To carry and deliver nitric oxide with a controlled redox state and rate is crucial for its pharmaceutical/medicinal applications. In this study, the capability of cationic {Fe(NO)} dinitrosyl iron complexes (DNICs) [(DDB)Fe(NO)] (R = Me, Et, Iso; DDB = N,N'-bis(2,6-dialkylphenyl)-1,4-diaza-2,3-dimethyl-1,3-butadiene) carrying nearly unperturbed nitric oxide radical to form [(DDB)Fe(NO)(NO)] was demonstrated and characterized by IR, UV-vis, EPR, NMR, and single-crystal X-ray diffractions. The unique triplet ground state of [(DDB)Fe(NO)(NO)] results from the ferromagnetic coupling between two strictly orthogonal orbitals, one from Fe d and the other a π* orbital of a unique bent axial NO ligand, which is responsible for the growth of a half-field transition (ΔM = 2) from 70 to 4 K in variable-temperature EPR measurements. Consistent with the NO radical character of coordinated axial NO ligand in complex [(DDB)Fe(NO)(NO)], the simple addition of MeCN/HO into CHCl solution of complexes [(DDB)Fe(NO)(NO)] at 25 °C released NO as a neutral radical, as demonstrated by the formation of [SFe(NO)] from [SFe(μ-S)FeS].
To produce and identify anti-inflammatory peptides, three commercial enzymes orientase, flavourzyme, and alcalase 2.4L were used to hydrolyze tuna cooking juice, and the protein hydrolysates were purified, before being evaluated for the ability to induce secretary and cellular responses in murine peritoneal macrophages RAW264.7. Alcalase hydrolysate (AH) exhibited the most potent inhibitory effect. AH was further purified using gel-filtration chromatography and high-performance liquid chromatography. The results showed that the peptide fractions with the molecular weight ranging from 204 to 1672.9 Da possessed the greatest anti-inflammatory activity. The amino acid sequences of the two anti-inflammatory peptides isolated from AH hydrolysates were Pro-Arg-Arg-Thr-Arg-Met-Met-Asn-Gly-Gly-Arg (1543.8 Da) and Met-Gly-Pro-Ala-Met-Met-Arg-Thr-Met-Pro-Gly (1211.5 Da). We thus conclude that anti-inflammatory hydrolysates from tuna cooking juice by-product may be useful ingredients in food and nutraceutical applications.
Development of efficient/robust/economical electrocatalysts for both the hydrogen evolution reaction (HER) and the oxygen evolution reaction (OER) is emerging as a grand challenge. In consideration of the OER activity of iron/cobalt oxides and the superior electroconductivity/propitious H atom binding energy of metallic iron/cobalt, bifunctional electrodeposited-film electrode CFeCoP composed of CoFe and CoFeP x O y (OH) z was prepared from the irreversible cathodic deposition of FeSO 4 and CoSO 4 on the surface of a graphite plate in 1 M phosphate buffer (pH = 7). The as-prepared CFeCoP electrode exhibits excellent HER activity (specific activity (j s ) = 0.169 mA/cm 2 ) with low charge transfer resistance (4.5 Ω) and an overpotential of 57 mV, achieving a current density of 10 mA/cm 2 , and it also shows OER activity (j s = 1.316 mA/cm 2 ) with low charge-transfer resistance (7.8 Ω) and 282 mV of overpotential, approaching a current density of 10 mA/cm 2 in a 1 M NaOH aqueous solution. In addition, the CFeCoP electrode displays long-term stability (139 h) for both HER and OER activity with a stable current density. In the whole cell, the CFeCoP−CFeCoP electrode-pair setting achieves a current density of 10 mA/cm 2 at a voltage of 1.56 V (Tafel slope of 51 mV/dec), close to those (10 mA/cm 2 at a voltage of 1.58 V (Tafel slope of 68 mV/dec)) of the Pt− IrO 2 electrode-pair device in a 1 M NaOH aqueous solution. On the basis of XPS, SEM-EDX, and pXRD, the fabric of metallic iron/cobalt buried in a metal-oxide matrix and iron/cobalt (oxy)hydroxides embedded in a metal-oxide matrix as films on the graphite surface for the CFeCoP electrode implies that the electrodeposition-derived film mainly made up of FeCo and FeCoP x O y (OH) z may mediate the kinetics that occurs at the catalyst−electrolyte interface and displays stability/intrinsic catalytic activity for overall water splitting.
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