Unprecedented Regio- and Stereoselective Synthesis of Pyrene-Grafted Dispiro[indoline-3,2'-pyrrolidine-3',3″-indolines]: Expedient Experimental and Theoretical Insights into Polar [3 + 2] Cycloaddition.

A series of dispiro[indoline-3,2'-pyrrolidine-3',3″-indolines] was synthesized via a multicomponent polar [3 + 2] cycloaddition (32CA) reaction of isatin derivatives, sarcosine and (E)-3-(2-oxo-2-(pyren-1-yl)ethylidene)indolin-2-one derivatives. The regio- and stereochemistries of the cycloadducts were established on the basis of one-dimensional (1D) (1H-, 13C-, 13C-CRAPT NMR) and two-dimensional (2D) homonuclear and heteronuclear correlation NMR spectrometry experiments (1H-1H gDQFCOSY, 13C-1H-HSQCAD, 13C-1H-HMBCAD, 1H-1H-ROESYAD). The molecular mechanism and regio- and stereoselectivities of the cycloaddition (CA) reaction have been investigated utilizing a density functional theory (DFT) method and were thoroughly explained based on the transition-state stabilities and global/local electrophilicity/nucleophilicity reactivity indices of the reactants.

Highly efficient ZnO/Au Schottky barrier dye-sensitized solar cells: Role of gold nanoparticles on the charge-transfer process.

Zinc oxide (ZnO) nanorods decorated with gold (Au) nanoparticles have been synthesized and used to fabricate dye-sensitized solar cells (DSSC). The picosecond-resolved, time-correlated single-photon-count (TCSPC) spectroscopy technique was used to explore the charge-transfer mechanism in the ZnO/Au-nanocomposite DSSC. Due to the formation of the Schottky barrier at the ZnO/Au interface and the higher optical absorptions of the ZnO/Au photoelectrodes arising from the surface plasmon absorption of the Au nanoparticles, enhanced power-conversion efficiency (PCE) of 6.49% for small-area (0.1 cm(2)) ZnO/Au-nanocomposite DSSC was achieved compared to the 5.34% efficiency of the bare ZnO nanorod DSSC. The TCSPC studies revealed similar dynamics for the charge transfer from dye molecules to ZnO both in the presence and absence of Au nanoparticles. A slower fluorescence decay associated with the electron recombination process, observed in the presence of Au nanoparticles, confirmed the blocking of the electron transfer from ZnO back to the dye or electrolyte by the Schottky barrier formed at the ZnO/Au interface. For large area DSSC (1 cm(2)), ~130% enhancement in PCE (from 0.50% to 1.16%) was achieved after incorporation of the Au nanoparticles into the ZnO nanorods.

A molecular magnet confined in the nanocage of a globular protein.

The effect of confinement and energy transfer on the dynamics of a molecular magnet, known as a model system to study quantum coherence, is investigated. For this purpose the well-known polyoxovanadate [V(15)As(6)O(42)(H(2)O)](6-) (V(15)) is incorporated into a protein (human serum albumin, HSA) cavity. Due to a huge overlap of the optical absorption spectrum of V(15) with the emission spectrum of a fluorescence center of HSA (containing a single tryptophan residue), energy transfer is induced and probed by steady-state and time-resolved fluorescence. The geometrical coordination and the distance of the confined V(15) to the tryptophan moiety of HSA are investigated at various temperatures. This effect is used as a local probe for the thermal denaturation of the protein at elevated temperatures.