OLIGOMERIC GUANIDINE-CONTAINING PROTON CATIONIC IONIC LIQUID

Oligomeric ionic liquids occupy an intermediate position between low molecular weight and polymeric. They are promising as polymer electrolytes in electrochemical devices for various purposes, membranes for the separation of gas mixtures, in sensor technologies, and so on. Oligomeric guanidinium ionic liquids are practically not described in the literature. In terms of studying the effect of the structure of the epoxy component on the properties of oligomeric ionic liquids of this type, it is advisable to introduce into its composition an aliphatic oligoether component. The choice of aliphatic oligoepoxide for the synthesis of guanidinium oligomeric ionic liquids is based on the fact that it is structurally similar to poly - and oligoethylene oxides, which are known to be non-toxic, biodegradable, and reactive oligomeric ionic liquids at elevated temperatures. A new type of reactive oligomeric proton cationic ionic liquid was synthesized by the reaction of oligomeric aliphatic diepoxide with guanidine, followed by neutralization of the product with hydrochloric acid. In this study, the synthesis of proton cationic oligomeric ionic liquids was based on the introduction of guanidinium fragments as end groups of the oligoether aliphatic chain. This reaction is attractive because of the ease of opening the oxirane ring with such a strong nucleophile as guanidine.The reaction forms a fragment with an aliphatic C-N bond, which retains the high basicity of the nitrogen atom. Its structure is characterized by the presence of guanidinium groups at the ends of the aliphatic hydroxyl-containing oligoether chain. The chemical structure of this compound is characterized by IR -, 1H ,13 C NMR spectroscopy methods, and its molecular mass characteristics are determined.The average molecular weight of the synthesized oligomeric ionic liquids is 610 g / mol.The value of the coefficient of polydispersity of the synthesized oligomeric ionic liquids is equal to 1.2. Determination of the content of amino groups in the guanidine-containing oligomer in the basic form by titrometric method allowed to establish that the value found is close to the theoretically calculated value. The synthesized oligomeric proton ionic liquid is characterized by an amorphous structure with two glass transition temperatures. The first lies in the range -70 °C, the second in the region of 70 °C, and the beginning of thermal oxidative destruction is located in the region of 148 °C. The temperature dependence of the ionic conductivity for this compound is nonlinear in the Arrhenius coordinates, which indicates the realization of ionic conductivity mainly due to the free volume in the system. The proton conductivity of this compound is 6.4·10-5–1·10-2Cm/cmin the range of 20–100 °C. The obtained compound exhibits surface-active properties characteristic of classical surfactants, as evidenced by the value of the limiting surface activity – 2.8·102 Nm2 / kmol. The value of CCM is 1.8·10-2 mol/l., and the value of the minimum surface tension – 37.70 mN / m. The synthesized oligomeric ionic liquid is of interest as electrolytes operating under anhydrous conditions, surfactants, disinfectants, and starting reagents for the synthesis of ion-containing blockopolymers.

Synthesis and Characterization of a Novel Class of Zwitterionic Fluorocarbon Surfactants Based on Perfluorobutyl

Perfluorooctane sulfonate (PFOS) and its derivatives had been banned due to their potential environmental hazards, although they possessed excellent surface activity. An effective method to solve this problem was to shorten the fluorocarbon chain of these surfactants from C°H17 to C4F9. As previous studies had shown, zwitterionic surfactants possess higher surface activity but have lower toxicity compared to other types of surfactants. In view of this, a class of novel zwitterionic fluorocarbon surfactants (n-CFNA-Br) with perfluorobutyl moiety was synthesized in this work. Their structures were characterized by FTIR, 1H NMR, 13C NMR, 19F NMR and MS. The results showed that all synthesized n-CFNA-Br had almost the same minimum surface tension, but their critical micelle concentration (CMC) decreased with increasing length of hydrophobic carbon chain. In pure water, the surface tension at the CMC (γCMC) of the four n-CFNA-Br were about 20 mN/m, and the CMC values were 7.73 mmol/L for 1-CFNA-Br, 4.70 mmol/L for 2-CFNA-Br, 4.13 mmol/L for 3-CFNA-Br, and 3.36 mmol/L for 4-CFNA-Br, indicating high efficiency and effectiveness. In 0.1 mol/L NaCl, the CMC values reduced to less than half of the CMC values measured in the pure aqueous surfactant solution, while the surface tensions γCMC remained almost unchanged, indicating good salinity tolerance of the synthesized surfactants. The acidic surfactant solutions exhibited similar CMC values to the saline solutions, but the surface tension γCMC increased slightly to 25 mN/m. However, further investigation showed that the n-CFNA-Br surfactants exhibited poor surface activity in alkaline solution (0.1 mol/L NaOH). In the pH range of 6.6 to 10.4, white precipitates appeared in the surfactant solutions after some time, indicating that the n-CFNA-Br are not suitable for use in alkaline systems with pH greater than 6.6.

Preparation and the Foaming Activity Study of Hydroxymethyl Cetyltrimethyl Ammonium Chloride

In this paper, hydroxymethyl cetyltrimethyl ammonium chloride (HM-CTAC) was prepared from cetyltrimethyl ammonium chloride (CTAC) and formaldehyde with different molar ratios (1:1 to 1: 4). The effects of reaction conditions (molar ratio) on surface properties were studied, including surface tension, foaming ability, high temperature resistance, methanol resistance and salt resistance. The results show that the minimum surface tension of HM-CTAC is lower than that of CTAC, and HM-CTAC (1:1) has the lowest surface tension of 31.89 mN · m–1. The foam volume of HM-CTAC with different molar ratios is higher than that of CTAC, and HM-CTAC (1:4) has a high foam volume of 435 mL. Compared to CTAC, the HM-CTAC under different reaction conditions has higher temperature resistance. At the methanol content of 10 wt.%, the initial foam volume of HM-CTAC is higher than that of CTAC, and the initial foam volume of HM-CTAC (1:2) is the highest with a volume of 21.5 mL. Among all the surfactants prepared under different reaction conditions, HM-CTAC (1:3) has the highest salt resistance with a relatively stable change in foam volume under different salt contents.

Restoration of surfactant activity by polymyxin B in lipopolysaccharide-potentiated injury of immature rabbit lungs

During postnatal adaptation pulmonary surfactant may be inactivated by lipopolysaccharide (LPS). We evaluated the effect of surfactant therapy in combination with antibiotic polymyxin B (PxB) in double-hit model of neonatal lung injury. Surfactant (poractant alfa, Curosurf) was exposed to smooth (S) LPS without/with PxB and tested in captive bubble surfactometer. Preterm rabbits received intratracheally saline (control) or S-LPS and were ventilated with 100% oxygen. After 30 min, LPS-treated animals received no treatment, or surfactant (200 mg/kg) without/with 3% PxB; controls received the same dose of surfactant. Animals were ventilated for further 2 h. In vitro, addition of 5% S-LPS to surfactant increased minimum surface tension (γmin) and addition of 1–3% PxB to surfactant/S-LPS mixture restored γmin to low values. Animals only given S-LPS had lower lung compliance and lung gas volume (LGV) compared to surfactant groups. Treatment with surfactant/PxB, but not with surfactant only, restored LGV. Addition of PxB to the surfactant increased the alveolar expansion. S-LPS interferes with surface activity of the pulmonary surfactant and PxB improves the resistance of surfactant to LPS-induced inactivation. In our neonatal model of respiratory distress syndrome surfactant gives positive response even in simultaneous exposure to S-LPS, when enriched with PxB.

Preparation and Properties of Amide Surfactants

Amide surfactants have modified structures with lipophilic groups connecting hydrophilic groups through amido bond. The preparation of three families of amide surfactants including long chain N-acyl sarcosinates, amidopropyl dimethyl hydroxypropyl sulfobetaines and lauryl amidopropyl trimethyl ammoniums were discussed. The study of the surface activity of these compounds by measuring the equilibrium surface tensions of their dilute aqueous solutions were described. The minimum surface tension and the critical micelle concentration values of these compounds are given.

The effect of medium composition on the production of sophorolipids and the tensiometric properties by Starmerella bombicola MTCC 1910

The effect of medium composition on the production of sophorolipids and the tensiometric properties by Starmerella bombicola MTCC 1910 Starmerella bombicola a teleomorph of Candida bombicola is capable of producing extracellular secondary metabolites known as sophorolipids. In the present work the performance of Starmerella in producing sophorolipids, with standard medium ingredients glucose, sunflower oil, yeast extract and urea was studied. The quantities of different medium ingredients were optimized to maximize the production of sophorolipids. Variation in tensiometric properties like surface tension and interfacial tension during the incubation period were also reported. The optimized mixed substrate composition was found to be 200 g/l, containing equal amounts of glucose and sunflower oil, 4 g/l of yeast extract and 0.6 g/l of urea. With the optimized substrate composition 38.6 g/l of sophorolipids was obtained. The minimum surface tension produced by the culture free cell broth was 36.2 mN/m. Increasing the temperature from 25°C to 35°C has shown adverse effects on sophorolipids production.

Surfactant phospholipid changes after antigen challenge: a role for phosphatidylglycerol in dysfunction

In asthma, inflammation-mediated surfactant dysfunction contributes to increased airway resistance, but the mechanisms for dysfunction are not understood. To test mechanisms that alter surfactant function, atopic asthmatics underwent endobronchial antigen challenge and bronchoalveolar lavage (BAL). BAL fluids were sequentially separated into cells, surfactant, and supernatant, and multiple end points were analyzed. Each end point's unique relationship to surfactant dysfunction was determined. Our results demonstrate that minimum surface tension (γmin) of surfactant after antigen challenge was significantly increased with a spectrum of responses that included dysfunction in 6 of 13 asthmatics. Antigen challenge significantly altered the partitioning of surfactant phospholipid measured as a decreased ratio of large surfactant aggregates (LA) to small surfactant aggregates (SA), LA/SA ratio. Phosphatidylglycerol (PG) was significantly reduced in the LA of the dysfunctional asthmatic BALs. There was a corresponding significant increase in the ratio of phosphatidylcholine to PG, which strongly correlated with both increased γmin and decreased LA/SA. Altered surfactant phospholipid properties correlated with surfactant dysfunction as well or better than either increased eosinophils or protein. Secretory phospholipase activity, measured in vitro, increased after antigen challenge and may explain the decrease in surfactant PG. In summary, alteration of phospholipids, particularly depletion of PG, in the LA of surfactant may be an important mechanism in asthma-associated surfactant dysfunction.

Surfactant from diving aquatic mammals

Diving mammals that descend to depths of 50-70 m or greater fully collapse the gas exchanging portions of their lungs and then reexpand these areas with ascent. To investigate whether these animals may have evolved a uniquely developed surfactant system to facilitate repetitive alveolar collapse and expansion, we have analyzed surfactant in bronchoalveolar lavage fluid (BAL) obtained from nine pinnipeds and from pigs and humans. In contrast to BAL from terrestrial mammals, BAL from pinnipeds has a higher concentration of phospholipid and relatively more fluidic phosphatidylcholine molecular species, perhaps to facilitate rapid spreading during alveolar reexpansion. Normalized concentrations of hydrophobic surfactant proteins B and C were not significantly different among pinnipeds and terrestrial mammals by immunologic assay, but separation of proteins by gel electrophoresis indicated a greater content of surfactant protein B in elephant seal surfactant than in human surfactant. Remarkably, surfactant from the deepest diving pinnipeds produced moderately elevated in vitro minimum surface tension measurements, a finding not explained by the presence of protein or neutral lipid inhibitors. Further study of the composition and function of pinniped surfactants may contribute to the design of optimized therapeutic surfactants.

Effects of fixatives on function of pulmonary surfactant

The structure of pulmonary surfactant films remains ill defined. Although plausible film fragments have been imaged by electron microscopy, questions about the significance of the findings and even about the true fixability of surfactant films by the usual fixatives glutaraldehyde (GA), osmium tetroxide (OsO4), and uranyl acetate (UA) have not been settled. We exposed functioning natural surfactant films to fixatives within a captive bubble surfactometer and analyzed the effect of fixatives on surfactant function. The capacity of surfactant to reach near-zero minimum surface tension on film compression was barely impaired after exposure to GA or OsO4. Although neither GA nor OsO4 prevented the surfactant from forming a surface active film, GA increased the equilibrium surface tension to above 30 mN/m, and both GA and OsO4 decreased film stability as seen in the slowly rising minimum surface tension from 1 to ∼5 mN/m in 10 min. In contrast, the effect of UA seriously impaired surface activity in that both adsorption and minimum surface tension were substantially increased. In conclusion, the fixatives tested in this study are not suitable to fix, i.e., to solidify, surfactant films. Evidently, however, OsO4 and UA may serve as staining agents.

Pulmonary Inflammation Disrupts Surfactant Function during Pneumocystis carinii Pneumonia

ABSTRACT During Pneumocystis carinii pneumonia (PCP) in mice, the degree of pulmonary inflammation correlates directly with the severity of lung function deficits. Therefore, studies were undertaken to determine whether the host inflammatory response contributes to PCP-related respiratory impairment, at least in part, by disrupting the pulmonary surfactant system. Protein and phospholipid content and surfactant activity were measured in the lavage fluid of infected mice in either the absence or presence of an inflammatory response. At 9 weeks postinfection with P. carinii, nonreconstituted SCID mice exhibited no signs of pulmonary inflammation, respiratory impairment, or surfactant dysfunction. Lavage fluid obtained from these mice had protein/phospholipid (Pr/PL) ratios (64% ± 4.7%) and minimum surface tension values (4.0 ± 0.9 mN/m) similar to those of P. carinii-free control mice. However, when infected SCID mice were immunologically reconstituted, an intense inflammatory response ensued. Pr/PL ratios (218% ± 42%) and minimum surface tension values (27.2 ± 2.7 mN/m) of the lavage fluid were significantly elevated compared to those of the lavage fluid from infected, nonreconstituted mice (P < 0.05). To examine the specific role of CD8+ T-cell-mediated inflammation in surfactant dysfunction during PCP, mice with defined T-cell populations were studied. P. carinii-infected, CD4+-depleted mice had elevated lavage fluid Pr/PL ratios (126% ± 20%) and elevated minimum surface tension values (16.3 ± 1.0 mN/m) compared to normal mice (P < 0.05). However, when infected mice were additionally depleted of CD8+ cells, Pr/PL ratios were normal and surfactant activity was improved. These findings demonstrate that the surfactant pathology associated with PCP is related to the inflammatory process rather than being a direct effect of P. carinii. Moreover, CD8+ lymphocytes are involved in the mechanism leading to surfactant dysfunction.