Organocatalyzed synthesis of fluorinated poly(aryl thioethers)

Park, Nathaniel H.; Gomes, Gabriel; Fèvre, Michel; Jones, Gavin O.; Alabugin, Igor V.; Hedrick, James L.

doi:10.1038/s41467-017-00186-3

Cited by 44 publications

(55 citation statements)

References 35 publications

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“…The propensity of simple elements to aggregate into clusters is observed at diverse length scales ranging from the sub-atomic level, where combinations of three quarks form baryons 1,2 , to the super-molecular level, where large macro-molecules are composed by smaller repeated units as in DNA 3 , proteins 4 , or synthetic plastics [5][6][7] , to the scale of the Universe, where thousands of stars congregate in galaxies 8,9 . In complex systems of a great multitude of components, cooperation among components and the emergence of collective phenomena yield unique properties that are not generally expressed by components of those systems taken in isolation [10][11][12][13] . Ferromagnetism 14,15 , phonon modes of an atomic lattice 16,17 , surface enhanced Raman spectroscopy 18,19 , superconductivity 20,21 , memory and cognitive functions of the brain 22,23 , depend less on the specialization of individual elements and more on the fact that these elements interact in long-range structures.…”

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confidence: 99%

Cortical-like mini-columns of neuronal cells on zinc oxide nanowire surfaces

Onesto

Villani

Narducci

et al. 2019

Sci Rep

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A long-standing goal of neuroscience is a theory that explains the formation of the minicolumns in the cerebral cortex. Minicolumns are the elementary computational units of the mature neocortex. Here, we use zinc oxide nanowires with controlled topography as substrates for neural-cell growth. We observe that neuronal cells form networks where the networks characteristics exhibit a high sensitivity to the topography of the nanowires. For certain values of nanowires density and fractal dimension, neuronal networks express small world attributes, with enhanced information flows. We observe that neurons in these networks congregate in superclusters of approximately 200 neurons. We demonstrate that this number is not coincidental: the maximum number of cells in a supercluster is limited by the competition between the binding energy between cells, adhesion to the substrate, and the kinetic energy of the system. Since cortical minicolumns have similar size, similar anatomical and topological characteristics of neuronal superclusters on nanowires surfaces, we conjecture that the formation of cortical minicolumns is likewise guided by the interplay between energy minimization, information optimization and topology. For the first time, we provide a clear account of the mechanisms of formation of the minicolumns in the brain. opeNThere are amendments to this paper Scientific RepoRts | (2019) 9:4021 | https://doi.org/10.1038/s41598-019-40548-z www.nature.com/scientificreports www.nature.com/scientificreports/ architectures can direct, control and, in some cases, improve the organization of simple elements into clusters [38][39][40][41][42][43] . Nano-topography is especially important in guiding cell fate at the bio-interface, and is therefore of interest in neural tissue engineering, bio computing, biosensors operations and neural cell based sensors, the diagnosis and analysis of neurodegenerative disorders, neural development [44][45][46] . In previously reported studies 39,47,48 , we examined patterns of neuroblastoma N2A cells on meso-porous silicon. We observed that N2A cells on a surface with nano-scale motifs display an increased ability to create patterns in which the nodes of the patterns form highly clustered groups and the elements of the groups are connected by a finite, and generally low, number of steps. Networks with similar characteristics are named small world networks 49,50 . In ref. 46 we demonstrated that neural networks with a small world topology on rough silicon substrates feature enhanced signal propagation speed and computational capabilities compared to regular grids of the same size on flat surfaces.Here, we present zinc oxide nanowire surfaces with variable nanowire density that achieve a tight interface with hippocampal neurons to direct their assembly into clusters. Resulting neuronal networks show a high sensitivity to the geometrical characteristics of the nanowires. For certain combinations of fractal dimension and nanowires density, neurons accumulate into clusters with ~200 neurons per clu...

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confidence: 99%

Cortical-like mini-columns of neuronal cells on zinc oxide nanowire surfaces

Onesto

Villani

Narducci

et al. 2019

Sci Rep

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“…In spite of the wide range of applications for surface and side‐chain post‐functionalization polymerization modifications, the synthesis of a linear polymer via PFTR‐reaction has received little attention, and remained a challenge until a recent study published by Hedrick and co‐workers ( Scheme ) . In their study, trimethylsilyl (TMS)‐protected thioether was reacted with hexafluorobenzene at ambient temperature.…”

Section: Chemistrymentioning

confidence: 99%

Sulfur Chemistry in Polymer and Materials Science

Mutlu

Ceper

et al. 2018

Macromol. Rapid Commun.

254

220

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The ORCID identification number(s) for the author(s) of this article can be found under https://doi.org/10.1002/marc.201800650. ChemistryBefore moving to the recent advances within the last 5 years in the diverse applications of sulfur chemistry in polymer and Sulfur-Containing PolymersSulfur and its functional groups are major players in an area of exciting research taking place in modern polymer and materials science, both in academia and industry. In fact, manifold sulfur-based reactions that are both exceptionally versatile as well as tremendously useful have been implemented, and further utilized for the design and preparation of polymeric materials that lead to a plethora of applications ranging from medicine to optics and nanotechnology to separation science. Hence, within this review, an overview of strategies and developments used over the last 5 years to reinforce the importance of the sulfur functional group in modern polymer and materials science is presented. In particular, many important references in the primary literature of sulfur chemistry are referred to, including thiol-ene, thiol-yne, thiol-Michael addition, disulfide cross-linking, and thiol-disulfide exchange, among others, by explaining and illustrating the important principles. Last but not least, the grand aim to underpin the importance of sulfur in modern polymer and materials science is achieved by presenting selected examples in diverse fields and postulating the respective potential for real-world applications. he is now a full professor at KIT.sulfur atoms, and tetraphenylethene-bearing di(alkyl bromide) (Scheme 3). The yield of the polymerization was dependent on the di(alkyl bromide) monomer; the longer spacer between the aromatic moiety and the reactive bromide end groups Scheme 1. The discussion henceforth focuses on the synthesis of polymers possessing the depicted sulfur functional groups. Scheme 2.Representative examples of polythioethers prepared via A) the nucleophilic substitution reaction between an electrophilic dihalide with nucleophilic derivatives of dithiols under alkaline conditions; B) the thiol-ene/yne addition reaction between AA and BB type monomers (i.e., dithiols and dienes/diynes); and C) radical or ionic ring-opening of sulfurcontaining strained rings.Scheme 3. The thiol-bromo polymerization of conformationally fixed monomers to provide multifunctional polymers. [19] Macromol. Rapid Commun. 2019, 40, 1800650 Scheme 4. The regioselective selective nucleophilic aromatic substitution between thiol and fluorinated aromatic compounds, the para-fluorothiol reaction (PFTR).Scheme 5. Synthesis of a linear polymer via PFTR-reaction. [21]

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“… Mechanism of a self‐propagated PFTR. When X is a silyltrimethyl moiety, the fluoride triggers the deprotection of the thiol as reported by Hedrick and co‐workers . When X is a proton, the fluoride deprotonates the thiol and forms hydrogen fluoride.…”

Section: Methodsmentioning

confidence: 70%

“…Recently, Hedrick and co‐workers reported an organocatalysed thiol–fluorine substitution . By employing perfluorinated aryl monomers and trimethylsilyl‐protected dithiols in the presence of base or fluoride ions, they were able to synthesise fluorinated poly(aryl thioethers).…”

Section: Methodsmentioning

confidence: 99%

Self‐Propagated para‐Fluoro‐Thiol Reaction

Cavalli

Bloesser

Barner‐Kowollik

et al. 2019

Chemistry A European J

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We introduce a protecting‐group‐free concept for the powerful para‐fluoro‐thiol reaction (PFTR) employing a source of fluoride ions as base. The reaction is shown to be self‐propagating, with under‐stoichiometric amounts of base, thus effectively foregoing the need for high base concentrations. Careful tuning of the solvent–thiol combination allows for quantitative conversion, in some cases within a short timeframe, when only minimal amounts of base are used, allowing the PFTR reaction to essentially proceed base‐free.

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Organocatalyzed synthesis of fluorinated poly(aryl thioethers)

Cited by 44 publications

References 35 publications

Cortical-like mini-columns of neuronal cells on zinc oxide nanowire surfaces

Cortical-like mini-columns of neuronal cells on zinc oxide nanowire surfaces

Sulfur Chemistry in Polymer and Materials Science

Self‐Propagated para‐Fluoro‐Thiol Reaction

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