Minireview: Versatile Melatonin: A Pervasive Molecule Serves Various Functions in Signaling and Protection

Melatonin, which is able to enter all tissues and all compartments of the cell, acts in a highly pleiotropic fashion. Some melatonin effects are mediated by membrane receptors, others are receptor independent. Melatonin is produced in the pineal gland and various extrapineal organs of vertebrates, but is also found in invertebrates, angiosperms, and unicells. In mammals, melatonin elicits various secondary humoral responses, e.g., in the immune system via interleukin-4 and other cytokines and in the brain by modulation of NO formation. Melatonin is also a powerful radical scavenger, terminating free radical reaction chains initiated by photooxidants, hydroxyl or peroxyl radicals. The protective potency of this indoleamine is demonstrated by various experiments.     

Enzymatic polymerization on the surface of functionalized cellulose fibers

Enzymatic coating of functionalized cellulose fibers with catechol was performed in the presence of Trametes hirsuta laccase. Cellulose functionalization was done by covalent fixation of aromatic amines onto the cellulose surface using a dyeing procedure with C.I. Reactive Black 5 (RB5) followed by reduction with sodium hydrosulfite. Cellulase enzymes were used on coated and control samples to obtain the analytes linked with the soluble sugars in solution, to prove the reaction concepts described in this paper. Hydrolyzed coated-cellulose showed lower concentration of reducing sugars (1188 mg/L) than control samples (2011 mg/L). The structures of these compounds were checked by LC/MS analysis confirming the presence of functionalized glucose and cellobiose units coupled to poly(catechol) molecules (m/z 580 and m/z 633). Alkali extraction method showed to be very promising to coat cellulose fibers with phenols in the presence of enzymes, at mild conditions of temperature and pH.     

Physiological behaviour, oxidative damage and antioxidative protection of olive trees grown under different irrigation regimes

Irrigation effects were investigated on an 8-year-old olive (Olea europaea L., cv. Cobrançosa) commercial orchard located in northeast Portugal. Trees were subjected to a rainfed control (T0) and three treatments (T1, T2, T3) that received a seasonal water amount equivalent to 30%, 60% and 100% of the estimated local evaporative demand by a drip irrigation system. Irrigation increases the photosynthetic activity of olive trees, in association with increases in water status, and reduces the midday and afternoon depression in gas exchange. The closely association between photosynthetic rate (A) and stomatal conductance (g _s) revealed that the decline in net photosynthesis over the course of the day was largely a consequence of stomatal limitation. However, the ratio of intercellular to atmospheric CO₂ concentration increased markedly from morning to midday in non-irrigated plants, in spite of lower g _s, suggesting that non-stomatal limitations of photosynthesis also occur when environmental conditions become more stressful. The occurrence of perturbations at chloroplastic level in rainfed plants was demonstrated by a lower maximum photochemical efficiency of photosystem II during the afternoon. Chlorophyll fluorescence measurements also revealed the occurrence of a dynamic photoinhibition in irrigated trees, mainly in T2 and T3, which seemed to be effective in protecting the photosynthetic apparatus from photodamage. Irrigation enhances antioxidant protection and decreases the oxidative damage at leaf level. Leaves grown under rainfed conditions revealed symptoms of oxidative stress, like the reduction (14%) in chlorophyll concentration and the increased levels (57%) of lipid peroxidation. We also found that the scavenging function of superoxide dismutase was impaired in rainfed plants. In contrast, the low thiobarbituric acid reactive substances concentration in T3 indicates that irrigation enhances the repairing mechanisms and decreases the oxidative damage by lipid peroxidation. Accordingly, leaves in T3 treatment had high levels of –SH compounds and the highest antioxidant potential. Meanwhile, the finding that guaiacol peroxidase activity increased in rainfed plants, associated with the appearance of oxidative damage, suggests that this enzyme has no major antioxidative function in olive.     

Synthesis of anomeric sulfonamides and their behaviour under radical-mediated bromination conditions

O-Peracetylated methyl 3-(d-glycopyranosylthio)propanoates of β-d-gluco, and α- and β-d-galacto configurations were oxidized to the corresponding S,S-dioxides (sulfones) by Oxone^® or MCPBA. Oxidation of the β-d-gluco derivative with H₂O₂/Na₂WO₄ gave the corresponding S-oxide (sulfoxide). DBU-induced elimination of methyl acrylate from the β-d-gluco and β-d-galacto configured S,S-dioxides (sulfones) gave O-peracetylated β-d-glycopyranosyl-1-C-sulfinates which, on treatment with H₂NOSO₃H, furnished the corresponding β-d-glycopyranosyl-1-C-sulfonamides. Radical-mediated bromination of the protected methyl 3-(β-d-glycopyranosylthio)propanoate S,S-dioxides gave mixtures of 1-C- and 5-C-bromoglycosyl compounds. Similar brominations of the O-peracetylated β-d-glycopyranosyl-1-C-sulfonamides resulted in the formation of α-d-glycopyranosyl bromides and 1-C- and 5-C-bromoglycosyl sulfonamides. A rationale for these observations was proposed. Methyl 3-(β-d-glucopyranosylthio)propanoate, its S,S-dioxide, and β-d-glucopyranosyl-1-C-sulfonamide proved inefficient when tested as inhibitors of rabbit muscle glycogen phosphorylase b.     

Cancer Chemopreventive Effect of Bergenin from Peltophorum pterocarpum Wood

The aqueous extract of Peltophorum pterocarpum (Fabaceae) wood exhibited potent inhibitory effects against Epstein? Barr virus early antigen (EBV‐EA) activation induced with 12‐O‐tetradecanoylphorbol‐13‐acetate (TPA) in Raji cells and against melanogenesis in α‐melanocyte‐stimulating hormone (α‐MSH)‐stimulated B16 melanoma cells, as well as potent 1,1‐diphenyl‐2‐picrylhydrazyl (DPPH) free radical‐scavenging activity. Two phenolic acid derivatives, bergenin ( 1 ) and gallic acid ( 2 ), were isolated from the ethyl acetate (AcOEt)‐soluble fraction obtained from the extract. Compound 1 exhibited potent inhibitory effect against EBV‐EA activation and against skin tumor promotion in an in vivo two‐stage mouse skin carcinogenesis test based on 7,12‐dimethylbenz[a]anthracene (DMBA) as initiator, and with TPA as promoter. Both compounds 1 and 2 exhibited melanogenesis‐inhibitory activities in α‐MSH‐stimulated B16 melanoma cells, and, in addition, compound 2 showed strong DPPH radical‐scavenging activity.     

Endogenous and Dietary Indoles: A Class of Antioxidants and Radical Scavengers in the ABTS Assay

Indoles are very common in the body and diet and participate in many biochemical processes. A total of twenty-nine indoles and analogs were examined for their properties as antioxidants and radical scavengers against 2,2′-Azino-bis(3-ethylbenzthiazoline-6-sulfonic acid) ABTS^?+ radical cation. With only a few exceptions, indoles reacted nonspecifically and quenched this radical at physiological pH affording ABTS. Indoleamines like tryptamine, serotonin and methoxytryptamine, neurohormones (melatonin), phytohormones (indoleacetic acid and indolepropionic acid), indoleamino acids like l-tryptophan and derivatives (N-acetyltryptophan, l-abrine, tryptophan ethyl ester), indolealcohols (tryptophol and indole-3-carbinol), short peptides containing tryptophan, and tetrahydro-β-carboline (pyridoindole) alkaloids like the pineal gland compound pinoline, acted as radical scavengers and antioxidants in an ABTS assay-measuring total antioxidant activity. Their trolox equivalent antioxidant capacity (TEAC) values ranged from 0.66 to 3.9?mM, usually higher than that for Trolox and ascorbic acid (1?mM). The highest antioxidant values were determined for melatonin, 5-hydroxytryptophan, trp-trp and 5-methoxytryptamine. Active indole compounds were consumed during the reaction with ABTS^?+ and some tetrahydropyrido indoles (e.g. harmaline and 1-methyl-1,2,3,4-tetrahydro-β-carboline-3-carboxylic acid ethyl ester) afforded the corresponding fully aromatic β-carbolines (pyridoindoles), that did not scavenge ABTS^?+. Radical scavenger activity of indoles against ABTS^?+ was higher at physiological pH than at low pH. These results point out to structural compounds with an indole moiety as a class of radical scavengers and antioxidants. This activity could be of biological significance given the physiological concentrations and body distribution of some indoles.     

胸神经阻滞和肋间神经阻滞对乳腺癌根治术患者血流动力学、术后镇痛及呼吸功能的对比研究

目的:比较胸神经阻滞和肋间神经阻滞对乳腺癌根治术患者血流动力学、术后镇痛以及呼吸功能的影响,为乳腺癌根治术患者的临床麻醉选择提供参考。方法:选择2017年3月至2018年3月医院收治的120例行乳腺癌根治术的患者作为研究对象,按照麻醉方式不同分为观察组和对照组各60例,其中观察组患者给予胸神经阻滞复合全身麻醉,对照组患者给予肋间神经阻滞复合全身麻醉。比较两组患者术后2h、6h、12h、24h、48h的静态和动态的视觉模拟评分(VAS)评分,并比较两组患者切皮前5 min(T_0)、切皮即刻(T_1)、切皮后15 min(T_2)、30 min(T_3)、钉皮即刻(T_4)及拔管后15 min(T_5)的血流动力学以及呼吸功能指标,并分析两组患者术中用药、术后镇痛泵使用情况以及术后不良反应。结果:两组患者术后静息状态下不同时点的VAS评分差异无统计学意义(P0.05);动态状态下,观察组患者的VAS评分明显低于对照组(P0.05)。T_1-T_5期间,观察组患者的平均动脉压(MAP)、心率(HR)均明显低于对照组,每分钟通气量(MV)明显高于对照组(P0.05)。观察组患者的术中瑞芬太尼消耗量、丙泊酚用量、镇痛泵有效按压次数以及补救镇痛例数均明显低于对照组;恶心呕吐(PONV)、尿潴留、嗜睡等不良反应明显低于对照组(P0.05)。结论:与肋间神经阻滞相比,胸神经阻滞治疗乳腺癌根治术患者可以有效增强术后镇痛效果,术中血流动力学平稳,减少阿片类药物用量,降低术后不良反应发生率,改善术后呼吸功能,效果显著,值得临床推广使用。     

Essential Oil Phenyl Propanoids. Useful as OH Scavengers?

In order to search for radical scavengers which could be used as raw materials for cosmetics, phenyl propanoids (eugenol, isoeugenol, dehydrodieugenol, dehydrodieugenol B and coniferyl aldehyde) were examined for their hydroxyl radical (· OH) scavenging ability. A Fenton system was used to produce -OH. In order to see scavenging by these phenyl propanoids, competition reactions between a spin trap, 5,5-dimethyl-1-pyrroline-N-oxide (DMPO), and these phenyl propanoids for -OH were studied. The relative yield of the spin adduct of -OH (DMPO-OH) was measured by electron spin resonance spectroscopy. The approximate rate constants of the reactions between these phenyl propanoids and -OH estimated by measuring the reduced height of the ESR signals of DMPO-OH were found to be at least in the order of 10⁹ M^-1 s^-1 (diffusion-controlled). Also, using the TBA tests, the reactions between ·OH and several compounds reactive with ·OH were investigated in the presence of the phenyl propanoids and it was found that the phenyl propanoids compete with such reactive compounds for ·OH. These results indicate that these phenyl propanoids can be used as antioxidants for skin damage perhaps caused by -OH generated by UV-light.