Iko Burgar

Microencapsulated Lactobacillus rhamnosus GG Powders: Relationship of Powder Physical Properties to Probiotic Survival during Storage

Freeze-dried commercial Lactobacillus rhamnosus GG (LGG) were encapsulated in an emulsion-based formulation stabilized by whey protein and resistant starch and either spray-dried or freeze-dried to produce probiotic microcapsules. There was no difference in loss of probiotics viability after spray drying or freeze drying. Particle size, morphology, moisture sorption, and water mobility of the powder microcapsules were examined. Particle size analysis and scanning electron microscopy showed that spray-dried LGG microcapsules (SDMC) were small spherical particles, whereas freeze-dried LGG microcapsules (FDMC) were larger nonspherical particles. Moisture sorption isotherms obtained using dynamic vapor sorption showed a slightly higher water uptake in spray-dried microcapsules. The effect of water mobility, as measured by nuclear magnetic resonance (NMR) spectroscopy, at various water activities (a(w) 0.32, 0.57, and 0.70) and probiotic viability during storage at 25 °C was also examined. Increasing the relative humidity of the environment at which the samples were stored caused an increase in water mobility and the rate of loss in viability. The viability data during storage indicated that SDMC had better storage stability compared to FDMC. Although more water was adsorbed for spray-dried than freeze-dried microcapsules, water mobility was similar for corresponding storage conditions because there was a stronger water-binding energy for spray-dried microcapsule. This possibly accounted for the improved survival of probiotics in spray-dried microcapsules.

Preparation of protic ionic liquids with minimal water content and 15N NMR study of proton transfer

Low-molecular-weight Brønsted acids and amine bases were used to reproducibly prepare very dry, high-purity room-temperature protic ionic liquids (PILs). A series of eight amine bases and six Brønsted acids were combined to produce 48 mixtures, of which 18 were liquid at room temperature. The phase transitions and thermal decomposition temperatures were determined for each mixture; whereas viscosity, density and conductivity were determined for the room-temperature liquids. By utilising (15)N NMR it was possible to distinguish between neutral and ionised amine bases (ammonia vs. ammonium-type ion), which indicated that the protic ionic liquids were completely ionised when made as a stoichiometric mixture. However, a Walden plot comparison of fluidity and molar conductivity indicated the majority of PILs had much lower conductivity than predicted by viscosity unless the base contained excess proton-donating groups. This disparity is indicative of protic ionic molecules forming neutral aggregates or non-Newtonian fluid hydrogen-bonded networks with a secondary Grotthuss proton-hopping mechanism arising from polyprotic bases.

Nonadditivity of Faradaic currents and modification of capacitance currents in the voltammetry of mixtures of ferrocene and the cobaltocenium cation in protic and aprotic ionic liquids.

Unexpected nonadditivity of currents encountered in the electrochemistry of mixtures of ferrocene (Fc) and cobaltocenium cation (Cc(+)) as the PF(6)(-) salt has been investigated by direct current (dc) and Fourier-transformed alternating current (ac) cyclic voltammetry in two aprotic (1-butyl-3-methylimidazolium tetrafluoroborate and 1-butyl-3-methylimidazolium hexafluorophosphate) and three protic (triethylammonium formate, bis(2-hydroxyethyl)ammonium acetate, and triethylammonium acetate) ionic liquids (ILs). The voltammetry of the individual Fc(0/+) and Cc(+/0) couples always exhibits near-Nernstian behavior at glassy carbon and gold electrodes. As expected for an ideal process, the reversible formal potentials and diffusion coefficients at 23 +/- 1 degrees C in each IL determined from measurement on individual Fc and Cc(+) solutions were found to be independent of electrode material, concentration, and technique used for the measurement. However, when Fc and Cc(+) were simultaneously present, the dc and ac peak currents per unit concentration for the Fc(0/+) and Cc(+/0) processes were found to be significantly enhanced in both aprotic and protic ILs. Thus, the apparent diffusion coefficient values calculated for Fc and Cc(+) were respectively found to be about 25 and 35% larger than those determined individually in the aprotic ILs. A similar change in the Fc(0/+) mass transport characteristics was observed upon addition of tetrabutylammonium hexafluorophosphate (Bu(4)NPF(6)), and the double layer capacitance also varied in distinctly different ways when Fc and Cc(+) were present individually or in mixtures. Importantly, the nonadditivity of Faradaic current is not associated with a change in viscosity or from electron exchange as found when some solutes are added to ILs. The observation that the (1)H NMR T(1) relaxation times for the proton resonance in Cc(+) also are modified in mixed systems implies that specific interaction with aggregates of the constituent IL ionic species giving rise to subtle structural changes plays an important role in modifying the mass transport, double layer characteristics, and dynamics when solutes of interest in this study are added to ILs. Analogous voltammetric changes were not observed in studies in organic solvent media containing 0.1 M added supporting electrolyte. Implications of the nonadditivity of Faradaic and capacitance terms in ILs are considered.

Extraction of Copper(II) Ions from Aqueous Solutions with a Methimazole-Based Ionic Liquid

The recently synthesized ionic liquid (IL) 2-butylthiolonium bis(trifluoromethanesulfonyl)amide, [mimSBu][NTf(2)], has been used for the extraction of copper(II) from aqueous solution. The pH of the aqueous phase decreases upon addition of [mimSBu](+), which is attributed to partial release of the hydrogen attached to the N(3) nitrogen atom of the imidazolium ring. The presence of sparingly soluble water in [mimSBu][NTf(2)] also is required in solvent extraction studies to promote the incorporation of Cu(II) into the [mimSBu][NTf(2)] ionic liquid phase. The labile copper(II) system formed by interacting with both the water and the IL cation component has been characterized by cyclic voltammetry as well as UV-vis, Raman, and (1)H, (13)C, and (15)N NMR spectroscopies. The extraction process does not require the addition of a complexing agent or pH control of the aqueous phase. [mimSBu][NTf(2)] can be recovered from the labile copper-water-IL interacting system by washing with a strong acid. High selectivity of copper(II) extraction is achieved relative to that of other divalent cobalt(II), iron(II), and nickel(II) transition-metal cations. The course of microextraction of Cu(2+) from aqueous media into the [mimSBu][NTf(2)] IL phase was monitored in situ by cyclic voltammetry using a well-defined process in which specific interaction with copper is believed to switch from the ionic liquid cation component, [mimSBu], to the [NTf(2)] anion during the course of electrochemical reduction from Cu(II) to Cu(I). The microextraction-voltammetry technique provides a fast and convenient method to determine whether an IL is able to extract electroactive metal ions from an aqueous solution.

Physical and electrochemical properties of thioether-functionalized ionic liquids.

The preparation and characterization of a series of ionic liquids based on S-alkyl thiolonium, S-alkyl thiotetrazolium, or S-alkyl thiobenzolium cations coupled with bis(trifluoromethanesulfonyl)amide, trifluoromethanesulfonate, alkyl phosphate, chloride, and hexafluorophosphate anions are reported. All are liquid at room temperature, except the chloride salt, which has a melting point of 92 degrees C. The electrochemical characteristics of this class of ionic liquid have been determined by cyclic voltammetry. Potential windows of the ionic liquids have been obtained at glassy carbon, platinum, and gold electrodes and found to be the largest at glassy carbon, but are limited by oxidation of the thioether-functionalized cation. The voltammetry of IUPAC reference potential scale systems, ferrocene/ferrocenium, cobaltocenium/cobaltocene, and decamethylferrocene/decamethylferrocenium have been evaluated, with the last being most widely applicable. Nonadditivity of Faradaic current is found in the voltammograms of decamethylferrocene in the presence of ferrocene and cobaltocenium. Diffusion coefficient, viscosity, ionic conductivity, double layer capacitance, and other physical properties have also been measured. The dependence of the diffusion coefficient vs viscosity follows the Stokes-Einstein relationship. The properties of the ionic liquids are compared with the related imidazolium family of ionic liquids.

NMR Relaxation and Self-Diffusion Study at High and Low Magnetic Fields of Ionic Association in Protic Ionic Liquids

NMR relaxation and diffusion characterization of several protic ionic liquids at high and low magnetic fields are reported. The dynamics of cations and anions were similar at both frequencies, with similar trends and magnitudes for a fixed component paired with oppositely charged species. An Arrhenius relationship was displayed between the molecular motion and the glass transition temperature. The diffusion of ions showed a strong degree of ion correlation between cation and anion, and Arrhenius plots of relaxation and diffusion indicated that the ions diffused as a pair. At high field diffusion was dominated by mobile species that followed Stokes-Einstein behavior. Conversely, diffusion observed at low field emphasized relatively immobile species that displayed fractional Stokes-Einstein behavior. No evidence was found to indicate the influence of magnetic field on structural and dynamic properties of the studied ILs; however, variation between diffusion coefficients at different magnetic fields indicated dynamic heterogeneities (or temporal aggregates) within the ionic liquid.

Water sorption properties, molecular mobility and probiotic survival in freeze dried protein–carbohydrate matrices

The moisture uptake and molecular mobility of freeze-dried powders containing whey protein isolate-carbohydrate matrices (1WPI:2maltodextrin; 1WPI:1maltodextrin:1d-glucose; and 1WPI:1maltodextrin:1l-glucose) and encapsulated Lactobacillus rhamnosus GG (LGG) in these matrices were investigated at 25 °C and 33% and 70% relative humidity (RH). The inactivation rate constant for probiotics in freeze-dried matrices were positively correlated (R(2) = 0.98) to moisture uptake and molecular mobility measured by NMR relaxometry. The stability of probiotics in glassy protein-carbohydrate matrices was dependent on the composition of the matrix. The partial substitution of maltodextrin with glucose (d- or l-) which improved microbial survival at 33% RH was related to the reduced molecular mobility and lower water uptake of the matrix. This study suggests that moisture uptake properties and molecular mobility of the matrix composition, as opposed to the relative humidity of the environment, are better determinants of probiotic viability during storage. Dynamic vapour sorption and NMR relaxometry are promising tools to assist in the selection of protein-carbohydrate matrices for enhancing probiotic viability during storage.

Nitrile functionalized methimazole-based ionic liquids

The alkylation reaction of 2-mercapto-1-methylimidazole 1b with 2-chloroacetonitrile and 2-chloropropionitrile produced S-alkyl methimazole chlorides 2a and 2b which were subjected to anion metathesis with lithium bis(trifluoromethanesulfonyl)amide, LiNTf(2), to afford nitrile functionalized methimazole-based room temperature ionic liquids 3a and 3b in 94% and 89% yields, respectively. Ionic liquids 3a and 3b have reasonably wide electrochemical windows. The efficient extraction of Ag(+) from aqueous media into 3a and 3b is also reported.

Synthesis, X-ray structure and electrochemical oxidation of palladium(II) complexes of ferrocenyldiphenylphosphine

Four new complexes, [PdX(κ(2)-2-C(6)R(4)PPh(2))(PPh(2)Fc)] [X = Br, R = H (1), R = F (2); X = I, R = H (3), R = F (4)], containing ferrocenyldiphenylphosphine (PPh(2)Fc) have been prepared and fully characterised. The X-ray structures of complexes trans-1, cis-2 and cis-4, and that of a decomposition product of 4, [Pd(κ(2)-2-C(6)F(4)PPh(2))(μ-I)(μ-2-C(6)F(4)PPh(2))PdI(PPh(2)Fc)] (5), have been determined. These complexes show a distorted square planar geometry about the metal atom, the bite angles of the chelate ligands being about 69°, as expected. The cis/trans ratio of 1-4 in solution is strongly dependent on solvent. The new complexes and the uncoordinated PPh(2)Fc ligand were electrochemically characterised by cyclic and rotating disk voltammetry, UV-visible spectroelectrochemistry, and bulk electrolysis in dichloromethane and acetonitrile. In both cases, oxidation occurs at both the ferrocene and phosphine centres, but the complexes oxidise at more positive potentials than uncoordinated PPh(2)Fc; subsequently, the metal-phosphorus bond is cleaved, leading to free PPh(2)Fc(+), which undergoes further chemical and electrochemical reactions.

Methimazole-based ionic liquids.

The alkylation reaction of 2-mercapto-1-methylimidazole 1a with iodoethane and chlorobutane produced S-alkylmethimazole halides 2a and 2b which were subjected to anion metathesis with two different metal salts (MA) to afford methimazole-based room-temperature ionic liquids 3a, 3b, and 3c in 82%, 85%, and 87% yields, respectively. S-Alkylation giving 2a and 2b suggests that methimazole reacts through the thione tautomer.