Altered mechanisms of reactions of phosphate esters bridging a dinuclear metal center

Kinetic isotope effects in the nucleophile and leaving group were obtained for the reaction of p-nitrophenyl phosphate monoester coordinated to a dinuclear Co(III) complex. The metal complex of the p-nitrophenyl phosphate monoester was found to hydrolyze by a single-step concerted mechanism, with significant nucleophilic participation in the transition state. By contrast, the hydrolysis of uncomplexed p-nitrophenyl phosphate occurs by a very loose transition state with little bond formation to the nucleophile. Previously, the metal complex of the diester methyl-p-nitrophenyl phosphate was found to hydrolyze via a two-step addition-elimination mechanism, in contrast to the concerted hydrolysis mechanism followed by uncomplexed diesters with the p-nitrophenolate leaving group. These results show that coordination to a metal complex can significantly alter the mechanism of phosphoryl transfer.     

An altered mechanism of hydrolysis for a metal-complexed phosphate diester

Isotope effects in the nucleophile and in the leaving group were measured to gain information about the mechanism and transition state of the hydrolysis of methyl p-nitrophenyl phosphate complexed to a dinuclear cobalt complex. The complexed diester undergoes hydrolysis about 1011 times faster than the corresponding uncomplexed diester. The kinetic isotope effects indicate that this rate acceleration is accompanied by a change in mechanism. A large inverse 18O isotope effect in the bridging hydroxide nucleophile (0.937 +/- 0.002) suggests that nucleophilic attack occurs before the rate-determining step. Large isotope effects in the nitrophenyl leaving group (18Olg = 1.029 +/- 0.002, 15N = 1.0026 +/- 0.0002) indicate significant fission of the P-O ester bond in the transition state of the rate-determining step. The data indicate that in contrast to uncomplexed diesters, which undergo hydrolysis by a concerted mechanism, the reaction of the complexed diester likely proceeds via an addition-elimination mechanism. The rate-limiting step is expulsion of the p-nitrophenyl leaving group from the intermediate, which proceeds by a late transition state with extensive bond fission to the leaving group. This represents a substantial change in mechanism from the hydrolysis of uncomplexed aryl phosphate diesters.     

Bond breaking coupled with translation in rolling of covalently bound molecules

The response of a C60 molecule to manipulation across a surface displays a long range periodicity which corresponds to a rolling motion. A period of three or four lattice constants is observed and is accompanied by complex subharmonic structure due to molecular hops through a regular, repeating sequence of adsorption states. Combining experimental data and ab initio calculations, we show that this response corresponds to a rolling motion in which two of the four Si-C60 covalent bonds act as a pivot over which the molecule rotates while moving through one lattice constant and identify a sequence of C60 bonding configurations that accounts for the periodic structure.     

Donor‐π‐Acceptors Containing the 10‐(1,3‐Dithiol‐2‐ylidene)anthracene Unit for Dye‐Sensitized Solar Cells

Two donor–acceptor molecular tweezers incorporating the 10‐(1,3‐dithiol‐2‐ylidene)anthracene unit as donor group and two cyanoacrylic units as accepting/anchoring groups are reported as metal‐free sensitizers for dye‐sensitized solar cells. By changing the phenyl spacer with 3,4‐ethylenedioxythiophene (EDOT) units, the absorption spectrum of the sensitizer is red‐shifted with a corresponding increase in the molar absorptivity. Density functional calculations confirmed the intramolecular charge‐transfer nature of the lowest‐energy absorption bands. The new dyes are highly distorted from planarity and are bound to the TiO₂ surface through the two anchoring groups in a unidentate binding form. A power‐conversion efficiency of 3.7 % was obtained with a volatile CH₃CN‐based electrolyte, under air mass 1.5 global sunlight. Photovoltage decay transients and ATR‐FTIR measurements allowed us to understand the photovoltaic performance, as well as the surface binding, of these new sensitizers.     

The Influence of Charge Transport and Recombination on the Performance of Dye‐Sensitized Solar Cells

Electrochemical impedance spectroscopy (EIS) and transient voltage decay measurements are applied to compare the performance of dye sensitized solar cells (DSCs) using organic electrolytes, ionic liquids and organic‐hole conductors as hole transport materials (HTM). Nano‐crystalline titania films sensitized by the same heteroleptic ruthenium complex NaRu(4‐carboxylic acid‐4′‐carboxylate) (4,4′‐dinonyl‐2,2′‐bipyridyl)(NCS)₂ , coded Z‐907Na are employed as working electrodes. The influence of the nature of the HTM on the photovoltaic figures of merit, that is, the open circuit voltage, short circuit photocurrent and fill factor is evaluated. In order to derive the electron lifetime, as well as the electron diffusion coefficient and charge collection efficiency, EIS measurements are performed in the dark and under illumination corresponding to realistic photovoltaic operating conditions of these mesoscopic solar cells. A theoretical model is established to interpret the frequency response off the impedance under open circuit conditions, which is conceptually similar to photovoltage transient decay measurements. Important information on factors that govern the dynamics of electron transport within the nanocrystalline TiO₂ film and charge recombination across the dye sensitized heterojunction is obtained.     

Biocompatible surfactants for water-in-fluorocarbon emulsions

Drops of water-in-fluorocarbon emulsions have great potential for compartmentalizing both in vitro and in vivo biological systems; however, surfactants to stabilize such emulsions are scarce. Here we present a novel class of fluorosurfactants that we synthesize by coupling oligomeric perfluorinated polyethers (PFPE) with polyethyleneglycol (PEG). We demonstrate that these block copolymer surfactants stabilize water-in-fluorocarbon oil emulsions during all necessary steps of a drop-based experiment including drop formation, incubation, and reinjection into a second microfluidic device. Furthermore, we show that aqueous drops stabilized with these surfactants can be used for in vitro translation (IVT), as well as encapsulation and incubation of single cells. The compatability of this emulsion system with both biological systems and polydimethylsiloxane (PDMS) microfluidic devices makes these surfactants ideal for a broad range of high-throughput, drop-based applications.     

Dianhydride-amine hydrogen bonded perylene tetracarboxylic dianhydride and tetraaminobenzene rows

We have investigated the coadsorption of perylene tetracarboxylic dianhydride (PTCDA) and tetraaminobenzene (TAB) on the Ag/Si(111)-square root(3) x square root(3) R30 degree surface using scanning tunneling microscopy. At room temperature, PTCDA islands with square and herringbone ordering are formed which, on exposure to TAB, are converted into an intermixed phase in which PTCDA and TAB form alternating rows. From our images, we determine the relative placement of TAB and PTCDA molecules and conclude that the row structure is stabilized by hydrogen bonding between dianhydride and diamine groups. We confirm that this hydrogen bonding junction is stable using ab initio calculations and show that the proposed geometry is consistent with calculated intermolecular dimensions.