The high efficiency all-small-molecule organic solar cells (OSCs) normally require optimized morphology in their bulk heterojunction active layers. Herein, a small-molecule donor is designed and synthesized, and single-crystal structural analyses reveal its explicit molecular planarity and compact intermolecular packing. A promising narrow bandgap small-molecule with absorption edge of more than 930 nm along with our home-designed small molecule is selected as electron acceptors. To the best of our knowledge, the binary all-small-molecule OSCs achieve the highest efficiency of 14.34% by optimizing their hierarchical morphologies, in which the donor or acceptor rich domains with size up to ca. 70 nm, and the donor crystals of tens of nanometers, together with the donor-acceptor blending, are proved coexisting in the hierarchical large domain. All-small-molecule photovoltaic system shows its promising for high performance OSCs, and our study is likely to lead to insights in relations between bulk heterojunction structure and photovoltaic performance.

The cytochrome P450 enzyme CYP199A4, from Rhodopseudomonas palustris HaA2, can efficiently demethylate 4-methoxybenzoic acid. It is also capable of oxidising a range of other related substrates. By investigating substrates with different substituents and ring systems we have been able to show that the carboxylate group and the nature of the ring system and the substituent are all important for optimal substrate binding and activity. The structures of the veratric acid, 2-naphthoic acid and indole-6-carboxylic acid substrate-bound CYP199A4 complexes reveal the substrate binding modes and the side-chain conformational changes of the active site residues to accommodate these larger substrates. They also provide a rationale for the selectivity of product oxidation. The oxidation of alkyl substituted benzoic acids by CYP199A4 is more complex, with desaturation reactions competing with hydroxylation activity. The structure of 4-ethylbenzoic acid-bound CYP199A4 revealed that the substrate is held in a similar position to 4-methoxybenzoic acid, and that the C(β) C-H bonds of the ethyl group are closer to the heme iron than those of the C(α) (3.5 vs. 4.8 Å). This observation, when coupled to the relative energies of the reaction intermediates, indicates that the positioning of the alkyl group relative to the heme iron may be critical in determining the amount of desaturation that is observed. By mutating a single residue in the active site of CYP199A4 (Phe185) we were able to convert the enzyme into a 4-ethylbenzoic acid desaturase.

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The crystal structures of the 4-methoxybenzoate bound forms of cytochrome P450 enzymes CYP199A2 and CYP199A4 from the Rhodopseudomonas palustris strains CGA009 and HaA2 have been solved. The structures of these two enzymes, which share 86% sequence identity, are very similar though some differences are found on the proximal surface. In these structures the enzymes have a closed conformation, in contrast to the substrate-free form of CYP199A2 where an obvious substrate access channel is observed. The switch from an open to a closed conformation arises from pronounced residue side-chain movements and alterations of ion pair and hydrogen bonding interactions at the entrance of the access channel. A chloride ion bound just inside the protein surface caps the entrance to the active site and protects the substrate and the heme from the external solvent. In both structures the substrate is held in place via hydrophobic and hydrogen bond interactions. The methoxy group is located over the heme iron, accounting for the high activity and selectivity of these enzymes for oxidative demethylation of the substrate. Mutagenesis studies on CYP199A4 highlight the involvement of hydrophobic (Phe185) and hydrophilic (Arg92, Ser95 and Arg243) amino acid residues in the binding of para-substituted benzoates by these enzymes.

The composition of the lamina propria in human vocal folds has been shown to affect vocal performance. Elastin plays a significant role in the biomechanical effects of the lamina propria. We obtained 19 larynges from the state medical examiner from subjects whose cause of death was unrelated to the trachea and laryngeal regions. The sample contained male and female subjects in the infant, adult, and geriatric age groups. We stained the vocal folds for elastin with Verhoeff's elastic tissue stain and studied them with use of an image analysis system configured for light microscopy. Distributions of elastin were measured from superficial to deep within the lamina propria (from epithelium to vocal muscle). These elastin distributions were then compared with the use of statistical software. The data showed that there was an increase in elastin content from the infant through geriatric stages. No gender-related differences were found. Infant folds had about 23% of the elastin found in adults, and geriatric subjects had about 879% of the elastin found in adults. Both of these results were statistically significant (p < 0.05). The distributions were consistent with previous observations that the lamina propria is a layered structure with most of the elastin present in the intermediate layer. This layer was larger in geriatric subjects than in adult and pediatric subjects. We observed that the fiber diameter appeared to be larger in geriatric subjects (this observation is currently being verified with electron microscopy) whereas smaller, spiraled fibers appeared in pediatric subjects.

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The optimization of bulk heterojunction morphology is one of the most challenging topics in all‐small‐molecule organic solar cells. Herein, three small molecular donors based on dithieno[2,3‐d;2′,3′‐d′]benzo[1,2‐b;4,5‐b′]dithiophene (DTBDT) unit by systematically moving the branching point of the alkyl chain have been designed, synthesized, and applied in organic solar cells. Modifying the branching points enables the properties of the aggregation state to be tuned, and an efficient nanofiber‐based hierarchical morphology is successfully demonstrated by combining with different nonfullerene acceptors. The molecules with far branching points can form nanofibers in active layers, and theses nanofibers help the charge separation and charge transport in a large donor‐rich or acceptor‐rich domain of approximately 100 nm. Using nonfullerrene Y6 as an acceptor, the highest power conversion efficiency of 14.78% is obtained, which is one of the highest efficiencies in all‐small‐molecule organic solar cells. The strategy of modification of alkyl side chain branching points can be a practical way to actualize crystallinity control and active layer morphology for improving the performance of all‐small‐molecule organic solar cells.

Compared with nonfullerene‐based polymer solar cells, all‐small‐molecule solar cells normally show low power conversion efficiencies (PCEs) due to their low fill factors (FFs). Molecular stacking orientation and phase separation are the main factors affecting the performance of all‐small‐molecule solar cells. In this work, two liquid‐crystalline small‐molecule donors are designed and synthesized and a novel nonfullerene acceptor with good crystallinity developed. Owing to the face‐on orientation of the component molecules and appropriate phase separation in the active layer, a high FF of over 70% and a PCE of 10.7% are obtained from the resulting solar cells; these values are among the best obtained thus far for all‐small‐molecule solar cells. The high FF reported here is significant for a further design of high‐performance all‐small‐molecule solar cells.