A series of novel porous polymer frameworks (PPFs) with [3 + 4] structure motif have been synthesized from readily accessible building blocks via imine condensation, and the dependence of gas adsorption properties on the building block dimensions and functionalities was studied. The resulting imine-linked frameworks exhibit high surface area: the Brunauer–Emmett–Teller (BET) specific surface area up to 1740 m2 g–1, and a Langmuir surface area up to 2157 m2 g–1. More importantly, the porous frameworks exhibit outstanding H2 (up to 2.75 wt %, 77 K, 1 bar), CO2 (up to 26.7 wt %, 273 K, 1 bar), CH4 (up to 2.43 wt %, 273 K, 1 bar), and C2H2 (up to 17.9 wt %, 273 K, 1 bar) uptake, which are among the highest reported for organic porous materials. PPFs exhibit good ideal selectivities for CO2/N2 (14.5/1–20.4/1), and CO2/CH4 adsorption (8.6/1–11.0/1), and high thermal stabilities (up to 500 °C), thus showing a great potential in gas storage and separation applications.
Substituted trimethylammonium cations serve as small molecule analogues for tetherable cations in anion exchange membranes. In turn, these membranes serve as the basis for alkaline membrane fuel cells by allowing facile conduction of hydroxide. As these cations are susceptible to hydroxide attack, they degrade over time and greatly limit the lifetime of the fuel cell. In this research, we performed density functional theory calculations to investigate the degradation pathways of substituted trimethylammonium cations to probe the relative durability of cation tethering strategies in alkyl and aromatic tethers. Our results show that significant changes in calculated energy barriers occur when substitution groups change. Specifically, we have found that, when available, the Hofmann elimination pathway is the most vulnerable pathway for degradation; however, this barrier is also found to depend on the carbon chain length and number of hydrogens susceptible to Hofmann elimination. SN2 barriers were also investigated for both methyl groups and substitution groups. The reported findings give important insight into potential tethering strategies for trimethylammonium cations in anion exchange membranes.
A series of novel organic cage compounds 1-4 were successfully synthesized from readily available starting materials in one-pot in decent to excellent yields (46-90%) through a dynamic covalent chemistry approach (imine condensation reaction). Covalently cross-linked cage framework 14 was obtained through the cage-to-framework strategy via the Sonogashira coupling of cage 4 with the 1,4-diethynylbenzene linker molecule. Cage compounds 1-4 and framework 14 exhibited exceptional high ideal selectivity (36/1-138/1) in adsorption of CO(2) over N(2) under the standard temperature and pressure (STP, 20 °C, 1 bar). Gas adsorption studies indicate that the high selectivity is provided not only by the amino group density (mol/g), but also by the intrinsic pore size of the cage structure (distance between the top and bottom panels), which can be tuned by judiciously choosing building blocks of different size. The systematic studies on the structure-property relationship of this novel class of organic cages are reported herein for the first time; they provide critical knowledge on the rational design principle of these cage-based porous materials that have shown great potential in gas separation and carbon capture applications.
The structure and properties of oligonucleotide conjugates possessing stilbenedicarboxamide chromophores at both ends of a poly(dA):poly(dT) base-pair domain of variable length have been investigated using a combination of spectroscopic and computational methods. These conjugates form capped hairpin structures in which one stilbene serves as a hairpin linker and the other as a hydrophobic end-cap. The capping stilbene stabilizes the hairpin structures by ca. 2 kcal/mol, making possible the formation of a stable folded structure containing a single A:T base pair. Exciton coupling between the stilbene chromophores has little effect on the absorption bands of capped hairpins. However, exciton-coupled circular dichroism (EC-CD) can be observed for capped hairpins possessing as many as 11 base pairs. Both the sign and intensity of the EC-CD spectrum are sensitive to the number of base pairs separating the stilbene chromophores, as a consequence of the distance and angular dependence of exciton coupling. Calculated spectra obtained using a static vector model based on canonical B-DNA are in good agreement with the experimental spectra. Molecular dynamics simulations show that conformational fluctuations of the capped hairpins result in large deviations of the averaged spectra in both the positive and negative directions. These results demonstrate for the first time the ability of B-DNA to serve as a helical ruler for the study of electronic interactions between aligned chromophores. Furthermore, they provide important tests for atomistic theoretical models of DNA.
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