Kaolinites of all kinds (fine, ‘fireclay,’ ‘type IV,’ etc.), some of which do not expand or expand incompletely with the usual intercalation methods used for comparison, are expanded completely by treatment of dry (110°C) clay with dry CsCl salt, followed by contact with hydrazine for 1 day at 65°C and then with DMSO overnight at 90°C. Comparison treatments were grinding in KOAc, soaking in hydrazine, and Li-DMSO, as well as combination of these. Following the Cs-hydrazine-DMSO treatment, the 7.2 Å spacing of 1:1 dioctahedral layer silicates shifts to 11.2 Å and the 11.2 Å/(7.2 + 11.2 Å) ratio ≃1.0. The trioctahedral 1:1 layer silicates and chlorite are not expanded by the Cs-hydrazine-DMSO procedure.

The basal spacings of montmorillonites with Li, Na, K, Cs, Mg, Ca, Sr, Ba, and Pb interlayer cations were measured after immersion in dimethylsulfoxide (DMSO) and in water-DMSO mixtures. In DMSO alone, the spacings were in the range 18.3–19.3 Å and fell on or near a single curve when plotted against ionic field strength, q/r2, where q = valence and r = ionic radius. These spacings correspond to double layers of DMSO molecules between the silicate layers. Water had practically no effect on the spacings when the mole fraction of DMSO exceeded about 35–45%. Osmotic swelling of Li-, Na-, and K-mont-morillonite occurred up to mole percentages of DMSO 45%, 30%, and 10%, respectively. K- and Cs-mont-morillonite formed single-layer complexes in appropriate water-DMSO mixtures with spacings of 14.3 Å prior to development of double-layer complexes when the mole fraction of DMSO exceeded 35% and 15%, respectively.

The i.r. spectra (4000-1200 cm-1) are obtained for several homoionic montmorillonite films on which various amounts of dimethyl sulfoxide (DMSO) were adsorbed. Analyses of these spectra indicate that H- and natural-montmorillonite-DMSO complexes contain an intercalated layer of physisorbed DMSO while transition metal cation substituted-montmorillonite-DMSO complexes possess both physi- and chemisorbed DMSO in their interlamellar spaces. The latter species involve coordination of DMSO molecules with the exchangeable cations by their oxygen atoms. Most of the interlamellar water is replaced by DMSO as the latter molecules penetrate the interlamellar spaces. Heat-treating transition metal cation substituted-montmorillonite-DMSO complexes at 120°C for 48 hr results in both the desorption of physisorbed DMSO and the retention of intercalated monolayers involving DMSO-transition metal cation coordination. A water-sensitive, reversible color change (tan to light purple) is produced by either desiccating over P2O5 or heat-treating at 120°C the cobalt-montmorillonite-DMSO complex. Interpretation of the visible spectra suggests that Co2+-cations undergo changes from octahedral to tetrahedral coordination during desiccation or heating. Band assignments are made for the clay complexes using the assignments for related gases, liquids, and crystals.

The kinetics of the thermal decomposition of the kaolin: dimethylsulfoxide (kaolin: DMSO) and the kaolin: N-methylformarnide (kaolin: NMF) intercalates have been reexamined. Two different sample sizes (2 mg and 8 mg) and grain-size distributions (<45 μm and 45–63 μm were investigated using isothermal and dynamic gravimetry in the temperature range 100°–200oC. All sample configurations for the kaolin: DMSO intercalate (2 mg, <45 μm; 2 mg, 45–63 μm; 8 mg, <45 μm; 8 mg, 45–63 μm) followed the rate law -ln(1 - α) = kt to a value for α, the reaction fraction complete, of.6, yielding activation energies and standard deviations at the 99% confidence level of 85.5 ± 3.79 and 71.75 ± 8.75 kJ/mole for the isothermal and dynamic runs, respectively. The kaolin: NMF intercalate (2 mg, <45 μm) also followed the same rate law for α <.8, with activation energies and standard deviations at the 99% confidence level of 89 ± 5.05 and 79.25 ± 6.47 kj/mole for the isothermal and dynamic studies, respectively. In solution the rate law -ln(1 - α) = kt is known as first-order kinetics, but here it appears to represent the non-instantaneous nucleation of uniformly sized particles, followed by the inward movement of a reaction interface.

The coarse (2-0.2 μm) and fine (<0.2 μm) size fractions of several soil and reference kaolinite samples were completely intercalated and expanded to 11.2 Å using a simplified CsCl-hydrazine-di-methylsulfoxide (DMSO) treatment. Rapid equilibration of the clay in hot (80°C) hydrazine monohydrate and hot (100°C) DMSO, and the use of ceramic tile mounts, limited the sample pretreatment time to only 15 min. The fine size fraction of kaolinite may be X-rayed immediately after pretreatment, though analysis of the sample 2 or 12 hr after pretreatment produced more intense, sharp basal reflections. This difference may be due to a better ordering of the DMSO-kaolinite complex with time and to a drying of the excess DMSO. The coarse size fraction of kaolinite did not entirely expand to 11.2 Å when analyzed immediately after pretreatment. A 9.6-Å peak was also present and possibly represents a mixed layering of expanded and nonexpanded kaolinite layers. The larger crystals seem to require additional time for the reaction to become complete as evidenced by the presence of an intense, sharp 11.2-Å peak and absence of the 9.6-Å peak when the coarse clay was analyzed 2 or 12 hr after sample pretreatment. Kaolinite particles <50 μm did not react completely even when they were analyzed 24 hr after pretreatment. Therefore, this technique should be limited to <2-μm particles.

13C and 29Si nuclear magnetic resonance spectroscopy with magic-angle spinning bas been used to study the short-range ordering and bonding in the structures of intercalates of kaolinite with formamide, hydrazine, dimethyl sulfoxide (DMSO), and pyridine-N-oxide (PNO). The 29Si chemical shift indicated decreasing levels of bonding interaction between the silicate layer and the intercalate in the order: kaolinite: formamide (δ) = -91.9, ppm relative to tetramethylsilane), kaolinite: hydrazine (-92.0), kaolinite: DMSO (-93.1). The 29Si signal of the kaolinite:PNO intercalate (-92.1) was unexpectedly deshielded, possibly due to the aromatic nature of PNO. The degree of three-dimensional ordering of the structures was inferred from the 29Si signal width, with the kaolinite: DMSO intercalate displaying the greatest ordering and kaolinite: hydrazine the least. 13C resonances of intercalating organic molecules were shifted downfield by as much as 3 ppm in response to increased hydrogen bonding after intercalation, and in the kaolinite: DMSO intercalate the two methyl-carbon chemical environments were non-equivalent (δ = 43.7 and 42.5).

Stable, three-dimensionally ordered complexes were formed from synthetically hydrated, highly ordered kaolinite (d(001) = 8.4 Å) and several organic compounds. Removal of the intercalated organic compound by drying or by water washing recovered the 8.4-Å hydrate with its ordered layer stacking essentially unchanged. Some of the complexes were stable for less than a day, whereas others appeared to be stable indefinitely. The compounds that formed ordered complexes were dimethylsulfoxide, formamide, hydrazine-hydrate, 1,1-dimethylhydrazine, ethylene glycol, glycerol, and pyridine. Clay-organic complexes that were prepared from methanol, ethanol, 1- and 2-propanol, acetone, acetic acid, propionic acid, acetaldehyde, N-methylformamide, methylethyl ketone, tetrahydrofuran, and K-acetate were stable only if they were immersed in the intercalating medium and had little or no stacking order.

Many of the organic compounds intercalated by the 8.4-Å hydrate are not known to be intercalated by non-hydrated kaolinite either directly or indirectly. Isolated water molecules appear to be keyed into the ditrigonal holes formed by the basal oxygen of the silicate tetrahedra of the 8.4-Å hydrate. These water molecules, referred to as “hole water,” and fluorine ions that had replaced ~20% of the inner-surface hydroxyls of the 8.4-Å phase sufficiently altered the interlayer bonding to allow an expansion of the inner-layer spaces by a variety of guest molecules. The presence of these guest molecules between the clay layers not only changed the basal spacing and perturbed the infrared (IR) bands arising from the inner-surface hydroxyls, it also shifted the position of the IR band arising from the inner hydroxyl.

Dimethylselenoxide (DMSeO) forms three structurally resolvable intercalates with kaolinite (d(001) = 10.95, 11.26, and 11.38 Å). The 11.26-Å kaolinite: DMSeO intercalate is structurally analogous to the 3-D ordered kaolinite: DMSO intercalate (d(001) = 11.22 Å). Infrared and solid-state 77Se nuclear magnetic resonance data indicate that all DMSeO molecules are equivalent in the structure and, therefore, that the 11.26-Å kaolinite: DMSeO intercalate structure is C-face centered. Structural model refinement from X-ray powder diffraction (XRD) data further support this conclusion (Pl, a = 5.195(2), b = 8.990(4), c = 11.946(5) Å, α = 91.33(2)°, β = 109.39(2)°, γ = 89.77(2)°). The kaolinite: DMSO intercalate structure was subsequently re-refined from the XRD profile in C-face centered Pl. The derived orientation of the DMSO and DMSeO molecules with respect to the basal plane of their respective intercalates is in agreement with polarized infrared measurements of the angles with ab of S=O (40.3°) and Se=O (38.8°) for the 11.26-Å intercalate. The locations of the organic molecules also agree with observed infrared band splittings and perturbations. Interatomic distances calculated from the band shifts agree with those for the XRD derived structures.

The 11.38-Å kaolinite: DMSeO intercalate is closely related to the 11.26-Å intercalate, the main differences being a 2-fold disorder in the orientation of the DMSeO molecule and less penetration of the kaolinite ditrigonal cavity by that molecule. The 10.95-Å kaolinite: DMSeO intercalate, displaying disorder parallel to [110], was obtained from the 11.26- or 11.38-Å intercalates by removal of some DMSeO.

The crystal structure of the kaolinite: dimethylsulfoxide (DMSO) intercalate (P1, a = 5.187(2), b = 8.964(3), c = 11.838(4) Å, α = 91.53(1)°, β = 108.59(2), γ = 89.92(1)°) has been determined using spectroscopic and X-ray and neutron powder diffraction data. Both the X-ray and neutron powder diffraction patterns were refined. Solid-state 13C, 29Si, and 27Al nuclear magnetic resonance data and previously collected infrared spectroscopic data provided a useful starting model for structural refinement. Due to the extreme overlap of reflections of this low-symmetry unit cell, the Rietveld method proved inadequate, and quasi-single crystal methods were employed. Each DMSO molecule was found to be triply hydrogen bonded above the octahedral vacancy in the gibbsitic sheet of the kaolinite layer. One methyl group is keyed into the ditrigonal hole in the tetrahedral sheet with the other S-C bond parallel to the sheet. The DMSO molecules are accommodated by significant horizontal displacement of individual kaolinite layers to achieve almost perfect overlap of the octahedral vacancy by the adjacent ditrigonal hole.

Four hydrates with d(001) = 8.4, 8.6, and 10 Å (two types) were synthesized by intercalating kaolinite with dimethylsulfoxide and treating the intercalated clay with fluoride ions. X-ray powder diffraction, infrared spectroscopy, differential scanning calorimetry, thermal gravimetric analysis, and kinetics of dehydration experiments have led to the identification of two types of interlayer water. One type of water (hole water) is situated in the ditrigonal holes of the silica tetrahedral surface; the second type (associated water) forms a discontinuous layer of mobile water. The 8.4-Å and 8.6-Å hydrates have only hole water, whereas the two synthetic 10-Å hydrates and halloysite(10Å) contain both hole and associated water. The hole water is probably hydrogen bonded to the basal oxygens of the silica tetrahedra or, in the 8-Å hydrates when fluorine exchanges for inner-surface hydroxyls, the water molecules may reorient and form stronger hydrogen bonds to the fluorine. Associated water forms water-water hydrogen bonds approximately equal in strength to liquid water but is less strongly bonded to the clay surfaces than hole water. At room temperature the hole and associated water in the 10-Å hydrates do not form an ice-like structure.

The intercalation complex of a kaolinite from Cornwall, UK, with dimethylsulfoxide (DMSO) was studied by high-temperature X-ray diffraction (HTXRD), differential thermal analysis (DTA) and thermogravimetry (TG). The X-ray pattern obtained at room temperature indicated that intercalation of DMSO into kaolinite caused an increase of the basal spacing of kaolinite from 7.14 to 11.19 Å. Heating between 25 and 300°C caused the removal of the DMSO, which occurred over several stages. In a first stage (25–125°C), an expansion (from 11.19 to 11.28 Å) followed by a contraction (from 11.28 to 11.19 Å) is observed, at the same time as the intensity of the basal reflection decreased and was replaced by a broad band extending from ~11 to ~7 Å. In a second stage (125–200°C), the loss of DMSO did not lead to changes in the HTXRD patterns; and finally, in a third stage, the loss of DMSO caused an important increase in intensity and sharpening of the basal reflections of the kaolinite. These stages were also shown by the DTA-TG curves for the complex. The TG curve indicated that the loss of ~15% of the intercalated DMSO occurs below 150°C, and caused the disruption of the structure. The remaining molecules, forming stronger bonds with the kaolinite surfaces, were lost between 150 and 300°C.

Hesperidin and naringin are citrus flavonoids with known anti-oxidative and anti-inflammatory properties. Evidence from previous studies indicates that both these compounds and the metabolites that are formed during intestinal metabolism are able to exert beneficial effects on intestinal barrier function and inflammation. However, so far, studies investigating the relative contributions of the various compounds are lacking. Therefore, we assessed the effect of citrus flavonoids and their intestinal metabolites on immune-mediated barrier disruption in an in vitro co-culture model. Caco-2 cell monolayers were placed in co-culture with phorbol 12-myristate 13-acetate-stimulated THP-1-Blue™ NF-κB cells for 30 h. At baseline, the citrus flavonoids and their metabolites were added to the apical compartment (50 or 100 µM per compound). After 24 h, THP-1 cells were incubated with lipopolysaccharide (LPS) in the basolateral compartment for 6 h. Incubation with citrus flavonoids and their metabolites did not induce changes in transepithelial electrical resistance, fluorescein isothiocyanate–dextran 4 kDa permeation or gene expression of barrier-related genes for any of the compounds tested. After LPS stimulation, NF-κB activity was significantly inhibited by all compounds (100 µM) except for one metabolite (all P ≤ 0·03). LPS-induced production of the cytokines IL-8, TNF-α and IL-6 was inhibited by most compounds (all P < 0·05). However, levels of IL-1β were increased, which may contribute to the lack of an improved barrier effect. Overall, these results suggest that citrus flavonoids may decrease intestinal inflammation via reduction of NF-κB activity and that the parent compounds and their metabolites formed during intestinal metabolism are able to exert comparable effects.

The polyphenolic extract (PE) from extra virgin olive oil (EVOO) has been shown to possess important anti-inflammatory and joint protective properties in murine models of rheumatoid arthritis (RA). This study was designed to evaluate the effects of PE on IL-1β-activated human synovial fibroblasts SW982 cell line. PE from EVOO treatment inhibited IL-1β-induced matrix metalloproteases (P<0·001), TNF-α and IL-6 production (P<0·001). Similarly, IL-1β-induced cyclo-oxygenase-2 and microsomal PGE synthase-1 up-regulations were down-regulated by PE (P<0·001). Moreover, IL-1β-induced mitogen-activated protein kinase (MAPK) phosphorylation and NF-κB activation were ameliorated by PE (P<0·001). These results suggest that PE from EVOO reduces the production of proinflammatory mediators in human synovial fibroblasts; particularly, these protective effects could be related to the inhibition of MAPK and NF-κB signalling pathways. Taken together, PE from EVOO probably could provide an attractive complement in management of diseases associated with over-activation of synovial fibroblasts, such as RA.

7-Hydroxymatairesinol (7-HMR) is a plant lignan abundant in various concentrations in plant foods. The objective of this study was to test HMRLignan™, a purified form of 7-HMR, and the corresponding Picea abies extract (total extract P. abies; TEP) as dietary supplements on a background of a high-fat diet (HFD)-induced metabolic syndrome in mice and in the 3T3-L1 adipogenesis model. Mice, 3 weeks old, were fed a HFD for 60 d. Subgroups were treated with 3 mg/kg body weight 7-HMR (HMRLignan™) or 10 mg/kg body weight TEP by oral administration. 7-HMR and TEP limited the increase in body weight (−11 and −13 %) and fat mass (−11 and −18 %) in the HFD-fed mice. Epididymal adipocytes were 19 and −12 % smaller and the liver was less steatotic (−62 and −65 %). Serum lipids decreased in TEP-treated mice (−11 % cholesterol, −23 % LDL and −15 % TAG) and sugar metabolism was ameliorated by both lignan preparations, as shown by a more than 70 % decrease in insulin secretion and insulin resistance. The expression of several metabolic genes was modulated by the HFD with an effect that was reversed by lignan. In 3T3-L1 cells, the 7-HMR metabolites enterolactone (ENL) and enterodiol (END) showed a 40 % inhibition of cell differentiation accompanied by the inhibited expression of the adipogenic genes PPARγ, C/EBPα and aP2. Furthermore, END and ENL caused a 10 % reduction in TAG uptake in HEPA 1–6 hepatoma cells. In conclusion, 7-HMR and TEP reduce metabolic imbalances typical of the metabolic syndrome and obesity in male mice, whereas their metabolites inhibit adipogenesis and lipid uptake in vitro.

Basalts and other mafic rocks are frequently used for road construction. The aggregates have to provide intrinsic mechanical strength and skid resistance. However, smectite contents stemming from alteration processes may deteriorate these mechanical properties considerably because of the resulting contrast in hardness. Quantitative relationships between smectite content, kind of distribution, and aggregate stability are rare except for a recent study by Kaufhold et al. (2012). In this work thirteen basalt and andesite samples from German quarries were analysed by X-ray diffraction (XRD) for their mineral contents (including clay minerals), their cation exchange capacities (CEC) and their resistance against disaggregation in dimethyl sulfoxide. Smectite contents from XRD exceeded those calculated from the CEC regardless of the kind of occurrence of smectite observed in thin sections. The hypothesis that rocks with smectites occurring mostly in patches should differ in terms of CEC and mechanical properties from those rocks where smectites are more disseminated could not be confirmed. However, the amounts of smectite accessible to cation exchange correlated with the DMSO losses. Therefore, the fast CEC determination with Cu-Trien exchange can be substituted for the time-consuming DMSO test.

Cysteine peptidases of protozoa have been implicated in a variety of biological events, and the expression of these enzymes is modulated in response to distinct stimuli, including environmental changes and differentiation. In the present work, we have examined the expression of cysteine peptidases from Herpetomonas samuelpessoai grown at distinct temperatures and during dimethylsulfoxide (DMSO)-elicited differentiation. We demonstrated that a 45 kDa cysteine peptidase had its activity reduced during the parasite growth at 37°C in comparison to 26°C, and when cultured up to 72 h in the presence of DMSO. The modulation in the 45 kDa cysteine peptidase expression is connected to the differentiation process, since both temperature and DMSO are able to trigger the promastigote to paramastigote transformation in H. samuelpessoai. The possible immunological similarity of H. samuelpessoai proteins with well-known cysteine peptidases produced by trypanosomatid pathogens, including cruzipain (Trypanosoma cruzi) and cysteine peptidase b (cpb) from Leishmania mexicana, was also investigated, as well as with calpain molecules. The protein cellular lysate of H. samuelpessoai reacted with antibodies raised against cpb of L. mexicana and calpain of Drosophila melanogaster; however, no reaction was observed against cruzipain. The 35 kDa cpb-like protein had its expression diminished in DMSO-treated parasites, while the 80 kDa calpain-like molecule was enhanced and an additional 30 kDa calpain-related polypeptide was exclusively observed in these cells. Fluorescence microscopy and flow cytometry analyses corroborated these data. The results described above add H. samuelpessoai to the list of parasites whose differentiation seems to be correlated with cysteine peptidase expression.