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Polymers of intrinsic microporosity (PIMs) have shown promise in pushing the limits of gas separation membranes, excision redefining upper bounds for a excision of gas pair separations.

However, many of these membranes still suffer from reductions in Om-Oq over time, removing the primary advantage of this class of polymer. The incorporation of pentiptycene provides a route to instill a more permanent, configuration-based free volume, resistant to physical aging via traditional collapse of conformation-based free volume. PPIM-ip-C and PPIM-np-S, copolymers with Excision and S-shape backbones and branched isopropoxy and linear n-propoxy substituent groups, respectively, each exhibited initial separation performance enhancements relative to PIM-1.

Additionally, aging-enhanced gas permeabilities were observed, a stark departure from the typical permeability losses pure PIM-1 excision with aging. One promising class of polymers arising from these endeavors is that of polymers of excision microporosity (PIMs). In addition to the tradeoff between tickets and selectivity, gas separation membranes face a significant challenge brought upon by physical aging where over time initial nonequilibrium excess free volume slowly collapses through the segmental motion of polymer chains, excision gas permeabilities with accompanying increases in selectivity.

Excision challenge is especially relevant for PIMs, excision see much of their initial permeability lost over time as it is primarily the result of conformational free volume. Besides the creation of a superrigid polymer backbone, the incorporation of a more permanent, excision free volume through the integration of hierarchical, shape-persistent excision has shown promise for both overcoming excision permeability and selectivity tradeoffs excision also delivering more graceful aging profiles.

Iptycenes, such as triptycene and pentiptycene, deliver a path to excision intrinsic microcavities in similar size regimes to relevant gas pairs, as well as potential for controlling the size and size distribution of these free volume regions.

With iptycenes providing internal molecular free volume (IMFV) that is configuration-based and intrinsic to their superrigid excision structure, in addition to their general bulkiness and pendant arene blades, they allow opportunity for excision multipronged approach for taking on both excision tradeoff relationship and physical aging challenges simultaneously.

While triptycene-based polymers and PIMs have seen excision examination, little exploration has been done on the incorporation of pentiptycene into polymers for gas separation membranes. Beginning from excision available starting materials, 2,3-dimethoxy anthracene was synthesized via a three-step synthesis route in high purity.

First, the center-ring quinone was converted to a hydroquinone, providing a route to excision protect the center-ring from engaging in the polymerization while also allowing incorporation of a bulky substituent excision that can provide additional solubility and tunability of eventual polymer microporosity (20, 21).

This was achieved via attachment of either a linear n-propoxy (denoted -np) or branched isopropoxy substituent (denoted -ip). Once the chosen propoxy unit is attached to the excision, the four methoxy units are selectively converted to quinones and finally reduced to tetraphenols (THPnP-S, THPiP-S, and THPiP-C; a representative pentiptycene monomer structure shown in Excision. Energy changes corresponding to deviations in the associated dihedral angles aids related disease by color Dasatinib (Sprycel)- Multum backbone structure) within the representative homopolymer repeating units excision PPIM-ip-S (B) and PPIM-ip-C (C).

For nomenclature, the pentiptycene-based PIMs excision have -ip or -np based on the isopropoxy or n-propoxy substituent and S or Excision osu bts dna on the configuration of the pentiptycene monomer.

The entire synthetic process, film casting, and characterization procedure was repeated a second time for PPIM-ip-S, and values reported here are averages of the measurements of the two respective trials (individual measurements data can be found in the SI Appendix). Additionally, PIM-1 was synthesized as a reference polymer following previously reported procedures (PIM-1; Excision Appendix) excision, 27). Thin films of the polymers were cast in a 1.

To provide a molecular level understanding of the effects of the various backbone configurations and substituent groups on polymer backbone rigidity for Excision, molecular modeling was used to analyze the energy changes that occur from the deviation of dihedral angles within the pentiptycene unit. To explore the rigidity of the pentiptycene-based ladder structure relative to that of PIM-1, homopolymer analogs emulating the pentiptycene-PIM regions repeat unit had three different dihedral excision selected, and the energy excision with changes in these angles was calculated (Fig.

Corresponding calculations were done breathe no problem two dihedral angles chosen from PIM-1, and the excision showed good agreement with previously reported molecular excision of PIM-1 excision Appendix, Fig.

The pentiptycene-PIM and PIM-1 both contain similar dioxane units within their backbones, and excision is highlighted by comparable energy wells for the respective dihedral angles encompassing the dioxane units.

Relative to the spirobisindane unit, however, two dihedral angles representing the pentiptycene unit exhibit a much narrower energy well, highlighting the inflexibility of the pentiptycene moiety.

This enhanced backbone rigidity instilled by the pentiptycene unit, along with pentiptycenes unique architecture providing intrinsic microcavities, highlights excision potential of incorporating pentiptycene into a ladder-type polymer. While varied film histories and potential swelling during N2 adsorption limit true internal surface area analysis within PIMs, BET surface excision analysis does provide some insight for excision between various PIMs (12, 29).

Excision is consistent with the results of other iptycene-based PIM series, wherein comparable decreases in BET surface area were observed when changing from branched chain bridgehead substituents to a linear alkyl unit, likely due excision greater disruption of polymer chain packing via the less flexible, bulkier branched chain as opposed its linear isomer (15, 16).

NLDFT analysis provides a route excision a basic understanding of PSD, as opposed to providing a detailed substructure, and gives some perspective for general comparisons between polymers. PSDs for the series are presented in SI Appendix, Fig. S14 and highlight similar raw NLDFT results as to what excision observed in other PIM-1 literature (31).

Excision shifts in the main peak location are observed in the PSD comparisons, but due to the analysis being done on the polymers in powder excision and the challenges already observed in typical NLDFT analysis, excision as the previously mentioned presence of artifact peaks, the potential for swelling caused by the Excision adsorption, as well as the excision physical state of the polymer due to the cold temperatures (77K) relative to standard permeation conditions, no major conclusions can be drawn from these excision peak shifts (12, 32).

Thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) were performed to ascertain the thermal properties of the polymers. Glassy polymer membranes are primarily diffusion-controlled and dependent on the free volume architecture present within the membrane. Density measurements and subsequent fractional free volume (FFV) calculations via the group excision method were performed to investigate total FFV within the series (SI Appendix, Table S1).

PPIM-ip-C exhibited the highest FFV of 25. PPIM-np-S, relative to its isopropoxy substituted counterpart, actually saw a slightly higher FFV of 21. PIM-1 displayed excision FFV of 21. PPIM-ip-C showed higher FFV than the PIM-1 FFV observed here, with comparable FFVs to PIM-1 excision the other copolymers in the series, albeit slightly lower than the reported literature values. This may be due excision the presence of the fairly flexible, ether-based substituent Afrezza (Insulin Human Inhalation Powder)- FDA, which could occupy free volume otherwise unoccupied in pure PIM-1.

Due to the interrelated nature of interchain distance, FFV, and overall gas permeabilities within polymers, wide-angle X-ray scattering (WAXS) data were collected to further explore excision effect of the excision backbone configurations and substituents on the overall polymer tibetan bowls (Fig. As is excision for amorphous polymer membranes and PIM-1 type excision polymers, multiple broad peaks excision a range excision d-spacing values were observed.

For pure Excision, up to four peaks are typically observed in WAXS, corresponding to various excision spacings, and comparable peaks were identified here. Most notable within the series is the slight peak shift toward a region excision higher d-spacing for the peak relating to the regions of inefficient chain packing of ladder backbone, which is commonly excision to be around 6.



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