Microwave-Assisted Desulfation of the Hemolytic Saponins Extracted from Holothuria scabra Viscera

Saponins are plant and marine animal specific metabolites that are commonly considered as molecular vectors for chemical defenses against unicellular and pluricellular organisms. Their toxicity is attributed to their membranolytic properties. Modifying the molecular structures of saponins by quantitative and selective chemical reactions is increasingly considered to tune the biological properties of these molecules (i) to prepare congeners with specific activities for biomedical applications and (ii) to afford experimental data related to their structure–activity relationship. In the present study, we focused on the sulfated saponins contained in the viscera of Holothuria scabra, a sea cucumber present in the Indian Ocean and abundantly consumed on the Asian food market. Using mass spectrometry, we first qualitatively and quantitatively assessed the saponin content within the viscera of H. scabra. We detected 26 sulfated saponins presenting 5 different elemental compositions. Microwave activation under alkaline conditions in aqueous solutions was developed and optimized to quantitatively and specifically induce the desulfation of the natural saponins, by a specific loss of H2SO4. By comparing the hemolytic activities of the natural and desulfated extracts, we clearly identified the sulfate function as highly responsible for the saponin toxicity.

High-Efficiency Chemical Mechanical Polishing of Ti-6Al-4V Alloy via the Synergistic Action of H2O2 and K+ Under Alkaline Conditions

Ti-6Al-4V (TC4) alloy has been widely used for implants, and excellent surface quality is required for satisfactory performance. In this study, chemical mechanical polishing (CMP) was introduced to process TC4 alloy. H2O2 and K+ were used to enhance the CMP efficiency. It is revealed that, at pH 10, the material removal rate (MRR) of TC4 alloy increases with the increasing H2O2. A synergistic action between H2O2 and K+ exists under alkaline conditions. With H2O2 and at pH 10, as the K+ concentration increases, the MRR of TC4 alloy first increases and then levels off. The anions have little influence on the CMP performance. After polishing, the surface is smooth without scratches, and the substrate underneath the surface film has no processing damage. For the synergistic action, K+ ions are adsorbed on the Stern layer of the TC4 alloy surface and the silica particles, screening the surface negative charge. Firstly, OOH- produced from H2O2 and OH- can approach the TC4 alloy surface easily, promoting the corrosion. Secondly, more silica particles come into contact with the TC4 alloy surface, enhancing the interactions. Therefore, the MRR increases. The research work brings about a promising high-efficiency CMP process for titanium alloys.

Simultaneous Detoxification of Aflatoxin B1, Zearalenone and Deoxynivalenol by Modified Montmorillonites

Raw Ca-based montmorillonite (MMT) was treated by H2SO4, calcination and organic compounds (hexadecyltrimethyl ammonium bromide (HTAB), cetylpyridinium chloride (CPC) and chitosan (CTS)), respectively. The modified montmorillonites were characterized by different methods and their adsorption performances for three mycotoxins (Aflatoxin B1 (AFB1), zearalenone (ZEA) and deoxynivalenol (DON)) were evaluated at pH = 2.8 and 8.0, respectively. The results indicate that surfactants (CPC and HTAB) intercalation is the most efficient modification, which obviously improves the adsorption performance of montmorillonite for mycotoxins, with adsorption efficiency of above 90% for AFB1 and ZEA whether under acid or alkaline conditions, due to the increase in basal spacing and the improvement of hydrophobicity. Moreover, the adsorption efficiencies of AFB1 and ZEA over CPC-modified montmorillonite (CPC-AMMT-3) coexisting with vitamin B6 or lysine are still at a high level (all above 94%). All modified montmorillonites, however, have low adsorption efficiency for DON, with somewhat spherical molecular geometry.

Mechanism and Structural Insights Into a Novel Esterase, E53, Isolated From Erythrobacter longus

Esterases are a class of enzymes that split esters into an acid and an alcohol in a chemical reaction with water, having high potential in pharmaceutical, food and biofuel industrial applications. To advance the understanding of esterases, we have identified and characterized E53, an alkalophilic esterase from a marine bacterium Erythrobacter longus. The crystal structures of wild type E53 and three variants were solved successfully using the X-ray diffraction method. Phylogenetic analysis classified E53 as a member of the family IV esterase. The enzyme showed highest activity against p-nitrophenyl butyrate substrate at pH 8.5–9.5 and 40°C. Based on the structural feature, the catalytic pocket was defined as R1 (catalytic center), R2 (pocket entrance), and R3 (end area of pocket) regions. Nine variants were generated spanning R1–R3 and thorough functional studies were performed. Detailed structural analysis and the results obtained from the mutagenesis study revealed that mutations in the R1 region could regulate the catalytic reaction in both positive and negative directions; expanding the bottleneck in R2 region has improved the enzymatic activity; and R3 region was associated with the determination of the pH pattern of E53. N166A in R3 region showed reduced activity only under alkaline conditions, and structural analysis indicated the role of N166 in stabilizing the loop by forming a hydrogen bond with L193 and G233. In summary, the systematic studies on E53 performed in this work provide structural and functional insights into alkaliphilic esterases and further our knowledge of these enzymes.

Development and Characterization of Curcumin-Silver Nanoparticles as a Promising Formulation to Test on Human Pterygium-Derived Keratinocytes

Pterygium is a progressive disease of the human eye arising from sub-conjunctival tissue and extending onto the cornea. Due to its invasive growth, pterygium can reach the pupil compromising visual function. Currently available medical treatments have limited success in suppressing efficiently the disease. Previous studies have demonstrated that curcumin, polyphenol isolated from the rhizome of Curcuma longa, induces apoptosis of human pterygium fibroblasts in a dose- and time-dependent manner showing promising activity in the treatment of this ophthalmic disease. However, this molecule is not very soluble in water in either neutral or acidic pH and is only slightly more soluble in alkaline conditions, while its dissolving in organic solvents drastically reduces its potential use for biomedical applications. A nanoformulation of curcumin stabilized silver nanoparticles (Cur-AgNPs) seems an effective strategy to increase the bioavailability of curcumin without inducing toxic effects. In fact, silver nitrates have been used safely for the treatment of many ophthalmic conditions and diseases for a long time and the concentration of AgNPs in this formulation is quite low. The synthesis of this new compound was achieved through a modified Bettini’s method adapted to improve the quality of the product intended for human use. Indeed, the pH of the reaction was changed to 9, the temperature of the reaction was increased from 90 °C to 100 °C and after the synthesis the Cur-AgNPs were dispersed in Borax buffer using a dialysis step to improve the biocompatibility of the formulation. This new compound will be able to deliver both components (curcumin and silver) at the same time to the affected tissue, representing an alternative and a more sophisticated strategy for the treatment of human pterygium. Further in vitro and in vivo assays will be required to validate this formulation.

Fabrication of Polyvinylidene Difluoride Membrane with Enhanced Pore and Filtration Properties by Using Tannic Acid as an Additive

Potential use of tannic acid (TA) as an additive for fabrication of polyvinylidene difluoride (PVDF) membrane was investigated. The TA was introduced by blending into the dope solution with varying concentrations of 0, 1, 1.5, and 2 wt%. The prepared membranes were characterized and evaluated for filtration of humic acid (HA) solution. The stability of the membrane under harsh treatment was also evaluated by one-week exposure to acid and alkaline conditions. The results show that TA loadings enhanced the resulting membrane properties. It increased the bulk porosity, water uptake, and hydrophilicity, which translated into improved clean water flux from 15.4 L/m2.h for the pristine PVDF membrane up to 3.3× for the TA-modified membranes with the 2 wt% TA loading. The flux recovery ratio (FRR) of the TA-modified membranes (FRRs = 78–83%) was higher than the pristine one (FRR = 58.54%), with suitable chemical stability too. The improved antifouling property for the TA-modified membranes was attributed to their enhanced hydrophilicity thanks to improved morphology and residual TA in the membrane matric.

Photolysis of the Insensitive Explosive 1,3,5-Triamino-2,4,6-trinitrobenzene (TATB)

The explosive 1,3,5-triamino-2,4,6-trinitrobenzene (TATB) is of particular interest due to its extreme insensitivity to impact, shock and heat, while providing a good detonation velocity. To determine its fate under environmental conditions, TATB powder was irradiated with simulated sunlight and, in water, under UV light at 254 nm. The hydrolysis of particles submerged in neutral and alkaline solutions was also examined. We found that, by changing experimental conditions (e.g., light source, and mass and physical state of TATB), the intermediates and final products were slightly different. Mono-benzofurazan was the major transformation product in both irradiation systems. Two minor transformation products, the aci-nitro form of TATB and 3,5-diamino-2,4,6-trinitrophenol, were detected under solar light, while 1,3,5-triamino-2-nitroso-4,6-dinitrobenzene, 1,3,5-triamino-2,4-dinitrobenzene and mono-benzofuroxan were produced under UV light. The product identified as 3,5-diamino-2,4,6-trinitrophenol was identical to the one formed in the dark under alkaline conditions (pH 13) and in water incubated at either 50 °C or aged at ambient conditions. Interestingly, when only a few milligrams of TATB were irradiated with simulated sunlight, the aci-isomer and mono-benzofurazan derivative were detected; however, the hydrolysis product 3,5-diamino-2,4,6-trinitrophenol formed only much later in the absence of light. This suggests that the water released from TATB to form mono-benzofurazan was trapped in the interstitial space between the TATB layers and slowly hydrolyzed the relatively stable aci-nitro intermediate to 3,5-diamino-2,4,6-trinitrophenol. This environmentally relevant discovery provides data on the fate of TATB in surface environments exposed to sunlight, which can transform the insoluble substrate into more soluble and corrosive derivatives, such as 3,5-diamino-2,4,6-trinitrophenol, and that some hydrolytic transformation can continue even without light.

Periodic Expansion and Contraction Phenomena in a Pendant Droplet Associated with Marangoni Effect

A spontaneous oscillation between the expansion and contraction of a nitrobenzene pendant droplet containing di-(2-ethylhexyl)phosphoric acid (DEHPA) was observed in an aqueous phase under alkaline conditions. We described this phenomenon as the spontaneous oscillation of the oil–water interfacial tension. The oscillation characteristics such as the induction period and the interfacial-tension oscillation frequency were investigated under different temperatures and aqueous phase polarities. The effects of the interfacial tension of the biphasic pendant-droplet, the surface excess of the surfactant molecules, and the amount of nitrobenzene elution from the droplet to the aqueous phase on the oscillation characteristics were investigated. Consequently, the periodic expansion–contraction oscillation mechanism was explained through the adsorption–desorption cycle of DEHPA with respect to the aggregate formation of the inverted micelle of DEHPA. This study was based on a simple vibration phenomenon of interfacial tension, and is extremely important for clarifying the predominant factors that cause fluctuations in the free interface energy, which has been ambiguous.