Head group specificity of novel functionalized surfactants: synthesis,self-assembly and calcium tolerance

The present work describes the synthesis, characterization and application of functionalized surfactants derived through simple organic reaction steps. These surfactants have been particularly tailor made to resist hardness due to calcium ions in water. It is unique of its kind because here the surfactants have an analogous hydrophobic chain but differ structurally in the composition of the head groups in terms of the position of attachment of the chain. The effect of this small variability in the head group on the surfactant property, adsorption, self assembly and calcium tolerance behaviour has been studied in detail. This kind of phenol–keto surfactants has not been reported before. It was also found that one of the surfactants was more tolerant towards Ca²⁺ ion than the other. The individual packing behaviour of the surfactants at the air–water interface has been projected to cause this difference which is very interesting.     

聚乙烯醇/壳聚糖复合水凝胶的物理化学性质

测定了聚乙烯醇(PVA)和壳聚糖(CS)复合水凝胶的平衡含水量、熔融焓、等温溶胀动力学和非等温失水动力学等性质,讨论了水凝胶的组成和制备参数对这些性质的影响.结果显示:PVA/CS复合水凝胶具有适宜于软骨修复替代材料的网络结构和平衡含水量.CS与PVA复合减弱了凝胶的结晶度,但却增强了水与凝胶支架的相互作用.尽管水凝胶力学拉伸强度有所降低,但却优化了凝胶的生物相容性和降解能力.PVA/CS复合水凝胶是一种潜在的软骨修复材料,作为一种理论研究的模型体系,它将促进热力学在复杂医用材料方面的应用.     

Unified Approach to Diverse Fused Fragments via Catalytic Dehydrative Cyclization

A range of highly functionalized polycyclic fragments have been synthesized, employing a catalytic dehydrative cyclization. A range of nucleophiles are shown to be successful, with the reaction producing numerous high value motifs.     

Exogenous Sodium Nitroprusside Mitigates Salt Stress in Lentil (Lens culinaris Medik.) by Affecting the Growth,Yield, and Biochemical Properties

Soil salinity disrupts the physiological and biochemical processes of crop plants and ultimately leads to compromising future food security. Sodium nitroprusside (SNP), a contributor to nitric oxide (NO), holds the potential to alleviate abiotic stress effects and boost tolerance in plants, whereas less information is available on its role in salt-stressed lentils. We examined the effect of exogenously applied SNP on salt-stressed lentil plants by monitoring plant growth and yield-related attributes, biochemistry of enzymes (superoxide dismutase (SOD), catalase (CAT), and peroxidase (POD)) amassing of leaf malondialdehyde (MDA) and hydrogen peroxide (H₂O₂). Salinity stress was induced by NaCl application at concentrations of 50 mM (moderate salinity) and 100 mM (severe salinity), while it was alleviated by SNP application at concentrations of 50 µM and 100 µM. Salinity stress severely inhibited the length of roots and shoots, the relative water content, and the chlorophyll content of the leaves, the number of branches, pods, seeds, seed yield, and biomass per plant. In addition, MDA, H₂O₂ as well as SOD, CAT, and POD activities were increased with increasing salinity levels. Plants supplemented with SNP (100 µM) showed a significant improvement in the growth- and yield-contributing parameters, especially in plants grown under moderate salinity (50 mM NaCl). Essentially, the application of 100 µM SNP remained effective to rescue lentil plants under moderate salinity by regulating plant growth and biochemical pathways. Thus, the exogenous application of SNP could be developed as a useful strategy for improving the performance of lentil plants in salinity-prone environments.     

Oral delivery of therapeutic proteins bioencapsulated in plant cells: Preclinical and clinical advances

Oral delivery of protein drugs (PDs) made in plant cells could revolutionize current approaches to their production and delivery. Expression of PDs reduces their production cost by elimination of prohibitively expensive fermentation, purification, cold transportation/storage, and sterile injections and increases their shelf life for several years. The ability of plant cell wall to protect PDs from digestive acids/enzymes, commensal bacteria to release PDs in gut lumen after lysis of plant cell wall, and the role of gut-associated lymphoid tissue in inducing tolerance facilitate prevention or treatment of allergic, autoimmune diseases or antidrug antibody responses. The delivery of functional proteins facilitates treatment of inherited or metabolic disorders. Recent advances in making PDs free of antibiotic resistance genes in edible plant cells, long-term storage at ambient temperature maintaining their efficacy, production in Current Good Manufacturing Practice (cGMP) facilities, Investigational New Drug (IND)-enabling studies for clinical advancement, and Food and Drug Administration approval of orally delivered PDs augur well for advancing this novel drug delivery platform technology.     

Effect of Filtrated Osmotic Solution Based on Concentrated Chokeberry Juice and Mint Extract on the Drying Kinetics,Energy Consumption and Physicochemical Properties of Dried Apples

Background: Filtration of osmotic solution affects selective penetration during osmotic dehydration (OD), and after drying is finished, this can influence the chemical composition of the material, which is also modified by OD. Methods: Osmotic dehydration was carried out in filtrated and non-filtrated concentrated chokeberry juice with the addition of mint infusion. Then, this underwent convective drying, vacuum-microwave drying and combined convective pre-drying, followed by vacuum-microwave finishing drying. Drying kinetics were presented and mathematical models were selected. The specific energy consumption for each drying method was calculated and the energy efficiency was determined. Results and Discussion: The study revealed that filtration of osmotic solution did not have significant effect on drying kinetics; however, it affected selective penetration during OD. The highest specific energy consumption was obtained for the samples treated by convective drying (CD) (around 170 kJ·g⁻¹ fresh weight (fw)) and the lowest for the samples treated by vacuum-microwave drying (VMD) (around 30 kJ·g⁻¹ fw), which is due to the differences in the time of drying and when these methods are applied. Conclusions: Filtration of the osmotic solution can be used to obtain the desired material after drying and the VMD method is the most appropriate considering both phenolic acid content and the energy aspect of drying.     

Following Solid‐Acid‐Catalyzed Reactions by MAS NMR Spectroscopy in Liquid Phase—Zeolite‐Catalyzed Conversion of Cyclohexanol in Water

A microautoclave magic angle spinning NMR rotor is developed enabling in situ monitoring of solid–liquid–gas reactions at high temperatures and pressures. It is used in a kinetic and mechanistic study of the reactions of cyclohexanol on zeolite HBEA in 130 °C water. The ¹³C spectra show that dehydration of 1‐¹³C‐cyclohexanol occurs with significant migration of the hydroxy group in cyclohexanol and the double bond in cyclohexene with respect to the ¹³C label. A simplified kinetic model shows the E1‐type elimination fully accounts for the initial rates of 1‐¹³C‐cyclohexanol disappearance and the appearance of the differently labeled products, thus suggesting that the cyclohexyl cation undergoes a 1,2‐hydride shift competitive with rehydration and deprotonation. Concurrent with the dehydration, trace amounts of dicyclohexyl ether are observed, and in approaching equilibrium, a secondary product, cyclohexyl‐1‐cyclohexene is formed. Compared to phosphoric acid, HBEA is shown to be a more active catalyst exhibiting a dehydration rate that is 100‐fold faster per proton.     

具有优异甲醇耐受性的Rh掺杂PdCu有序金属间化合物纳米粒子增强氧还原电催化

Direct methanol fuel cells (DMFCs), as one of the important energy conversion devices, are of great interest in the fields of energy, catalysis and materials. However, the application of DMFCs is presently challenged because of the limited activity and durability of cathode catalysts as well as the poisoning issues caused by methanol permeation to the cathode during operation. Herein, we report a new class of Rh-doped PdCu nanoparticles (NPs) with ordered intermetallic structure for enhancing the activity and durability of the cathode for oxygen reduction reaction (ORR) and achieving superior methanol tolerance. The disordered Rh-doped PdCu NPs can be prepared via a simple wet-chemical method, followed by annealing to convert it to ordered phases. The results of transmission electron microscopy (TEM), scanning electron microscopy-energy dispersive X-ray spectroscopy (SEM-EDS), power X-ray diffraction (PXRD) analysis and high resolution TEM (HRTEM) successfully demonstrate the formation of near-spherical NPs with an average size of 6.5 ± 0.5 nm and the conversion of the phase structure. The complete phase transition temperatures of Rh-doped PdCu NPs and PdCu are 500 and 400 ℃, respectively. The molar ratio of Rh/Pd/Cu in the as-synthesized Rh-doped PdCu NPs is 5/48/47. Benefitting from Rh doping and the presence of the ordered intermetallic structure, the Rh-doped PdCu intermetallic electrocatalyst achieves the maximum ORR mass activity of 0.96 A·mg^-1 at 0.9 V versus reversible hydrogen electrode (RHE) under alkaline conditions—a 7.4-fold enhancement compared to the commercial Pt/C catalyst. For different electrocatalysts, the ORR activities follow the sequence, ordered Rh-doped PdCu intermetallics > ordered PdCu intermetallics > disordered Rh-doped PdCu NPs > disordered PdCu NPs > commercial Pt/C catalyst. In addition, the distinct structure endows the Rh-doped PdCu intermetallics with highly stable ORR durability with unaltered half-wave potential (E_1/2) and mass activity after continuous 20000 cycles, which are higher than those of other electrocatalysts. Furthermore, the E_1/2 of the Rh-doped PdCu intermetallics decreases by only 5 mV after adding 0.5 mol·L^-1 methanol to the electrolyte, while the commercial Pt/C catalyst negatively shifts by 235 mV and a distinct oxidation peak can be observed. The results indicate that the ORR activity of the Rh-doped PdCu intermetallic electrocatalyst can be well maintained even in the presence of poisoning environment. Our results have demonstrated that Rh-doped PdCu NPs with ordered intermetallic structures is a potential electrocatalyst toward the next-generation high-performance DMFCs.     

Dehydration‐fragmentation mechanism of cathinones and their metabolites in ESI‐CID

Various cathinone‐derived designer drugs (CATs) have recently appeared on the drug market. This study examined the mechanism for the generation of dehydrated ions for CATs during electrospray ionization collision‐induced dissociation (ESI‐CID). The generation mechanism of dehydrated ions is dependent on the amine classification in the cathinone skeleton, which is used in the identification of CATs. The two hydrogen atoms eliminated during the dehydration of cathinone (primary amine) and methcathinone (secondary amine) were determined, and the reaction mechanism was elucidated through the deuterium labeling experiments. The hydrogen atom bonded to the amine nitrogen was eliminated with the proton added during ESI, in both of the tested compounds. This provided evidence that CATs with tertiary amine structures (such as dimethylcathinone and α‐pyrrolidinophenones [α‐PPs]) do not undergo dehydration. However, it was shown that the two major tertiary amine metabolites (1‐OH and 2″‐oxo) of CATs generate dehydrated ions in ESI‐CID. The dehydration mechanisms of the metabolites of α‐pyrrolidinobutiophenone (α‐PBP) belongs to α‐PPs were also investigated. Stable‐isotope labeling showed the dehydration of the 1‐OH metabolite following a simple mechanism where the hydroxy group was eliminated together with the proton added during ESI. In contrast, the dehydration mechanism of the 2″‐oxo metabolite involved hydrogen atoms in three or more locations along with the carbonyl group oxygen, indicating that dehydration occurred via multiple mechanisms likely including the rearrangement reaction of hydrogen atoms. These findings presented herein indicate that the dehydrated ions in ESI‐CID can be used for the structural identification of CATs.     

耐有机溶剂脂肪酶产生菌的筛选和鉴定

从国内各地采取土样分离筛选产耐有机溶剂脂肪酶的新菌株,通过形态和生理生化特征以及系统进化树分析,筛选到的新菌株命名为Pseudomonas aeruginosa CS-2.来自Pseudomonas aeruginosa CS-2的粗脂肪酶液在乙腈中酶活提高,在苯、氯仿、正己烷、石油醚和异辛烷中表现出较高的稳定性.