- Lithium-Conducting Self-Assembled Organic Nanotubes
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Supramolecular polymers are compelling platforms for the design of stimuli-responsive materials with emergent functions. Here, we report the assembly of an amphiphilic nanotube for Li-ion conduction that exhibits high ionic conductivity, mechanical integrity, electrochemical stability, and solution processability. Imine condensation of a pyridine-containing diamine with a triethylene glycol functionalized isophthalaldehyde yields pore-functionalized macrocycles. Atomic force microscopy, scanning electron microscopy, and in solvo X-ray diffraction reveal that macrocycle protonation during their mild synthesis drives assembly into high-aspect ratio (>103) nanotubes with three interior triethylene glycol groups. Electrochemical impedance spectroscopy demonstrates that lithiated nanotubes are efficient Li+ conductors, with an activation energy of 0.42 eV and a peak room temperature conductivity of 3.91 ± 0.38 × 10-5 S cm-1. 7Li NMR and Raman spectroscopy show that lithiation occurs exclusively within the nanotube interior and implicates the glycol groups in facilitating efficient Li+ transduction. Linear sweep voltammetry and galvanostatic lithium plating-stripping tests reveal that this nanotube-based electrolyte is stable over a wide potential range and supports long-term cyclability. These findings demonstrate how the coupling of synthetic design and supramolecular structural control can yield high-performance ionic transporters that are amenable to device-relevant fabrication, as well as the technological potential of chemically designed self-assembled nanotubes.
- Strauss, Michael J.,Hwang, Insu,Evans, Austin M.,Natraj, Anusree,Aguilar-Enriquez, Xavier,Castano, Ioannina,Roesner, Emily K.,Choi, Jang Wook,Dichtel, William R.
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supporting information
p. 17655 - 17665
(2021/11/04)
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- Homoallylglycine residues are superior precursors to orthogonally modified thioether containing polypeptides
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Homoallylglycine N-carboxyanhydride, Hag NCA, monomers were synthesized and used to prepare polypeptides containing Hag segments with controllable lengths of up to 245 repeats. Poly(l-homoallylglycine), GHA, was found to adopt an α-helical conf
- Perlin, Pesach,Gharakhanian, Eric G.,Deming, Timothy J.
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p. 6196 - 6199
(2018/06/18)
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- Solid phase synthesis of oligoethylene glycol-functionalized quinolinecarboxamide foldamers with enhanced solubility properties
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A series of octameric quinoline oligoamide foldamers has been synthesized consisting exclusively of monomers which display mono-, di-, tri- or tetra-ethylene glycol side-chains. These oligomers adopt stable helical conformations. New Fmoc-acid monomer precursors were first developed. The microwave assisted solid-phase synthesis (SPS) methodology for oligomer preparation is described, and it is demonstrated that small adjustments in side-chain length translate into large differences in the solubility profile of the oligomers. The impact of such modifications on foldamer preparation, handedness inversion kinetics and potential applications is also discussed.
- Tsiamantas, Christos,Dawson, Simon J.,Huc, Ivan
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p. 132 - 142
(2016/03/23)
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- Interfacial strain-promoted alkyne-azide cycloaddition (I-SPAAC) for the synthesis of nanomaterial hybrids
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An interfacial strain promoted azide-alkyne cycloaddition (I-SPACC) is introduced as a method to prepare robust nanomaterial hybrids. This is demonstrated with a reaction between a novel dibenzocyclooctyne-modified single walled carbon nanotubes (DBCO-SWC
- Gobbo, Pierangelo,Novoa, Samantha,Biesinger, Mark C.,Workentin, Mark S.
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p. 3982 - 3984
(2013/07/25)
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- Improved methodology for the preparation of water-soluble maleimide-functionalized small gold nanoparticles
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Improved methodology to prepare maleimide-functionalized, water-soluble, small (3 nm) gold nanoparticles using a retro-Diels-Alder strategy that we developed for similar organic-soluble AuNP's is described. Importantly, our results suggest that a recent paper by Zhu, Waengler, Lennox, and Schirrmacher describing a similar strategy gave results inconsistent with the formation of the titled maleimide-modified AuNP (Zhu, J.; Waengler, C.; Lennox, R. B.; Schirrmacher, R. Langmuir2012, 28, 5508) as the major product, but consistent with the major product being an adduct derived from the hydrolysis of maleimide formed under the conditions used for the required deprotection of the maleimide. Our methodology provides an efficient and accessible route to pure maleimide-modified small AuNP's that circumvents the formation of the hydrolysis product. The maleimide-modified small AuNP's are versatile because they are soluble in water and in a wide range of organic solvents and their reactivity can now be properly exploited as a reactive moiety in Michael addition for bioconjugation studies in aqueous solution.
- Gobbo, Pierangelo,Workentin, Mark S.
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p. 12357 - 12363
(2012/11/07)
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- Amphiphilic silicone architectures via anaerobic Thiol-Ene chemistry
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Despite broad application, few silicone-based surfactants of known structure or, therefore, surfactancy have been prepared because of an absence of selective routes and instability of silicones to acid and base. Herein the synthesis of a library of explic
- Keddie, Daniel J.,Grande, John B.,Gonzaga, Ferdinand,Brook, Michael A.,Dargaville, Tim R.
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supporting information; experimental part
p. 6006 - 6009
(2012/01/06)
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- Biofunctional silicon nanoparticles by means of thiol-ene click chemistry
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The preparation and characterization of butylene-terminated silicon nanoparticles (SiNPs) and their functionalization using thiol-ene chemistry is described, as well as the coupling of DNA strands. Bromide-terminated SiNPs were prepared by means of the oxidation of magnesium silicide and functionalized with butylene chains through treatment with the corresponding Grignard reagent. The successful coupling was confirmed by NMR and FTIR spectroscopy. TEM measurements revealed a silicon-core diameter of (2.4±0.5)nm. The fluorescence emission maximum is at λmax=525nm when excited at λexc=430nm. The conjugation of these alkene-terminated SiNPs by means of thiol-ene chemistry is described for a variety of functional thiols. Efficient coupling was evidenced by NMR and FTIR spectroscopy. Moreover, the characteristic fluorescence properties of the SiNPs remained unaltered, thus demonstrating the value of this approach towards functional oxide-free SiNPs. Activation of the attached carboxylic acid moieties allowed for conjugation of NH2-terminated oligo-ssDNA (ss=single strand) to the SiNPs. Successful coupling was confirmed by a characteristic new UV absorption band at 260nm, and by the still-present distinctive fluorescence of the SiNPs at 525nm. Gel electrophoresis confirmed coupling of 2 to 3 DNA strands onto the SiNPs, whereas no uncoupled DNA was observed.
- Ruizendaal, Loes,Pujari, Sidharam P.,Gevaerts, Veronique,Paulusse, Jos M. J.,Zuilhof, Han
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supporting information; experimental part
p. 2776 - 2786
(2012/06/01)
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- Mono-amine functionalized phthalocyanines: Microwave-assisted solid-phase synthesis and bioconjugation strategies
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(Chemical Equation Presented) Phthalocyanines (Pcs) are excellent candidates for use as fluors for near-infrared (near-IR) fluorescent tagging of biomolecules for a wide variety of bioanalytical applications. Monofunctionalized Pcs, having two different t
- Erdem, S. Sibel,Nesterova, Irina V.,Soper, Steven A.,Hammer, Robert P.
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supporting information; experimental part
p. 9280 - 9286
(2010/03/24)
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- Conversion of alcohols to thiols via tosylate intermediates
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High yielding syntheses of mercapto terminated mono-disperse dimer, trimer, and tetramer ethyleneoxide oligomers and of p-hydroxyphenethyl thiol via an alcohol-tosylate-thiol route are reported. Comparisons are made with the more conventional alcohol-bromide-thiol route.
- Snow, Arthur W.,Foos, Edward E.
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p. 509 - 512
(2007/10/03)
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- Synthesis and characterization of novel tetra- and octa-triethyleneoxysulfanyl substituted phthalocyanines forming lyotropic mesophases
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Metal-free phthalocyanines and nickel phthalocyanines carrying four or eight oligo(ethyleneoxy)thia groups of peripheral positions have been synthesized from new phthalonitrile derivatives. These phthalocyanine derivatives were characterized both thermotropic and lyotropic mesophases by DSC and X-ray.
- Dabak, Salih,Ahsen, Vefa,Heinemann, Frauke,Zugenmaier, Peter
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p. 111 - 127
(2007/10/03)
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- 2-sulphinyl-acetyl-1,3-thiazolidines, their preparation and pharmaceutical compositions
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Thiazolidines of formula I STR1 wherein R is H, C1 -C4 -alkyl, allyl or propargyl; X is O, CH2, S; R1 is C1 -C6 -linear or branched alkyl, phenyl, benzyl, or a group of formula CH2 --CH2 --O--(CH2 --CH2 --O)n --Ra wherein n is zero or an integer from 1 to 3 and Ra is H, benzyl or C1 -C6 -linear or branched alkyl. Compounds I are endowed with favourable therapeutical properties for pathologies of the respiratory system.
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- 2-Sulphinyl-acetyl-1,3-thiazolidines, their preparation and pharmaceutical compositions
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Thiazolidines of formula I - wherein R is H, C1-C4-alkyl, allyl or propargyl;, - X is O, CH2, S;, - R1 is C1-C6-linear or branched alkyl, phenyl, benzyl, or a group of formula CH2-CH2-O-(CH2-CH2-O)n-Ra, wherein n is zero or an integer from 1 to 3 and Ra is H, benzyl or C1-C6-linear or branched alkyl. Compounds I are endowed with favourable therapeuti-cal properties for pathologies of the respiratory system.
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