Evaluations of vertical resolution of conductive polymer three-dimensional microstructures photofabricated in transparent polymer sheet

Conductive polymer three-dimensional microstructures were photofabricated utilizing the two-photon absorption of a sensitizer dye. The resulting three-dimensional structures were excised from the transparent polymer sheet using a micro-manipulator. The processing precisions for the vertical direction of the conductive polymer three-dimensional microstructure obtained in the transparent polymer sheet were evaluated in the present study. As a result, for the configurations of the obtained polypyrrole line deposition, the line height/line width ratios were around 5: 1; this ratio is higher than that of other UV resin works (h: w 2:4–3: 1) and the cross section distortion is not negligible for maintaining the higher reproducibility of the photofabrication.     

Rhodium(I)‐Catalyzed Enantioselective Cyclization of Enynes by Intramolecular Cleavage of the Rh−C Bond by a Tethered Hydroxy Group

Rhodium(I)‐catalyzed enantioselective intramolecular cyclization of enynes having a hydroxy group in the tether was investigated, and various cyclic compounds possessing a chiral quaternary carbon center were obtained in high yields with high ees. In this cyclization, a Rh?C(sp²) bond in the rhodacyclopentene intermediate, which was formed by enantioselective oxidative cycloaddition of enynes to a chiral rhodium(I) complex, was intramolecularly cleaved by σ‐bond metathesis of a tethered O?H bond in the substrate. Furthermore, it was found that the cyclic compounds were obtained with high ees even when the starting materials having a racemic secondary alcohol moiety were used in this reaction.     

Mixture Complexity and Its Application to Gradual Clustering Change Detection

We consider measuring the number of clusters (cluster size) in the finite mixture models for interpreting their structures. Many existing information criteria have been applied for this issue by regarding it as the same as the number of mixture components (mixture size); however, this may not be valid in the presence of overlaps or weight biases. In this study, we argue that the cluster size should be measured as a continuous value and propose a new criterion called mixture complexity (MC) to formulate it. It is formally defined from the viewpoint of information theory and can be seen as a natural extension of the cluster size considering overlap and weight bias. Subsequently, we apply MC to the issue of gradual clustering change detection. Conventionally, clustering changes have been regarded as abrupt, induced by the changes in the mixture size or cluster size. Meanwhile, we consider the clustering changes to be gradual in terms of MC; it has the benefits of finding the changes earlier and discerning the significant and insignificant changes. We further demonstrate that the MC can be decomposed according to the hierarchical structures of the mixture models; it helps us to analyze the detail of substructures.     

Summarizing Finite Mixture Model with Overlapping Quantification

Finite mixture models are widely used for modeling and clustering data. When they are used for clustering, they are often interpreted by regarding each component as one cluster. However, this assumption may be invalid when the components overlap. It leads to the issue of analyzing such overlaps to correctly understand the models. The primary purpose of this paper is to establish a theoretical framework for interpreting the overlapping mixture models by estimating how they overlap, using measures of information such as entropy and mutual information. This is achieved by merging components to regard multiple components as one cluster and summarizing the merging results. First, we propose three conditions that any merging criterion should satisfy. Then, we investigate whether several existing merging criteria satisfy the conditions and modify them to fulfill more conditions. Second, we propose a novel concept named clustering summarization to evaluate the merging results. In it, we can quantify how overlapped and biased the clusters are, using mutual information-based criteria. Using artificial and real datasets, we empirically demonstrate that our methods of modifying criteria and summarizing results are effective for understanding the cluster structures. We therefore give a new view of interpretability/explainability for model-based clustering.     

Regioselective Alkynylation of Allylic Phosphates with Alkynyl Copper Reagents

We developed an alkynylation of allylic phosphates with acetylenes in the presence of copper and magnesium salts. The reaction proceeded regioselectively to afford the corresponding 1,4-enynes. Furthermore, the functional group tolerance of this reaction was established. As an application, the 1,4-enyne intermediate involved in the synthesis of 13R,19S,20S-trihydroxydocosapentaenoic acid could be efficiently synthesized.