analogues produced, N-(2-cyclohexylamino)-1-(4-methoxyphenyl)-2-oxoethyl-N-(3,5-dimethoxyphenyl)propiolamide, returned average GI50 values of ≤1 μM across the cancer cell lines evaluated. Combined, these data suggest that analogues of this nature are interesting potential anti-cancer development leads.

Tang, Huiling; Nie, Wenbing; Xiao, Jinna; Zha, Zhengqi; Chen, Qiuli; Yin, Hongping

doi: 10.1039/c8ra10347jpmid: 35521177

The galactoglucan ACP2 was isolated from cultured Antrodia camphorata mycelium through anion-exchange column chromatography and Sephadex G-100 chromatography and shown to exhibit hepatoprotective function in L02 cells. Based on monosaccharide composition analysis, ACP2 was mainly composed of glucose, galactose, and 6-deoxyglucose in a molar ratio of 5 : 2 : 1. The average molecular weight of ACP2 was 1.93 × 104 Da. The primary structure of ACP2 was elucidated with Fourier-transform infrared spectroscopy, gas chromatography-mass spectrometry, and nuclear magnetic resonance spectroscopy. The results indicated the following composition: →6)-linked-β-d-Galp-(1→, →6)-linked-α-d-Glcp-(1→, →3)-linked-α-d-Glcp-(1→, and →2,4)-linked-β-d-Glcp-(1→, with terminal 6-deoxy-α-d-Glcp and α-d-Glcp. ACP2 alleviated lipopolysaccharide-induced hepatocyte inflammation by down-regulating the expressions of COX-2, IL-1β, TNF-α and IL-6. The decreased expressions of TLR4, MyD88, NF-κB, and phosphorylated p38 in ACP2-treated L02 cells indicated that ACP2 might ameliorate inflammation through the TLR4 and p38/NF-κB signaling pathways.