There has been growing interest in polyproline type II (PPII) helices since PPII helices have been found in folded and unfolded proteins and involved in a variety of biological activities. Polyproline can also form type I helices (PPI) which are very different from PPII conformation and only exist in certain organic solvents. Recent studies have shown that stereoelectronic effects play a critical role in stabilizing a PPI or PPII helix. Here, we have synthesized a series of host-guest peptides with an electron-withdrawing substituent at the 4R or 4S position of proline and used a kinetic approach to further explore stereoelectronic effects on the transition barrier of the interconversion between PPI and PPII conformations. Time-dependent circular dichroism measurements revealed that the rates of PPII fi PPI conversion were reduced upon incorporating the hydroxyl-, fluoro-, and methoxy-groups at the 4R position while the rates would be increased if these substituents were at the 4S position. We quantified the changes in transition free energy by comparing their rate constants. (4R,2S)-4-Fluoroproline and (4S,2S)-4-fluoroproline have the largest effect on the transition energy barrier for PPII fi PPI conversion. Our results provide important insights into the role of stereoelectronic effects on the PPII fi PPI transition state barrier, which has not been reported in past thermodynamic studies.

A facile, one-step, template-less, surfactant-free hydrothermal process, using a metal salt as the precursor, is developed to prepare submicrometer sized mesoporous TiO 2 nanoparticle aggregates (NPGs). The as-prepared TiO 2 NPGs are crystalline of the anatase phase, with a high specific surface area of 166 m 2 /g, an average pore size of 8.9 nm, and an average NPG size of 840 nm. With these NPGs, a new form of composite photoanode, consisting of the mesoporous TiO 2 NPGs and xerogels, is proposed for high efficiency dye-sensitized solar cells (DSSCs). TiO 2 xerogels are incorporated into the TiO 2 NPGs layer with an impregnation process to form the TiO 2 NPGs/xerogels composite. A high power conversion efficiency of 8.41% is achieved for DSSCs based on the TiO 2 NPGs/xerogels composite photoanode, representing a 38% efficiency boost over the efficiency of 6.11% achieved with a P25 TiO 2 based cell. The success of the present composite TiO 2 nanostructure can be attributed to the effective utilization of the inter-NPG space with the infiltration of the TiO 2 xerogels, the excellent structural connectivity within and across the NPG and xerogel domains for fast electron transport, the high specific surface areas of both the NPGs and xerogels for providing abundant dye adsorption for generation of photoinduced electrons, the formation of a TiO 2 xerogel blocking layer on top of the photoanode substrate, and the submicrometer size of the NPGs for much improved light harvesting efficiency. This new type of composite photoanode, different from the 0D/1D nanostructure based ones, proves effective by taking structural advantages from both constituent nanostructures, the mesoprous NPGs and xerogels, and opens up a new way of thinking in the structural design of the photoanodes.

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