Evolution of Oxygen–Metal Electron Transfer and Metal Electronic States During Manganese Oxide Catalyzed Water Oxidation Revealed with In Situ Soft X‐Ray Spectroscopy

Manganese oxide (MnO_x) electrocatalysts are examined herein by in situ soft X‐ray absorption spectroscopy (XAS) and resonant inelastic X‐ray scattering (RIXS) during the oxidation of water buffered by borate (pH 9.2) at potentials from 0.75 to 2.25 V vs. the reversible hydrogen electrode. Correlation of L‐edge XAS data with previous mechanistic studies indicates Mn^IV is the highest oxidation state involved in the catalytic mechanism. MnO_x is transformed into birnessite at 1.45 V and does not undergo further structural phase changes. At potentials beyond this transformation, RIXS spectra show progressive enhancement of charge transfer transitions from oxygen to manganese. Theoretical analysis of these data indicates increased hybridization of the Mn?O orbitals and withdrawal of electron density from the O ligand shell. In situ XAS experiments at the O K‐edge provide complementary evidence for such a transition. This step is crucial for the formation of O₂ from water.     

Generation and characterization of phenylsulfanylcarbene

A photosensitive precursor (1) to phenylsulfanylcarbene 2 has been synthesized. Laser flash photolysis (308 nm) of 1 and chemical trapping studies of 2 are reported. [structure: see text]     

4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH): a new chromophoric reagent for quantitative monitoring of solid-phase aldehydes(1-3)

A direct method for quantifying solid-phase aldehydes has been developed, using a new reagent, 4-(9-fluorenylmethyloxycarbonyl)phenylhydrazine (FmPH). The FmPH reagent was synthesized in three steps (24% overall yield) from commercially available p-hydrazinobenzoic acid. Resin-bound aldehydes reacted quantitatively with FmPH, in the presence of trimethylorthoformate (TMOF) as a dehydrating agent, to form a highly conjugated, immobilized FmPH-hydrazone. Next, mild treatment of the hydrazone with an excess of piperidine-N,N-dimethylformamide (1:1) released the piperidine-dibenzofulvene adduct chromophore (epsilon(301nm) = 7800 M(-1) cm(-1)) from the support. FmPH quantitation of aldehydes proved to be a straightforward, sensitive, and reproducible technique for monitoring resin-bound aldehydes [albeit insufficiently reactive to allow reliable quantification of ketones]. The FmPH aldehyde assay is applicable to a range of solid supports, as demonstrated specifically for poly(ethylene glycol)-polystyrene (PEG-PS), aminomethylpolystyrene (AMP), and cross-linked ethoxylate acrylate resin (CLEAR).     

Cationic dirhodium carboxylate-catalyzed synthesis of dihydropyrimidones from propargyl ureas

Cationic Rh(II) complexes are able to catalyze the regioselective hydroamination of propargyl ureas in a 6-endo fashion. This transformation permits access to interesting substitution patterns of dihydropyrimidines, which have found use as nucleotide exchange factor inhibitors.     

Role of reversible dimerization in reactions of amphoteric aziridine aldehydes

Unprotected aziridine aldehydes belong to the amphoteric class of molecules by virtue of their dual nucleophilicity/electrophilicity. The dimeric nature of these molecules, brought together by a weak and reversible aminal "connection", was found to be an important element of reactivity control. We present evidence that reversible dimer dissociation is instrumental in aziridine aldehyde transformations. We anticipate further developments that will unveil other synthetic consequences of remote control of selectivity through forging reversible covalent interactions.     

Adsorption of polyelectrolyte modified graphene to silica surfaces: monolayers and multilayers

Exfoliated graphene particles stabilised by the cationic polyelectrolyte polyethyleneimine (PEI) were used in conjunction with an anionic polyelectrolyte, poly(acrylic acid), to construct multilayers using the layer-by-layer technique on a silica substrate. In the first adsorption step, the surface excess of the cationic graphene was dependent on the overall charge on the nanoparticle which in turn can be tuned through modifying solution pH as PEI has weakly ionisable charged amine groups. The adsorbed amount onto the silica surface increased as the solution pH increased. Subsequently, a layer of PAA was adsorbed on top of the cationic graphene through electrostatic interaction. The multilayer could be assembled through this alternate deposition, with the influence of solution conditions investigated. The pH of the adsorbing solutions was the chief determinant of the overall adsorbed amounts, with more mass added at the elevated pH of 9 in comparison with pH 4. Atomic force microscopy confirmed that the graphene particles were adsorbed to the silica interface and that the surface coverage of the disc-like nanoparticles was complete after the deposition of five graphene-polyelectrolyte bi-layers. Furthermore, the graphene nanoparticles themselves could be modified through the consecutive addition of the oppositely charged polymers. A multilayered assembly of negatively charged graphene sheets modified with a bi-layer of PEI and PAA was also deposited on a silica surface with adsorbed PEI.     

Screening the optical properties of Ag-Au alloy gradients formed by bipolar electrodeposition using surface enhanced Raman spectroscopy

We report the synthesis of Ag-Au alloy gradients on stainless steel substrates using bipolar electrodeposition (BP-ED), a technique based on the existence of a potential gradient at the interface of a bipolar electrode (BPE) and an electrolytic solution. The interfacial potential gradient causes the rates of electrodeposition of Ag and Au to vary along the length of the BPE, leading to the electrodeposition of a chemical concentration gradient. The surface morphology of the electrodeposits was characterized using scanning electron microscopy (SEM), and their chemical composition was determined using energy dispersive X-ray spectroscopy (EDX). Self-assembled monolayers of a Raman-active probe molecule (benzene thiol) were allowed to form on the surface of the alloy gradients, and confocal Raman microscopy was employed to determine the alloy composition that resulted in the maximum surface enhanced Raman scattering (SERS) intensity. An alloy composition of ca. 70% Ag/30% Au was found to be optimum for SERS excited using 514.5 nm radiation, and it is explained on the basis of composition-dependent changes in the local surface plasmon resonance (LSPR) of the electrodeposited Ag-Au alloy.     

Fluorescence correlation spectroscopy evidence for structural heterogeneity in ionic liquids

In this work, we provide new experimental evidence for chain length-dependent self-aggregation in room temperature ionic liquids (RTILs) using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [C(n)MPy][Tf(2)N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decreased with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chain [C(n)MPy][Tf(2)N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [C(n)MPy](+).     

Kinetics of disassembly of a DNA-bound porphyrin supramolecular array

trans-Bis(N-methylpyridinium-4-yl)diphenylporphine forms extended, organized assemblies on DNA templates under appropriate conditions of concentration, ionic strength, and temperature. Addition of beta-cyclodextrin to these arrays leads to their disassembly as evidenced by changes in extinction, circular dichroism, and resonance light scattering spectra. The structure or flexibility of the polymer template has an effect on the rate of disassembly; the reaction is faster on a poly(dG-dC)(2) surface than on ct DNA. The kinetic profiles for the disassembly process can be fit with great precision with a two-kinetic parameter equation in which the rate constant is itself a function of time. The reaction rate, studied in the presence of excess beta-CD, shows a dependence on the mode of detection. A model is presented to account for these observations in which the arrays become increasingly reactive with time due to beta-CD attack at the interior of the porphyrin assemblies as well as the ends.