Programmable self-assembly has been widely studied because of its capability to create ordered patterns from a group of multiple disordered agents without an external controller. To achieve this, assembly units must exhibit different characteristics: they need to be small, to have the ability to latch and unlatch, and low-power consumption. In addition, they need to be easily programmable and able to communicate with each other. This thesis presents an experimental robotic platform for programmable self-assembly. In this work, we build in the Usbot modular robotic cubes making use of their advantages and simplicity as its passive magnetic latching mechanism, and we endow them with communication capabilities. The system allows only local communication between the modules, specifically with the most recent linked neighbor cube. The transmission of the relevant cube data is performed by a pair of LED and ambient light sensors in a binary format. The different experiments demonstrate and compare distributed programmable self-assembly using various algorithms from the literature as Singleton and Lynchpin.

Substituted heterocycles are common building-blocks for biologically relevant molecules and represent challenging synthetic targets. Due to limited methods available for their preparation and derivatization, direct C-H functionalization protocols offer considerable advantages. Radical chemistry has shown great potential in this regard; however traditional approaches are unattractive due to poor selectivity and harsh reaction conditions. Visible light photoredox catalysis, on the other hand, is a mild alternative for alkyl radical generation and has proven its utility in organic synthesis. The work encompassed in this thesis details the efforts towards the development of practical photoredox-based functionalizations of heterocycles. Specific focus is placed upon overcoming obstacles pertaining to H-atom abstraction, back electron transfer, and redox strength of photocatalysts to achieve efficient C-Br bond reductions, amine oxidations, and C-C bond formations. In pursuit of these objectives, a C2-selective malonation of indoles and other electron-rich heteroarenes was accomplished in high yields using photocatalyst Ru(bpy)3Cl2, p-CH3OC6H4NPh, and blue LEDs as the light source. Use of a triarylamine over a trialkylamine suppressed H-atom abstraction and promoted C-C bond formation. Subsequent exploitation of the reductive quenching cycle of Ru(bpy)3Cl2 and use of Cl3CBr as an alternative oxidant led to an oxidative nucleophilic trapping of tetrahydroisoquinolines to provide a diverse set of analogues. Finally, photoredox catalysis was utilized for the creation of C-C bonds in the context of complex molecule synthesis. A variety of bromopyrroloindolines and indoles were coupled to furnish C3-C3' and C3-C2' bisindole alkaloids, which was successfully applied to the total synthesis of gliocladin C and related analogues. Moreover, fine-tuning of the redox cycle with photocatalyst Ir(ppy)2(dtbbpy)PF6 and LiB(cat)2 as the reductive quencher enabled the coupling less-reactive substrates and suppression of back electron transfer.

Indiana University-Purdue University Indianapolis (IUPUI) / Aromatic rings are universal motifs in natural products, pharmaceuticals, agrochemicals, and wide variety of organic materials. Aromatic halides are widely used as synthetic precursors in all these applications. Therefore, tremendous effort has been devoted to activate aryl halides in the past decades. The common methods to activate aryl halides require the use of transition- metals either in the form of Grignard reagents or through the use of transition-metal catalysis. Over the past decade, photoredox catalysis has attracted significant attention as a cogent tool to develop greener synthetic processes and enable new molecular activation pathways under mild conditions. The most common of these approaches uses a photoredox/nickel dual catalytic cycle. While this technology has greatly expanded the toolbox of organic chemists, this method still requires expensive rare-metal-based catalyts. Herein, we present a series of visible light-induced methods that are transition-metal-free. These new base-promoted transformations and their mechanistic work will be discussed in the following order: We will first present our discovery that the dimsyl anion enables visible-light-promoted charge transfer in cross-coupling reactions of aryl halides. This work was applied to the synthesis of unsymmetrical diaryl chalcogenides. This method has a broad scope and functional group tolerance. An electron-donor-acceptor (EDA) complex between a dimsyl anion and the aryl halide is formed during the reaction and explains the observed aryl radical reactivity observed. Then, a visible-light-induced borylation and phosphorylation of aryl halides under mild conditions was developed. Inspired by the mechanistic breakthroughs observed in the previous work. The mechanism of this reaction also involves an aryl radical that is presumed to be formed also via an EDA complex. In other work, a photo-induced phosphonation of ArI using N,N- diisopropylethylamine (DIPEA) and trialkyl phosphites was developed. This method uses very mild conditions, which allowed the preparation a wide variety of functionalized aromatic phosphonates derivatives, including natural products and medicinal compounds. Finally, a photochemical amination of amides was developed via a C(sp 3 )–H bond functionalization process under visible light irradiation. This reaction showed good functional group compatibility without the use of external radical initiators, strong oxidants, or heat source. An EDA complex between N-bromophthalimide and LiOtBu is formed during the reaction.

京都大学 / 0048 / 新制・課程博士 / 博士(理学) / 甲第20198号 / 理博第4283号 / 新制||理||1615(附属図書館) / 京都大学大学院理学研究科化学専攻 / (主査)准教授 中西 和樹, 教授 北川 宏, 教授 島川 祐一 / 学位規則第4条第1項該当 / Doctor of Science / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21119号 / 工博第4483号 / 新制||工||1697(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 阿部 竜, 教授 安部 武志, 教授 陰山 洋 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DGAM

京都大学 / 0048 / 新制・課程博士 / 博士(工学) / 甲第21775号 / 工博第4592号 / 新制||工||1715(附属図書館) / 京都大学大学院工学研究科物質エネルギー化学専攻 / (主査)教授 阿部 竜, 教授 作花 哲夫, 教授 安部 武志 / 学位規則第4条第1項該当 / Doctor of Philosophy (Engineering) / Kyoto University / DFAM

An emerging concern for employers is the impact of visible body modification (VBM) in the workplace. Visible body modification includes tattoos, piercings, or implants that are both visible and observable on an individual’s body. The extant research on VBM suggests that employers are hesitant to hire those with visible tattoos or piercings, but fails to address how employees with VBM influence organizational outcomes. This dissertation examines how a specific type of VBM, visible tattoos, influences training and learning by investigating how a trainer’s visible tattoos affect trainees’ perceived trustworthiness and learning in a training context. The study used a sample of 164 undergraduate students and Amazon Mechanical Turk workers to assess reactions to a trainer’s visible tattoos. Subjects were randomly assigned to one of three treatment groups, with the two experimental groups having a trainer with one tattoo or full tattoo sleeves. The results indicated that there were no significant differences between groups for perceived trustworthiness or learning. Similarly, there was no support for the moderating effect of openness to experience, authoritarianism, or learning goal orientation. Social distance was found to moderate the relationship between the treatment and perceived trustworthiness. The findings of this study suggest that for the trainer and tattoos used, visible tattoos do not an impact on training outcomes. As this study was limited to one trainer with one type of tattoos, this preliminary evidence suggests that more research is needed to address the diversity of tattooing and VBM as a whole.

The purpose of the study was to examine seven upper-secondary school students' perceptions of teachers' use of formative assessment and feedback in the classroom. The basis for the study was Wiliam (2017) and Hattie's (2008) theories on formative assessment and visible learning. The study was conducted using semi-structured interviews with seven students from six different schools to find out what their perceptions were about the use of formative assessment in the school environment. The interviews were analyzed using thematic analysis. The results of the study show that most students experience a fear of failure in their studies. More specifically, the students reported that they had difficulty understanding and using the teachers’ feedback and that this feedback was often perceived as negative. They also find it difficult to interpret what the teacher wants to say with their feedback and they do not dare to challenge themselves in the tasks they are given by teachers due to the fear of making mistakes. There are challenges in how teachers give students feedback and also how feedback is used by students. Mostly the challenge concerns the time it takes for students to get feedback from their teachers, also the difficulty for teachers and students to work formatively with learning platforms. The students reported that learning platforms risk acting more as a way for students to see what level they are reaching in courses, rather than helping students to develop.

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