Globin ferryl species: what is the nature of the protonation event at pH < 5?

The ferryl state in globins has previously been reported to undergo a protonation event below pH 5, as assessed using pH jump experiments with stopped-flow UV-Vis spectroscopy. This protonation entails hypsochromic shifts in the α and β bands (~ 20 to 40 nm) and an ~ 10 nm reduction in the energy difference between these two bands. We now report that in Mb this event is also characterized by a hypsochromic shift in the Soret band (~ 5 nm).

Binuclear methylphosphinidine complexes of cyclopentadienylruthenium carbonyls: effects of the higher ligand field strength of ruthenium derivatives relative to iron derivatives.

The structures and energetics of the binuclear methylphosphinidene complexes of cyclopentadienylruthenium carbonyls of the type [MePRu(CO)Cp] ( = 4, 3, 2, 1) have been investigated for comparison with their previously studied iron analogues. For the tetracarbonyls and tricarbonyls [MePM(CO)Cp] ( = 4, 3) substituting ruthenium for iron has relatively little effect on the energetically preferred structures. Thus such structures have two-electron donor bridging MeP groups with no metal-metal bond for the tetracarbonyls and a metal-metal single bond for the tricarbonyls.

Sonochemical synthesis, optical properties and DFT studies on novel (N-arylamino)phenothiazinium dyes suitable for fluorescence cells imaging.

Novel (N-arylamino)phenothiazinium dyes containing meta-substituted-arylamine auxochrome units were successfully obtained by applying a sonochemical protocol designed for a more efficient energy usage in the preparation of methylene blue (MB) analogues. Single crystal X-ray diffraction analysis revealed the spatial arrangement in aggregated crystalline state of (N-(meta-bromoaryl)amino)phenothiazinium dye with minor variances induced by the nature of the halogenide counterion (iodide or chloride). The optical UV-vis properties of the novel (N-arylamino)phenothiazinium dyes were comparable to those of the parent MB, with the longest wavelength absorption maxima situated in the visible range (640-680 nm), large molar extinction coefficients (log ε = 4.

Transient radical species and oxygen colorimetric indicators grounded on phenothiazinium dyes.

This study investigates four phenothiazinium dyes including methylene blue (MB) and three analogues containing auxochrome variation 2-4 as oxygen colorimetric indicators prepared by their incorporation into two types of oxygen permeable materials containing: a) polyvinyl alcohol substrate with additional TiO photocatalysts (PhOxIn), and b) carboxymethylcellulose polymer matrix containing glucose and KOH (ChOxIn). In vacuum packages where volumetric concentrations of oxygen were below 0.01 %, the leuco forms of the tested phenothiazinum dyes were readily oxidised, initiating the colour turn from white to blue.

A biomimetic assay for antioxidant reactivity, based on liposomes and myoglobin.

Antioxidant assays are typically based on non-physiologically relevant reagents. We describe here a quantitative assay based on the inhibition of the liposome autooxidation in the presence of myoglobin (ILA-Mb), an oxidative process with direct biomedical relevance. Additional advantages of the assay include the use of standard and readily available reagents (lecithin and myoglobin) and the applicability to lipophilic antioxidants.

Redox Reactivity of Nonsymbiotic Phytoglobins towards Nitrite.

Nonsymbiotic phytoglobins (nsHbs) are a diverse superfamily of hemoproteins grouped into three different classes (1, 2, and 3) based on their sequences. Class 1 Hb are expressed under hypoxia, osmotic stress, and/or nitric oxide exposure, while class 2 Hb are induced by cold stress and cytokinins. Both are mainly six-coordinated.

Decarbonylation Products of Binuclear Methylphosphinidene Complexes of Cyclopentadienyliron Carbonyls: Triplet and Quintet Structures Are Favored Energetically over Singlet Structures with Iron-Iron Multiple Bonding.

The structures, energetics, and energetically preferred spin states of methylphosphinidene-bridged binuclear cyclopentadienyliron carbonyl complexes MePFe(CO)Cp ( = 4, 3, 2, and 1) related to the experimentally known (μ-RP)Fe(μ-CO)(CO)Cp (R = cyclohexyl, phenyl, mesityl, and 2,4,6-tBuCH) complexes have been investigated by density functional theory. Singlet structures having a pyramidal pseudotetrahedral phosphorus environment with 18-electron iron configurations are energetically preferred in the tricarbonyl and tetracarbonyl systems MePFe(CO)Cp ( = 4 and 3) with the lowest energy structures of the tricarbonyl very closely resembling the experimentally determined structures. For the more unsaturated dicarbonyl and monocarbonyl systems MePFe(CO)Cp ( = 2 and 1), higher spin state triplet and quintet structures are energetically preferred over singlet structures.

The Iodine/Iodide/Starch Supramolecular Complex.

The nature of the blue color in the iodine-starch reaction (or, in most cases, iodine-iodide-starch reaction, i.e., I as well as I are typically present) has for decades elicited debate.

Species: Comparative Evaluation of Phenolic Profile and Antimicrobial and Antioxidant Potential.

This study aimed to investigate the polyphenolic composition and antioxidant and antimicrobial potential of six Romanian Stachys species: , , , , , and . The LC-MS/MS method was used to analyze the polyphenolic profile, while the phenolic contents were spectrophotometrically determined. The antioxidant activity was evaluated using the following methods: DPPH, FRAP, nitrite-induced autooxidation of hemoglobin, inhibition of cytochrome -catalyzed lipid peroxidation, and electron paramagnetic resonance spectroscopy.

Trends in the texts of national anthems: A comparative study.

In a recent previous investigation of national anthems, preferred topics and their bias (e.g., towards identity, fighting, or well-being) were identified subjectively (Silaghi-Dumitrescu, 2020).

Comorbidities of COVID-19 Patients.

The novel Severe Acute Respiratory Syndrome Coronavirus 2 (SARS-CoV-2) responsible for the coronavirus disease outbreak initiated in 2019 (COVID-19) has been shown to affect the health of infected patients in a manner at times dependent on pre-existing comorbidities. Reported here is an overview of the correlation between comorbidities and the exacerbation of the disease in patients with COVID-19, which may lead to poor clinical outcomes or mortality. General medical issues are also reviewed, such as the types of symptoms present in people infected with SARS-CoV-2, the long-term effects of COVID-19 disease, and the types of treatment that are currently used.

The adducts of cyano- and aquacobalamin with hypochlorite.

Hypochlorite is known to oxidatively degrade the corrin ring of cobalamin. Here, transient reaction intermediates are described in the reaction of aqua as well as of cyano-cobalamin with hypochlorite, using stopped-flow UV-vis kinetics. For aqua-cobalamin, the intermediate is assigned as arising from substitution of the aqua ligand with hypochlorite.

Selective Attachment of Polyethylene Glycol to Hemerythrin for Potential Use in Blood Substitutes.

Due to its ability to reversibly bind O, alongside a relatively low redox reactivity and a limited cytotoxicity, the oxygen-carrying protein hemerythrin has been considered as an alternative to hemoglobin in preparing blood substitutes. In order to increase the hydrodynamic volume and lower antigenicity, two site-directed variants, H82C and K92C, were engineered that contained a single cysteine residue on the surface of each hemerythrin octamer for the specific attachment of polyethylene glycol (PEG). A sulfhydryl-reactive PEGylation reagent with a 51.

On the Origin of the Blue Color in The Iodine/Iodide/Starch Supramolecular Complex.

The nature of the blue color in the iodine-starch reaction is still a matter of debate. Some textbooks still invoke charge-transfer bands within a chain of neutral I molecules inside the hydrophobic channel defined by the interior of the amylose helical structure. However, the consensus is that the interior of the helix is not altogether hydrophobic-and that a mixture of I molecules and iodide anions reside there and are responsible for the intense charge-transfer bands that yield the blue color of the "iodine-starch complex".

Preparation and In Vitro Characterization of Gels Based on Bromelain, Whey and Quince Extract.

The growing interest in the appearance and color of teeth has led to the emergence of a wide range of teeth whitening methods, both in dental offices and in patients' homes. Concerns about the possible side effects or toxic effects of peroxide-based whitening gels leads to the identification of alternative whitening methods, based on natural compounds with mild action on tooth enamel and remineralizing effect. In this context, this study describes the preparation and in vitro analysis of whitening gels based on natural active agents-bromelain, quince and whey-using organic (polyacrylate, polyethylene glycol) and/or inorganic (silicate) excipients.

Adduct of Aquacobalamin with Hydrogen Peroxide.

Aquacobalamin binds hydrogen peroxide reversibly to form a cobalt(III) hydroperoxo adduct with a 0.25 mM dissociation constant, as evidenced by UV-vis absorption spectroscopy and corroborated by NMR, Raman spectroscopy, stopped-flow UV-vis measurements, and density functional theory calculations.

Excess Ascorbate is a Chemical Stress Agent against Proteins and Cells.

Excess ascorbate (as expected in intravenous treatment proposed for COVID-19 management, for example) oxidizes and/or degrades hemoglobin and albumin, as evidenced by UV-vis spectroscopy, gel electrophoresis, and mass spectrometry. It also degrades hemoglobin in intact blood or in isolated erythrocytes. The survival rates and metabolic activities of several leukocyte subsets implicated in the antiviral cellular immune response are also affected.

On the Stability of Glutaraldehyde in Biocide Compositions.

Glutaraldehyde (GA) is used as biocide in hospitals. Recent public investigations on the chemical composition of biocides used in Romania have in some cases found GA, as a key ingredient, to be apparently diluted. However, these data did not explicitly consider the complex chemical equilibria inherent to GA.

On the Apparent Redox Reactivity of "Oxygen-Enriched Water".

Molecular oxygen-enriched water (OxEW) is advocated in popular media as useful for various health issues, presumably due to involvement of a purported antioxidant activity and to such notions as "active oxygen." To our knowledge, there are no explicit reports in the scientific literature where such redox reactivity would be described and explained. Reported here are data showing that a commercial preparation of OxEW does display a measurable, albeit very small, antioxidant activity as monitored by reaction with a standard reagent, DPPH.

"Yellow" laccase from Sclerotinia sclerotiorum is a blue laccase that enhances its substrate affinity by forming a reversible tyrosyl-product adduct.

Yellow laccases lack the typical blue type 1 Cu absorption band around 600 nm; however, multi-copper oxidases with laccase properties have been reported. We provide the first evidence that the yellow laccase isolated from Sclerotinia sclerotiorum is obtained from a blue form by covalent, but nevertheless reversible modification with a phenolic product. After separating the phenolics from the extracellular medium, a typical blue laccase is obtained.

Neutral Rhenadicarbaboranes with Re(CO)(NO) Vertices: A Theoretical Study of Building Blocks for Rhenacarborane-Based Drug Delivery Agents.

The rhenadicarbaborane carbonyl nitrosyls (CBH)Re(CO)(NO), ( = 8 to 12), of interest in drug delivery agents based on the experimentally known CBHRe(CO)(NO) and related species, have been investigated by density functional theory. The lowest energy structures of these rhenadicarbaboranes are all found to have central ReCB most spherical deltahedra in accord with their 2 + 2 Wadean skeletal electrons. Carbon atoms are found to be located preferentially at degree 4 vertices in such structures.

Importance of the iron-sulfur component and of the siroheme modification in the resting state of sulfite reductase.

The active site of sulfite reductase (SiR) consists of an unusual siroheme-FeS assembly coupled via a cysteinate sulfur, and serves for multi-electron reduction reactions. Clear explanations have not been demonstrated for the reasons behind the choice of siroheme (vs. other types of heme) or for the single-atom coupling to an FeS center (as opposed to simple adjacency or to coupling via chains consisting of more than one atom).