Antioxidation Activity Enhancement by Intramolecular Hydrogen Bond and Non-Browning Mechanism of Active Ingredients in Rosemary: Carnosic Acid and Carnosol.

Rosemary is one of the most promising, versatile, and studied natural preservatives. Carnosic acid (CA) and carnosol (CARN), as the primary active ingredients of rosemary extracts, have little difference in structure, but their antioxidant activities vary significantly, depending on the system studied. The underlying molecular mechanisms remain unclear.

Efficacy of fecal microbiota transplantation in type 2 diabetes mellitus: a systematic review and meta-analysis.

Objective: Type 2 diabetes mellitus (T2DM) is one of the common metabolic diseases worldwide, and studies have found significant differences in the composition and ratio of intestinal flora between patients with T2DM and normal glucose tolerance, and fecal microbiota transplantation (FMT) may modulate the composition of the intestinal microbiota thereby alleviating the hyperglycemic state. We conducted a meta-analysis and systematic review of existing randomized controlled trials (RCTs) to assess the efficacy of FMT in T2DM.

Methods: We conducted a computer search of PubMed, Embase, The Cochrane Library, and Web of Science to screen randomized controlled trials studies on FMT treatment for T2DM and extracted data from studies that met inclusion criteria.

Double-Site Binding and Anti-/Pro-oxidation of Luteolin on Bovine Serum Albumin Mediated by Copper(II) Coordination.

The interactions of luteolin (Lut) with bovine serum albumin (BSA) mediated by Cu(II) were investigated by spectroscopic, calorimetric, and molecular dynamic (MD) methods. Fluorescence studies showed that the binding of Lut to BSA was significantly enhanced by Cu(II) coordination with the number of binding sites and binding constant increasing from = 1 and = 3.2 × 10 L·mol for Lut to = 2 and = 7.

Promotion effects of flavonoids on browning induced by enzymatic oxidation of tyrosinase: structure-activity relationship.

Tyrosinase, widely distributed in nature, is a copper-containing polyphenol oxidase involved in the formation of melanin. Flavonoids are most often considered as tyrosinase inhibitors but have also been confirmed to be tyrosinase substrates. Four structure-related flavonoids including flavones (apigenin and luteolin) and flavonols (kaempferol and quercetin) are found to promote not inhibit browning induced by tyrosinase catalyzed oxidation both in model systems and in mushrooms under aerobic conditions.

Peroxyl radical induced membrane instability of giant unilamellar vesicles and anti-lipooxidation protection.

The present work is intended to investigate the morphological instability of lipid membrane induced by peroxyl radical (ROO) and the underlying mechanism. To this end, the giant unilamellar vesicle (GUV) made from phosphatidylcholine was employed as a membrane model, and the azo compounds 2,2'-azobis(2,4-dimethylvaleronitrile) (AMVN) and 2,2'-azobis(2-amidinopropane) dihydrochloride (AAPH) were used as the precursors of ROO. Upon mild pyrolysis, the GUV immobilized in agarose gel was followed by conventional optical microscopy in real time, and the morphological variation was quantified by the image heterogeneity, perimeter and area all as a function of time for up to an hour.

Alkaline earth metal ion coordination increases the radical scavenging efficiency of kaempferol.

Flavonoids are used as natural additives and antioxidants in foods, and after coordination to metal ions, as drug candidates, depending on the flavonoid structure. The rate of radical scavenging of the ubiquitous plant flavonoid kaempferol (3,5,7,4'-tetrahydroxyflavone, Kaem) was found to be significantly enhanced by coordination of Mg(ii), Ca(ii), Sr(ii), and Ba(ii) ions, whereas the radical scavenging rate of apigenin (5,7,4'-trihydroxyflavone, Api) was almost unaffected by alkaline earth metal (AEM) ions, as studied for short-lived β-carotene radical cations (β-Car˙) formed by laser flash photolysis in chloroform/ethanol (7 : 3) and for the semi-stable 2,2-diphenyl-1-picrylhydrazyl radical, DPPH˙, in ethanol at 25 °C. A 1 : 1 Mg(ii)-Kaem complex was found to be in equilibrium with a 1 : 2 Mg(ii)-Kaem complex, while for Ca(ii), Sr(ii) and Ba(ii), only 1 : 2 AEM(ii)-Kaem complexes were detected, where all complexes showed 3-hydroxyl and 4-carbonyl coordination and stability constants of higher than 10 L mol.

Kinetic Studies on Radical Scavenging Activity of Kaempferol Decreased by Sn(II) Binding.

Sn(II) binds to kaempferol (HKaem, 3,4',5,7-tetrahydroxy-2-(4-hydroxyphenyl)-4-1-benzopyran-4-one) at the 3,4-site forming [Sn(II)(Kaem)] complex in ethanol. DPPH scavenging efficiency of HKaem is dramatically decreased by SnCl coordination due to formation of acid inhibiting deprotonation of HKaem as ligands and thus reduces the radical scavenging activity of the complex via a sequential proton-loss electron transfer (SPLET) mechanism. Moderate decreases in the radical scavenging of HKaem are observed by Sn(CHCOO) coordination and by contact between Sn and HKaem, in agreement with the increase in the oxidation potential of the complex compared to HKaem, leading to a decrease in antioxidant efficiency for fruits and vegetables with Sn as package materials.

Synergy between plant phenols and carotenoids in stabilizing lipid-bilayer membranes of giant unilamellar vesicles against oxidative destruction.

We have investigated the synergism between plant phenols and carotenoids in protecting the phosphatidylcholine (PC) membranes of giant unilamellar vesicles (GUVs) from oxidative destruction, for which chlorophyll-a (Chl-a) was used as a lipophilic photosensitizer. The effect was examined for seven different combinations of β-carotene (β-CAR) and plant phenols. The light-induced change in GUV morphology was monitored via conventional optical microscopy, and quantified by a dimensionless image-entropy parameter, ΔE.

Copper(II) Coordination and Translocation in Luteolin and Effect on Radical Scavenging.

Luteolin differs as a radical scavenger dramatically from apigenin in response to Cu(II) coordination despite a minor structural difference. Coordination of Cu(II) increases the radical scavenging efficiency of luteolin, especially at low pH, while decreases the efficiency of apigenin at both low and higher pH as studied by ABTS radical scavenging. Luteolin forms a 1:1 complex with Cu(II) binding to 4-carbonyl and 5-phenol for pH <6 and to 3',4'-catechol for pH >6.

Kaempferol Binding to Zinc(II), Efficient Radical Scavenging through Increased Phenol Acidity.

Zinc(II) enhances radical scavenging of the flavonoid kaempferol (Kaem) most significantly for the 1:1 Zn(II)-Kaem complex in equilibrium with the 1:2 Zn(II)-Kaem complex both with high affinity at 3-hydroxyl and 4-carboxyl coordination. In methanol/chloroform (7/3, v/v), 1:1 Zn(II)-Kaem complex reduces β-carotene radical cation, β-Car, with a second-order rate constant, 1.88 × 10 L·mol·s, while both Kaem and 1:2 Zn(II)-Kaem complex are nonreactive, as determined by laser flash photolysis.

Integrity of Membrane Structures in Giant Unilamellar Vesicles as Assay for Antioxidants and Prooxidants.

We have attempted to evaluate, on the basis of optical microscopy for a single giant unilamellar vesicle (GUV), the potency of antioxidants in protecting GUV membranes from oxidative destruction. Photosensitized membrane budding of GUVs prepared from soybean phosphatidylcholine with chlorophyll a (Chl a) and β-carotene (β-Car) as photosensitizer and protector, respectively, were followed by microscopic imaging. A dimensionless entropy parameter, ΔE, as derived from the time-resolved microscopic images, was employed to describe the evolution of morphological variation of GUVs.

Genistein Binding to Copper(II)-Solvent Dependence and Effects on Radical Scavenging.

Genistein, but not daidzein, binds to copper(II) with a 1:2 stoichiometry in ethanol and with a 1:1 stoichiometry in methanol, indicating chelation by the 5-phenol and the 4-keto group of the isoflavonoid as demonstrated by the Jobs method and UV-visible absorption spectroscopy. In ethanol, the stability constants had the value 1.12 × 10 L²∙mol for the 1:2 complex and in methanol 6.

Bio-Inspired Synthesis of an Ordered N/P Dual-Doped Porous Carbon and Application as an Anode for Sodium-Ion Batteries.

Carbonaceous materials are one of the most promising anode materials for sodium-ion batteries, because of their abundance, stability, and safe usage. However, the practical application of carbon materials is hindered by poor specific capacity and low initial Coulombic efficiency. The design of porous structure and doping with heteroatoms are two simple and effective methods to promote the sodium storage performance.

Singlet Fission Reaction of Light-Exposed β-Carotene Bound to Bovine Serum Albumin. A Novel Mechanism in Protection of Light-Exposed Tissue by Dietary Carotenoids.

We have attempted to investigate the role of carotenoids (Car) in protecting pigment-protein complexes against light-induced degradation. Upon direct photoexcitation of β-carotene (β-Car), nanosecond flash photolysis and femtosecond time-resolved spectroscopy detected a substantial population of triplet states for β-Car aggregates associated with bovine serum albumin (BSA) or dispersed in aqueous phase with 10% tetrahydrofuran (THF), but none were observed for monomeric β-Car in neat THF. The direct photogeneration of triplet states was on the time scale of <1 ps, indicating that the underlying reaction mechanism was singlet fission (SF).

Nanostructured potassium and sodium ion incorporated Prussian blue frameworks as cathode materials for sodium-ion batteries.

Nanostructured KNaMnFe(CN) (x + y ≤ 2) has been synthesized via a facile co-precipitation method. As a cathode, KNMF-3 presents a highly reversible capacity of 133.3 mA h g at 20 mA g as well as an excellent rate capacity of 92.

Regeneration of β-Carotene from Radical Cation by Eugenol, Isoeugenol, and Clove Oil in the Marcus Theory Inverted Region for Electron Transfer.

The rate of regeneration of β-carotene by eugenol from the β-carotene radical cation, an initial bleaching product of β-carotene, was found by laser flash photolysis and transient absorption spectroscopy to be close to the diffusion limit in chloroform/methanol (9:1, v/v), with a second-order rate constant (k) of 4.3 × 10 L mol s at 23 °C. Isoeugenol, more reducing with a standard reduction potential of 100 mV lower than eugenol, was slower, with k = 7.

Binding to Bovine Serum Albumin Protects β-Carotene against Oxidative Degradation.

Binding to bovine serum albumin (BSA) was found to protect β-carotene (β-Car) dissolved in air-saturated phosphate buffer solution/tetrahydrofuran (9:1, v/v) efficiently against photobleaching resulting from laser flash excitation at 532 nm. From dependence of the relative photobleaching yield upon the BSA concentration, an association constant of Ka = 4.67 × 10(5) L mol(-1) for β-Car binding to BSA was determined at 25 °C.

Astaxanthin Protecting Membrane Integrity against Photosensitized Oxidation through Synergism with Other Carotenoids.

Incorporation of astaxanthin or zeaxanthin in giant unilamellar vesicles (GUVs) of phosphatidylcholine resulted in a longer lag phase than incorporation of β-carotene or lycopene for the onset of budding induced by chlorophyll a photosensitization and quantified by a dimensionless entropy parameter using optical microscopy and digital image heterogeneity analysis. The lowest initial rate of GUV budding after the lag phase was seen for GUVs with astaxanthin as the least reducing carotenoid, while the lowest final level of entropy appeared for those with lycopene or β-carotene as a more reducing carotenoid. The combination of astaxanthin and lycopene gave optimal protection against budding with respect to both a longer lag phase and lower final level of entropy by combining good electron acceptance and good electron donation.

Regeneration of β-Carotene from the Radical Cation by Tyrosine and Tryptophan.

The phenolic amino acid tyrosine (Tyr) was found more efficient in regenerating β-carotene (β-Car) from the radical cation (β-Car(•+)) than tryptophan (Trp) in the presence of base for conditions where the reduction potentials for Trp and Tyr are comparable. Electron transfer from Tyr in 4:1 chloroform/methanol to β-Car(•+) in the presence of excess base, (CH3)4N(+)OH(-), had a rate close to diffusion control and a second-order rate constant in agreement with the Marcus theory for electron transfer when compared to plant phenols. A maximum of 40% β-Car was regenerated for ten times excess of Tyr as studied by 532 nm laser flash photolysis followed by transient absorption spectroscopy in the visible and near-infrared regions.

Dinitrosyl iron complexes with cysteine. Kinetics studies of the formation and reactions of DNICs in aqueous solution.

Kinetics studies provide mechanistic insight regarding the formation of dinitrosyl iron complexes (DNICs) now viewed as playing important roles in the mammalian chemical biology of the ubiquitous bioregulator nitric oxide (NO). Reactions in deaerated aqueous solutions containing FeSO4, cysteine (CysSH), and NO demonstrate that both the rates and the outcomes are markedly pH dependent. The dinuclear DNIC Fe2(μ-CysS)2(NO)4, a Roussin's red salt ester (Cys-RSE), is formed at pH 5.

β-Carotene As a Lipophilic Scavenger of Nitric Oxide.

The efficient bleaching following continuous bubbling of gaseous nitric oxide (NO(•)) to β-carotene (β-Car) dissolved in n-hexane under anaerobic conditions results from an initial addition of two NO(•) followed by fragmentation coupled with further NO(•) addition as shown by mass spectrometry (MS). Density functional theory (DFT) calculations demonstrated that hydrogen atom transfer (HAT) and electron transfer (ET) from β-Car to NO(•) are strongly energetically unfavorable in contrast to radical adduct formation (RAF) followed by degradation. The results indicated the lowest energy for addition of the first NO(•) at C7 with an activation free energy of ΔG(≠) = 74.

Nutritional aspects of β-carotene and resveratrol antioxidant synergism in giant unilamellar vesicles.

Giant unilamellar vesicles of soy phosphatidylcholine are found to undergo budding when sensitized with chlorophyll a ([phosphatidylcholine] : [chlorophyll a] = 1500 : 1) under light irradiation (400-440 nm, 16 mW mm(-2)). 'Entropy' as a dimensionless image heterogeneity measurement is found to increase linearly with time during an initial budding process. For β-carotene addition ([phosphatidylcholine] : [β-carotene] = 500 : 1), a lag phase of 23 s is observed, followed by a budding process at an initial rate lowered by a factor of 3.

Electron transfer from plant phenolates to carotenoid radical cations. Antioxidant interaction entering the Marcus theory inverted region.

β-Carotene, lycopene, and zeaxanthin are maximally regenerated by plant phenolates from their radical cations formed during laser flash photolysis in 9:1 (v/v) chloroform/methanol for a driving force corresponding to the reorganization energy according to the Marcus theory. For β-carotene, the reorganization energy has values of 0.41 ± 0.

Efficient scavenging of β-carotene radical cations by antiinflammatory salicylates.

The radical cation generated during photobleaching of β-carotene is scavenged efficiently by the anion of methyl salicylate from wintergreen oil in a second-order reaction approaching the diffusion limit with k2 = 3.2 × 10(9) L mol(-1) s(-1) in 9 : 1 v/v chloroform-methanol at 23 °C, less efficiently by the anion of salicylic acid with 2.2 × 10(8) L mol(-1) s(-1), but still of possible importance for light-exposed tissue.

The effect of the skeleton structure of flavanone and flavonoid on interaction with transferrin.

Transferrin has been exploited as a potential drug carrier for targeted drug delivery into cancer cells, which express high levels of transferrin receptors. In the present study, we identified specific structural features in flavonoids that were critical for binding to transferrin. Flavanone naringenin and flavonoid apigenin, two flavonoids with characteristic flavonoid core structures were selected for the study of the effects of C2-C3 single bond in the C-ring on transferrin binding.