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At least 307 records · Page 17

Pressure-stable supported ionic liquid membranes using isoporous supports for evaluating pure- and mixed-gas light paraffin fractionation

Advances in horizontal drilling and hydraulic fracturing have spurred the growth of domestic U.S. energy production. Membranes, typically silicone rubbers, have found utility in shale gas treatment as fuel gas conditioning units to selectively remove C 2 + hydrocarbons at pressures up to 30 bar, producing clean CH 4 for gas engines. However, more selective materials could be beneficial for broader shale gas treatment applications, such as dew point control units. Supported ionic liquid membranes (SILMs) offer a potential opportunity for improving C 3 H 8 /CH 4 selectivity, but they lack pressure-stability. Here, we report C 3 H 8 /CH 4 selective and pressure-stable SILMs using isoporous supports. SILMs with supports that had minimal defects remained stable up to 15 bar of transmembrane pressure. This stability allowed for pure- and mixed-gas testing of the resulting membranes at elevated pressures. Furthermore, these tests revealed that low viscosity ILs (<100 cp) may display mixed-gas permeances and permselectivity nearly identical to pure-gas results. On the other hand, higher viscosity ILs may display increasing permeances and permselectivity with increasing C 3 H 8 fugacity, similar to rubbery polymers. Ultimately, the SILMs demonstrated relatively high pressure-stability due to the isoporous supports and competitive mixed-gas C 3 H 8 /CH 4 permselectivity compared to silicone rubber.

Rosenthal, Justin J. [University of Texas at Austi↗

Molecular dynamics simulations of a dicationic ionic liquid for CO 2 capture

A dicationic ionic liquid ([DBU-PEG][Tf 2 N] 2 ) was studied using classical molecular dynamics simulations to examine its structural and gas separation properties. The dication was designed in an attempt to improve CO 2 solubility by means of tuning the cation-anion interactions of the ionic liquid (IL). The computational model was compared to experimentally obtained density, viscosity, and powder X-ray diffraction spectra. The structure of the IL was further investigated with radial distribution functions and free volume analysis through cavity distributions. It was found that the shape and charge distribution of the dication enhances CO 2 interaction: the CO 2 molecule is hugged by the dication along the PEG linker and close to one of the cationic ends. Here, the geminal design of the dication allows for strong interaction with CO 2 , showing promise as a means of carbon capture.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Why does a phosphonium-phosphinate ionic liquid protect the contact surfaces from wear and micropitting but increase vibration when used as an additive in rolling-sliding lubrication?

A phosphonium-phosphinate ionic liquid (IL) was studied as a lubricant additive for rolling-sliding contacts. The bench-scale test was designed to simulate automotive rear axle operation during cold start, highway towing, and overload conditions. Adding such an IL (2%) into a base oil significantly reduced wear loss and rolling contact fatigue, e.g., microcracking and micropitting, but made the vibrational noise notably higher under a low (-1.5%) sliding roll ratio (SRR). Additionally, worn surface characterization revealed an interesting texture pattern with alternating smoother plateaus and rougher valleys, which is believed to cause the high vibration. No increased vibration was observed at a high (-30%) SRR, possibly because the more aggressive sliding abrasion prevented such a surface texture from forming.

36 MATERIALS SCIENCE↗

Exosomes derived from thymic stromal lymphopoietin-treated dendritic cells regulate T helper 17/regulatory T cell differentiation via miR-21/Smad7 axis

Highlights: • Exosomes from TSLP-treated DCs promote Th17 differentiation. • Exosomes from TSLP-treated DCs inhibit Tregs differentiation. • MiR-21 is highly expressed in exosomes from TSLP-treated DCs. • Exosomal miR-21 regulates Th17/Treg differentiation by targeting Smad7. Thymic stromal lymphopoietin (TSLP) is associated with fungal keratitis. This work aims to investigate whether TSLP can regulate T helper (Th) 17 and regulatory T cell (Treg) differentiation. We separated dendritic cells (DCs) from peripheral blood of healthy volunteers. DCs were treated with TSLP to activate DCs, and exosomes were obtained. CD{sup +} T cells were incubated with exosomes from TSLP-treated DCs. We found that exosomes from TSLP-treated DCs notably promoted the proportions of Th17 cells and inhibited the proportions of Tregs in the CD4{sup +} T cells. Moreover, exosomes from TSLP-treated DCs enhanced the expression of retinoid-related orphan receptor γt (RORγt) and interleukin 17 (IL-17), and repressed the expression of forkhead box protein P3 (Foxp3) and interleukin 10 (IL-10) in the CD4{sup +} T cells. Furthermore, miR-21 was highly expressed in exosomes from TSLP-treated DCs. Exosomes from TSLP-treated miR-21-silenced DCs promoted Treg differentiation and suppressed Th17 differentiation. Smad7 up-regulation repressed Th17 differentiation and enhanced Treg differentiation, which was abolished by miR-21 overexpression. Smad7 overexpression rescued the effect of exosomes from TSLP-treated DCs on Th17/Treg differentiation. In conclusion, our article confirms that TSLP induces DCs to deliver miR-21 by secreting exosomes, and thus miR-21 regulates Th17/Treg differentiation by inhibiting Smad7. Thus, this work further reveals the biological role of miR-21 in fungal keratitis.

60 APPLIED LIFE SCIENCES↗

Long noncoding RNA MEG3 expressed in human dental pulp regulates LPS-Induced inflammation and odontogenic differentiation in pulpitis

Highlights: • LncRNA MEG3, upregulated in inflamed dental pulp, is involved in the inflammation and regeneration in pulpitis. • The expression of lncRNA MEG3 was semiquantitatively detected in the pulp tissue by the innovative RNAscope® technique. • MEG3 downregulation can inhibit inflammatory cytokines secretion and also promote the odontogenic differentiation of hDPCs. • LncRNA MEG3 can be a potential therapeutic target in the inflammation and regeneration of dentin-pulp complex in pulpitis. Pulpitis refers to inflammation of the inner pulp by invading microbes, and tissue repair occurs due to odontogenic differentiation of human dental pulp cells (hDPCs) with multidifferentiation potential. Long noncoding RNAs (lncRNAs) can modulate numerous pathological and biological processes; however, the role of lncRNAs in the inflammation and regeneration of the dentin-pulp complex in pulpitis is unclear. Here, we performed high-throughput sequencing to identify differentially expressed lncRNAs between human normal and inflamed pulp and concluded that lncMEG3 (lncRNA maternally expressed gene 3, MEG3) was signicantly upregulated in both inflamed pulp and LPS-treated hDPCs. MEG3 expression in the pulp tissue was detected using the RNAscope® technique. RNA pulldown assays identified the MEG3-interacting proteins and the potential mechanisms. With MEG3 knockdown, we investigated the role of MEG3 in the secretion of inflammatory cytokines in LPS-treated hDPCs and odontogenic differentiation of hDPCs. MEG3 downregulation inhibited the secretion of TNF-α, IL-1β and IL-6 in LPS-treated hDPCs, and the p38/MAPK signaling pathway may be related to this effect. MEG3 knockdown promoted odontogenic differentiation of hDPCs by regulating the Wnt/β-catenin signaling pathway. Our study suggested that MEG3 has a negative effect on inflammation and regeneration of the dentin-pulp complex in pulpitis.

60 APPLIED LIFE SCIENCES↗

Crosstalk between cyclophilins and T lymphocytes in coronary artery disease

Highlights: • CD147 receptor expression is elevated in T lymphocytes from CAD patients. • Intracellular CypA and B expression are augmented in T lymphocytes from CAD patients. • CypA, B and C, and IL-1β and IL-6 serum levels are increased in patients with CAD. • CypA and B levels in T lymphocytes are correlated with CypA and B serum levels, respectively. Cardiovascular diseases and atherosclerosis are currently some of the most widespread diseases of our time. Within cardiovascular disease, coronary artery disease and underlying atherosclerosis were recently linked with systemic and local inflammation. Cyclophilins participate in the initiation and progression of these inflammatory-related diseases. Cyclophilins are released into the extracellular space upon inflammatory stimuli and participate in the pathology of cardiovascular diseases. The cell surface receptor for extracellular cyclophilins, the CD147 receptor, also contributes to coronary artery disease pathogenesis. Nevertheless, the physiological relevance of cyclophilin's family and their receptor in cardiovascular diseases remains unclear. The present study aimed to better understand the role of cyclophilins in cardiovascular artery disease and their relationship with inflammation. Hence, cyclophilins and pro-inflammatory interleukins were measured in the serum of 30 subjects (divided into three groups according to coronary artery disease status: 10 patients with acute coronary syndrome, 10 patients with chronic coronary artery disease, and 10 control volunteers). In addition, cyclophilin levels and CD147 receptor expression were measured in T lymphocytes purified from these subjects. Cyclophilin A, B, and C, pro-inflammatory interleukins, and CD147 membrane expression were significantly elevated in patients with coronary artery disease.

60 APPLIED LIFE SCIENCES↗

Ergothioneine alleviates senescence of fibroblasts induced by UVB damage of keratinocytes via activation of the Nrf2/HO-1 pathway and HSP70 in keratinocytes

Highlights: • EGT activated Nrf2/HO-1 pathway and HSP70 in UVB-irradiated keratinocytes. • EGT alleviated ROS production, apoptosis, and inflammation in UVB-irradiated keratinocytes. • EGT suppressed senescence and collagen imbalance in fibroblasts by inhibiting the keratinocyte-secreted factors. • EGT suppresses photoaging by UVB irradiation in a keratinocyte/fibroblast co-culture system. Ultraviolet B (UVB) irradiation induces skin damage and photoaging through several deleterious effects, including generation of reactive oxygen species (ROS), apoptosis of epidermal cells, inflammation, and collagen degradation in fibroblasts. Ergothioneine (EGT) is a naturally occurring amino acid with potential biological properties. We evaluated whether EGT protects against UVB-induced photoaging using a keratinocyte/fibroblast co-culture system. Keratinocytes were pretreated with EGT, irradiated with UVB, and co-cultured with fibroblasts. In keratinocytes, ROS production and apoptosis were assessed. We also analyzed the Nrf2/HO-1 pathway, HSP70, proapoptotic proteins, and paracrine cytokines by Western blotting and real-time PCR. Collagen degradation-related genes and senescence were also assessed in fibroblasts. EGT pretreatment of keratinocytes significantly inhibited downregulation of the Nrf2/HO-1 pathway and HSP70, and protected keratinocytes by suppressing production of ROS and cleavage of proapoptotic proteins, including caspase-8 and PARP. Furthermore, EGT significantly reduced the paracrine cytokines, including IL-1β, IL-6, and TNF-α. In co-cultures of fibroblasts with EGT-treated keratinocytes, the expression levels of collagen degradation-related genes and fibroblast senescence were significantly decreased; however, synthesis of procollagen type I was significantly increased. Our results confirm that EGT suppresses the modification of collagen homeostasis in fibroblasts by preventing downregulation of the Nrf2/HO-1 pathway and HSP70 in keratinocytes following UVB irradiation.

60 APPLIED LIFE SCIENCES↗

Up-regulating TIPE2 alleviates inflammatory pain by suppressing microglial activation-mediated inflammatory response via inhibiting Rac1/NF-κB pathway

TNF-α-inducible protein 8-like 2 (TIPE2) is a recently discovered regulator of inflammation that can maintain immune homeostasis, exerting a significant role in the development of inflammation-related diseases. Here, we aimed to explore the role and potential regulatory mechanism of TIPE2 in the progression of inflammatory pain. In the present study, a mouse BV2 microglia cell activation-mediated inflammatory model was developed with LPS induction, and a mouse inflammatory pain model was established with complete Freund's adjuvant (CFA) injection. In vitro, the TIPE2 expression was decreased in LPS-induced BV2 cells. Overexpression of TIPE2 mitigated LPS-medicated microglial activation via decreasing nitric oxide (NO) generation and the expression of microglia marker IBA-1. Notably, increasing TIPE2 expression alleviated microglial activation-triggered expression levels and releases of proinflammatory factors such as TNF-α, IL-1β, and IL-6. Mechanism analysis verified that overexpression of TIPE2 blunted Rac1-mediated activation of NF-κB pathway following LPS stimulation. More importantly, CFA injection reduced the expression of TIPE2 in a mouse inflammatory pain model and overexpression of TIPE2 alleviated CFA-mediated pain hypersensitivity and inflammatory response, and inactivated microglia cell in vivo. Furthermore, overexpression of TIPE2 decreased Rac1 expression and suppressed the activation of NF-κB pathway in spinal cord after CFA injection. In summary, the present study revealed that overexpression of TIPE2 mitigated inflammatory pain through suppressing microglial activation-induced inflammation by inactivating Rac1/NF-κB pathway. The study provides a novel theoretical foundation for the therapy of inflammatory pain.

60 APPLIED LIFE SCIENCES↗

Necrosulfonamide reverses pyroptosis-induced inhibition of proliferation and differentiation of osteoblasts through the NLRP3/caspase-1/GSDMD pathway

The acute inflammatory stimulation occurring after a bone fracture regulates the repair and healing of local bone injury; however, under certain conditions, pyroptosis may occur in osteoblasts, which affects osteoblast proliferation and differentiation, thereby affecting the growth, development and morphological changes of bone tissue. The aim of the present study was to examine the effect of the pyroptosis inhibitor necrosulfonamide (NSA) on the proliferation and differentiation of osteoblasts and elucidate the underlying mechanism. The results revealed that NSA reversed the effects of ATP/lipopolysaccharide (LPS) on cell viability and pyroptosis, and on the mRNA and protein expression of pyroptosis-related genes. It also suppressed the secretion of IL-6, TNF-α and IL-1β and reversed the effects of ATP/LPS on the activity of ALP and the mRNA expression of differentiation-related genes in osteoblasts. The fact that overexpression of caspase-1, gasdermin D (GSDMD) and NLRP3 abolished the effects of NSA on the viability and pyroptosis of osteoblasts, as well as the mRNA expression of differentiation-related genes and the activity of ALP in osteoblasts, indicated that NSA promoted the proliferation and differentiation of osteoblasts by inhibiting the NLRP3/caspase-1/GSDMD pyroptosis pathway. The present study provides proof supporting the potential application of NSA for improving the function of osteoblasts in fracture repair and indicates the value of the NLRP3/caspase-1/GSDMD pyroptosis pathway as a pharmaceutical target.

60 APPLIED LIFE SCIENCES↗

Development of a recombinant anti-VEGFR2-EPCAM bispecific antibody to improve antiangiogenic efficiency

Highlights: • Targeted therapy can be a useful therapeutic method along with traditional methods for breast cancer treatment. • Decreasing Akt/Nf-Kβ signaling pathway is crucial target in order to decreasing angiogenesis in TNBC. • The recombinant antibody can have inhibitory effects on production IL6,8, MMP2, and MMP9. Tumor progression and metastasis, especially in invasive cancers (such as triple-negative breast cancer [TNBC]), depend on angiogenesis, in which vascular epithelial growth factor (VEGF)/vascular epithelial growth factor receptor [1] has a decisive role, followed by the metastatic spread of cancer cells. Although some studies have shown that anti-VEGFR2/VEGF monoclonal antibodies demonstrated favorable results in the clinic, this approach is not efficient, and further investigations are needed to improve the quality of cancer treatment. Besides, the increased expression of epithelial cell adhesion molecule (EpCAM) in various cancers, for instance, invasive breast cancer, contributes to angiogenesis, facilitating the migration of tumor cells to other parts of the body. Thus, the main goal of our study was to target either VEGFR2 or EpCAM as pivotal players in the progression of angiogenesis in breast cancer. Regarding cancer therapy, the production of bispecific antibodies is easier and more cost-effective compared to monoclonal antibodies, targeting more than one antigen or receptor; for this reason, we produced a recombinant antibody to target cells expressing EpCAM and VEGFR2 via a bispecific antibody to decrease the proliferation and metastasis of tumor cells. Following the cloning and expression of our desired anti-VEGFR2/EPCAM sequence in E. coli, the accuracy of the expression was confirmed by Western blot analysis, and its binding activities to VEGFR2 and EPCAM on MDA-MB-231 and MCF-7 cell lines were respectively indicated by flow cytometry. Then, its anti-proliferative potential was indicated by 3-(4,5-dimethylthiazol-2-yl)-2,5-diphenyltetrazolium bromide (MTT) and apoptosis assay to evaluate inhibitory effects of the antibody on tumor cells. Subsequently, the data indicated that migration, invasion, and angiogenesis were inhibited in breast cancer cell lines via the bispecific antibody. Furthermore, cytokine analysis indicated that the bispecific antibody could moderate interleukin 8 (IL-8) and IL-6 as key mediators in angiogenesis progression in breast cancer. Thus, our bispecific antibody could be considered as a promising candidate tool to decrease angiogenesis in TNBC.

60 APPLIED LIFE SCIENCES↗

Establishment and characterization of a novel conditionally immortalized human parietal epithelial cell line

Highlights: • A novel conditionally immortalized human parietal epithelial cell (ciPEC) line was created. • ciPECs were isolated out of fresh human kidney tissue from an infant. • ciPECs show specific PEC characteristics. • ciPECs show no or little podocyte and glomerular endothelial cell marker expression. • ciPECs can be activated by IL-1β treatment. Parietal epithelial cells (PECs) are epithelial cells in the kidney, surrounding Bowman's space. When activated, PECs increase in cell volume, proliferate, migrate to the glomerular tuft and excrete extracellular matrix. Activated PECs are crucially involved in the formation of sclerotic lesions, seen in focal segmental glomerulosclerosis (FSGS). In FSGS, a number of glomeruli show segmental sclerotic lesions. Further disease progression will lead to increasing number of involved glomeruli and gradual destruction of the affected glomeruli. Although the involvement of PECs in FSGS has been acknowledged, little is known about the molecular processes driving PEC activation. To get more insights in this process, accurate in vivo and in vitro models are needed. Here, we describe the development and characterization of a novel conditionally immortalized human PEC (ciPEC) line. We demonstrated that ciPECs are differentiated when grown under growth-restrictive conditions and express important PEC-specific markers, while lacking podocyte and endothelial markers. In addition, ciPECs showed PEC-like morphology and responded to IL-1β treatment. We therefore conclude that we have successfully generated a novel PEC line, which can be used for future studies on the role of PECs in FSGS.

60 APPLIED LIFE SCIENCES↗

Anhydrous vs Hydrated f-Element Acetate Polymers Dictated by the Stoichiometry of Protic Acidic/Basic Azole Mixtures

Continuing our investigations of ionic liquid (IL) based routes to a library of f-element/soft donor complexes which could be studied crystallographically, we have explored the dissolution of f-element salts in protic imidazole-based ILs containing only soft donors at high temperatures to drive off volatiles, including water and carboxylic or mineral acids. Here we present our results, reacting acidic and basic azoles in 1:3 or 1:1 stoichiometric compositions at elevated temperature, followed by saturation with Nd(OAc) 3 ·xH 2 O or Ce(OAc) 3 ·xH 2 O, which led to 13 new metal–acetate polymeric complexes identified by single-crystal X-ray diffraction. We found that the diversity in coordination modes of the simple acetate ligand that interfere with substitution of the softer N donors led to several readily crystallizable complexes forming two distinct groups with respect to f-element interaction with the ionic liquid precursors. When the acidic/basic azole ratio was 1:3, acetate and a neutral basic azole were found to be coordinated to the metal centers but no water, although in one case (2) water was observed in the secondary coordination sphere: [Ce(μ 2 -OAc) 3 (C 1 im)] n (1, C 1 im = 1-methylimidazole), [Nd(μ 2 -(OAc) 3 (C 1 im)] n ·nH 2 O (2), [Ce(μ 2 -OAc) 3 (C 2 im)] n (3, C 2 im = 1-ethylimidazole), [Ln(μ 2 -OAc) 3 DMF] n (Ln = Nd (4), Ce (5); dimethylformamide (DMF) was substituted for the azole mixture), and [Nd(μ 2 -OAc) 3 (C 4 im)] n (6, C 4 im = 1-butylimidazole). However, when the stoichiometric ratio was 1:1, water was always observed coordinated to the metal ions with the acidic azole included in the structure as a solvate or cocrystal, despite a higher reaction temperature: [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(1,2,3-Taz) (7, 1,2,3-Taz = 1,2,3-triazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(4,5-DCim) (Ln = Nd (8), Ce (9), 4,5-DCim = 4,5-dicyanoimidazole), [Ln(μ 2 -OAc) 3 (OH 2 )] n ·n(3,5-diNH 2 -1,2,4-Taz) (Ln = Nd (10), Ce (11), 3,5-diNH 2 -1,2,4-Taz = 3,5-diamino-1,2,4-triazole), [Ce(μ 2 -OAc) 3 (OH 2 )] n ·n(3-NH 2 -1,2,4-Taz) (12, 3-NH 2 -1,2,4-Taz = 3-amino-1,2,4-triazole), and [Nd(μ 2 -OAc) 3 (OH 2 )] n ·n(5-NH 2 -Tz) (13, 5-NH2-Tz = 5-aminotetrazole). All of the compounds retain the Ln:OAc– ratio of 1:3 and form 1D polymeric chains; however, they exhibit a variety of coordination modes affecting the degree of chain condensation. The isolation of both hydrated and anhydrous products revealed different abilities of the investigated soft N-donors to compete with O-donors finding their place in the coordination sphere of the lanthanide or in the crystal lattice.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Recent Advances in the Use of Ionic Liquids and Deep Eutectic Solvents for Lignocellulosic Biorefineries and Biobased Chemical and Material Production

Biorefineries, which process biomass feedstocks into valuable (bio)products, aim to replace fossil fuel-based refineries to produce energy and chemicals, reducing environmental and health hazards, including climate change, and supporting a sustainable economy. In particular, lignocellulose-based biorefineries, utilizing the most abundant renewable feedstock on Earth, have significant potential to supply sustainable energy, chemicals and materials. Ionic liquids (ILs, organic salts with low melting temperatures) and deep eutectic solvents (DESs, mixtures with eutectic points lower than the ideal mixture) are capable of dissolving some of the key lignocellulose polymers, and even the whole biomass. Furthermore, they have intrinsic advantages over molecular solvents, including safer usage profiles and high tunability, which allow tailored physicochemical properties. Such properties provide unique opportunities for the development of new processes that could unlock the full potential of future biorefineries. Here, we review the current state of lignocellulosic biomass processing with ILs and DESs, with a specific focus on the pretreatment chemistry, process flow and products from each component; followed by discussions on sustainability assessments and technological challenges. We aim to inform the research community about the opportunities, challenges and perspectives in developing truly sustainable lignocellulose-based biorefineries.

09 BIOMASS FUELS↗

Molecular Dynamics Simulations of Complexation of Am(III) with a Preorganized Dicationic Ligand in an Ionic Liquid

Preorganized ligands with imidazolium arms have been found to be highly selective in extracting Am(III) into ionic liquids (ILs), but the detailed structure and mechanism of the complexation process in the ionic solvation environment are unclear. Here, we carry out molecular dynamics simulation of the complexation of Am(III) with a preorganized 1,10-phenanthroline-2,9-dicarboxamide complexant (L) functionalized with alkyl chains and imidazolium cations in the butylmethylimidazolium bistriflimide ([BMIM][NTf 2 ]) IL. Both Am:L (1:1) and Am:L 2 (1:2) complexes are examined. In the absence of the ligand, Am(III) is found to be coordinated by six NTf 2 anions via nine O donors in the first solvation shell. In the Am:L complex, Am(III) is coordinated to the ligand via two O donors and four NTf 2 anions via seven O donors in the first coordination shell. In the Am:L 2 complex, Am(III) is coordinated to the two ligands via four O donors and four NTf 2 anions via five O donors. The imidazolium arms of the ligands play an important role in the secondary solvation environment by attracting NTf 2 anions closer to the metal center. As a result, we find that the binding free energy for the second L 2+ ligand is twice that for the first L 2+ ligand, making the Am:L 2 complex significantly more stable than the Am:L complex. This study highlights the multiple factors and tunability in using preorganized ligands with charged functional groups in an ionic solvation environment, which could hold the key to achieving desired selectivity in ion extraction efficiency.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Transport and Energetics of Carbon Dioxide in Ionic Liquids at Aqueous Interfaces

A major hurdle in utilizing carbon dioxide (CO 2 ) lies in separating it from industrial flue gas mixtures and finding suitable storage methods that enable its application in various industries. To address this issue, we utilized a combination of molecular dynamics simulations and experiments to investigate the behavior of CO 2 in common room-temperature ionic liquids (RTIL) when in contact with aqueous interfaces. Here, our investigation of RTILs, [EMIM][TFSI] and [OMIM][TFSI], and their interaction with a pure water layer mimics the environment of a previously developed ultrathin enzymatic liquid membrane for CO 2 separation. We analyzed diffusion constants and viscosity, which reveals that CO 2 molecules exhibit faster mobility within the selected ILs compared to what would be predicted solely based on the viscosity of the liquids using the standard Einstein–Stokes relation. Moreover, we calculated the free energy of translocation for various species across the aqueous–IL interface, including CO 2 and HCO 3 – . Free energy profiles demonstrate that CO 2 exhibits a more favorable partitioning behavior in the RTILs compared to that in pure water, while a significant barrier hinders the movement of HCO 3 – from the aqueous layer. Experimental measurement of the CO 2 transport in the RTILs corroborates the model. These findings strongly suggest that hydrophobic RTILs could serve as a promising option for selectively transporting CO 2 from aqueous media and concentrating it as a preliminary step toward storage.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Structure of Novel Phosphonium-Based Ionic Liquids with S and O Substitutions from Experiments and a Mixed Quantum-Classical Approach

This article presents experimental characterization information and synchrotron X-ray scattering measurements on a set of novel O- and S-substituted phosphonium-based ionic liquids (ILs) all coupled with the bis(fluorosulfonyl)imide (FSI-) anion. The ILs include the ethoxyethyltriethylphosphonium (P 222(2O2) + ) and triethyl[2-(ethylthio)ethyl]phosphonium (P 222(2S2) + ) cations, and we contrast results on these with those for unsubstituted triethylpentylphosphonium (P 2225 + ). The article also introduces a physics-based protocol that combines classical force field studies on larger simulation boxes with classical and first-principles studies on smaller boxes. The method produces significantly improved S(q) functions in the regime which in prior publications we have associated with inter- and intraionic adjacency correlations. By understanding which shorter-range structural changes improve S(q) in the q-regime of interest, we are also able to pinpoint specific deficiencies in the classical force field model. The approach we take should be quite general and could help study other complex liquids on different length scales.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Charge Tethering Drives Intermediate-Range Order and Slow Dynamics in Zwitterionic Liquids

We have synthesized and characterized a family of zwitterionic liquids (ZwLs) based on the poly(ethylene oxide) imidazolium cation and the alkyl sulfonate anion. To better rationalize ZwLs′ structural behavior and networkforming properties, we have computationally studied them in contrast to isostructural but chemically untethered ionic liquid (IL) analogues. Perhaps surprisingly, it is the molecular liquids and not the ILs that show the most selfassembly and intermediate-range order associated with scattering prepeaks; the ZwLs display also the slowest dynamics. This is consistent with prior work showing the importance of networks in considering the viscoelastic relaxation of liquids. We find that, because of their significantly large molecular dipoles, these zwitterions are versatile network-building blocks that result in highly viscous liquids. From a structural perspective, networks in these ZwLs sit somewhere in between what would be true chemical connectivity and the Coulombic networks observed in ionic liquids.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗

Tethered from the Head and from the Tail: The Structure of Hydroxyl-Functionalized Ionic Liquids

Ionic liquids with special functionalities are synthesized with the specific purpose of creating new patterns of interaction in the condensed phase. This Letter discusses the case of alcohol-functionalized ILs, the so-called HFILs, which are part of the larger cohort of task-specific ionic liquids. We find that this small chemical modification can cause massive changes in the liquid landscape when the cationic tails are longer. For prototypical ionic liquids, larger alkyl tails act as separators of charge networks, but in the case of HFILs these become physical charge network linkers. The OH functionality adds a large repertoire of interactions and correlations that were mostly unavailable to traditional ILs.

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗