Terminal Sulfonate Groups Research Articles

PROTIC POLYMERIC IONIC LIQUID OF A BLOCK OLIGOMERIC STRUCTURE WITH IONIC BONDS IN THE MAIN CHAIN

A method for the synthesis of protic polymeric ionic liquid (PIL) of a block oligomeric structure with ionic bonds in the main chain, which turns into a liquid state at temperatures below 50 °C, was developed. Ionic bonding was used to form a polymer chain. It was formed as a result of neutralization reaction between oligomers of telechelic structure with terminal acidic and basic groups. A new linear oligomer containing basic tertiary nitrogen atoms at the ends of the oligoether chain (PEO-2NEt2) was obtained by reaction of α,ω-diglycidyl ether of polyethylene glycol MW 1000 with N,N-diethylamine. A linear oligomer with terminal sulfonic acid groups (PEO-2SO3H), which is a product of the interaction of polyethylene glycol (MW 1000) with the cyclic anhydride of 2-sulfobenzoic acid, was used as an acidic linear oligomer. The synthesis of PIL [PEO-2H-2NEt2]2+ [PEO-2SO3]2- was carried out by neutralization of basic oligomer PEO-2NEt2 with the acidic oligomer PEO-2SO3H in their molar ratio of 1:1. The structure of the obtained compound was characterized by the methods of FTIR and 1H NMR spectroscopy. According to the DSC data, the synthesized PIL contains an amorphous phase with a glass transition temperature of -49.7 °С and a crystalline phase with a melting temperature of 34.5 °С. The decomposition onset temperature corresponding to 5% weight loss is 271 °C according to the TGA. The ionic conductivity of PIL studied by dielectric relaxation spectroscopy under anhydrous conditions in the range from 40 °C to 100 °C increases with increase in temperature and reaches 2.7·10-4 S/cm. The resulting compound is promising as a proton-conducting medium for various electrochemical devices.

Two-Dimensional Sulfonate-Functionalized Metal-Organic Framework Membranes for Efficient Lithium-Ion Sieving.

Two-dimensional (2D) membranes have shown promising potential for ion-selective separation but often suffer from the trade-off between permeability and selectivity. Herein, we report an ultrathin 2D sulfonate-functionalized metal-organic framework (MOF) membrane for efficient lithium-ion sieving. The narrow pores with angstrom precision in the MOF assist hydrated ions to partially remove the hydration shell, according to different hydration energies. The abundant sulfonate groups in the MOF channels serve as hopping sites for fast lithium-ion transport, contributing to a high Li-ion permeability. Then, the difference in affinity of the Li+, Na+, K+, and Mg2+ ions to the terminal sulfonate groups further enhances the Li-ion selectivity. The reported ultrathin MOF membrane overcomes the trade-off between permeability and selectivity and opens up a new avenue for highly permselective membranes.

Flattening of a Bent Sulfonated MOF Linker: Impact on Structures, Flexibility, Gas Adsorption, CO2/N2 Selectivity, and Proton Conduction.

Rational design of organic building blocks provides opportunities to control and tune various physicochemical properties of metal-organic frameworks (MOFs), including gas handling, proton conduction, and structural flexibility, the latter of which is responsible for new adsorption phenomena and often superior properties compared to rigid porous materials. In this work, we report synthesis, crystal structures, gas adsorption, and proton conduction for a flexible two-dimensional cadmium-based MOF (JUK-13-SO3H-SO2) containing a new sulfonated 4,4'-oxybis(benzoate) linker with a blocking SO2 bridge. This two-dimensional (2D) MOF is compared in detail with a previously reported three-dimensional Cd-MOF (JUK-13-SO3H), based on analogous, but nonflat, SO2-free sulfonated dicarboxylate. The comprehensive structure-property relationships and the detailed comparisons with insights into the networks flexibility are supported by five guest-dependent structures determined by single-crystal X-ray diffraction (XRD), and corroborated by spectroscopy (IR, 1H NMR), powder XRD, and elemental/thermogravimetric analyses, as well as by volumetric adsorption measurements (for N2, CO2, H2O), ideal adsorbed solution theory (IAST), density-functional theory (DFT+D) quantum chemical and grand-canonical Monte Carlo (GCMC) calculations, and electrochemical impedance spectroscopy (EIS) studies. Whereas both dynamic MOFs show moderate proton conductivity values, they exhibit excellent CO2/N2 selectivity related to the capture of CO2 from flue gases (IAST coefficients for 15:85 mixtures are equal to ca. 250 at 1 bar and 298 K). The presence of terminal sulfonate groups in both MOFs, introduced using a unique prechlorosulfonation strategy, is responsible for their hydrophilicity and water-assisted proton transport ability. The dynamic nature of the MOFs results in the appearance of breathing-type adsorption isotherms that exhibit large hysteresis loops (for CO2 and H2O) attributed to strong host-guest interactions. Theoretical modeling provides information about the adsorption mechanism and supports interpretation of experimental CO2 adsorption isotherms.

Protic ion-crosslinked polymer ionic liquid (PIL) based on linear oligomers

A method for the synthesis of a protic ion-crosslinked polymeric ionic liquid (PIL) which turns into a liquid state at a temperature below 50 °C using a reaction of basic and acidic linear oligomers was developed. The product of interaction of α,ω-diglycidyl ester of oligoethylene oxide MM 1000 with an excess of 1-(3-aminopropyl)imidazole (PEO–2Im) was used as the basic oligomer. It contains two types of basic centers with a significant difference in basicity (aliphatic secondary amino groups and imidazole heterocycles), as well as secondary hydroxyl groups at the ends of oligoether chain. A linear oligomer with terminal sulfonic acid groups (PEO–2SO3H) was obtained by the interaction of of oligoethylene oxide MM 1000 with 2-sulfobenzoic acid cyclic anhydride. Protic ion-crosslinked PIL was synthesized by completely neutralization of basic centers of oligomer PEO–2Im by acidic oligomer PEO–2SO3H at their molar ratio 1:2 respectively. The structure of the obtained PIL was characterized by FTIR and 1Н NMR- spectroscopy methods. According to DSC, the synthesized ion-crosslinked PIL contains two types of crystalline formations with melting temperatures of 36,3 °C and 45,8 °C formed by fragments of oligoethylene oxide during the transfer of protons between different types of ion centers. Determined by the TGA method the temperature of the onset of decomposition, which corresponds to 5% mass loss, is 265 °C. The proton conductivity of the ion-crosslinked PIL was studied by the DRS method in anhydrous conditions in the temperature range from 40 to 100 °C. At a temperature of 100 °C, the proton conductivity is 3,1·10-4 S/cm. The achieved values of proton conductivity and thermal stability make the obtained compound promising as a proton-conducting medium for various electrochemical devices.

Mechanism for the adsorption of Per- and polyfluoroalkyl substances on kaolinite: Molecular dynamics modeling

Per- and polyfluoroalkyl substances (PFAS) have been detected in ecosystems globally and pose a serious threat to human health. Clay minerals are promising adsorbents for PFAS removal from contaminated water, thus it is crucial to understand the interactions between PFAS and clay minerals. This paper performed molecular dynamics simulations to reveal the complex behaviors and fundamental mechanisms of the adsorption of perfluoroalkyl sulfonic acids (PFSA) on the siloxane and hydroxyl external basal surfaces of kaolinite. The results demonstrate that adsorption is favorable on both the surfaces; however, their mechanisms are distinct. On the hydroxyl surface, PFSA anions exhibit a steady “point adsorption” mode, with the diffusion coefficients considerably lower than those in bulk aqueous solution. The terminal sulfonate groups form hydrogen bonds with the surface hydrogen atoms like a “three-pin plug”, with a matching molecular geometry. The molecular force and molecular electrostatic potential analyses suggest that the Coulomb electrostatic attraction force from kaolinite to the terminal sulfonate groups of PFAS anions is the predominant driving force of adsorption for the hydroxyl surface. The potential of mean force (PMF) calculations show that the PFSA anions have to go over an energy barrier, which is induced by hydration of the hydroxyl surface, to reach the stable adsorption position. On the siloxane surface, PFSA anions exhibit a mobile “surface adsorption” mode, with a relatively high freedom along the plane parallel to the surface. The diffusion coefficients of the PFSA anions adsorbed on the siloxane surface are slightly lower than those in bulk aqueous solution. The non-polar CF chains lie flat above the siloxane surface due to the hydrophobic interaction, while the terminal sulfonate groups stay relatively far away from the siloxane surface. A greater van der Waals repulsive force from the outer water molecules to the CF chains is the predominant driving force of adsorption, and pushes PFSA anions to the siloxane surface as PFSA anions approach kaolinite. The minimum values of the PMF of adsorbed PFSA anions on the siloxane surface are lower than those on the hydroxyl surface, indicating that adsorption stability is higher for the siloxane surface.

Functionalized Metallic 2D Transition Metal Dichalcogenide-Based Solid-State Electrolyte for Flexible All-Solid-State Supercapacitors.

Highly efficient and durable flexible solid-state supercapacitors (FSSSCs) are emerging as low-cost devices for portable and wearable electronics due to the elimination of leakage of toxic/corrosive liquid electrolytes and their capability to withstand elevated mechanical stresses. Nevertheless, the spread of FSSSCs requires the development of durable and highly conductive solid-state electrolytes, whose electrochemical characteristics must be competitive with those of traditional liquid electrolytes. Here, we propose an innovative composite solid-state electrolyte prepared by incorporating metallic two-dimensional group-5 transition metal dichalcogenides, namely, liquid-phase exfoliated functionalized niobium disulfide (f-NbS2) nanoflakes, into a sulfonated poly(ether ether ketone) (SPEEK) polymeric matrix. The terminal sulfonate groups in f-NbS2 nanoflakes interact with the sulfonic acid groups of SPEEK by forming a robust hydrogen bonding network. Consequently, the composite solid-state electrolyte is mechanically/dimensionally stable even at a degree of sulfonation of SPEEK as high as 70.2%. At this degree of sulfonation, the mechanical strength is 38.3 MPa, and thanks to an efficient proton transport through the Grotthuss mechanism, the proton conductivity is as high as 94.4 mS cm-1 at room temperature. To elucidate the importance of the interaction between the electrode materials (including active materials and binders) and the solid-state electrolyte, solid-state supercapacitors were produced using SPEEK and poly(vinylidene fluoride) as proton conducting and nonconducting binders, respectively. The use of our solid-state electrolyte in combination with proton-conducting SPEEK binder and carbonaceous electrode materials (mixture of activated carbon, single/few-layer graphene, and carbon black) results in a solid-state supercapacitor with a specific capacitance of 116 F g-1 at 0.02 A g-1, optimal rate capability (76 F g-1 at 10 A g-1), and electrochemical stability during galvanostatic charge/discharge cycling and folding/bending stresses.

One-step introduction of terminal sulfonic groups into a proton-conducting metal-organic framework by concerted deprotonation-metalation-hydrolysis reaction.

Terminal sulfonic acid groups characterize various proton conducting materials including metal-organic frameworks (MOFs). These groups, however, show strong coordination ability that hinders their direct intact incorporation. We present a strategy for introducing pendant SO3H groups into frameworks from sulfonyl chloride precursors. The strategy using concerted deprotonation-metalation-hydrolysis reaction yields a new MOF capable of proton transport.

Effect of the Specific Adsorption of Sulfonate Group in Ionomer and Adsorbed Oxide Species on the Oxygen Reduction Reaction Activity of PEFC Catalyst

Introduction For wide spread of Polymer Electrolyte Fuel Cell (PEFC), It is necessary to improve the oxygen reduction reaction (ORR) activity of cathode catalyst. While the Ionomer (e.g., Nafion®) have been used in commercial PFEC to improve the triple-phase boundary [1]and the effect of side-chain in perfluoro-sulfonic acid ionomers adsorbing on the surface of Pt has been discussed. [2,3] For the terminal sulfonate group is adsorbed on Pt by one or two oxygen atom(s) and the oxygen atom of ether group also interaction with the Pt, it’s shown that the existence of ionomer will block the oxygen reduction reaction. [4]In this study, the weight ratio of Ionomer and carbon which was used in the catalyst (I/C) has been changed to control the degree of specific adsorption in order to analysis the effect of specific activity and construct a model of specific adsorption on the surface of Pt. Experiment Core-shell catalyst (Pd@Pt@Vulcan) is used to eliminate the signal from bulk of Pt catalyst while XAFS measurement. Catalyst ink is made by mixture Catalyst powder(6.446mg) with ultrapure water (7.6ml), isopropanol (2.4ml) and 5wt% Nafion®solution (quantity is changed with I/C) then bath sonicated in ice bath for 20 mins to obtain well-dispersed ink. Thin-film Rotating Disk Electrode (TF-RDE) technique is used to get a homogeneous catalyst layer. Finally, 10μl aliquots of the ink were subsequently pipetted on to the GC disk and get a catalyst layer with ~12μgcatalyst/cm2. For ORR activity measurements, the limiting current is calculated from the raw currents at 0.90V and analyzed to determine the specific activity. Results and Discussion In compare with tiny changes of ECSA, the ORR activity shows evident decrease along with I/C increasing, the more Nafion®is mixed in the ink, the more catalyst will be covered by ionomer which lead to more specific adsorption. For the specific adsorption is only happening at the interface of ionomer and the catalyst, ORR activity of catalyst will not be decreasing continuously with the degree of ionomer increasing. When the amount of Nafion®reaches a certain level the ORR activity is expected to be constant. In this research the I/C increase over about 1.0, there was not any changes have been shown about ORR activity. Reference [1] Kazuma Shinozaki, Yu Morimoto, Bryan S. Pivovar , Shyam S. Kocha, Journal of Power Sources. 325,745(2016) [2]Kazuma Shinozaki, Jason W. Zack,Svitlana Pylypenko, Bryan S. Pivovar,Shyam S. Kocha, Journal of The Electrochemical Society, 162(12) F1384-F1396 (2015) [3]Ram Subbaraman, Dusan Strmcnik, Vojislav Stamenkovic, Nenad M Markovic, J. Phys. Chem. C .114, 8414–8422 (2010) [4] Kensaku Kodama,Kenta Motobayashi, Akihiro Shinohara, Naoki Hasegawa, Kenji Kudo, Ryosuke Jinnouchi, Masatoshi Osawa, Yu Morimoto, ACS Catal. 8, 694(2018) Acknowledgments This research is based on results obtained from a project commissioned by the New Energy and Industrial Technology Development Organization (NEDO)

Zwitterionic Poly(vinylidene fluoride) Graft Copolymer with Unexpected Fluorescence Property.

Recently, there has been a growth of research on the nonconjugated polymer exhibiting fluorescence property and it would be exciting if fluorescence property is developed in zwitterionic polymers because of their good water solubility. Poly(vinylidene fluoride) (PVDF) grafted with poly(dimethyl amino ethyl methacrylate) (PDMAEMA) is fractionated and a highly water-soluble fraction (PVDM-1) is quaternized with 1,3-propane sultone, producing a zwitterionic polymer, PVDF- g-PDMAEMA-sultone (PVDMS). PVDM-1 shows the fluorescence property with very low quantum yield (1%) in water, but on quaternization, fluorescence quantum yield increases to 8%. Transmission electron microscopy results indicate that the PVDM-1 cast from water has vesicular morphology, whereas PVDMS exhibits aggregated vesicular morphology. The 1H NMR spectra indicate the presence of 72 mol % DMAEMA in PVDM-1 wherein 66% of -NMe2 groups is quaternized upon postpolymerization modification. PVDM-1 exhibits absorption peaks at 210, 276, and 457 nm with a hump at 430 nm, whereas PVDMS exhibits two absorption peaks at 203 and 297 nm. PVDM-1 exhibits a broad emission peak at 534 nm, whereas PVDMS exhibits a sharp emission peak at 438 nm. An attempt has been made from density functional theory calculations to shed light on the origin of fluorescence in both PVDM-1 and in the zwitterionic PVDMS. The excitonic decay occurs from the lowest unoccupied molecular orbital (LUMO) of carbonyl group to the highest occupied molecular orbital (HOMO) of tertiary amine group for PVDM-1, whereas in PVDMS, the excitonic transition occurs from the LUMO situated over the quaternary ammonium group to the HOMO located on the electron-rich terminal sulfonate group.

Effect of the Side-Chain Structure of Perfluoro-Sulfonic Acid Ionomers on the Oxygen Reduction Reaction on the Surface of Pt

The effect of side-chain structures in perfluoro-sulfonic acid ionomers on the adsorption of the terminal sulfonate moiety on the surface of Pt is investigated with voltammetry and surface-enhanced infrared absorption spectroscopy (SEIRAS). Analyses with low-molecular-weight model anions with and without an ether group in the perfluoro-alkyl chain indicate that the anions are adsorbed on Pt through one or two oxygen atom(s) of the terminal sulfonate group and that the oxygen atom of the ether group also interacts with the Pt surface, leading to stronger adsorption of the anions with an ether group. On the basis of the results obtained with the model anions, the adsorption of the terminal sulfonate moieties in perfluorinated sulfonic acid ionomers and its effect on oxygen reduction reaction (ORR) is discussed. It is shown that the ionomers having longer side chains more strongly block ORR due to the flexibility of the side chains.

Impact of Substituents in Tumor Uptake and Fluorescence Imaging Ability of Near-Infrared Cyanine-like Dyes.

This report presents a simple strategy to introduce various functionalities in a cyanine dye (bis-indole-N-butylsulfonate-polymethine bearing a fused cyclic chloro-cyclohexene ring structure), and assess the impact of these substitutions in tumor uptake, retention and imaging. The results obtained from the structural activity relationship (SAR) study demonstrate that certain structural features introduced in the cyanine dye moiety make a remarkable difference in tumor avidity. Among the compounds investigated, the symmetrical CDs containing an amino-phenyl thioether group attached to a cyclohexene ring system and the two N-butyl linkers with terminal sulfonate groups in benzoindole moieties exhibited excellent tumor imaging ability in BALB/c mice bearing Colon26 tumors. Compared to indocyanine green (ICG), approved by FDA as a blood pooling agent, which has also been investigated for the use in tumor imaging, the modified CD selected on the basis of SAR study produced enhanced uptake and longer retention in tumor(s). A facile approach reported herein for introducing a variety of functionalities in tumor-avid CD provides an opportunity to create multi-imaging modality agent(s). Using a combination of mass spectrometry and absorbance techniques, the photobleaching of one of the CDs was analyzed and significant regioselective photooxidation was observed.

Characterization of post-translationally modified peptides by hydrophilic interaction and reverse phase liquid chromatography coupled to quadrupole-time-of-flight mass spectrometry

This work explores the use of both hydrophilic interaction liquid chromatography (HILIC) and reverse phase liquid chromatography (RPLC) for the separation and subsequent characterization of bovine caseinomacropeptide (CMP) phosphopeptides and O-glycopeptides using a quadrupole-time-of-flight (QTOF) mass spectrometer with electrospray ionization. Two neutral, ethylene bridged hybrid (BEH) amide and polyhydroxyethyl aspartamide (PHEA), and a zwitterionic, sulfobetaine (ZIC), stationary phases were used for the HILIC mode, whilst an octadecylsilane (C18) stationary phase was employed for the RPLC separation. Overall, developed HILIC-QTOF method using the ZIC or BEH amide stationary phases resulted to be the most efficient methods to separate and characterize post-translationally modified (PTM) peptides without the need of any previous fractionation or derivatization step. The separation of phosphopeptides and differently sialylated O-glycopeptides in the ZIC stationary phase was dominated by an electrostatic repulsion interaction mechanism between the negatively charged phosphate groups or sialic acid moieties and the negatively charged terminal sulfonate group of the stationary phase, whereas the separation of either non-modified peptides or neutral O-glycopeptides both free of basic amino acids was based on a partitioning mechanism. In neutral amide columns, the separation was mainly dominated by hydrophilic partitioning, leading to a higher retention of the post-translationally modified peptides than the unmodified counterparts due to the hydrophilicity provided by the phosphate groups and/or O-glycans. As a consequence, HILIC-ESI-QTOF MS operating in the positive ion mode is a powerful tool for the characterization of underivatized O-glycopeptides and phosphopeptides.

Self-oscillating Water Chemiluminescence Modes and Reactive Oxygen Species Generation Induced by Laser Irradiation; Effect of the Exclusion Zone Created by Nafion.

Samples of water inside and outside an exclusion zone (EZ), created by Nafion swollen in water, were irradiated at the wavelength l = 1264 nm, which stimulates the electronic transition of dissolved oxygen from the triplet state to the excited singlet state. This irradiation induces, after a long latent period, chemiluminescence self-oscillations in the visible and near UV spectral range, which last many hours. It occurs that this effect is EZ-specific: the chemiluminescence intensity is twice lower than that from the bulk water, while the latent period is longer for the EZ. Laser irradiation causes accumulation of H2O2, which is also EZ-specific: its concentration inside the EZ is less than that in the bulk water. These phenomena can be interpreted in terms of a model of decreasing O2 content in the EZ due to increased chemical activity of bisulfite anions (HSO3-), arisen as the result of dissociation of terminal sulfonate groups of the Nafion. The wavelet transform analysis of the chemiluminescence intensity from the EZ and the bulk water gives, that self-oscillations regimes occurring in the liquid after the latent period are the determinate processes. It occurred that the chemiluminescence dynamics in case of EZ is characterized by a single-frequency self-oscillating regime, whereas in case of the bulk water, the self-oscillation spectrum consists of three spectral bands.

Effect of single-walled carbon nanotubes on the transport properties of sulfonated poly(styrene–isobutylene–styrene) membranes

Transport properties of polymer nanocomposite membranes (PNM) of sulfonated poly(styrene–isobutylene–styrene) (SIBS) were determined as a function of sulfonation level (0–89.7%), single-walled carbon nanotubes (SWCNT) loading (0.01, 0.1 and 1.0wt%), and chemical functionalization (carboxylic acid, aminomethanesulfonic acid and p-aminobenzoic acid) for direct methanol fuel cells and chemical and biological protective clothing applications. Transport properties increased with sulfonation level, as the ionic domains interconnect; however, at very high sulfonation levels a morphological transition to a more complex structure caused a decrease in transport properties. Proton conductivity increased with water content, but was sensitive to the type of water present (bound vs. bulk), especially in the SWCNT. Water bound to the ionic domains had the most significant effect on the proton conductivity. Methanol permeability was very sensitive to the incorporation of SWCNT addition, since its transport mechanism seems more dependent on free-volume; increasing SWCNT loading reduced the methanol permeability further. The selectivity (i.e., proton conductivity/methanol permeability) of the studied membranes was determined and compared to SIBS and Nafion® 117, suggesting an optimum SWCNT loading (0.1wt%) and functionalization (with terminal sulfonic groups), to balance the improvement in proton conductivity while reducing the methanol permeability. The selectivity of the membranes for vapor permeation of dimethyl methylphosphonate (DMMP) and water was best (up to 8.47) for the highest sulfonated membrane (SIBS 89.7) with the highest SWCNT loading (1.0wt%) and the SWCNT functionalized with terminal sulfonic groups.

Steric and electrostatic surface forces on sulfonated PEG graft surfaces with selective albumin adsorption

Addition of ionized terminal groups to PEG graft layers may cause additional interfacial forces to modulate the net interfacial interactions between PEG graft layers and proteins. In this study we investigated the effect of terminal sulfonate groups, characterizing PEG-aldehyde (PEG-CHO) and sulfonated PEG (PEG-SO3) graft layers by XPS and colloid probe AFM interaction force measurements as a function of ionic strength, in order to determine surface forces relevant to protein resistance and models of bio-interfacial interaction of such graft coatings. On the PEG-CHO surface the measured interaction force does not alter with ionic strength, typical of a repulsive steric barrier coating. An analogous repulsive interaction force of steric origin was also observed on the PEG-SO3 graft coating; however, the net interaction force changed with ionic strength. Interaction forces were modelled by steric and electrical double layer interaction theories, with fitting to a scaling theory model enabling determination of the spacing and stretching of the grafted chains. Albumin, fibrinogen, and lysozyme did not adsorb on the PEG-CHO coating, whereas the PEG graft with terminal sulfonate groups showed substantial adsorption of albumin but not fibrinogen or lysozyme from 0.15M salt solutions. Under lower ionic strength conditions albumin adsorption was again minimized as a result of the increased electrical double-layer interaction observed with the PEG-SO3 modified surface. This unique and unexpected adsorption behaviour of albumin provides an alternative explanation to the “negative cilia” model used by others to rationalize observed thromboresistance on PEG-sulfonate coatings.

Syntheses of 8-quinolinolatocobalt(iii) complexes containing cyclen based auxiliary ligands as models for hypoxia-activated prodrugs

New ligands H(2)L2-H(2)L6 comprise the cyclen macrocycle which is N,N'-dialkylated at the 1,7-nitrogen atoms by three- and four-carbon alkyl chains bearing terminal sulfonic (C(3) H(2)L2), phosphonic (C(3) H(2)L3, C(4) H(2)L4) or carboxylic acid (C(3) H(2)L5, C(4) H(2)L6) groups, and HL7 is N-monoalkylated by a four-carbon sulfonic acid group. The ligands were prepared by alkylation of a bridged bisaminal intermediate. The syntheses of cobalt(III) complexes containing a tetradentate cyclen, N,N'-1,7-Me(2)cyclen, cyclam or L2-L7 ligand together with the bidentate 8-quinolinato (8QO(-)) ligand, of interest as it is a model for a more potent cytotoxic analogue, were investigated. Coordination of ligands (L) cyclen, N,N'-1,7-Me(2)cyclen or cyclam to cobalt(III) was achieved using Na(3)[Co(NO(6))] to form [Co(L)(NO(2))(2)](+). HOTf (trifluoromethansulfonic acid) was used to prepare the triflato complexes [Co(L)(OTf)(2)](+), followed by substitution of the labile triflato ligands to yield [Co(L)(8QO)](ClO(4))(2) isolated as the perchlorate salts. One further example containing cyclam and the 5-hydroxymethyl-8-quinolinato ligand was also prepared by this method. Complexes containing the pendant arm ligands L2-L6 were prepared from the cobalt precursor trans-[Co(py)(4)Cl(2)](+). Reaction of this complex with H(2)L2·4HCl and 8QOH produced [Co(L2)(8QO)] in one step and contains two deprotonated sulfonato pendant arms. The reaction of H(2)L3·4HBr with [Co(py)(4)Cl(2)](+) gave [Co(L3)]Cl in which L3 acts as a hexadenate ligand with the three-carbon phosphonato side chains coordinated to cobalt. H(2)L5·4HCl bearing three-carbon carboxylic acid pendant arms gave a similar result. The four-carbon ligands were coordinated to cobalt by reaction of [Co(py)(4)Cl(2)](+) with H(2)L4·4HBr or H(2)L6·4HCl to give [Co(HL4)Cl(2)] or [Co(H(2)L6)Cl(2)]Cl, which in turn with 8QOH gave the 8QO(-) complexes [Co(L4)(8QO)] bearing anionic phosphate pendant arms or [Co(H(2)L6)(8QO)]Cl(2) containing neutral carboxylic acid side chains. The reaction of Na(3)[Co(CO(3))(3)] with the mono-N-alkylated ligand HL7·4HCl and then HOTf gave [Co(L7)(CO(3))] and then in turn [Co(L7)(OTf)(2)]. The carbonato complex [Co(L7)(CO(3))] with [8QO](2)[SO(4)] produced [Co(L7)(CO(3))]. All complexes containing L7 bear an anionic sulfonato group on the side chain. The synthesis and characterisation of the six new ligands based on N-alkylated cylen ligand and the cobalt complexes outlined above are described, along with cyclic voltammograms of the 8QO(-) complexes and the molecular structures determined by X-ray crystallography of [Co(cyclen)(H(2)O)(2)](OTf)(3) (formed by aquation of the triflato complex), [Co(cyclen)(8QO)](ClO(4))(2), Co(L2)(8QO)·2H(2)O, Co(L4)(8QO)·6H(2)O and [Co(H(2)L6)Cl(2)]Cl·H(2)O. These demonstrate the coordination of the cyclen ligand in the folded anti-O,syn-N configuration with the N-alkylated nitrogens occupying apical positions.

X-ray microscopy study of chromonic liquid crystal dry film texture

Soft x-ray spectromicroscopy has been used to investigate the degree of the molecular alignment of sulfonated benzo[de]benzo[4.5]imidazo[2,1-a]isoquinoline[7,1], a lyotropic chromonic liquid crystal (LCLC). LCLC thin films cast from concentrated aqua solution (20%wt.) , aligned by shear flow and dried, show strong linear dichroism in their C-, N-, O-, S- K edge near edge x-ray spectra (NEXAFS). The carbon K edge has been used for quantitative evaluation of the orientational texture of the films at a submicron spatial scale. This has verified there is predominantly in-plane alignment of the LC director. To highlight the role of hydrophobic-hydrophilic interactions, two stereoisomers of the same dye has been synthesized with different positioning of terminal sulfonate groups, in the form of a mixture of isomers with sulfonate groups in 2,10 and 2,11 positions (Y104 compound) and in a 5,10-disulfo arrangement (Y105). Both compounds develop characteristic herringbone-type texture with similar domain sizes. Polarized optical microscopy and higher resolution x-ray microscopy show sinusoidal-like undulations of the molecular director, with occasional crisscross appearance. Such behavior is found to be consistent with earlier observation of striations, characteristic of the columnar phase. The drastic difference in the degree of undulation ( +/-15 degrees in Y104 and +/-7 degrees in Y105 films) and long period of undulation (approaching the film thickness) requires further analysis. It was also found that the degree of in-plane order within domains changes from 0.8 for Y104 to >0.9 in Y105 films.

Removal of methyl tert-butyl ether (MTBE) with Nafion

A solid organic polymer, Nafion, is tested for the removal of methyl tert-butyl ether (MTBE) in water. Nafion with perfluorosulfonic acid backbone and terminal sulfonic acid groups has a surface acidity similar to 100% sulfuric acid, and has been commonly used as a strong-acid catalyst in many organic reactions. Sorption and subsequent transformation of MTBE were observed in batch experiments. The transformation of MTBE by porous nanocomposite Nafion SAC-13 to tert-butyl alcohol (TBA), acetone, isobutene and probably methanol was found. Subsequent transformation of TBA to acetone was also observed. Results suggest that transformational pathways may include hydrolysis, dehydrogenation and oxidation. Dissolved oxygen is needed for the oxidation of isobutene to acetone. As Nafion is insoluble in water, chemically stable, and regenerable, its use in packed-bed reactors for MTBE removal looks promising.

Molecular Modeling of the Short-Side-Chain Perfluorosulfonic Acid Membrane

Presented here is a first principles based molecular modeling investigation of the possible role of the side chain in effecting proton transfer in the short-side-chain perfluorosulfonic acid fuel cell membrane under minimal hydration conditions. Extensive searches for the global minimum energy structures of fragments of the polymer having two pendant side chains of distinct separation (with chemical formula: CF(3)CF(O(CF(2))(2)SO(3)H)(CF(2))(n)CF(O(CF(2))(2)SO(3)H)CF(3), where n = 5, 7, and 9) with and without explicit water molecules have shown that the side chain separation influences both the extent and nature of the hydrogen bonding between the terminal sulfonic acid groups and the number of water molecules required to transfer the proton to the water molecules of the first hydration shell. Specifically, we have found that fully optimized structures at the B3LYP/6-311G** level revealed that the number of water molecules needed to connect the sulfonic acid groups scaled as a function of the number of fluoromethylene groups in the backbone, with one, two, and three water molecules required to connect the sulfonic acid groups in fragments with n = 5, 7, and 9, respectively. With the addition of explicit water molecules to each of the polymeric fragments, we found that the minimum number of water molecules required to effect proton transfer also increases as the number of separating tetrafluoroethylene units in the backbone is increased. Furthermore, calculation of water binding energies on CP-corrected potential energy surfaces showed that the water molecules bound more strongly after proton dissociation had occurred from the terminal sulfonic acid groups independent of the degree of separation of the side chains. Our calculations provide a baseline for molecular results that can be used to assess the impact of changes of polymer chemistry on proton conduction, including the side chain length and acidic functional group.

Ethane-bridged hybrid mesoporous functionalized organosilicas with terminal sulfonic groups and their catalytic applications

The synthesis of a new class of sulfuric acid-functionalized ethane-bridged, mesoporous hybrid organosilicas is reported where the propylsulfonic groups attached with ethane-bridged silica exhibited reasonable catalytic activity in esterification of acetic acid with ethanol as well as the hydrolysis of cyclohexylacetate. Materials were synthesized by co-condensation of ethane-bridged organosilane (MeO)3SiCH2CH2Si(OMe)3 with 3-mercaptopropyltrimethoxysilane (MeO)3SiCH2CH2CH2SH in the presence of octadecyltrimethylammonium chloride surfactant. Powder X-ray diffraction patterns and nitrogen sorption analysis reveal the formation of mesoporous material with uniform porosity. The maximum content of incorporated mercaptopropylsilane in the mesoporous framework obtained was 3.45 mmol g−1. The thiol (–SH) moieties of mercaptopropyl groups that protrude into the pore channels are readily accessible for further oxidation. The surface moieties functionalized with propylsulfonic groups (–CH2CH2CH2–SO3H) were generated by the controlled oxidation of propylthiol surface groups using concentrated HNO3. A maximum acid exchange capacity (acid–base titration methods) of 1.38 H+ mmol g−1 was achieved after oxidation. Further, the materials were characterized using elemental analysis, FT-IR, 29Si and 13C MAS-NMR, transmission electron microscopy and TGA. Two probe reactions, the esterification of acetic acid with ethanol and its reverse the hydrolysis of cycloacetonate, showed the significance of the material in catalytic applications. The catalytic results showed the esterification activity is comparable to that of commercial Nafion-H and also the involvement of hydrophobic nature of the material in the hydrolysis reaction.