Organometallic complexes of the general formula [(η(6)-arene)Ru(N⁁N)Cl](+) and [(η(5)-Cp*)Rh(N⁁N)Cl](+) where N⁁N is a 2,2'-dipyridylamine (DPA) derivative carrying a thiol-targeted maleimide group, 2,2'-bispyridyl (bpy), 1,10-phenanthroline (phen) or ethylenediamine (en) and arene is benzene, 2-chloro-N-[2-(phenyl)ethyl]acetamide or p-cymene were identified as catalysts for the stereoselective reduction of the enzyme cofactors NAD(P)(+) into NAD(P)H with formate as a hydride donor. A thorough comparison of their effectiveness towards NAD(+) (expressed as TOF) revealed that the Rh(III) complexes were much more potent catalysts than the Ru(II) complexes. Within the Ru(II) complex series, both the N⁁N and arene ligands forming the coordination sphere had a noticeable influence on the activity of the complexes. Covalent anchoring of the maleimide-functionalized Ru(II) and Rh(III) complexes to the cysteine endoproteinase papain yielded hybrid metalloproteins, some of them displaying formate dehydrogenase activity with potentially interesting kinetic parameters.
Sensitive skin is a common condition characterized by discomfort with visible symptoms such as dryness and redness, usually triggered by hypersensitivity to a range of stimuli -physical, chemical, and hormonal. Previous studies have shown that impaired barrier function as one of the most predisposing factors in triggering skin sensitivity. In addition, decreased levels of intercellular lipids, impaired epidermal cohesion, and overreactive sensory receptors was observed in individuals with sensitive skin. However, there are very limited treatment options that are effective in treating sensitive skin. Here, we designed a cosmetic formulation to target 3 key factors that can help alleviate symptoms associated with skin sensitivity: a combination of lipid profile identical to the skin's natural ratio -1:3:1 ceramides, cholesterol and fatty acids, a nociceptor (TRPV-1) antagonist, and a botanical extract that reduces the expression of proinflammatory cytokines. An IRB approved, controlled clinical study was conducted to evaluate facial redness in volunteers with moderate to persistent facial redness after 4 weeks and barrier recovery at 24 hrs. following barrier disruption via tape stripping. The cosmetic formulation significantly decreased visible redness after 2 and 4 weeks compared to baseline and accelerated barrier recovery compared to untreated controls. This formulation provides an effective treatment to alleviate 2 of the most common concerns associated with sensitive skin.
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