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One strategy for overcoming infectious diseases caused by drug-resistant fungi involves combining drugs rendered inactive by resistance with agents targeting the drug resistance mechanism. The antifungal activity of n-dodecanol disappears as incubation time passes. In Saccharomyces cerevisiae, anethole, a principal component of anise oil, prolongs the transient antifungal effect of dodecanol by downregulating genes of multidrug efflux pumps, mainly PDR5. However, the detailed mechanisms of dodecanol's antifungal action and the anethole-induced prolonged antifungal action of dodecanol are unknown. Screening of S. cerevisiae strains lacking genes related to Ca2+ homeostasis and signaling identified a pmr1Δ strain lacking Golgi Ca2+-ATPase as more sensitive to dodecanol than the parental strain. Dodecanol and the dodecanol + anethole combination significantly increased intracellular Ca2+ levels in both strains, but the mutant failed to clear intracellular Ca2+ accumulation. Further, dodecanol and the drug combination reduced PMR1 expression and did not lead to specific localization of Pmr1p in the parental strain after 4-h treatment. By contrast with the parental strain, dodecanol did not stimulate PDR5 expression in pmr1Δ. Based on these observations, we propose that the antifungal activity of dodecanol is related to intracellular Ca2+ accumulation, possibly dependent on PMR1 function, with anethole enabling Ca2+ accumulation by restricting dodecanol efflux., (© FEMS 2020.)

FAVs (fatty acid vesicles), originated from natural biomass and created available biointerface, have advantages of biocompatibility, low-cost, and easy self-assembly in aqueous solution due to their dynamic feature. However, there is no example of applying FAVs in contact with human body since they are inherently alkaline-adapted and pH windows for the FAV formation and application are very narrow and far away from the physiological pH range. In this work an attempt to turn the alkaline-adapted FAVs into neutral and acid-adapted ones was made by fabricating the amphiphile-hybrid vesicles of CLA (conjugated linoleic acid) with a typical cosmetic emulsifier SDS (sodium dodecylsulfate) and/or a co-emulsifier DA (dodecyl alcohol). pH windows for the SDS- and/or DA-hybrid FAV formation of CLA were judged by using dynamic light scattering criterion, and confirmed by small-angle X-ray scattering and room temperature transmission electron microscopy. The experimental results show that with the aid of H-bonding and ion-dipole forces among molecules of CLA, SDS and DA within the hybrid vesicle walls that were identified by Fourier transform infrared analysis, much wider pH windows of 2.5-11.7 for the hybrid FAVs were obtained by expansion from 8.0-9.0 for FAV of CLA alone, which was composition-dependent and made the hybrid FAVs become neutral and acid-adapted., (Copyright © 2018 Elsevier B.V. All rights reserved.)

Azelaic acid (AzA) and its derivatives have been known to be effective in the treatment of acne and various cutaneous hyperpigmentary disorders. The esterification of azelaic acid with lauryl alcohol (LA) to produce dilaurylazelate using immobilized lipase B from Candida antarctica (Novozym 435) is reported. Response surface methodology was selected to optimize the reaction conditions. A well-fitting quadratic polynomial regression model for the acid conversion was established with regards to several parameters, including reaction time and temperature, enzyme amount, and substrate molar ratios. The regression equation obtained by the central composite design of RSM predicted that the optimal reaction conditions included a reaction time of 360 min, 0.14 g of enzyme, a reaction temperature of 46 °C, and a molar ratio of substrates of 1:4.1. The results from the model were in good agreement with the experimental data and were within the experimental range (R² of 0.9732).The inhibition zone can be seen at dilaurylazelate ester with diameter 9.0±0.1 mm activities against Staphylococcus epidermidis S273. The normal fibroblasts cell line (3T3) was used to assess the cytotoxicity activity of AzA and AzA derivative, which is dilaurylazelate ester. The comparison of the IC 50 (50% inhibition of cell viability) value for AzA and AzA derivative was demonstrated. The IC 50 value for AzA was 85.28 μg/mL, whereas the IC 50 value for AzA derivative was more than 100 μg/mL. The 3T3 cell was still able to survive without any sign of toxicity from the AzA derivative; thus, it was proven to be non-toxic in this MTT assay when compared with AzA., Competing Interests: The authors declare no conflict of interest.

Plastic labware is used in all processes of modern pharmaceutical research, including compound storage and biological assays. The use of these plastics has created vast increases in productivity and cost savings as experiments moved from glass test tubes and capillary pipettes to plastic microplates and multichannel liquid handlers. One consequence of the use of plastic labware, however, is the potential release of contaminants and their resultant effects on biological assays. We report herein the identification of biologically active substances released from a commonly used plastic microplate. The active contaminants were identified by gas chromatography-mass spectroscopy as dodecan-1-ol, dodecyl 3-(3-dodecoxy-3-oxopropyl)sulfanylpropanoate, and dodecanoic acid, and they were found to be selective monoamine oxidase-B inhibitors., (© 2014 Society for Laboratory Automation and Screening.)

A key challenge in biomass conversion is how to achieve valuable molecules with optimal reactivity in the presence of immiscible reactants. This issue is usually tackled using either organic solvents or surfactants to promote emulsification, making industrial processes expensive and not environmentally friendly. As an alternative, Pickering emulsions using solid particles with tailored designed surface properties can promote phase contact within intrinsically biphasic systems. Here we show that amphiphilic silica nanoparticles bearing a proper combination of alkyl and strong acidic surface groups can generate stable Pickering emulsions of the glycerol/dodecanol system in the temperature range of 35-130°C. We also show that such particles can perform as Pickering Interfacial Catalysts for the acid-catalyzed etherification of glycerol with dodecanol at 150°C. Our findings shed light on some key parameters governing emulsion stability and catalytic activity of Pickering interfacial catalytic systems. This understanding is critical to pave the way toward technological solutions for biomass upgrading able to promote eco-efficient reactions between immiscible organic reagents with neither use of solvents nor surfactants., (Copyright © 2013 Elsevier Inc. All rights reserved.)

A simple, rapid, effective and eco-friendly preconcentration method, vortex-assisted low density solvent based solvent demulsified dispersive liquid-liquid microextraction (VLDS-SD-DLLME), followed by high performance liquid chromatography-diode array detector (HPLC-DAD) analysis, has been developed for the first time for the determination of four organophosphorus pesticides (OPPs) (e.g., azinphos-methyl, parathion-methyl, fenitrothion and diazinon) in environmental water samples. In this preconcentration procedure, an emulsion was obtained after the mixture of extraction solvent (1-dodecanol) and dispersive solvent (acetonitrile, ACN) was injected rapidly into 10 mL of the sample solution. The vortex agitator aided the dispersion of the extraction solvent into the sample solution. After the formation of an emulsion, the demulsifier (ACN) was added, resulting in the rapid separation of the mixture into two phases without centrifugation. Under optimal conditions, the proposed method provided high extraction efficiency (90-99%), good linearity range (0.5-500 ng mL(-1)), low limits of detection (0.25-1 ng mL(-1)) and good repeatability and recoveries were obtained., (Copyright © 2013 Elsevier Ltd. All rights reserved.)

Synthetic amino acid-based surfactants possess versatile aggregation properties and are typically more biocompatible and biodegradable than surfactants with conventional headgroups. This opens the possibility of a myriad of specialty applications, namely in pharmaceutics, cosmetics, biomedicine, and nanotemplating chemistry. In this work, we have investigated the interfacial and self-assembling properties in aqueous medium of novel double-chained lysine-based surfactants, with particular focus on the behavior of the dodecyl derivative, 12Lys12. Upon cooling from dilute isotropic micellar solutions, this surfactant crystallizes into micrometer-sized tubular structures that induce gelation of the system. The tubules have been characterized in terms of morphology, assembly process, thermal behavior, and stability, by using differential scanning calorimetry, light and scanning electron microscopy, and deuterium NMR. Possible mechanisms for tubule assembly are discussed, on the basis of surfactant molecular shape, H-bonding and electrostatic interactions, and chirality effects.

Pentabromocyclododecanols (PBCDOHs) are potential environmental transformation products of hexabromocyclododecanes (HBCDs). They are also potential stage one metabolites of biological HBCD transformations. Herein, we present analytical evidence that PBCDOHs are also constituents of technical HBCDs and flame-proofed polystyrenes (FP-PSs). PBCDOHs are possibly formed during the synthesis of technical HBCD, presumably during the bromination of cyclododecatrienes in aqueous isobutanol together with isobutoxypentabromocyclododecanes (iBPBCDs), which have been identified in these materials recently. Of the 64 stereoisomers possible, eight pairs of enantiomers, named α-, β-, γ-, δ-, ε-, ζ-, η-, and θ-PBCDOHs were separated with a combination of normal-, reversed- and chiral-phase LC. Crystal structure analysis revealed the stereochemistry of the α-PBCDOH pair of enantiomers, which was assigned to (1S,2S,5R,6S,9S,10R)-2,5,6,9,10-pentabromocyclododecanol and its enantiomer. Mass spectrometric data are in accordance with the expected isotope patterns. On a C(18)-RP-column, the polar PBCDOHs eluted before the HBCD and iBPBCD classes of compounds. PBCDOHs were also found in FP-PS materials. The stereoisomer patterns varied considerably in these materials like those of HBCDs and iBPBCDs. Expanded polystyrenes were rich in late-eluting stereoisomers, similar to technical HBCD mixtures. Extruded polystyrenes contained more of the polar, faster-eluting isomers. The presented chromatographic and analytical methods allow a stereoisomer-specific search for PBCDOHs in biota samples, which might have experienced metabolic HBCD transformation reactions. Besides this potential source, it has to be recognized that PBCDOHs are by-products in technical HBCDs and in flame-proofed polystyrenes. Therefore, it is likely that PBCDOHs and iBPBCDs are released to the environment together with HBCD-containing plastic materials., (Copyright © 2012 Elsevier Ltd. All rights reserved.)

In an earlier study, biocatalytic carbon oxyfunctionalization with water serving as oxygen donor, e.g., the bioconversion of quinaldine to 4-hydroxyquinaldine, was successfully achieved using resting cells of recombinant Pseudomonas putida, containing the molybdenum-enzyme quinaldine 4-oxidase, in a two-liquid phase (2LP) system (Ütkür et al. J Ind Microbiol Biotechnol 38:1067-1077, 2011). In the study reported here, key parameters determining process performance were investigated and an efficient and easy method for product recovery was established. The performance of the whole-cell biocatalyst was shown not to be limited by the availability of the inducer benzoate (also serving as growth substrate) during the growth of recombinant P. putida cells. Furthermore, catalyst performance during 2LP biotransformations was not limited by the availability of glucose, the energy source to maintain metabolic activity in resting cells, and molecular oxygen, a possible final electron acceptor during quinaldine oxidation. The product and the organic solvent (1-dodecanol) were identified as the most critical factors affecting biocatalyst performance, to a large extent on the enzyme level (inhibition), whereas substrate effects were negligible. However, none of the 13 alternative solvents tested surpassed 1-dodecanol in terms of toxicity, substrate/product solubility, and partitioning. The use of supercritical carbon dioxide for phase separation and an easy and efficient liquid-liquid extraction step enabled 4-hydroxyquinaldine to be isolated at a purity of >99.9% with recoveries of 57 and 84%, respectively. This study constitutes the first proof of concept on an integrated process for the oxyfunctionalization of toxic substrates with a water-incorporating hydroxylase.

A transdermal formulation of indomethacin (IMC) was developed by incorporation into cholesteryl cetyl carbonate (CCC). The liquid crystalline phase properties of the IMC-CCC mixture were detected by polarized light microscopy and differential scanning calorimetry. A low drug loading was obtained (1-5 %) similar to that used in conventional topical IMC in a clinical setting. A controlled release of IMC was found over 12 h. A low amount of IMC in 1 % IMC-CCC permeated the stratum corneum. Further formulation development has been carried out by the addition of lauryl alcohol into 5 % IMC-CCC mixture it was found that the permeation of IMC was significantly improved to 45 % within 24 h.

A poly(N-isopropylacrylamide) film was modified on an indium-tin oxide electrode in order to immobilize bacterial luciferase (BL) on the electrode surface. By using the modified electrode, flavin mononucleotide (FMN) was electrochemically reduced to FMNH(2), which is one of the substrates of the BL luminescence reaction, to control the bioluminescence reaction by BL. The BL reaction in the modified film could be promoted and controlled by the electrochemical generation of FMNH(2). This BL luminescence system was evaluated as a model system for the inhibitory assay of hydrophobic molecules on protein functions.

In this study, molecular packing in lamellar liquid crystals in poly(oxyethylene) dodecyl ether(C(12)EO(n)) pure systems and the two surfactant mixtures of C(12)EO(8)/1-dodecanol(C(12)EO(0)), C(12)EO(8)/lipophilic sucrose laurate (L-595), hydrophilic sucrose laurate (L-1695)/C(12)EO(2) is investigated in terms of mean molecular area and partial molecular area (PMA). Lamellar liquid crystals formed in the C(12)EO(8)/C(12)EO(0) mixed system show higher melting temperatures than those in the C(12)EO(n) pure systems, even though the average number of EO units in the mixed surfactant system is the same as in the pure system. We compared the mean molecular area at the interface between hydrophilic and lipophilic moieties in the lamellar liquid crystals in each system. In the mixed system, the molecules are packed more tightly than in the pure system. Among the C(12)EO(n) and sucrose laurate mixtures, the L-1695/C(12)EO(2) mixed system showed a smaller mean molecular area per lipophilic chain than the C(12)EO(8)/L-595 mixed system. We investigated the effect of mixing two surfactants with different head group geometry on molecular packing by comparing the PMA of each surfactant., (Copyright © 2011 Elsevier Inc. All rights reserved.)

The purpose of this study was to optimize the concentration of a fatty alcohol, in addition to internal phase, for formulating a stable O/W emulsion, by using artificial neural networks (ANNs). Predictions from ANNs are accurate and allow quantification of the relative importance of the inputs. Furthermore, by varying the network topology and parameters it was possible to obtain output values that were close to experimental values. The ANN model's predictive results and the actual output values were compared. R(2) values depict the percentage of response variability for the model; R(2) value of 0.84 for the model suggested adequate modeling, which is supported by the correlation coefficient value of 0.9445.

Even though sodium dodecyl sulphate (SDS) is the most frequently studied surfactant, its properties at liquid interfaces are not easily accessible. This is mainly caused by the fact that in aqueous solution SDS is subject to hydrolysis, by which the homologous dodecanol (C12OH) is formed. Due to its enormously high surface activity it competes with SDS at the interface. We demonstrate here that this "natural" impurity C12OH does not remarkably affect the adsorption dynamics of SDS at the water/hexane interface, due to its high solubility in hexane. Therefore, the dynamic adsorption properties can be determined independent of disturbing dodecanol effects. The surfactant adsorbs diffusion controlled and the interfacial tension isotherm at the water/hexane interface is well described by a Frumkin model. However complementary experiments via direct admixture of dodecanol in hexane indicate a significant decrease in interfacial tension of the water-hexane interface at concentrations higher than 10(-3) mol/l in hexane. This condition may happen when the oil phase is distributed as small droplets in a high concentrated solution of SDS. The distribution coefficient of C12OH between water and hexane is estimated from adsorption experiments to be K(p)=c(o)/c(w)=6.7×10(3)., (Copyright © 2010 Elsevier Inc. All rights reserved.)

A monolithic column of macro porous poly (glycidyl methacrylate-divinylbenzene) (poly(GMA-DVB)) has been prepared by free radical polymerization within the confines of a chromatographic stainless steel tube (50 mm x 4.6 mm). For the best separation and low back pressure, orthogonal experiments were carried out with V (cyclohexanol): V (dodecanol), V (GMA): V (DVB) and BPO dosage as the three main factors. The characteristic feature of the column, including specific surface area, pore volume as well as pore diameter distribution, was studied by scanning electron microscopy (SEM), mercury intrusion porosimetry analysis and BET analysis. The obtained optimum preparation conditions were that the volume ratio of GMA, DVB, cyclohexanol and dodecanol was 0.825: 0.825: 1.32: 2.03 and the BPO dosage was 0.7% (mass percentage), then it was heated at 70 degrees C for 24 h. Using this monolithic column, benzene and ethylbenzene and a drug of oxiracetam can be well separated on a high performance liquid chromatographic (HPLC) system equipped with a ultraviolet (UV) detector at 254 nm. A solution of acetonitrile-water (50 : 50, v/v) for the separation of benzene and ethylbenzene, and acetonitrile-water (80 : 20, v/v) for the separation of oxiracetam were used as mobile phases at a flow rate of 1 mL/min. The theoretical plate number was 37 000 plates/m and the resolution of peak width at half height (R1/2) was 7.14. The separation time was less than 10 min. The monolithic column prepared by this method is reproducible and has high column efficiency. It is an economical method to prepare monolithic column, which can be applied to separate small molecules.

Recent experimental and theoretical results have firmly established the existence of enhanced concentrations of selected ions at the air/water interface. Ion adsorption to aqueous interfaces involving complex organic molecules is relevant to biology in connection with the familiar but incompletely understood Hofmeister effects. Here, we describe resonant UV second harmonic generation (SHG) studies of the strongly chaotropic thiocyanate ion adsorbed to the interface formed by water and a monolayer of dodecanol, wherein the Gibbs free energy of adsorption was determined to be -6.7 +/- 1.1 and -6.3 +/- 1.8 kJ/mol for sodium and potassium thiocyanate, respectively, coincident with the value determined for thiocyanate at the air/water interface. Interestingly, near 4 M and higher concentrations, the resonant SHG signal increases discontinuously, indicating a structural change in the interfacial region.

The effect of long-chain alcohols (C(n)OH for n=8, 10, 12, 14, 16, 18) on the partitioning of sodium dodecyl sulfate (SDS) to the oil/water interface in oil-in-water macroemulsions was investigated and related to emulsion droplet size and total interfacial area (TIA) contributed by SDS. Alcohols were solubilized in hexadecane and emulsified in SDS solutions. Ultrafiltration was carried out in centrifuge tubes having nanoporous filters with a 30,000 molecular weight cutoff (MWCO), so that emulsion droplets would not pass through, and only SDS that is in the bulk water phase as monomers or micelles (i.e., not at the interface) could pass through. The results showed a chain-length compatibility effect; the maximum amount of SDS partitioned to the interface when dodecanol (C(12)OH) was added to the oil. The results also showed that partitioning of SDS is affected only when dodecanol is added. All other alcohols had no significant influence on SDS partitioning to the oil/water interface. Droplet size measurements revealed a minimum in droplet size for emulsions with added C(12)OH. In order to explain the results, it was proposed that the penetration of alcohol molecules into the interfacial film occur at the interface, resulting in more cohesive molecular packing at the interface, and the minimum droplet size and maximum partitioning of SDS at the oil/water interface for C(12)OH/SDS emulsion system. The TIA provided by the SDS molecules, as determined from our ultrafiltration method, was two orders of magnitude greater than that calculated from the droplet size measured by light scattering. Possible explanations for this disparity are discussed.

We report results of drainage in aqueous foams of small bubble size D (D=180 microm) prepared with SDS-dodecanol solutions. We have performed free-drainage experiments in which local drainage rates are measured by electrical conductivity and by light scattering techniques. We have investigated the role of the surfactant-cosurfactant mass ratio on the drainage regime. The results confirm that a drainage regime corresponding to a high surface mobility can indeed be found for such small bubbles, and show that an increase in the cosurfactant content can induce a transition to a low surface mobility drainage regime. We show that the transition is not linked to variations of the bulk properties, but rather to variations of the interfacial properties. However, the results show that the added amount of dodecanol to trigger the transition is quite high, evidencing that the relevant control parameter for drainage regimes includes both bubble size and interfacial contributions.

Adsorption layers of n-dodecanol at the water/air interface show phase transitions at low temperatures [Vollhardt, Fainerman, Emrich, J. Phys. Chem. B 104 (2000) 8536]. Using a drop shape technique it is shown that the dilational elasticity disappears in the coexistence region of the adsorption layer. The relaxation time between the condensed and liquid-like surface states is in the sub-second time range.

The influence of esterification reactions on the surface chemistry and colloid stability of hydroxyapatite (HAP) was studied by aging nanophase HAP in dodecyl alcohol at elevated temperatures (115 degrees C and 190 degrees C). The esterified HAP particles were characterized by X-ray diffraction, transmission electron microscopy, diffuse reflectance infra-red Fourier transform spectroscopy (DRIFTS), thermal gravimetric analysis, sedimentation time studies, and electrophoretic mobility (mu) measurements in water and ethyl alcohol. DRIFTS analysis revealed that the HAP surface was modified by dodecyl groups based on the appearance of C-H stretch vibrational modes at 2962, 2930, and 2860cm(-1). Dodecyl alcohol modified HAP exhibited a larger TGA mass loss upon heating (up to 4.8%) compared to untreated HAP (2.5-3.2wt%). Sedimentation studies revealed the following stability trends: HAP dispersed in water was approximately the same as esterified HAP in water (a few hours)

Dynamic surface tension and its diffusional decay have been studied with four different polydisperse C12E7 at different temperatures and different concentrations. The CMC and the headgroup area from equilibrium surface tension were shown with polydispersity and temperature. The chain length of oxyethylene on the surface was derived from comparison between the headgroup area of monodisperse dodecyl ethoxylates and that of polydisperse C12E7. The values for (Deff/D) were deduced with a diffusion-controlled adsorption model using parameters obtained from equilibrium surface tension. It was shown at short adsorption time that molecules were really adsorbed onto the surface in a diffusion-controlled manner. At a comparably long adsorption time, the ratios (Deff/D) were calculated by assuming the selective adsorption onto the surface. The modified Arrhenius-type equation was proposed by putting a concentration term in front of the exponential terms. The modified Arrhenius-type equation gave Ea=30 kJ/mole for this system. Ea directly derived without an Arrhenius plot was between 9 to 11 kJ/mole. It was an indication that the activation energy alone was not enough to explain the decay of dynamic surface tensions.