Role Of Molecular Structure Research Articles

Computational Study of Asphaltene Adsorption on Carbonate Surface: Role of Molecular Structure and Oil Phase

Computational Study of Asphaltene Adsorption on Carbonate Surface: Role of Molecular Structure and Oil Phase

Quantitative structure-biotransformation relationships of organic micropollutants in aerobic and anaerobic wastewater treatments

Biotransformation is one of the dominant processes to remove organic micropollutants (OMPs) in wastewater treatment. However, studies on the role of molecular structure in determining the biotransformation rates of OMPs are limited. We evaluated the biotransformation of 14 OMPs belonging to different chemical classes under aerobic and anaerobic conditions, and then explored the quantitative structure-biotransformation relationships (QSBRs) of the OMPs based on biotransformation rates using valid molecular structure descriptors (electrical and physicochemical parameters). Pseudo-first-order kinetic modeling was used to fit the biotransformation rate, and only 2 of the 14 OMPs showed that the biotransformation rate constant (kbio) values were higher under anaerobic conditions than aerobic conditions, indicating that aerobic conditions were more favorable for biotransformation of most OMPs. QSBRs infer that the electrophilicity index (ω) is a reliable predictor for OMPs biotransformation under aerobic conditions. ω corresponds to the interaction between OMPs and microbial enzyme active sites, this process is the rate-limiting step of biotransformation. However, under anaerobic conditions the QSBR based on ω was not significant, indicating that specific functional groups may be more critical than electrophilicity. In conclusion, QSBRs can serve as alternative tools for the prediction of the biotransformation of OMPs and provide further insights into the factors that influence biotransformation.

Catalytic pyrolysis of straight-run light oil to light olefins: Role of molecular structure and catalytic materials

The development of straight-run light oil catalytic pyrolysis to light olefins process is an important approach of achieving the transformation and upgrading of the current oil refining industry. However, the industrialization of the catalytic pyrolysis process for straight-run light oil has been slow. Herein, we investigated the decomposition of complex straight-run light oil into different structural units and further examined their effects on light olefins production. The results indicated that the yields of light olefins cracked over MFI zeolite were about 45 % and 30 % for alkane structure and cycloalkane ring structure, respectively. Further analysis showed that the olefin structure could theoretically be cracked to 100 % light olefins, but in fact, 40 % of the light olefins were lost due to the transfer of 10 % hydrogen. Subsequently, the effects of zeolite topology and acid properties on the cracking of different structural units were further analyzed. It was found that zeolites with MTT and MFI topologies contributed to the catalytic pyrolysis of chain and cycloalkane ring structures, respectively, because appropriate pore size helped diffusion of hydrocarbon molecules and inhibited side reactions such as hydrogen transfer. Compared with MFI zeolite, the light olefins yield produced by chain structure cracking over MTT zeolite increased by 5.83 %-10.54 %. In addition, it was discovered that zeolites with total and strong acids in the range of 0.2–0.4 mmol/g and 0.1–0.2 mmol/g, respectively, were beneficial for the cracking of light alkanes in straight-run light oils to light olefins. This work provides useful insights into the fundamental understanding and development of straight-run light oil catalytic pyrolysis to light olefins process.

Large-amplitude oscillatory shear flow from general rigid bead-rod theory

Oscillatory shear flow, performed at small-amplitude, interrogates polymeric liquids in their equilibrium states. The fluid responds in sinusoidal shear stress waves whose amplitude and phase lead depend on the dimensionless frequency (called the Deborah number). By contrast, this same flow field, performed at large-amplitude, probes departures from the equilibrium state, and the fluid responds with shear stress in the form of a Fourier series, whose component amplitudes and phase leads depend on both the dimensionless frequency (called the Deborah number) and the dimensionless shear rate amplitude (called the Weissenberg number). The physics of these departures from equilibrium in an oscillatory shear flow may be explained by (i) chain disentanglement or (ii) motion along the polymer chain axes (called reptation) or (iii) macromolecular orientation. Of these radically different and yet otherwise equally effective approaches, only (iii) allows the macromolecular structure to be varied arbitrary so that the effect of molecular architecture on the rheology can be explored. Though much has been written about a large-amplitude oscillatory shear flow, we understand little about the role of molecular structure on the measured behaviors, and this has limited its usefulness. In this work, we explain the higher harmonics of both the shear stress (first and third), the first normal stress differences (zeroth, second, and fourth), and the second normal stress differences (zeroth and second) arriving at analytical expressions for all three. These expressions, written in dimensionless form, express the dimensionless rheological responses in large-amplitude oscillatory shear flow in terms of the ratio of the two principal macromolecular moments of inertia. To get these expressions, we derive the first five terms of the orientation distribution function, by solving the general diffusion equation in Euler coordinates. We then integrate in phase space with this orientation result to arrive at our expression for the first seven terms of the polymer contribution to the extra stress tensor. From this tensor, we next write down the Fourier coefficients for the shear stress responses, and the normal stress difference responses, in large-amplitude oscillatory shear flow for a suspension of macromolecules sculpted from a rigid bead-rod structure of any arbitrary axisymmetric shape.

RETRACTED: Solvent role in molecular structure, thermodynamic quantities, reactions and electronic transitions (TDDFT) on 2-[piperidin-1-yl] phenol

Vibrational analysis and skeletal parameter were computed using B3LYP method. The stabilization energy of 2PYP was computed. The charge excitation, hole – electron distribution and overlap were studied using multiwfn software. Electron localization function, localised orbital locator and thermodynamical analysis were done to 2PYP to find electron density and thermodynamic function (entropy, enthalpy and specific heat capacity). NLO parameters, MESP, UV–vis analysis, HOMO-LUMO analysis were done in non-polar, polar aprotic and polar protic.

The Role of Molecular Structure in Monte Carlo Simulations of the Secondary Electron Yield and Backscattering Coefficient from Methacrylic Acid.

In this paper, we show the influence of the chemical structure of four different conformers on the secondary electron emission and backscattering of an electron beam from a gel of methacrylic acid. The conformers have different permanent dipole moments, which determines the cross sections for elastic collisions with electrons. The cross sections are used in Monte Carlo simulations of an electron beam, which enters the gel of methacrylic acid. The secondary electron yield and the backscattering coefficient are computed as a function of the beam energy.

Molecular understanding of the morphology and properties of lignin nanoparticles: unravelling the potential for tailored applications.

Studies have shown that the size of LNP depends on the molecular weight (Mw) of lignin. There is however need for deeper understanding on the role of molecular structure on LNP formation and its properties, in order to build a solid foundation on structure-property relationships. In this study, we show, for similar Mw lignins, that the size and morphology of LNPs depends on the molecular structure of the lignin macromolecule. More specifically, the molecular structure determined the molecular conformations, which in turn affects the inter-molecular assembly to yield size- and morphological-differences between LNPs. This was supported by density functional theory (DFT) modelling of representative structural motifs of three lignins sourced from Kraft and Organosolv processes. The obtained conformational differences are clearly explained by intra-molecular sandwich and/or T-shaped π-π stacking, the stacking type determined by the precise lignin structure. Moreover, the experimentally identified structures were detected in the superficial layer of LNPs in aqueous solution, confirming the theoretically predicted self-assembly patterns. The present work demonstrates that LNP properties can be molecularly tailored, consequently creating an avenue for tailored applications.

Ongoing relevance of Oldroyd 8-constant fluids

• Behaviors of the Oldroyd 8-constant framework under many important rheological flows are reviewed. • Model restrictions and attributes are summarized. • Discussion of relevant entangle polymer network and polymer solutions is provided. • Brief discussion of relevant statistical tools is provided. • The interconnection of The Oldroyd 8-constant framework and molecular theories is provided. Of the many seminal contributions by Oldroyd to science and engineering, his weightiest embodies his 1958 general vision of the expected and allowable constitutive behaviors of elastic liquids. This remarkable vision is reflected in his constitutive framework which incorporates all possible tensorial products of the extra stress and rate-of-deformation tensors, along with all possible terms that are quadratic in the rate-of-deformation tensor. This framework involves exactly 8 constants, the most fundamental of which are the zero-shear viscosity, and the relaxation and retardation times. Oldroyd gives the general solution for the complex viscosity for all reduced cases of his framework in terms of the latter three constants. Further, Oldroyd gives the general solution for the steady shear viscosity for all reduced cases of his framework in terms of all eight constants. Since 1958, the framework has embraced many new constitutive equations as its reduced cases, and in this sense, its relevance continues to this day. Many of these reduced cases have led to exact analytical solutions for polymer processing problems, allowing continuing exploration of the role of melt elasticity. Moreover, when the Oldroyd framework is bridged to macromolecular theory, the role of molecular structure in polymer processing is uncovered, and this exciting use for the framework continues to this day. In this review, we make the case for the ongoing relevance of Oldroyd 8-constant fluids.

New insights into the role of molecular structures on the fate and behavior of antibiotics in an osmotic membrane bioreactor

Osmotic membrane bioreactors (OMBRs) have been applied to enhance removal of antibiotics, however, information on the effects of molecular structures on the behavior of antibiotics is still lacking. Herein, adsorption kinetics, transformation pathways, and membrane rejection mechanisms of OMBRs were investigated by adding two typical antibiotics (i.e., sulfadiazine, SDZ, and tetracycline hydrochloride, TC-HCl). 80.70–91.12% of TC-HCl was removed by adsorption and biodegradation, while 17.50–75.14% of SDZ was removed by membrane rejection; this depended on its concentration due to reduced electrostatic interactions and hydrophobic adsorption. The adsorption capacity of TC-HCl (i.e., 1.34±0.01 mg/g) was significantly higher than that of SDZ (i.e., 0.18±0.03 mg/g) due to enhanced π-π interactions, hydrogen bonding and improved electrostatic interactions. The abundant production of polysaccharide-like substances from TC-HCl biodegradation contributed to microbial metabolism and thus enhanced microbial function during TC-HCl biotransformation. The primary degradation pathways were determined by microbial function analysis, and the primary intermediates from TC-HCl degradation were less toxic than those from SDZ degradation due to the different reactions of amino groups. These results and the corresponding mechanism provide a theoretical foundation for the further development of OMBR technology for highly efficient treatment of antibiotic wastewater.

Role of Molecular Structure on Modulating the Interfacial Dynamics for Shallow Trench Isolation (STI) Chemical Mechanical Planarization (CMP) Applications

As feature sizes continue to shrink well beyond the 7 nm node, understanding the delicate balance present in the chemical mechanical planarization (CMP) process is of utmost importance. In order to achieve high through-put and defect-free CMP processes it is critical to develop predictive analytical techniques that directly correlate to macroscopic STI CMP performance metrics (i.e. oxide/nitride removal, defectivity, and dishing/erosion). This work employed a suite of techniques to monitor the CeO2 nanoparticle interfacial redox processes in the presence of structurally diverse rate modulating additives. Specifically, utilizing a UV–vis spectroscopic technique, the Ce3+/Ce4+ ratio in the presence of different slurry additives was monitored and proved to directly correlate to removal rate performance (i.e. an increase in Ce3+/Ce4+ ratio shows an increase in rate). This finding coupled with the rate of dissolved O2 evacuation and a modified QCM technique determined the mode of interaction/adsorption which validates that the mechanism of oxide removal does not strictly depend on redox capacity, but also depends on the dynamic O2 equilibrium at the CeO2 nanoparticle surface. It was determined that the modulation of oxide removal was directly related to the distribution of interactions (i.e. steric vs redox) and was highly dependent on the slurry additive functionality.

Thermo-associating polymers based on cross-linked 2-acrylamido-methylpropane sulfonic acid, part B: Effect of co-solutes on solution behavior

Thermo-thickening copolymers have gained prominence in technological advancements due to its attractive properties and great potential to overcome the deficiency of viscosity of conventional copolymer upon increasing temperature and salinity. The work in this paper was devoted to examine the aqueous solution viscosity behavior of a new class thermo-thickening copolymer, poly(sodium 2-acrylamido-2-methylpropanesulfonic acid-co-N,N’-methylenebisacrylamide)-g-poly(acrylamide-co-N, N’-diethylacrylamide) denoted as CGBA in the presence of co-solutes. CGBA, which were reported in our previous work manifested notable viscosity enhancement macroscopically above the threshold temperature. However, the effect of small molecules on thermo-associative behavior was still unsettled. Based on structure/properties dependence of CGBA, this work aimed to explore the effect of small molecules and the role of molecular structure on aqueous solution viscosity behavior. The contributions of various added co-solutes such as anionic surfactant, acidic specie, monovalent and divalent salts were considered. For that purpose, three copolymers having distinctive composition of side-arms and length of side-arms were selected and their thermo-associating behaviors were followed by viscosity measurement. Results from rheological tests showed that these co-solutes induced notable modifications in the characteristic of thermo-thickening behavior. For all the co-solutes used, it was observed a strong dependence between the side-arms/water/co-solutes ternary system and the macroscopic property upon heating. Spectrofluorimetric and environmental scanning electron microscope (ESEM) tests were used to gain a deeper insight into the precise mechanism of phase transition process. Results from spectrofluorimetric experiment indicated that, only when the fraction of DEAm in CGBA was higher enough, it would appear strong abrupt macroscopic property above the threshold temperature, which could delay the offset of hydrophobic association phenomenon in the presence of anionic surfactant. Similar effect was also observed in the presence of added acidic specie. Conversely, the addition of monovalent and divalent salts showed dissimilar effects. ESEM revealed that, in comparison with monovalent salt, divalent salt favored the formation of larger and more condensed CGBA skeleton above the threshold temperature which led to an improved macroscopic response. This work demonstrates for the first time the micro-structure changes of copolymer, which was probably the main reason for the changes in magnitude of thermo-thickening effect in different divalent salt dosages.

Role of Molecular Structure in the Production of Water-Soluble Species by Photo-oxidation of Petroleum.

Asphaltenes are high-boiling and recalcitrant compounds that are generally minor components of crude oil (∼0.1-15.0 wt %) but dominate the composition of heavily weathered spilled petroleum. These solid residues exhibit a high structural complexity, comprised of polycyclic aromatic hydrocarbons (PAHs) that are a mixture of single-core (island) and multicore (archipelago) structural motifs. The mass fraction of each motif is sample-dependent. Thus, knowledge of a potential structural dependence (single- versus multicore) on the production of water-soluble species from asphaltene samples is key to understanding the contribution of photochemically generated dissolved organic matter from oil spills. In this work, asphaltene samples with enriched mass fractions of either island (single-core) or archipelago (multicore) structural motifs are photo-oxidized on artificial seawater by the use of a solar simulator. Molecular characterization of oil- and water-soluble photoproducts, conducted by Fourier transform ion cyclotron resonance mass spectrometry, reveals that island motifs exhibit very limited production of water-soluble species, and their oil-soluble products reflect the molecular composition of the starting material. Conversely, archipelago motifs yield a water-soluble compositional continuum of Ox, SxOy, and NxOy containing hydrocarbons species that exhibit the typical molecular fingerprint of dissolved organic matter (DOM). The lower carbon number and aromaticity of the archipelago-derived asphaltene photoproducts suggest the occurrence of photofragmentation (or photolysis) reactions. To investigate the possibility of the opposite reaction (photopolymerization), the photo-oxidation of small PAHs isolated from a low-boiling petroleum distillation cut was also performed. It yielded water-soluble compounds with carbon number and aromaticity up to 2-fold higher than the starting material, strongly suggesting that polymerization (addition reactions) occurs. Collectively, the results indicate that the presence of archipelago motifs and the occurrence of cracking/polymerization reactions are central in the production of dissolved organic matter from fossil fuels.

Assessing Parameter Suitability for the Strength Evaluation of Intramolecular Resonance Assisted Hydrogen Bonding in o-Carbonyl Hydroquinones.

Intramolecular hydrogen bond (IMHB) interactions have attracted considerable attention due to their central role in molecular structure, chemical reactivity, and interactions of biologically active molecules. Precise correlations of the strength of IMHB’s with experimental parameters are a key goal in order to model compounds for drug discovery. In this work, we carry out an experimental (NMR) and theoretical (DFT) study of the IMHB in a series of structurally similar o-carbonyl hydroquinones. Geometrical parameters, as well as Natural Bond Orbital (NBO) and Quantum Theory of Atoms in Molecules (QTAIM) parameters for IMHB were compared with experimental NMR data. Three DFT functionals were employed to calculated theoretical parameters: B3LYP, M06-2X, and ωB97XD. O…H distance is the most suitable geometrical parameter to distinguish among similar IMHBs. Second order stabilization energies ΔEij(2) from NBO analysis and hydrogen bond energy (EHB) obtained from QTAIM analysis also properly distinguishes the order in strength of the studied IMHB. ΔEij(2) from NBO give values for the IMHB below 30 kcal/mol, while EHB from QTAIM analysis give values above 30 kcal/mol. In all cases, the calculated parameters using ωB97XD give the best correlations with experimental 1H-NMR chemical shifts for the IMHB, with R2 values around 0.89. Although the results show that these parameters correctly reflect the strength of the IMHB, when the weakest one is removed from the analysis, arguing experimental considerations, correlations improve significantly to values around 0.95 for R2.

From PCBM-Polymer to Low-Cost and Thermally Stable C60/C70-Polymer Solar Cells: The Role of Molecular Structure, Crystallinity, and Morphology Control.

The adoption of neat-fullerene (C60 and C70) in polymer solar cells offers opportunities to develop cost-effective and thermally stable devices. Here, through rational side-chain engineering of low optical-gap polymer poly(benzodithiophene-furan-diketopyrrolopyrrole)s (PBDs), we demonstrated for the first time a polymer/C70 blend exhibited higher efficiency (best 6.1%) compare to their polymer/[70]PCBM (best 5.7%) counterparts, and the best efficiency is at the front of efficient polymer/neat-fullerene solar cells. More importantly, we first demonstrated the morphology optimization methodology for solution-processed polymer/neat-fullerene blends in order to reduce the strong crystallization and aggregation of neat-fullerene molecules. In comparison with previous work, these results can provide not only material design strategy but also fundamental difference between polymer/neat-fullerene and polymer/PCBM blend morphology, which allow us better understanding of how to choose proper materials and optimize blend morphology in polymer/neat-fullerene based device to deliver higher photovoltaic performance.

Excited state intramolecular proton transfer induced fluorescence in triphenylamine molecule: Role of structural conformation and reversible mechanofluorochromism

Triphenylamine (TPA) based Schiff base molecules (1–4) were synthesized and role of molecular structure and conformation on excited state intramolecular proton transfer (ESIPT) induced fluorescence in both solution as well as solid state has been explored. 1 and 2, which are not hydrogen bonding donor to form intramolecular H-bonding, basis for ESIPT, are non-fluorescent in solution as well as solid. The incorporation of hydroxyl group in 3 and 4 promoted intramolecular H-bonding that could facilitate ESIPT. Interestingly, 3 showed strong fluorescence in solution (λmax = 489–540 nm, Φf = 0.337–0.018 compared to standard fluorescein) as well as solid state (λmax = 553 nm, Φf = 4.84% (absolute quantum yield) whereas structurally similar 4 did not show fluorescence. Further 3 also showed reversible mechanofluorochromism (MFC) due to the incorporation of non-planar TPA. Solid state structural analysis confirmed intramolecular H-bonding in 3 and 4 but 3 showed coplanar conformation between TPA phenyl and imine group whereas one of the molecules in the asymmetric unit of 4 revealed slightly twisted conformation. Powder X-ray diffraction studies of 3 indicated reversible conversion of crystalline to amorphous and vice versa. Computational studies of 3 and 4 provided insight on the ESIPT properties of 3.

Interaction between structurally different heteroexopolysaccharides and β-lactoglobulin studied by solution scattering and analytical ultracentrifugation

Despite a very large number of bacterial exopolysaccharides have been reported, detailed knowledge on their molecular structures and associative interactions with proteins is lacking. Small-angle X-ray scattering, dynamic light scattering and analytical ultracentrifugation (AUC) were used to characterize the interactions of six lactic acid bacterial heteroexopolysaccharides (HePS-1–HePS-6) with β-lactoglobulin (BLG). Compared to free HePSs, a large increase in the X-ray radius of gyration RG, maximum length L and hydrodynamic diameter dH of HePS-1–HePS-4 mixed with BLG revealed strong aggregation, the extent of which depended on the compact conformation and degree of branching of these HePSs. No significant effects were observed with HePS-5 and HePS-6. Turbidity and AUC analyses showed that both soluble and insoluble BLG–HePS complexes were formed. The findings provide new insights into the role of molecular structures in associative interactions between HePSs and BLG which has relevance for various industrial applications.

(Invited) Ion Transport in Polymerized Ionic Liquids: Structure-Morphology-Property Relationships

Polymerized ionic liquids (PolyILs) are a novel class of functional polymers that combine the unique physicochemical properties of molecular ionic liquids with the outstanding mechanical characteristics of polymers. This special mix of features might help to circumvent the key limitations of low molecular weight ionic liquids, namely, leakage and poor mechanical properties while utilizing their outstanding characteristics such as low vapor pressures, wide liquidus ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. PolyILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices, among others. Despite their promising prospects as ideal polymer electrolytes, the role of molecular structure, morphology, and polymer dynamics on charge transport in PolyILs remains poorly understood. According to classical theories, the self-diffusion and ion transport in electrolytes are controlled by structural relaxation. These approaches predict similar temperature dependence for the dc conductivity and structural dynamics. Although this prediction has been shown to hold reasonably well for low molecular weight aprotic ionic liquids, it fails for PolyILs. In addition, the impact of morphology on charge transport is not considered within the framework of these theories. This talk will focus on new insights obtained from experimental studies employing broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, rheology, and scattering techniques to elucidate the impact of morphology on charge transport and structural dynamics in systematic series of polymerized ammonium- and imidazolium- based ionic liquids. Detailed analyses reveal strong decoupling of these processes in the PolyILs, implying the limitation of the classical theories in describing charge transport and molecular dynamics in these materials, in contrast to low molecular weight systems. In addition, the strong correlation observed between ionic conductivity from dielectric experiments and morphologies from scattering and computational studies will be discussed.

The role of molecular structure on impact resistance and bending strength of photocured urethane-dimethacrylate polymer networks

The objective of this study was to investigate the influence of molecular structure on impact resistance (an) and bending strength (σ) of photocured urethane-dimethacrylate polymer networks. Urethane-dimethacrylate (UDMA) monomers were synthesized through reaction of oligoethylene glycol monomethacrylate (OEGMMA) with diisocyanate (DI). OEGMMA varied within the length of the oligooxyethylene chain, which consisted of one to four oxyethylene units. DI varied in chemical character: aliphatic, cycloaliphatic or aromatic. The molecular structure of UDMA polymers was characterized by X-ray powder diffraction, which allowed the calculation of the d-spacing (d) and dimensions of microgel agglomerates (D). The measurements of the polymerization shrinkage were used for the determination of the degree of conversion (DC), whereas the concentration of double bonds was used as a measure of the crosslink density (q). It was found that all structural parameters depend on the UDMA chemical structure. The increasing length of the oligooxyethylene chains caused the decrease in d and q, in contrast to the increase in D and DC. The DI chemical character caused the increase in the DC and q accordingly: symmetrical cycloaliphatic or aromatic < asymmetrical cycloaliphatic and aromatic < substituted aliphatic < linear aliphatic. The compact packing and high DC in polymers derived from aliphatic DIs gave rise to the decrease in d and the increase in D. The non-planar conformation of cycloaliphatic DIs emerged in high d as well as D. The planar conformation of aromatic DIs resulted in the decrease in d as well as D. The study indicated that mechanical behavior of UDMA polymer networks can be explained in terms of the structural parameters. DC and q appeared to be the main factors determining both mechanical properties of poly(UDMA)s. The an was also shown to be affected by d. Particularly high linear correlations were found on a semi-logarithmic scale for the DC and d with an. an increased as the DC increased, whereas d decreased.

(Invited) Charge Transport and Structural Dynamics in Bulk and Ultrathin Films of Polymerized Ionic Liquids

Polymerized ionic liquids (PolyILs) are a novel class of functional polymers that combine the unique physicochemical properties of molecular ionic liquids with the outstanding mechanical characteristics of polymers [1,2]. This special mix of features might help to circumvent the key limitations of low molecular weight ionic liquids, namely, leakage and poor mechanical properties while utilizing their outstanding characteristics such as low vapor pressures, wide liquidus ranges, high thermal stability, high ionic conductivity, and wide electrochemical windows. PolyILs have shown remarkable advantages when employed in electrochemical devices such as dye-sensitized solar cells, lithium batteries, actuators, field-effect transistors, light emitting electrochemical cells, and electrochromic devices, among others. Despite their promising prospects as ideal polymer electrolytes, the role of molecular structure, morphology, and polymer dynamics on charge transport in PolyILs remains poorly understood. According to classical theories, the self-diffusion and ion transport in electrolytes are controlled by structural relaxation. These approaches predict similar temperature dependence for the dc conductivity and structural dynamics. Although this prediction has been shown to hold reasonably well for low molecular weight aprotic ionic liquids, it fails for PolyILs [2,3]. In addition, the impact of morphology charge transport is not considered within the framework of these theories. The first part of this talk will focus on new insights obtained from experimental studies employing broadband dielectric spectroscopy, temperature-modulated differential scanning calorimetry, rheology, and scattering techniques to elucidate charge transport and structural dynamics in a systematic series of bulk polymerized ammonium- and imidazolium- based ionic liquids. Detailed analyses reveal strong decoupling of these processes in the PolyILs, implying the limitation of the classical theories in describing charge transport and molecular dynamics in these materials, in contrast to low molecular weight systems (4,5). In addition, the strong correlation observed between ionic conductivity from dielectric experiments and morphologies from scattering studies will be reviewed. In the second part of this talk, our recent results from a new approach to dielectric experiments yielding details about ion dynamics in ultrathin films of polymerized ionic liquids down to sub-5nm film thicknesses will be discussed. While the characteristic charge transport rates remain bulk-like down to about 5 nm film thicknesses, ionic-liquid/substrate interactions play an increasingly significant role in determining ion dynamics in confined polymerized ionic liquids (5). These results will be considered within the context of recent models of charge transport and polymer dynamics under confinement. References 1) Mecerreyes, D. Progress in Polymer Science 2011, 36, 1629. 2) Sangoro, J. R. and Kremer, F. Accounts of Chemical Research 2012, 45, 525 3) Sangoro, J. R. et al., Soft Matter 2014, 10, 3536. 4) Wojnarowska, Z. et al., Macromolecules 2015, 48 (23), 8660-8666. 5) Heres, M. F. et al., Submitted.

Designing for selectivity: weak interactions and the competition for reactive sites on gold catalysts.

A major challenge in heterogeneous catalysis is controlling reaction selectivity, especially in complex environments. When more than one species is present in the gas mixture, the competition for binding sites on the surface of a catalyst is an important factor in determining reaction selectivity and activity. We establish an experimental hierarchy for the binding of a series of reaction intermediates on Au(111) and demonstrate that this hierarchy accounts for reaction selectivity on both the single crystal surface and under operating catalytic conditions at atmospheric pressure using a nanoporous Au catalyst. A partial set of measurements of relative binding has been measured by others on other catalyst materials, including Ag, Pd and metal oxide surfaces; a comparison demonstrates the generality of this concept and identifies differences in the trends. Theoretical calculations for a subset of reactants on Au(111) show that weak van der Waals interactions are key to predicting the hierarchy of binding strengths for alkoxides bound to Au(111). This hierarchy is key to the control of the selectivity for partial oxidation of alcohols to esters on both Au surfaces and under working catalytic conditions using nanoporous gold. The selectivity depends on the competition for active sites among key intermediates. New results probing the effect of fluorine substitution are also presented to extend the relation of reaction selectivity to the hierarchy of binding. Motivated by an interest in synthetic manipulation of fluorinated organics, we specifically investigated the influence of the -CF3 group on alcohol reactivity and selectivity. 2,2,2-Trifluoroethanol couples on O-covered Au(111) to yield CF3CH2O-C([double bond, length as m-dash]O)(CF3), but in the presence of methanol or ethanol it preferentially forms the respective 2,2,2-trifluoroethoxy-esters. The ester is not the dominant product in any of these cases, though, indicating that the rate of β-H elimination from adsorbed trifluoroethoxy is slower than that for either adsorbed methoxy or ethoxy, consistent with their relative estimated β-C-H bond strengths. The measured equilibrium constants for the competition for binding to the surface are 2.9 and 0.38 for ethanol and methanol, respectively, vs. 2,2,2-trifluoroethanol, indicating that the binding strength of 2,2,2-trifluoroethoxy is weaker than ethoxy, but stronger than methoxy. These results are consistent with weakening of the interactions between the surface and the alkyl group due to Pauli repulsion of the electron-rich CF3 group from the surface, which offsets the van der Waals attraction. These experiments provide guiding principles for understanding the effect of fluorination on heterogeneous synthesis and further demonstrate the key role of molecular structure in determining reaction selectivity.