Ionic Head Groups Research Articles

Thermodynamics of aggregate formation between a non-ionic polymer and ionic surfactants: An isothermal titration calorimetric study

This report examines the energetics of aggregate formation between hydroxypropyl methylcellulose (HPMC) and model ionic surfactants including sodium dodecyl sulfate (SDS) at pharmaceutically relevant concentrations using the isothermal titration calorimetry (ITC) technique and a novel treatment of calorimetric data that accounts for the various species formed. The influence of molecular weight of HPMC, temperature and ionic strength of solution on the aggregate formation process was explored. The interaction between SDS and HPMC was determined to be an endothermic process and initiated at a critical aggregation concentration (CAC). The SDS-HPMC interactions were observed to be cooperative in nature and dependent on temperature and ionic strength of the solution. Molecular weight of HPMC significantly shifted the interaction parameters between HPMC and SDS such that at the highest molecular weight (HPMC K–100M;>240kDa), although the general shape of the titration curve (enthalpogram) was observed to remain similar, the critical concentration parameters (CAC, polymer saturation concentration (Csat) and critical micelle concentration (CMC)) were significantly altered and shifted to lower concentrations of SDS. Ionic strength was also observed to influence the critical concentration parameters for the SDS-HPMC aggregation and decreased to lower SDS concentrations with increasing ionic strength for both anionic and cationic surfactant-HPMC systems. From these data, other thermodynamic parameters of aggregation such as ΔHagg°, ΔGagg°, Hagg°, ΔSagg°, and ΔCp were calculated and utilized to postulate the hydrophobic nature of SDS-HPMC aggregate formation. The type of ionic surfactant head group (anionic vs. cationic i.e., dodecyltrimethylammonium bromide (DTAB)) was found to influence the strength of HPMC-surfactant interactions wherein a distinct CAC signifying the strength of HPMC-DTAB interactions was not observed. The interpretation of the microcalorimetric data at different temperatures and ionic strengths while varying properties of polymer and surfactant was a very effective tool in investigating the nature and energetics of HPMC and ionic surfactant interactions.

The Influence of Water on the Alkyl Region Structure in Variable Chain Length Imidazolium-Based Ionic Liquid/Water Mixtures.

Solutions of room temperature ionic liquids (RTILs) and water were studied by observing the reorientational dynamics of the fluorescent probe perylene. Perylene is solvated in the alkyl regions of the RTILs. Its D2h symmetry made it possible to extract dynamical information on both in-plane and out-of-plane reorientation from time-resolved fluorescence anisotropy measurements. Perylene reorientation reports on its interactions with the alkyl chains. The RTILs were a series of 1-alkyl-3-methylimidazolium tetrafluoroborates (CnmimBF4, where n is the number of carbons in the alkyl chain), and the effects on perylene's dynamics were observed when varying the alkyl chain length of the cation (n = 4, 6, 8, and 10; butyl, hexyl, octyl, decyl) and varying the water content from pure RTIL to roughly three water molecules per RTIL ion pair. Time correlated single photon counting was used to measure the fluorescence anisotropy decays to determine the orientational dynamics. The friction coefficients for both the in-plane and out-of-plane reorientation were determined to eliminate the influence of changes in viscosity caused by both the addition of water and the different alkyl chain lengths. The friction coefficients provided information on the interactions of the perylene with the alkyl environment and how these interactions changed with chain length and water content. As the chain length increased, the addition of water had less of an effect on the local alkyl environment surrounding the perylene. The friction coefficients generally increased with higher water contents; the in-plane orientational motion was hindered significantly more than the out-of-plane motion. The restructuring of the alkyl regions is likely a consequence of a rearrangement of the ionic imidazolium head groups to accommodate partial solvation by water, which results in a change in the arrangement of the alkyl chains. At very high water content, BmimBF4 broke this general trend, with both in-plane and out-of-plane rotational friction decreasing above a water content of one water per ion pair. This decrease indicates a major reorganization of the overall liquid structure in high water content mixtures. In contrast to BmimBF4, the longer chain length RTILs are not infinitely miscible with water, and do not show evidence of a major reorganization before reaching saturation and phase-separating. The results suggest that phase separation in longer chain length BF4 RTILs is a consequence of their inability to undergo the reorganization of the alkyl regions necessary to accommodate high water concentrations.

Adsorption behavior, spreading and thermal stability of anionic-nonionic surfactants with different ionic headgroup

The anionic-nonionic surfactants have attracted great interest due to its particular molecular structure. To compare the effect of anionic headgroup on the performance of anionic-nonionic surfactants, the adsorption behavior at air/water and oil/water interface, spreading performance and thermal stability of anionic-nonionic surfactants, sodium alkyl polyethylene oxide carboxylate (AE3C), sodium alkyl polyethylene oxide sulfate (AE3S), and sodium alkyl polyethylene oxide sulfonate (AE3SO), were investigated by surface tension, interfacial tension, contact angle techniques and thermogravimetric analysis. The results of static surface tension and interfacial tension show that the AE3C has the best interfacial activity. Adsorption process for surfactants concentration above cmc is a mixed diffusion–kinetic adsorption mechanism, and below cmc is diffusion-controlled mechanism. Spreading ability on paraffin films of the three surfactants decreases in the order AE3C>AE3S>AE3SO. The thermal stability is in the sequence of AE3C>AE3SO>AE3S.

Induction of ionic smectic C phases: a systematic study of alkyl-linked guanidinium-based liquid crystals

ABSTRACTA series of ionic liquid crystals with an alkoxy biphenyl unit tethered via an alkyl spacer to a guanidinium head group were synthesised and the mesomorphic properties were studied by differential scanning calorimetry, polarising optical microscopy and X-ray diffraction (XRD; WAXS and SAXS). Whereas all symmetrical guanidinium chlorides with the same chain lengths in alkyl tail and spacer displayed enantiotropic SmA2 phases, monotropic SmC2 phases with 1–2 K temperature range were only formed for chain lengths ≥ C10. Shifting the calamitic core more closely to the ionic head group by decreasing the tether length and simultaneously increasing the terminal alkyl chain improved the stability of both SmA and SmC phases considerably and led to enantiotropic SmC phases for the guanidinium chloride with C14 alkyl tail and C6 spacer. An even more pronounced effect was detected during anion exchange. Bromide, iodide, hexafluorophosphate, thiocyanate and triflate suppressed any SmC phase, whereas tetrafluoroborate behaved similar to chloride maintaining the SmC phase. However, acetate stabilised the SmC phase at the expense of the SmA phase. Based on temperature-dependant XRD measurements, a bilayer structure was proposed.

Water Dynamics in Gyroid Phases of Self-Assembled Gemini Surfactants.

Water-mediated ion transport through functional nanoporous materials depends on the dynamics of water confined within a given nanostructured morphology. Here, we investigate H-bonding dynamics of interfacial water within a "normal" (Type I) lyotropic gyroid phase formed by a gemini dicarboxylate surfactant self-assembly using a combination of 2DIR spectroscopy and molecular dynamics simulations. Experiments and simulations demonstrate that water dynamics in the normal gyroid phase is 1 order of magnitude slower than that in bulk water, due to specific interactions between water, the ionic surfactant headgroups, and counterions. Yet, the dynamics of water in the normal gyroid phase are faster than those of water confined in a reverse spherical micelle of a sulfonate surfactant, given that the water pool in the reverse micelle and the water pore in the gyroid phase have roughly the same diameters. This difference in confined water dynamics likely arises from the significantly reduced curvature-induced frustration at the convex interfaces of the normal gyroid, as compared to the concave interfaces of a reverse spherical micelle. These detailed insights into confined water dynamics may guide the future design of artificial membranes that rapidly transport protons and other ions.

Aggregation properties of levofloxacin in water and ethanol and its interaction with sodium dodecyl sulphate: A thermodynamic study

This manuscript reports the determination of critical micelle concentration (CMC) of levofloxacin (LF) in two solvents, water and ethanol, by using surface tension, refractive index and absorbance measurements. The data thus obtained were used to calculate different thermodynamic parameters for micellization process like free energy of micellization, free energy of adsorption, entropy and enthalpy of micellization. The interaction of this drug with anionic surfactant (SDS) was also studied using UV/Visible spectroscopy and conductometry. With rise in temperature, CMC of the drug was found to decrease in ethanol and increase in aqueous solution indicating dominance of lipophobic desolvation over lipophilic desolvation in ethanol and reverse, in case of aqueous solution. A strong drug/surfactant interaction was found to exist. The data obtained from drug/surfactant interaction were also used to find different interaction parameters like partition constant, free energy of partition, binding constant and free energy of binding which are very useful to understand the phenomenon of solubilization. Critical micelle concentration of levofloxacin increases with temperature in aqueous solution and decreases in ethanol. Processes of micellization and adsorption of drug molecules at solution-air interface are spontaneous and results in increase in entropy. The drug shows strong interaction with anionic surfactant (SDS) due to solubilization of drug molecules between ionic head groups of micelles of SDS.

Synthesis and Solution Properties of a Double‐Tailed Quaternary Ammonium Surfactant with a Protrudent Head Group

AbstractModification of the molecular structure of surfactants is an effective method for exploring their self‐assembly. A double‐tailed quaternary ammonium surfactant with a protrudent head group, namely 2‐octyldecyltrimethylammonium bromide (2‐ODTAB) was synthesized, and the solution properties were investigated by surface tension, dynamic light scattering, and cryogenic TEM. A comparative study was also performed on the traditional double‐tailed homologue surfactants dioctyldimethylammonium bromide (8–8), didecyldimethylammonium bromide (10–10), and didodecyldimethylammonium bromide (12–12). The results showed that 2‐ODTAB was more effective at lowering surface tension and in forming stable vesicles than traditional double‐tailed surfactants with similar alkyl chain length. The reason is attributed to the improved structure of 2‐ODTAB, in which the two alkyl tails are connected to the ionic head group by one carbon atom. This structure imparts more freedom to the head group and thus favors formation of more stable aggregates at low concentration. In addition, the lower limit of the alkyl chain length of the double‐tailed surfactants for forming stable vesicles was illustrated.

Amino alcohol-derived chiral ionic liquids: structural investigations toward chiral recognition

From tentative beginnings, chiral ionic liquids have emerged into functionalized and tailor-made materials that provide novel input in classical asymmetric synthesis and separations. However, despite this broad application range the prediction of any chiral ionic liquids’ performance is difficult. We present a systematic study toward the chiral recognition properties of novel ionic liquids with an amino alcohol sub-structure derived from the chiral pool precursors ephedrine, prolinol, and phenylalaninol. The influence of different ionic head groups and core structures on the diastereomeric interactions between racemic Mosher’s acid carboxylate and enantiopure chiral ionic liquids was systematically investigated to provide insight into their recognition properties prior to application of these chiral ionic liquids in various fields.

Simulated Solvation of Organic Ions II: Study of Linear Alkylated Carboxylate Ions in Water Nanodrops and in Liquid Water. Propensity for Air/Water Interface and Convergence to Bulk Solvation Properties.

We investigated the solvation of carboxylate ions from formate to hexanoate, in droplets of 50 to 1000 water molecules and neat water, by computations using standard molecular dynamics and sophisticated polarizable models. The carboxylate ions from methanoate to hexanoate show strong propensity for the air/water interface in small droplets. Only the ions larger than propanoate retain propensity for the interface in larger droplets, where their enthalpic stabilization by ion/water dispersion is reduced there by 3 kcal mol(-1) per CH2 group. This is compensated by entropy effects over +3.3 cal mol(-1) K(-1) per CH2 group. On the surface, the anionic headgroups are strongly oriented toward the aqueous core, while the hydrophobic alkyl chains are repelled into air and lose their structure-making effects. These results reproduce the structure-making effects of alkyl groups in solution, and suggest that the hydrocarbon chains of ionic headgroups and alkyl substituents solvate independently. Extrapolation to bulk solution using standard extrapolation schemes yields absolute carboxylate solvation energies. The results for formate and acetate yield a proton solvation enthalpy of about 270 kcal mol(-1), close to the experiment-based value. The largest carboxylate ions yield a value smaller by about 10 kcal mol(-1), which requires studies in much larger droplets.

Simulated solvation of organic ions II: Study of linear alkylated

We investigated the solvation of carboxylate ions from formate to hexanoate, in droplets of 50 to 1000 water molecules and neat water, by computations using standard molecular dynamics and sophisticated polarizable models. The carboxylate ions from methanoate to hexanoate show strong propensity for the air/water interface in small droplets. Only the ions larger than propanoate retain propensity for the interface in larger droplets, where their enthalpic stabilization by ion/water dispersion is reduced there by 3 kcal mol–1 per CH2 group. This is compensated by entropy effects over +3.3 cal mol–1 K–1 per CH2 group. On the surface, the anionic headgroups are strongly oriented toward the aqueous core, while the hydrophobic alkyl chains are repelled into air and lose their structure-making effects. These results reproduce the structure-making effects of alkyl groups in solution, and suggest that the hydrocarbon chains of ionic headgroups and alkyl substituents solvate independently. Extrapolation to bulk solution using standard extrapolation schemes yields absolute carboxylate solvation energies. The results for formate and acetate yield a proton solvation enthalpy of about 270 kcal mol–1, close to the experiment-based value. The largest carboxylate ions yield a value smaller by about 10 kcal mol–1, which requires studies in much larger droplets.

Ionomer Self-Assembly in Dilute Solution: A Molecular Dynamics Study

Self-assembly of ionomer chains in dilute solution is studied by classical molecular dynamics. Based on a bead-spring ionomer model, the simulation approach captures formation of cylindrical, bundle-like [1] aggregates with a hydrophobic core region, a surface layer of charged anionic headgroups and a halo of counterions (protons) in the surrounding aqueous phase. Ionomer aggregation enforces the stretching and stiffening of ionomer chains, which is caused mainly by the repulsion of anionic headgroups. The strengths of hydrophobic and electrostatic interactions are varied to explore their effect on the aggregation process. Strong hydrophobicity of the ionomer main chain results in greater aggregate sizes. Figure 1a shows the result of the changes in the aggregate size, <k>, over the range of explored hydrophobicity. Strong electrostatic interaction of ionic headgroups decreases the aggregate size, results are shown in figure 1b. Simulations also show the spontaneous formation of networks of ionomer bundles. Results of simulations will be discussed in the context of experimental studies on the formation of rodlike structures in ionomer solutions [2-3] that form the mechanically stable skeleton of polymer electrolyte membranes such as Nafion [4]. Moreover, implications of simulation results for water sorption phenomena [5], proton conductivity [6], membrane degradation [7] and membrane failure will be discussed. Figure caption: Figure 1. Changes of the average aggregate size, <k>, as a function of variation in strengths of hydrophobic interactions (a) and electrostatic interactions (b). Strength of hydrophobic interactions are controlled through variation of strength of excluded volume interaction of hydrophobic monomeric beads while the electrostatic strength is varied through changes in the Bjerrum length.

Carbon Nanodots: Supramolecular Electron Donor-Acceptor Hybrids Featuring Perylenediimides.

We describe the formation of charge-transfer complexes that feature electron-donating carbon nanodots (CND) and electron-accepting perylenediimides (PDI). The functionalities of PDIs have been selected to complement those of CNDs in terms of electrostatic and π-stacking interactions based on oppositely charged ionic head groups and extended π-systems, respectively. Importantly, the contributions from electrostatic interactions were confirmed in reference experiments, in which stronger interactions were found for PDIs that feature positively rather than negatively charged head groups. The electronic interactions between the components in the ground and excited state were characterized in complementary absorption and fluorescence titration assays that suggest charge-transfer interactions in both states with binding constants on the order of 8×10(4) M(-1) (25 L g(-1) ). Selective excitation of the two components in ultrafast pump probe experiments gave a 210 ps lived charge-separated state.

Phase behavior of Langmuir monolayers with ionic molecular heads: Molecular simulations.

We carried out Monte Carlo simulations in the N,Π,T ensemble of a Langmuir monolayer coarse-grained molecular model. Considering that the hydrophilic groups can be ionized by modulating acid-base interactions, here we study the phase behavior of a model that incorporates the short-range steric and long-range ionic interactions. The simulations were carried out in the reduced temperature range 0.1≤T*<4.0, where there is a competition of these interactions. Different order parameters were calculated and analyzed for several values of the reduced surface pressure in the interval, 1≤Π*≤40. For most of the surface pressures two directions of molecular tilt were found: (i) towards the nearest neighbor (NN) at low temperatures, T*<0.7, and most of the values of Π* and (ii) towards next-nearest neighbors (NNN) in the temperature interval 0.7≤T*<1.1 for Π*<25. We also found the coexistence of the NN and NNN at intermediate temperatures and Π*>25. A low-temperature reentrant disorder-order-disorder transition in the positions of the molecular heads and in the collective tilt of the tails was found for all the surface pressure values. It was also found that the molecular tails arranged forming "rotating patterns" in the temperature interval, 0.5<T*<1.5, at intermediate surface pressures. We estimated the monolayer's surface pressure versus temperature and the temperature versus area per molecule phase diagrams. It was found that the LE↔LC phase transition shifts to smaller temperatures when the molecular heads carry an ion in qualitative agreement with experimental observations of fatty acid monolayers with ionic head groups. Two surface pressure versus area per molecule isotherms were also calculated. At low temperatures near the LC-NN ↔ LC-NNN transitions and at higher temperatures close to the LE ↔ LC transitions. From these isotherms the monolayer's area compression modulus was obtained and its variation ranges in the LE and LC phases were found to be consistent with the experimental values.

Micellization behavior of the mixtures of amino sulfonate amphoteric surfactant and octadecyltrimethyl ammonium bromide in aqueous solution at 40 °C: a tensiometric study

In aqueous solution at 40 °C, the micellization behavior of the binary mixtures constituted by an amphoteric sodium n-dodecyl diamine sulfonate and a cationic octadecyltrimethyl ammonium bromide has been investigated by the tensiometric technology. The values of critical micelle concentration (cmc) were determined by surface tension measurement of aqueous solution. The experimental data were analyzed according to various mixing thermodynamic models within the framework of the pseudophase separation model. The values of mixed cmc have been predicted successfully by both the Rubingh’s and Rodenas’s treatments. Various parameters like the mixed cmc, interaction parameters between surfactants (β12), the compositions and activity coefficients in mixed micelles as well as thermodynamic properties have been determined using Lang, Rubingh, Rodenas, and Rosen approach. Over the entire composition range investigated, the mixed micelle formation, non-ideal or ideal mixing, and synergistic effect or antagonism are explained by the electrostatic interaction between ionic headgroups of surfactants and the steric effect of surfactant. Thermodynamic parameters favor the process of micellization which is found to be entropy-driven.

Polar interactions trump hydrophobicity in stabilizing the self-inserting membrane protein Mistic.

Canonical integral membrane proteins are attached to lipid bilayers through hydrophobic transmembrane helices, whose topogenesis requires sophisticated insertion machineries. By contrast, membrane proteins that, for evolutionary or functional reasons, cannot rely on these machineries need to resort to driving forces other than hydrophobicity. A striking example is the self-inserting Bacillus subtilis protein Mistic, which is involved in biofilm formation and has found application as a fusion tag supporting the recombinant production and bilayer insertion of other membrane proteins. Although this unusual protein contains numerous polar and charged residues and lacks characteristic membrane-interaction motifs, it is tightly bound to membranes in vivo and membrane-mimetic systems in vitro. Therefore, we set out to quantify the contributions from polar and nonpolar interactions to the coupled folding and insertion of Mistic. To this end, we defined conditions under which the protein can be unfolded completely and reversibly from various detergent micelles by urea in a two-state equilibrium and where the unfolded state is independent of the detergent used for solubilizing the folded state. This enabled equilibrium unfolding experiments previously used for soluble and β-barrel membrane proteins, revealing that polar interactions with ionic and zwitterionic headgroups and, presumably, the interfacial dipole potential stabilize the protein much more efficiently than nonpolar interactions with the micelle core. These findings unveil the forces that allow a protein to tightly interact with a membrane-mimetic environment without major hydrophobic contributions and rationalize the differential suitability of detergents for the extraction and solubilization of Mistic-tagged membrane proteins.

Systematic Variation of Membrane Chemistry and Biofilm Composition in Strategic Modifications of Microbial Fuel Cells (MFC) and Other Bio-Electrochemical Systems (BES)

Microbial fuel cell (MFC) technology is under development for electricity production for cleansing of waste waters, but also for direct use of the electricity in bio-electrochemical systems (BES) geared to produce high added value products (e.g. acetate and other complex organics from CO2). The presentation will detail systematic examination of the chemical and biological variables in such systems. Both cation and anion exchange membranes of a range of controlled thickness as anode compartment and air cathode separator membrane will be outlined, with the accompanying variations in performance of otherwise similar cells. Both types of membrane can be readily tailored by their production using radiation-induced grafting of appropriately functionalized precursors and subsequent conversion to ionic head groups with accompanying ion-exchange properties.From extensive studies of a range of closely related MFCs, the role of variations in the composition of anode biofilms in operational MFCs have been characterized and compared to the population in suspension [1]. Film composition has been followed using DDGE, identifying the range of microbes present and variations in film composition during operation. Diversity of the community has been found to correlate with cell performance, and hence can be used as a predictor of cell behavior [2].Identification of the make-up of microbial communities in operating MFCs has led to studies of the electrogenic activities of individual strains, and of their interactions when more than one species is present, detecting synergistic or antagonistic relationships. Data on microbial oxidative activity (metabolic profiling) using a range of substrates and a Biolog instrument (multi-well UV-vis spectrometer) have characterized the behaviors of a range of species (e.g. C. denitrificans and B. graminisolvens) not normally considered of significance for power production in MFCs, both as single strains and in combination. “Synthetic communities” derived from these studies are indeed active in production of electricity in MFCs, with product analysis carried out by ion chromatography. A basic outline of the proposed metabolic profile of a synthetic community has been proposed, with individual species being classified as fermentative or electrogenic. The presence of fermentative species may lead to higher power output, contrary to previous orthodoxy. The potential for use of a complex waste (distiller’s dried grains with solubles, DDGS) for production of electricity or in the bio-electrochemical production of high added value products is also under investigation, with useable power densities being achieved Acknowledgements The UK’s SUPERGEN Biological Fuel Cells Consortium (8 univeristies) is led by RS and is funded by Research Councils UK (RCUK) under EPSRC grant EP/H019480/1. Further work in MFC science at Surrey is funded by RCUK under EPSRC grant EP/I004882/1 and BBSRC grant BB/J01916X/1.

Combined use of chiral ionic liquid surfactants and neutral cyclodextrins: Evaluation of ionic liquid head groups for enantioseparation of neutral compounds in capillary electrophoresis

Cyclodextrins (CDs) are most commonly used chiral selectors in capillary electrophoresis (CE). Although the use of neutral CDs and its derivatives have shown to resolve plethora of charged enantiomers, they cannot resolve neutral enantiomers. The use of ionic liquids (ILs) surfactants forming successful complex with CDs present itself an opportunity to resolve neutral enantiomers. In this work, the effect of IL head groups and their complexation ability with heptakis (2,3,6-tri-O-methyl)-β-cyclodextrin (TM-β-CD) was studied for the separation of neutral enantiomers by CE. First, cationic IL type surfactants with different chiral head groups were synthesized. Physicochemical properties such as critical micelle concentration were determined by surface tension, whereas aggregation and polarity were determined by fluorescence spectroscopy. The complexation ability of ILs with TM-β-CD was characterized in the gas phase by CE-mass spectrometry. The influence of the type of ILs head group and its concentration on chiral resolution, resolution per unit time and selectivity were investigated for four structurally diverse neutral compounds. The binding constants of the neutral analytes to the IL–CD complex were estimated by y-reciprocal method. The hydrophobicity of the side chain of the IL head group displayed significant effect on the binding constants and enantioseparations.

Bicontinuous microemulsions for high yield wet synthesis of ultrafine platinum nanoparticles: effect of precursors and kinetics.

We demonstrate that for high yield wet synthesis of monodispersed nanoparticles high surfactant content bicontinuous microemulsions offer an advantageous template as particle size is limited by the embedding matrix whereas particle aggregation is largely prohibited by its structure. We synthesized platinum nanoparticles varying the reaction rate, metal precursor and reducing agent type and concentration, and the composition of the microemulsion in water content and oil type. High yields of up to 0.4% of metal produced per weight of template were achieved without affecting the particle size, ca. 2 nm. We showed that our method is robust in the sense that particle size is hardly dependent on synthesis conditions. This is attributed to the fact that the packing of surfactant on nanoparticle surfaces is the only parameter determining the particle size. It can only be slightly varied with ionic strength, headgroup hydration, and tail solvency through oil variation. Water content mainly affects the microemulsion stability and through that the colloidal stability of the nanoparticles. Hydrazine as a reducing agent poses a special case as it causes dimerization of the surfactant and hence modifies the surfactant parameter as well as the stability. Finally, we highlighted the differences in comparison to nanoparticle synthesis in standard water-in-oil microemulsions, and we propose a mechanism of particle formation.

Dimer ion formation and intermolecular fragmentation of 1,2-diacylglycerols revealed by electrospray ionization Fourier transform ion cyclotron resonance mass spectrometry for more comprehensive lipid analysis.

The ionization of neutral diacylglycerols (DAGs) by electrospray ionization mass spectrometry (ESI-MS) is challenging compared with other lipid classes which possess ionic head group conjugations. Although ESI-MS is the method of choice in lipidomic analysis, it is questionable whether all lipid classes can be efficiently ionized by this method. Actually, various lipids were not efficiently detected (due to poor ionization) in many studies which claimed to comprehensively describe lipid profiles. Since neutral lipids are precursors for the biosynthesis of most other lipid classes, the necessity for improved or alternative ionization and identification schemes becomes obvious. We identified the 1,2-diacylglycerol (DAG) dimer ion formation in the gas phase by ultra-high-resolution Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR-MS) in negative electrospray ionization ((-)ESI) mode. The geometry of the dimer ion was investigated by accurate density functional theory (DFT) calculations at the B3LYP/6-311+G(d)//B3LYP/LANL2DZ level of theory. Fragmentation of the dimer ions of many investigated DAGs has been achieved via collision-induced dissociation (CID) experiments with several elevated collision energies (0-12 eV). We revealed the possibility to ionize neutral DAGs as dimer ions in the negative ESI mode. Quantum mechanical calculations revealed a polar head-to-head intermolecular interaction between one charged DAG and one DAG neutral. This represents an energy minimum structure for the DAG dimer ions. We could furthermore detect CID fragmentation product ions that can only result from intermolecular reactions in this head-to-head conformation (SN2 nucleophilic substitution reactions inside the dimer DAG ion). Here, we present for the first time the opportunity to ionize and identify DAGs as dimer ions. This new finding provides a new alternative for investigations of important diacylglycerol lipids and provides the opportunity to obtain complementary and more comprehensive results in future lipidomic studies.

Simulated solvation of organic ions: protonated methylamines in water nanodroplets. Convergence toward bulk properties and the absolute proton solvation enthalpy.

We applied an alternative, purely theoretical route to estimate thermodynamical properties of organic ions in bulk solution. The method performs a large ensemble of simulations of ions solvated in water nanodroplets of different sizes, using a polarizable molecular dynamics approach. We consider protonated ammonia and methylamines, and K(+) for comparison, solvated in droplets of 50-1000 water molecules. The parameters of the model are assigned from high level quantum computations of small clusters. All the bulk phase results extrapolated from droplet simulations match, and confirm independently, the relative and absolute experiment-based ion solvation energies. Without using experiment-based parameters or assumptions, the results confirm independently the solvation enthalpy of the proton, as -270.3 ± 1.1 kcal mol(-1). The calculated relative solvation enthalpies of these ions are constant from small water clusters, where only the ionic headgroups are solvated, up to bulk solution. This agrees with experimental thermochemistry, that the relative solvation energies of alkylammonium ions by only four H2O molecules reproduce the relative bulk solvation energies, although the small clusters lack major bulk solvation factors. The droplet results also show a slow convergence of ion solvation properties toward their bulk limit, and predict that the stepwise solvation enthalpies of ion/water droplets are very close to those of pure neutral water droplets already after 50 water molecules. Both the ionic and neutral clusters approach the bulk condensation energy very gradually up to 10,000 water molecules, consistent with the macroscopic liquid drop model for pure water droplets. Compared to standard computational methods based on infinite periodic systems, our protocol represents a new purely theoretical approach to investigate the solvation properties of ions. It is applicable to the solvation of organic ions, which are pivotal in environmental, industrial, and biophysical chemistry but have been little investigated theoretically up to the present.