The hydride transfer mechanism of the NAD+ model compound 1 to its 1,4-NADH derivative 3 [Eq. (1)] is proposed be a consequence critical role carbonyl group amide coordinate ring-slipped η5- η3-Cp*Rh metal center catalyst [Cp*Rh(bpy)H]+, prepared in situ from 2, while steric effect substituent position, for example, C(O)NEt2, was found totally inhibit this regioselective reduction. bpy=2,2′-bipyridine, Cp*=C5Me5, OTf=trifluoromethanesulfanate.

We have rationally synthesized and optimized catalytic nanoparticles consisting of a gold core, covered by palladium shell, onto which platinum clusters are deposited (Au@Pd@Pt NPs). The amount Pt Pd used is extremely small, yet they show unusually high activity for electrooxidation formic acid. structure has only 2 atomic layers half-monolayer equivalent (θPt ≈ 0.5) but further increase in the loading or will actually reduce activity, inferring that synergistic effect exists between three...

Don't slam the door! Cyclodextrins capped with an N-heterocyclic carbene (ICyDs) entrapped metal ions within their cavity through a novel set of interactions, including X⋅⋅⋅π, which enabled to be closed by ligand exchange (see scheme; Bn=benzyl). Although insulated from electrode, deeply buried retained catalytic activity. The influenced regio- and stereochemical outcome catalyzed reactions. As service our authors readers, this journal provides supporting information supplied authors. Such...

We have previously shown that modification of polyphenols with a ferrocenyl group can dramatically enhance their cytotoxicity. now present two new [3]ferrocenophane compounds, one which has an antiproliferative effect seven times stronger than the corresponding noncyclic species, IC50 values 90 and 94 nM on hormone-independent MDA-MB-231 breast PC-3 prostate cancer cell lines, respectively. Solubility studies in water using methylated β-cyclodextrin electron transfer are also presented.

Cofactor regeneration; i.e., regiospecific conversion of NAD+ to 1,4-NADH, has been extensively studied and is a crucial component in the eventual use 1,4-NADH variety bioorganic synthesis processes involving formation chiral organic compounds. We have reduction model compound, 1-benzylnicotinamide triflate, 1a, using [Cp*Rh(bpy)(H2O)]2+, 2 (Cp* = η5-C5Me5, bpy 2,2'-bipyridyl), as catalyst precursor sodium formate (HCO2Na) hydride source 1:1 H2O/THF found exclusive...

Abstract The complete oxidation sequence of a model for ferrociphenols, new class anticancer drug candidate, is reported. Cyclic voltammetry was used to monitor the formation intermediates on different timescales, thereby allowing electrochemical characterization both short‐lived and stable species obtained from successive electron‐transfer deprotonation steps. preparation ferrocenium intermediate enabled stepwise voltammetric determination compounds upon addition base as well electron...

The permeabilization of liposomes by melittin, an antimicrobial peptide (AMP), has been studied electrochemiluminescence (ECL) imaging strategy. methodology consisted first encapsulating ECL reagents in sealed giant asymmetrical (100 μm diameter) made DOPG/DOPC phospholipids (i.e., 1,2-dioleoyl-

Abstract Hydroxyferrocifen compounds are a new and promising class of ferrocifen‐type breast‐cancer drug candidates. They possess both endocrine‐modulating properties cytotoxic activity, which come from the tamoxifen skeleton presence ferrocene moiety, respectively. However, they suffer reduced solubility in water, presents problem for their eventual therapeutic use. Herein, we examined interactions hydroxyferrocifen with cyclodextrins (CDs) to evaluate whether or not electron‐transfer...

In this work, the characterization of release events from liposomes has been addressed quantitatively by an electrochemiluminescence (ECL) imaging strategy. First, ECL reagents ([Ru(bpy)3]2+ and tripropylamine) were encapsulated in sealed giant asymmetrical (100 μm diameter) made DOPG/DOPC phospholipids. After sedimentation on indium tin oxide electrode material, opening was triggered polarization surface. Under these conditions, amperometry, epifluorescence imaging, combined synchronized to...

Electrical synthesizer: Results of cyclic voltammetric studies on a range aminocyclopropanes in the absence or presence oxygen are full agreement with currently accepted autocatalytic mechanism for aerobic oxidation these compounds. A simple and efficient procedure was developed electrosynthesis corresponding endoperoxides (see scheme), some which exhibit moderate antimalarial activity. Supporting information this article is available WWW under...

Abstract Herein, the traditional views that contrast important areas of electrocatalysis and molecular electrochemistry are challenged. By extending Laviron′s seminal concept, we show these two domains only represent idealized limits a much broader continuum. More importantly, electrochemical systems apparently behave experimentally as if under diffusion control (i.e. obey founding paradigm) may be controlled by electrocatalytic steps, is, in which activation electroactive substrates...

Geschlossene Gesellschaft: Mit einem N-heterocyclischen Carben überdeckte Cyclodextrine (ICyDs) binden in ihrem Hohlraum Metallionen unter Beteiligung von X⋅⋅⋅π-Wechselwirkungen, was ein Verschließen des Hohlraums durch Ligandenaustausch ermöglicht (siehe Schema; Bn=Benzyl). Obwohl kein elektrischer Kontakt mit einer Elektrode besteht, behalten die tief vergrabenen ihre katalytische Aktivität. Der beeinflusste den regio- und stereochemischen Verlauf der katalysierten Reaktionen.

The synthesis and anti-tumoral properties of a series compounds possessing ferrocenyl group tethered to catechol via conjugated system is presented. On MDA-MB-231 breast cancer cell lines, the display similar or greater anti-proliferative potency (IC50 values ranging from 0.48–1.21 μM) than their corresponding phenolic analogues (0.57–12.7 μM), with highest activity found for species incorporating [3]ferrocenophane motif. electrochemical timescale, appear oxidize quinone methide, while...

The human brain is a complex and poorly accessible organ. Thus, new tools are required for studying the neural function in controllable environment that preserves multicellular interaction neuronal wiring. In particular, high-throughput methods alleviate need animal experiments essential future studies. Recent developments of induced pluripotent stem cell technologies have enabled vitro modeling by creating three-dimensional tissue mimic structures. To leverage these technologies, systematic...

Abstract Quinones are electrochemical probes which used for a large range of applications including bioenergetics. One feature quinones is their possible slow electron transfer kinetics. In this article we compared several towards kinetics and the ability anodic pretreatment to increase rate constant. Rotating disk electrode chronoamperometry measurements were revisit behavior. Additionally, number electrons exchanged as function characteristic time was proxy investigate kinetic limitations....

Abstract In this work, Fluorescent False Neurotransmitter 102 (FFN102), a synthesized analogue of biogenic neurotransmitters, was demonstrated to show both pH‐dependent fluorescence and electroactivity. To study secretory behaviors at the single‐vesicle level, FFN102 employed as new fluorescent/electroactive dual probe in coupled technique (amperometry total internal reflection microscopy (TIRFM)). We used N13 cells, stable clone BON specifically accumulate into their vesicles, then optical...

Abstract Three osmium analogues 3a – 3c of hydroxytamoxifen were prepared. The antiproliferative effects these complexes measured against two breast cancer cell lines (MCF‐7 and MDA‐MB‐231) compared with those their homologues ferrocene ( 1a 1c ) ruthenocene 2a–2c ). tamoxifen‐like 2c derived from ruthenium show good cytotoxicities the (IC 50 values between 2 3 μ M ), albeit lower than ferrocifen 0.5 0.8 These induce senescence cells at low concentration (0.5 mono‐ diphenol little...

This review discusses the state of art, challenges and perspectives in recent applications electrochemistry life sciences. It deals mainly with elucidation molecular mechanisms drug action, design development, involving electron transfer, pharmaco-electrochemistry (the combination electrochemical pharmacological assays), studies membrane models delivery. aims to shed light on question: does really contribute this area? includes a general introduction for use sciences, focus how can uniquely...

Three rhodamine derivatives exhibiting electrofluorochromic properties were investigated by cyclic voltammetry and UV–Vis/fluorescence spectroelectrochemistry. Rhodamine 101 (Rh101, compound 1) was used as a reference model. In 2, the carboxylate anion of Rh101 replaced an alkyne moiety to allow further functionalization. The 3 prepared from 2 conversion triazole group bearing alkyl chain with alcohol function. These three exhibited similar electrochemical behaviors. Their mono-electronic...

The study of the electrochemical behavior cobalt bromide, CoBr2, in presence zinc ZnBr2, and aryl halides, ArX, a dimethylformamide (DMF)/pyridine (9:1, v/v) mixture allowed us to complete mechanism conversion halides into arylzinc compounds by using catalysis. last step catalytic process has been shown be transmetalation reaction between arylcobalt(II) species ions that regenerates cobalt(II) catalyst. effect bromide on each cycle studied. It is especially ZnBr2 stabilizes electrogenerated...