Thermogravimetric Investigation of Antioxidant Activity of Selected Compounds in Lipid Oxidation

Uninhibited and inhibited autooxidation of ethyl linoleate(LnEt) in bulk phase initiated by 0.04 M azoisobutyronitrile (AIBN) was investigated by thermogravimetry in isothermal mode at 35, 40 and 50°C. LnEt oxidation was inhibited by:2,6-di-t-butyl-4-methylphenol (BHT), 2-t-butyl-6-methylphenol (BMP),2-hydroxyphenylacetic acid (PAA), 2-hydroxyacetophenone (HAP), α-tocopherol,2,2'-methylene-bis-(4-methyl-6-t-butylphenol) (BIS), caffeic acid andβ-carotene. All investigated compounds showed antioxidant activity measured by induction time, values of rate of oxidation during induction period (R _inh) and values of kinetic chain length ν. At lower temperatures the monohydroxyphenols are more efficient inhibitors than dihydroxyphenols while at 50°C dihydroxyphenols have better antioxidant efficiency. This revised version was published online in July 2006 with corrections to the Cover Date.     

Natural Compounds and Products from an Anti-Aging Perspective

Aging is a very complex process that is accompanied by a degenerative impairment in many of the major functions of the human body over time. This inevitable process is influenced by hereditary factors, lifestyle, and environmental influences such as xenobiotic pollution, infectious agents, UV radiation, diet-borne toxins, and so on. Many external and internal signs and symptoms are related with the aging process and senescence, including skin dryness and wrinkles, atherosclerosis, diabetes, neurodegenerative disorders, cancer, etc. Oxidative stress, a consequence of the imbalance between pro- and antioxidants, is one of the main provoking factors causing aging-related damages and concerns, due to the generation of highly reactive byproducts such as reactive oxygen and nitrogen species during the metabolism, which result in cellular damage and apoptosis. Antioxidants can prevent these processes and extend healthy longevity due to the ability to inhibit the formation of free radicals or interrupt their propagation, thereby lowering the level of oxidative stress. This review focuses on supporting the antioxidant system of the organism by balancing the diet through the consumption of the necessary amount of natural ingredients, including vitamins, minerals, polyunsaturated fatty acids (PUFA), essential amino acids, probiotics, plants’ fibers, nutritional supplements, polyphenols, some phytoextracts, and drinking water.     

天然黄酮类化合物清除羟基自由基的活性研究

采用分光光度法测定了黑沙蒿中黄酮类化合物清除羟基自由基的能力,以IC50值作为评价指标,初步探讨了黄酮类化合物清除羟基自由基的活性与结构之间的关系,为开发利用黑沙蒿提供了科学依据.     

Research Progress of Natural Small-Molecule Compounds Related to Tumor Differentiation

Tumor differentiation is a therapeutic strategy aimed at reactivating the endogenous differentiation program of cancer cells and inducing cancer cells to mature and differentiate into other types of cells. It has been found that a variety of natural small-molecule drugs can induce tumor cell differentiation both in vitro and in vivo. Relevant molecules involved in the differentiation process may be potential therapeutic targets for tumor cells. Compared with synthetic drugs, natural small-molecule antitumor compounds have the characteristics of wide sources, structural diversity and low toxicity. In addition, natural drugs with structural modification and transformation have relatively concentrated targets and enhanced efficacy. Therefore, using natural small-molecule compounds to induce malignant cell differentiation represents a more targeted and potential low-toxicity means of tumor treatment. In this review, we focus on natural small-molecule compounds that induce differentiation of myeloid leukemia cells, osteoblasts and other malignant cells into functional cells by regulating signaling pathways and the expression of specific genes. We provide a reference for the subsequent development of natural small molecules for antitumor applications and promote the development of differentiation therapy.     

The Cytotoxic Natural Product Vioprolide A Targets Nucleolar Protein 14, Which Is Essential for Ribosome Biogenesis

Novel targets are needed for treatment of devastating diseases such as cancer. For decades, natural products have guided innovative therapies by addressing diverse pathways. Inspired by the potent cytotoxic bioactivity of myxobacterial vioprolides A–D, we performed in‐depth studies on their mode of action. Based on its prominent potency against human acute lymphoblastic leukemia (ALL) cells, we conducted thermal proteome profiling (TPP) and deciphered the target proteins of the most active derivative vioprolide A (VioA) in Jurkat cells. Nucleolar protein 14 (NOP14), which is essential in ribosome biogenesis, was confirmed as a specific target of VioA by a suite of proteomic and biological follow‐up experiments. Given its activity against ALL cells compared to healthy lymphocytes, VioA exhibits unique therapeutic potential for anticancer therapy through a novel mode of action.     

Activity of Compounds from Temperate Propolis against Trypanosoma brucei and Leishmania mexicana

Ethanolic extracts of samples of temperate zone propolis, four from the UK and one from Poland, were tested against three Trypanosoma brucei strains and displayed EC₅₀ values < 20 µg/mL. The extracts were fractionated, from which 12 compounds and one two-component mixture were isolated, and characterized by NMR and high-resolution mass spectrometry, as 3-acetoxypinobanksin, tectochrysin, kaempferol, pinocembrin, 4′-methoxykaempferol, galangin, chrysin, apigenin, pinostrobin, cinnamic acid, coumaric acid, cinnamyl ester/coumaric acid benzyl ester (mixture), 4′,7-dimethoxykaempferol, and naringenin 4′,7-dimethyl ether. The isolated compounds were tested against drug-sensitive and drug-resistant strains of T. brucei and Leishmania mexicana, with the highest activities ≤ 15 µM. The most active compounds against T. brucei were naringenin 4′,7 dimethyl ether and 4′methoxy kaempferol with activity of 15–20 µM against the three T. brucei strains. The most active compounds against L. mexicana were 4′,7-dimethoxykaempferol and the coumaric acid ester mixture, with EC₅₀ values of 12.9 ± 3.7 µM and 13.1 ± 1.0 µM. No loss of activity was found with the diamidine- and arsenical-resistant or phenanthridine-resistant T. brucei strains, or the miltefosine-resistant L. mexicana strain; no clear structure activity relationship was observed for the isolated compounds. Temperate propolis yields multiple compounds with anti-kinetoplastid activity.     

The Role of Hydrogen Bond Donor on the Extraction of Phenolic Compounds from Natural Matrices Using Deep Eutectic Systems

Recently, deep eutectic systems (DESs) as extraction techniques for bioactive compounds have surfaced as a greener alternative to common organic solvents. In order to study the effect of these systems on the extraction of phenolic compounds from different natural sources, a comprehensive review of the state of the art was carried out. In a first approach, the addition of water to these systems and its effect on DES physicochemical properties such as polarity, viscosity, and acidity was investigated. This review studied the effect of the hydrogen bond donor (HBD) on the nature of the extracted phenolics. The effects of the nature of the HBD, namely carbon chain length as well as the number of hydroxyl, methyl, and carbonyl groups, have shown to play a critical role in the extraction of different phenolic compounds. This review highlights the differences between DES systems and systematizes the results published in the literature, so that a more comprehensive evaluation of the systems can be carried out before any experimental trial.     

Mammalian Arginase Inhibitory Activity of Methanolic Extracts and Isolated Compounds from Cyperus Species

Polyphenolic enriched extracts from two species of Cyperus, Cyperus glomeratus and Cyperus thunbergii, possess mammalian arginase inhibitory capacities, with the percentage inhibition ranging from 80% to 95% at 100 µg/mL and 40% to 64% at 10 µg/mL. Phytochemical investigation of these species led to the isolation and identification of two new natural stilbene oligomers named thunbergin A-B (1–2), together with three other stilbenes, trans-resveratrol (3), trans-scirpusin A (4), trans-cyperusphenol A (6), and two flavonoids, aureusidin (5) and luteolin (7), which were isolated for the first time from C. thunbergii and C. glomeratus. Structures were established on the basis of the spectroscopic data from MS and NMR experiments. The arginase inhibitory activity of compounds 1–7 was evaluated through an in vitro arginase inhibitory assay using purified liver bovine arginase. As a result, five compounds (1, 4–7) showed significant inhibition of arginase, with IC₅₀ values between 17.6 and 60.6 µM, in the range of those of the natural arginase inhibitor piceatannol (12.6 µM). In addition, methanolic extract from Cyperus thunbergii exhibited an endothelium and NO-dependent vasorelaxant effect on thoracic aortic rings from rats and improved endothelial dysfunction in an adjuvant-induced arthritis rat model.     

Pyridoxine‐Derived Organoselenium Compounds with Glutathione Peroxidase‐Like and Chain‐Breaking Antioxidant Activity

One of the vitamin B6 vitamers, pyridoxine, was modified to incorporate selenium in various oxidation states in place of the methyl group in position 2. Such compounds were conveniently accessed by treatment of bis‐4,5‐(carboethoxy)‐2‐iodo‐3‐pyridinol with disodium diselenide and LiAlH₄‐reduction. After work‐up, selone 7 was isolated in good yield as an air‐stable crystalline material. Hydrogen bonding to the neighboring hydroxyl group, as revealed by the short intramolecular Se ??? H distance in the crystal structure is likely to provide extra stabilization to the compound. Computational studies showed that selone 7 is more stable than the corresponding selenol tautomer by 12.2 kcal mol^?1. Hydrogen peroxide oxidation of the selone 7 afforded diselenide 12 , and, on further oxidation, seleninic acid 13 . Treatment of the seleninic acid with thiophenol provided an isolable selenosulfide 14 . The glutathione peroxidase‐like properties of the pyridoxine‐derived compounds were assessed by using the coupled reductase method. Seleninic acid 13 was found to be twofold more active than ebselen. The chain‐breaking capacity of the pyridoxine compounds were studied in a water/chlorobenzene membrane model containing linoleic acid as an oxidizable substrate and N‐acetylcysteine as a thiol reducing agent. Diselenide 15 could match α‐tocopherol when it comes to reactivity towards peroxyl radicals and inhibition time.     

N-Phenacyldibromobenzimidazoles—Synthesis Optimization and Evaluation of Their Cytotoxic Activity

Antifungal N-phenacyl derivatives of 4,6- and 5,6-dibromobenzimidazoles are interesting substrates in the synthesis of new antimycotics. Unfortunately, their application is limited by the low synthesis yields and time-consuming separation procedure. In this paper, we present the optimization of the synthesis conditions and purification methods of N-phenacyldibromobenzimidazoles. The reactions were carried out in various base solvent-systems including K₂CO₃, NaH, KOH, t-BuOK, MeONa, NaHCO₃, Et₃N, Cs₂CO₃, DBU, DIPEA, or DABCO as a base, and MeCN, DMF, THF, DMSO, or dioxane as a solvent. The progress of the reaction was monitored using HPLC analysis. The best results were reached when the reactions were carried out in an NaHCO₃–MeCN system at reflux for 24 h. Additionally, the cytotoxic activity of the synthesized compounds against MCF-7 (breast adenocarcinoma), A-549 (lung adenocarcinoma), CCRF-CEM (acute lymphoblastic leukemia), and MRC-5 (normal lung fibroblasts) was evaluated. We observed that the studied cell lines differed in sensitivity to the tested compounds with MCF-7 cells being the most sensitive, while A-549 cells were the least sensitive. Moreover, the cytotoxicity of the tested derivatives towards CCRF-CEM cells increased with the number of chlorine or fluorine substituents. Furthermore, some of the active compounds, i.e., 2-(5,6-dibromo-1H-benzimidazol-1-yl)-1-(3,4-dichlorophenyl)ethanone (4f), 2-(4,6-dibromo-1H-benzimidazol-1-yl)-1-(2,4,6-trichlorophenyl)ethanone (5g), and 2-(4,6-dibromo-1H-benzimidazol-1-yl)-1-(2,4,6-trifluorophenyl)ethanone (5j) demonstrated pro-apoptotic properties against leukemic cells with derivative 5g being the most effective.     

Short Overview of Some Assays for the Measurement of Antioxidant Activity of Natural Products and Their Relevance in Dermatology

Impaired systemic redox homeostasis is implicated in the onset and development of various diseases, including skin diseases. Therefore, continuous search for natural products with antioxidant bioactivities applicable in biomedicine is attractive topic of general interest. Research efforts aiming to validate antioxidant potentials of natural products has led to the development of several assays based on various test principles. Hence, understanding the advantages and limitations of various assays is important for selection of assays useful to study antioxidant and related bioactivities of natural products of biomedical interest. This review paper gives a short overview on some chemical and cellular bioassays used to estimate the antioxidant activity of chosen natural products together with a brief overview on the use of natural products with antioxidant activities as adjuvant medicinal remedies in dermatology.     

Probing the Antioxidant Activity of Polyphenols by CIDNP: From Model Compounds to Green Tea and Red Wine

Polyphenols occur naturally in a vast variety of plants. One of their predominant properties is their antioxidant activity. To provide a deeper understanding of the antioxidant mechanism, ¹H CIDNP spectroscopy (CIDNP=chemically induced dynamic nuclear polarization) is used to study model hydrogen abstraction reactions with four catechin‐based polyphenols: catechin (CA), gallocatechin (GC), epigallocatechin (EGC), and epigallocatechin gallate (EGCG). The experiments involve photoinduced hydrogen‐atom transfer to a hydrogen abstractor (e.g., excited isopropylthioxanthone) followed under steady‐state conditions and in a time‐resolved fashion (resolution 500 ns–1 ms). It is found that hydrogen abstraction is an essentially stochastic process with a slight preference for the B rings in the catechin‐based polyphenols. Remarkably, analogous reactivity patterns could be followed in the “real systems”, green tea and red wine. We also show that CIDNP can be used as a semiquantitative tool to assess chemical reactivity.     

Studies on 1,4-Quinone Derivatives Exhibiting Anti-Leukemic Activity along with Anti-Colorectal and Anti-Breast Cancer Effects

Colorectal cancer (CRC), breast cancer, and chronic myeloid leukemia (CML) are life-threatening malignancies worldwide. Although potent therapeutic and screening strategies have been developed so far, these cancer types are still major public health problems. Therefore, the exploration of more potent and selective new agents is urgently required for the treatment of these cancers. Quinones represent one of the most important structures in anticancer drug discovery. We have previously identified a series of quinone-based compounds (ABQ-1-17) as anti-CML agents. In the current work, ABQ-3 was taken to the National Cancer Institute (NCI) for screening to determine its in vitro antiproliferative effects against a large panel of human tumor cell lines at five doses. ABQ-3 revealed significant growth inhibition against HCT-116 CRC and MCF-7 breast cancer cells with 2.00 µM and 2.35 µM GI₅₀ values, respectively. The MTT test also showed that ABQ-3 possessed anticancer effects towards HCT-116 and MCF-7 cells with IC₅₀ values of 5.22 ± 2.41 μM and 7.46 ± 2.76 μM, respectively. Further experiments indicated that ABQ-3 induced apoptosis in both cell lines, and molecular docking studies explicitly suggested that ABQ-3 exhibited DNA binding in a similar fashion to previously reported compounds. Based on in silico pharmacokinetic prediction, ABQ-3 might display drug-like features enabling this compound to become a lead molecule for future studies.     

Antioxidant Activity of Graft Chitosan Derivatives

Graft chitosan derivatives (CMCTS‐g‐MAAS and CMCTS‐g‐AAS) were prepared by the graft copolymerization of methacrylic acid sodium (MAAS) and acrylic acid sodium (AAS) onto the etherification product of chitosan‐carboxymethyl chitosan (CMCTS). Their antioxidant activity was estimated as superoxide anion scavengers by chemiluminescence techniques. The derivatives with low grafting percentages have a relatively low 50% inhibition concentration (IC₅₀), which could be related to the fact that they have different contents of hydroxyl and amino groups in the polymer chains.

Superoxide radical scavenging activity of CMCTS‐g‐MAAS.     

天然产物黄酮类化合物的高效液相色谱分析

引用了自1997年以来的45篇文献,综述了黄酮类化合物的高效液相色谱（HPLC）分析方法,着重介绍了黄酮、黄酮醇和双氢黄酮等的定性和定量分析,同时简要介绍了指纹图谱及药代动力学研究,为黄酮类化合物今后在分离分析,质量控制和药理药效研究等方面的深入研究提供理论依据。     

Phenolic Compounds in Active Packaging and Edible Films/Coatings: Natural Bioactive Molecules and Novel Packaging Ingredients

In recent years, changing lifestyles and food consumption patterns have driven demands for high-quality, ready-to-eat food products that are fresh, clean, minimally processed, and have extended shelf lives. This demand sparked research into the creation of novel tools and ingredients for modern packaging systems. The use of phenolic-compound-based active-packaging and edible films/coatings with antimicrobial and antioxidant activities is an innovative approach that has gained widespread attention worldwide. As phenolic compounds are natural bioactive molecules that are present in a wide range of foods, such as fruits, vegetables, herbs, oils, spices, tea, chocolate, and wine, as well as agricultural waste and industrial byproducts, their utilization in the development of packaging materials can lead to improvements in the oxidative status and antimicrobial properties of food products. This paper reviews recent trends in the use of phenolic compounds as potential ingredients in food packaging, particularly for the development of phenolic compounds-based active packaging and edible films. Moreover, the applications and modes-of-action of phenolic compounds as well as their advantages, limitations, and challenges are discussed to highlight their novelty and efficacy in enhancing the quality and shelf life of food products.     

The Synthesis of Natural Acetylenic Compounds from Stereum hirsutum

The regioselective synthesis of two new acetylenic compounds, sterehirsutinal ( 1 ) and sterehirsutinol ( 2 ), isolated recently from culture medium of the fungus Stereum hirsutum, is reported.     

The Vital Role of Buffer Anions in the Antioxidant Activity of CeO2 Nanoparticles

Cerium oxide (CeO₂) nanoparticles display excellent antioxidant properties by scavenging free radicals. However, some studies have indicated that they can cause an adverse response by generating reactive oxygen species (ROS). Hence, it is important to clarify the factors that affect the oxidant/antioxidant activities of CeO₂ nanoparticles. In this work, we report the effects of different buffer anions on the antioxidant activity of CeO₂ nanoparticles. Considering the main anions present in the body, Tris‐HCl, sulfate, and phosphate buffer solutions have been used to evaluate the antioxidant activity of CeO₂ nanoparticles by studying their DNA protective effect. The results show that CeO₂ nanoparticles can protect DNA from damage in Tris‐HCl and sulfate systems, but not in phosphate buffer solution (PBS) systems. The mechanism of action has been explored: cerium phosphate is formed on the surface of the nanoparticles, which interferes with the redox cycling between Ce³⁺ and Ce⁴⁺. As a result, the antioxidant activity of CeO₂ nanoparticles is greatly affected by the external environment, especially the anions. These results may provide guidance for the further practical application of CeO₂ nanoparticles.