Solvent Molding of Organic Morphologies Made of Supramolecular Chiral Polymers

12sihe self-assembly and self-organization behavior of uracil-conjugated enantiopure (R)- or (S)-1,1'-binaphthyl-2,2'-diol (BINOL) and a hydrophobic oligo(p-phenylene ethynylene) (OPE) chromophore exposing 2,6-di(acetylamino)pyridine termini are reported. Systematic spectroscopic (UVvis, CD, fluorescence, NMR, and SAXS) and microscopic studies (TEM and AFM) showed that BINOL and OPE compounds undergo triple H-bonding recognition, generating different organic nanostructures in solution. Depending on the solvophobic properties of the liquid media (toluene, CHCl3, CHCl3/CHX, and CHX/THF), spherical, rod-like, fibrous, and helical morphologies were obtained, with the latter being the only nanostructures expressing chirality at the microscopic level. SAXS analysis combined with molecular modeling simulations showed that the helical superstructures are composed of dimeric double-cable tape-like structures that, in turn, are supercoiled at the microscale. This behavior is interpreted as a consequence of an interplay among the degree of association of the H-bonded recognition, the vapor pressure of the solvent, and the solvophobic/solvophilic character of the supramolecular adducts in the different solutions under static and dynamic conditions, namely solvent evaporation conditions at room temperature.partially_openopenĐorđević, Luka; Marangoni, Tomas; Miletić, Tanja; Rubio-Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, DavideĐorđević, Luka; Marangoni, Tomas; Miletic, Tanja; Rubio Magnieto, Jenifer; Mohanraj, John; Amenitsch, Heinz; Pasini, Dario; Liaros, Nikos; Couris, Stelios; Armaroli, Nicola; Surin, Mathieu; Bonifazi, David

Networks of Circular Economy Villages: Political Economic Principles and Spatial Potentials

Faced with the challenges to restructure societies for long term sustainability, greater attention should be given to the design of human settlements and their relationship to each other. This thesis explores the pattern of human settlements and the possibility of finding a solution in the form of networks of Circular Economy Villages (CEVs). Each CEV would integrate energy, water, food and building infrastructure, aligning these with local ecological cycles. This would maximise local production and improve energy efficiency, while reducing both financial and ecological costs. The research question is: How would human habitats be structured in a political economic paradigm wherein populations were mobilised to regenerate natural systems and, through this, to rehabilitate and regenerate the human condition? Asking the question in reverse: How might a disruptive model for building human habitats enable the development of such a regenerative political economic paradigm? Critiques are most effective when accompanied by a viable alternative vision and an implementation strategy. The vision is therefore described at the outset, contrasting it with present political economic arrangements. The latter centralises production in densely populated cities, surrounded by less-densely populated towns and villages. The vision proposes a more even distribution of populations—a network of communities, each responsible for, and dependent on, the land upon which they are located. This thesis adopts a dialectical method, comparing centralised with distributed systems, extractive with regenerative processes, and linear with circular economies. Circular patterns underpin and connect all the chapters, exploring relational, temporal, spatial and holistic perspectives of circularity. By contrasting present circumstances with a possible future, various implementation strategies are developed—including town planning policies, a financial plan, and design principles for building networks of CEVs

Elucidating complex triplet-state dynamics in the model system isopropylthioxanthone

This work was supported by National Science Foundation, grants CMMI-1449309 and CHE-1800491. NL acknowledges support by the Research Corporation for Science Advancement (RCSA) and the National Science Foundation through a Cottrell Fellowship. The Cottrell Fellowship Initiative is partially funded by a National Science Foundation award to RCSA (CHE-2039044)

A multimodal dataset for authoring and editing multimedia content:the MAMEM project

We present a dataset that combines multimodal biosignals and eye tracking information gathered under a human-computer interaction framework. The dataset was developed in the vein of the MAMEM project that aims to endow people with motor disabilities with the ability to edit and author multimedia content through mental commands and gaze activity. The dataset includes EEG, eye-tracking, and physiological (GSR and Heart rate) signals collected from 34 individuals (18 able-bodied and 16 motor-impaired). Data were collected during the interaction with specifically designed interface for web browsing and multimedia content manipulation and during imaginary movement tasks. The presented dataset will contribute towards the development and evaluation of modern human-computer interaction systems that would foster the integration of people with severe motor impairments back into society.</p

A twisted bay-substituted quaterrylene phosphorescing in the NIR spectral region

The preparation of the first soluble quaterrylene derivative featuring peripheral tert-butyl substituents and sterically hindering, core-anchored triflate groups has been achieved. This involves a facile synthetic route based on an oxidative coupling of perylene precursors in the presence of H2O2 as oxidant. The steric hindrance between the TfO substituents at the central bay position of the quaterrylene board triggers a strong deformation of the central perylene planarity, which forces the quaterrylene platform to adopt a twisted geometry as shown by X-ray analysis. Exceptionally, photophysical investigations show that the core-twisted quaterrylene phosphoresces in the NIR spectral region at 1716 nm. Moreover, third-order nonlinear optical measurements on solutions and thin film containing the relevant molecule showed very large second hyperpolarizability values, as predicted by theoretical calculations at the CAM-B3LYP/6-31G** level of theory, making this material very appealing for photonic applications