The Twin-Excited State as a Probe for the Transition State in Concerted Unimolecular Reactions: The Semibullvalene Rearrangement

A twin of the transition state , which can be investigated spectroscopically and can thus supply information about the structure of the transition state, has now been characterized for the Cope rearrangement of semibullvalene (shown below). It involves an excited state with B₂ symmetry and results from a linear combination of the ground-state wave functions of (mirror-image) reactant and product.     

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.     

How does product isotope effect prove the operation of a two-state "rebound" mechanism in C-H hydroxylation by cytochrome P450?

C-H hydroxylation is a fundamental process. In Nature it is catalyzed by the enzyme cytochrome P450, in a still-debated mechanism that poses a major intellectual challenge for both experiment and theory; currently, the opinions keep swaying between the original single-state rebound mechanism, a two-oxidant mechanism (where ferric peroxide participates as a second oxidant, in addition to the primary active species, the high-valent iron-oxo species), and two-state reactivity (TSR) mechanism (where two spin states are involved). Recent product isotope effect (PIE) measurements for the trans-2-phenyl-methyl cyclopropane probe (1), led Newcomb and co-workers (Newcomb, M.; Aebisher, D.; Shen, R.; Esala, R.; Chandrasena, P.; Hollenberg, P.; Coon, M. J. J. Am. Chem. Soc. 2003, 125, 6064-6065) to rule out TSR in favor of the two-oxidant scenario, since the direction of the PIE was at odds with the one predicted from calculations on methane hydroxylation. The present report describes a density functional theoretical study of C-H hydroxylation of the Newcomb probe, 1, leading to rearranged (3) and unrearranged (2) products. Our study shows that the reaction occurs via TSR in which the high-spin pathway gives dominant rearranged products, whereas the low-spin pathway favors unrearranged products. The calculated PIE(2/3) values based on TSR are found to be in excellent agreement with the experimental data of Newcomb and co-workers. This match between experiment and theory makes a strong case that the reaction occurs via TSR mechanism.     

An alternative efficient redox couple for the dye-sensitized solar cell system

A series of new cobalt complexes [Co(LLL)(2)X(2)] were synthesized and evaluated as redox mediators for dye-sensitized nanocrystalline TiO(2) solar cells. The structure of the ligand and the nature of the counterions were found to influence the photovoltaic performance. The one-electron-transfer redox mediator [Co(dbbip)(2)](ClO(4))(2) (dbbip = 2,6-bis(1'-butylbenzimidazol-2'-yl)pyridine) performed best among the compounds investigated. Photovoltaic cells incorporating this redox mediator yielded incident photon-to-current conversion efficiencies (IPCE) of up to 80%. The overall yield of light-to-electric power conversion reached 8 % under simulated AM1.5 sunlight at 100 W m(-2) intensity and more than 4% at 1000 W m(-2). Photoelectrodes coated with a 2 microm thick nanoporous layer and a 4 microm thick light-scattering layer, sensitized with a hydrophobic ruthenium dye, gave the best results.     

Phenanthrene‐Fused‐Quinoxaline as a Key Building Block for Highly Efficient and Stable Sensitizers in Copper‐Electrolyte‐Based Dye‐Sensitized Solar Cells

Dye‐sensitized solar cells (DSSCs) based on Cu^II/I bipyridyl or phenanthroline complexes as redox shuttles have achieved very high open‐circuit voltages (V_OC, more than 1 V). However, their short‐circuit photocurrent density (J_SC) has remained modest. Increasing the J_SC is expected to extend the spectral response of sensitizers to the red or NIR region while maintaining efficient electron injection in the mesoscopic TiO₂ film and fast regeneration by the Cu^I complex. Herein, we report two new D‐A‐π‐A‐featured sensitizers termed HY63 and HY64 , which employ benzothiadiazole (BT) or phenanthrene‐fused‐quinoxaline (PFQ), respectively, as the auxiliary electron‐withdrawing acceptor moiety. Despite their very similar energy levels and absorption onsets, HY64 ‐based DSSCs outperform their HY63 counterparts, achieving a power conversion efficiency (PCE) of 12.5 %. PFQ is superior to BT in reducing charge recombination resulting in the near‐quantitative collection of photogenerated charge carriers.     

Rapid determination of reduced and oxidized glutathione levels using a new thiol-masking reagent and the enzymatic recycling method: application to the rat liver and bile samples

A microtiter plate assay for quantitation of reduced (GSH) and oxidized (GSSG) glutathione in the rat liver tissue and bile is described. The assay is based on the established enzymatic recycling method and a new thiol-masking reagent, 1-methyl-4-vinyl-pyridinium trifluoromethane sulfonate (M4VP). Samples were first processed by homogenization with (liver) or addition of (bile) sulfosalicylic acid. The total glutathione and GSSG were then determined before and after rapid (≤2 min) and efficient (100%) masking of the GSH content of the samples with M4VP followed by the enzymatic recycling assay. The percentages of error and coefficient of variation of the assay were within the accepted guidelines, indicating the accuracy and precision of the assay in the range of 6.25–100 pmol GSH per microplate well and 2.17–140 pmol GSSG per well, with lower limit of quantitation of 6.25 and 2.17 pmol per well for GSH and GSSG, respectively. Furthermore, the recoveries of added GSH or GSSG from the liver and bile samples were accurate and precise. The assay was applied to measurement of GSH, GSSG, and GSH:GSSG ratio in the liver and serially collected bile samples in sham-operated and ischemic rat livers, demonstrating a depletion of glutathione and a decrease in the GSH:GSSG ratio as a result of ischemia. The developed assay is rapid, sensitive, accurate, and precise and is suitable for studies of the redox status of liver under physiologic and pathophysiologic conditions.     

Expeditious,Nano-BF3 · SiO2-Catalyzed Michaelis–Arbuzov Reaction in an Ionic Liquid: Synthesis of Privileged Aryl/Heterocyclic Phosphonates

An expeditious, simple, and green method was developed for the synthesis of privileged aryl/heterocyclicphosphonates, 8(a–c) to 13(a–c) through Michaelis–Arbuzov reaction of aryl/heterocyclic halides (Br), 1–6, and trialkylphosphites, 7(a–c), in room-temperature ionic liquid [bbim]Br using heterogeneous Lewis catalyst, nano-silica-supported boron trifluoride (BF₃-SiO₂). The advantages of this protocol are simplicity, good yield of the products, less reaction time (20–38 min), mild reaction conditions, easy workup, and reusability of the catalyst and ionic liquid. It is demonstrated that nano-BF₃-SiO₂ is a recoverable and easy accessible catalyst for the formation of C(sp²)-P bond in an ionic liquid.