How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as lm-n-lm], 2Br(-) (n = 2, 5, 6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units -(CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

How does spacer length of imidazolium gemini surfactants control the fabrication of 2D-Langmuir films of silver-nanoparticles at the air-water interface?

A series of gemini surfactants based on cationic imidazolium ring as polar headgroup, abbreviated as Im-n-Im], 2Br(-) (n = 2, 5,6 and 12), was synthesized. Their ability to stabilize silver nanoparticles in aqueous media was investigated. The resulting suspensions were characterized by UV-Vis spectroscopy and transmission electron microscopy (TEM). They exhibit specific morphologies by adopting different supramolecular assemblies in aqueous media depending on the internal packing arrangements and on the number of spacer methylene units -(CH2)(n)-]. Individual colloids were extracted from the aqueous to chloroform layer and spread at the air/water interface to allow the formation of well-defined Langmuir films. By analysis of the surface pressure-area isotherms, the details about the packing behavior and orientation of the imidazolium gemini surfactant capped silver nanoparticles were obtained. Morphological features of the dynamic process of monolayer compression at the air-water interface were elucidated using Brewster angle microscopy (BAM). These monolayers were further transferred on mica sheets by the Langmuir-Blodgett technique at their associated collapse pressure and the morphology of these monolayers was investigated by atomic force microscopy (AFM). The number of spacer methylene units (CH2)(n)-] of the gemini surfactants exerted critical influence in modulating the characteristics of the resulting Langmuir films. (C) 2014 Elsevier Inc. All rights reserved.

Efficacious Gene Silencing in Serum and Significant Apoptotic Activity Induction by Survivin Downregulation Mediated by New Cationic Gemini Tocopheryl Lipids

Nonviral gene delivery offers cationic liposomes as promising instruments for the delivery of double-stranded RNA (ds RNA) molecules for successful sequence-specific gene silencing (RNA interference). The efficient delivery of siRNA (small interfering RNA) to cells while avoiding unexpected side effects is an important prerequisite for the exploitation of the power of this excellent tool. We present here six new tocopherol based cationic gemini lipids, which induce substantial gene knockdown without any obvious cytotoxicity. All the efficient coliposomal formulations derived from each of these geminis and a helper lipid, dioleoylphosphatidylethanolamine (DOPE), were well characterized using physical methods such as atomic force microscopy (AFM) and dynamic light scattering (DLS). Zeta potential measurements were conducted to estimate the surface charge of these formulations. Flow cytometric analysis showed that the optimized coliposomal formulations could transfect anti-GFP siRNA efficiently in three different GFP expressing cell lines, viz., HEK 293T, HeLa, and Caco-2, significantly better than a potent commercial standard Lipofectamine 2000 (L2K) both in the absence and in the presence of serum (FBS). Notably, the knockdown activity of coliposomes of gemini lipids was not affected even in the presence of serum (10% and 50% FBS) while it dropped down for L2K significantly. Observations under a fluorescence microscope, RT-PCR, and Western blot analysis substantiated the flow cytometry results. The efficient cellular entry of labeled siRNA in GFP expressing cells as evidenced from confocal microscopy put forward these gemini lipids among the potent lipidic carriers for siRNA. The efficient transfection capabilities were also profiled in a more relevant fashion while performing siRNA transfections against survivin (an anti-apoptotic protein) which induced substantial apoptosis. Furthermore, the survivin downregulation improved the therapeutic efficacy levels of an anticancer drug, doxorubicin, significantly. In short, the new tocopherol based gemini lipids appear to be highly promising for achieving siRNA mediated gene knockdown in various cell lines.

A delocalizable cationic headgroup together with an oligo-oxyethylene spacer in gemini cationic lipids improves their biological activity as vectors of plasmid DNA

Lipoplex nano-aggregates constituted of plasmid DNA (pDNA) pEGFP-C3 and mixed cationic liposomes, consisting of several percentages of a gemini cationic lipid (GCL) of the 1,2-bis(hexadecyl imidazolium) oxyethylene series, referred to as (C(16)Im)(2)(C2O)(n), with oxyethylene spacers (n = 1, 2 or 3) between the imidazolium cationic groups and the DOPE zwitterionic helper lipid, have been characterized by various biophysical and biological approaches carried out at several GCL compositions (alpha), and either the mass or the effective charge ratio of the lipoplex. The electrochemical study by zeta-potential confirms that the three GCLs yield a 10% lower effective charge than the nominal one, while compacted pDNA yields only a 25% effective negative charge. The SAXS study reveals, irrespective of the spacer length (n) and effective charge ratio (rho(eff)), the presence of two lamellar structures, i.e., one (L-alpha,L-main) in the whole GCL composition and another (L-alpha,L-DOPE,L-rich) with higher periodicity values that coexists with the previous one at low GCL composition (alpha = 0.2). The cryo-TEM analysis shows two types of multilamellar structures consisting of cationic lipidic bilayers with pDNA sandwiched between them: a cluster-type (C-type) at low alpha = 0.2 and a fingerprint-type (FP-type) at alpha >= 0.5, both with similar interlamellar spacing (d) in agreement with the L-alpha,L-main structure determined by SAXS. Transfection efficacies (TEs) of each lipid mixture were determined in four different cell lines (HEK293T, HeLa, Caco-2 and A549) at several alpha and rho(eff) values in the absence and presence of serum (FBS). The optimized formulations (alpha = 0.2 and rho(eff) = 2.0) substantially transfect cells much better than a commercial transfection reagent, Lipofectamine 2000 and previously studied efficient lipoplexes containing other cationic head groups or spacers both in the absence and presence of serum. The activity of optimized formulations may be attributed to the combination of several factors, such as: (a) the fusogenic character of DOPE which results in higher fluidity of the lipoplexes at alpha = 0.2, (b) the coexistence of two lamellar structures at alpha = 0.2 that synergizes the TE of these lipid vectors, and mainly (c) the higher biocompatibility of the GCLs reported in this work due to the presence of two imidazolium cationic groups together with an oligo-oxyethylene spacer. The length of the spacer in the GCL seems to have less impact, although (C(16)Im)(2)(C2O)(n)/DOPEpDNA lipoplexes with n = 1 and 3 show higher gene transfection than n = 2. All the optimum formulations reported herein are all highly efficient with negligible levels of toxicity, and thus, may be considered as very promising gene vectors for in vivo applications.

Water Dispersible, Positively and Negatively Charged MoS2 Nanosheets: Surface Chemistry and the Role of Surfactant Binding

Stable aqueous dispersions of atomically thin layered MoS2 nanosheets have been obtained by sonication in the presence of ionic surfactants. The dispersions are stabilized by electrostatic repulsion between the sheets, and we show that the sign of the charge on the MoS2 nanosheets, either positive or negative, can be can be controlled by the choice of the surfactant. Using techniques from solution NMR, we show that the surfactant chains are weakly bound to the MoS2 sheets and undergo rapid exchange with free surfactant chains present in the dispersion. In situ nuclear Overhauser effect spectroscopic measurements provide direct evidence that the surfactant chains lie flat, arranged randomly on the basal plane of the MoS2 nanosheets with their charged headgroup exposed. These results provide a chemical perspective for understanding the stability of these inorganic nanosheets in aqueous dispersions and the origin of the charge on the sheets.

Efficacious redox-responsive gene delivery in serum by ferrocenylated monomeric and dimeric cationic cholesterols

Herein, we present the design and synthesis of new redox-active monomeric and dimeric (gemini) cationic lipids based on ferrocenylated cholesterol derivatives for gene delivery. The cationic cholesterols are shown to be transfection efficient after being formulated with the neutral helper lipid DOPE in the presence of serum (FBS). The redox activity of the resulting co-liposomes and their lipoplexes could be regulated using the alkanyl ferrocene moiety attached to the ammonium head groups of the cationic cholesterols. Atomic force microscopy (AFM), dynamic light scattering (DLS) and zeta potential measurements were performed to characterize the co-liposomal aggregates and their complexes with pDNA. The transfection efficiency of lipoplexes could be tuned by changing the oxidation state of the ferrocene moiety. The gene transfection capability was assayed in terms of green fluorescence protein (GFP) expression using pEGFP-C3 plasmid DNA in three cell lines of different origins, namely Caco-2, HEK293T and HeLa, in the presence of serum. The vesicles possessing ferrocene in the reduced state induced an efficient transfection, even better than a commercial reagent Lipofectamine 2000 (Lipo 2000) as evidenced by flow cytometry and fluorescence microscopy. All the co-liposomes containing the oxidized ferrocene displayed diminished levels of gene expression. Gene transfection events from the oxidized co-liposomes were further potentiated by introducing ascorbic acid (AA) as a reducing agent during lipoplex incubation with cells, leading to the resumption of transfection activity. Assessment of transfection capability of both reduced and oxidized co-liposomes was also undertaken following cellular internalization of labelled pDNA using confocal microscopy and flow cytometry. Overall, we demonstrate here controlled gene transfection activities using redox-driven, transfection efficient cationic monomeric and dimeric cholesterol lipids. Such systems could be used in gene delivery applications where transfection needs to be performed spatially or temporally.

Imidazolium based ionic liquid type surfactant improves activity and thermal stability of lipase of Rhizopus oryzae

Lipase and surfactant together form a potent pair in various biotransformation, industrial application and biotechnological studies. The present investigation deals with changes in the activity, stability and structure of lipase from Rhizopus oryzae NRRL 3562 in presence of long chain ionic liquid-type imidazolium surfactant. Both the activity and stability were found to be enhanced in presence of the surfactant at low concentration (1-125 mu M) followed by inhibition at high concentration. The activity increased by 80% and thermal deactivation temperature raised by 2.5 degrees C. Investigations by ultraviolet-visible spectroscopy and circular dichroism revealed structural changes leading to rise in beta-sheet content and lowering of a-helix at low surfactant concentrations. Deactivation at high concentration correlated with greater structural changes depicted by spectroscopic studies. Isothermal titration calorimetric studies showed the binding to be spontaneous in nature involving non-covalent interactions. High negative value of entropy signifies exposure of hydrophobic domains and increase in structural rigidity, which correlates with active site being more accessible and rigid in presence of the surfactant. Application of these surfactants hold greater potential in the field of lipase based biotransformations, enzyme structural modifications and studies. (C) 2015 Elsevier B.V. All rights reserved.

THE EFFECTS OF SURFACTANT ON SIMPLEX NOZZLE SPRAY BEHAVIOR AND ITS COMPARISON TO LIQUID FUELS

Pressure-swirl nozzles (simplex nozzles) are used in various field applications such as aero-engines, power generation, spray painting and agricultural irrigation. For this particular nozzle, research in the past decade has dealt with the development of numerical models for predicting droplet distribution profiles. Although these results have been valuable, the experimental results have been contradictory, therefore fundamental understanding of the influence of properties in nozzle is important. This paper experimentally investigates the effect of surfactants on breakup and coalescence. Since most of the fuels and biofuels have low surface tension compared to water, a comparative analysis between a surfactant solution and a liquid fuel is imperative. For this experimental study, a simplex nozzle characterized as flow number 0.4 will be utilized. The injection pressures will range from 0.3 - 4Mpa while altering the surface tension from 72 to 28mN/m. By applying Phase Doppler Particle Anemometry (PDPA) which is a non-intrusive laser diagnostic technique, the differences in spray characteristics due to spray surface tension can be highlighted. The average droplet diameter decreases for a low surface tension fluid in the axial direction in comparison to pure water. The average velocity of droplets is surprisingly lower in the same spray zone. Measurements made in the radial direction show no significant changes, but at the locations close to the nozzle, water droplets have larger diameter and velocity. The results indicate the breakup and coalescence regimes have been altered when surface tension is lowered. A decrease in surface tension alters the breakup length while increasing the spray angle. Moreover, higher injection pressure shortens the breakup length and decrease in overall diameter of the droplets. By performing this experimental study the fundamentals of spray dynamics, such as spray formation, liquid breakup length, and droplet breakup regimes can be observed as a function of surface tension and how a surrogate fuel compares with a real fuel for experimental purposes. This knowledge potentially will lead to designing a better atomizer or new biofuels.

Simulations of impinging droplets with surfactant-dependent dynamic contact angle

An arbitrary Lagrangian-Eulerian (ALE) finite element scheme for computations of soluble surfactant droplet impingement on a horizontal surface is presented. The numerical scheme solves the time-dependent Navier-Stokes equations for the fluid flow, scalar convection-diffusion equation for the surfactant transport in the bulk phase, and simultaneously, surface evolution equations for the surfactants on the free surface and on the liquid-solid interface. The effects of surfactants on the flow dynamics are included into the model through the surface tension and surfactant-dependent dynamic contact angle. In particular, the dynamic contact angle (theta(d)) of the droplet is defined as a function of the surfactant concentration at the contact line and the equilibrium contact angle (theta(0)(e)) of the clean surface using the nonlinear equation of state for surface tension. Further, the surface forces are included into the model as surface divergence of the surface stress tensor that allows to incorporate the Marangoni effects without calculating the surface gradient of the surfactant concentration on the free surface. In addition to a mesh convergence study and validation of the numerical results with experiments, the effects of adsorption and desorption surfactant coefficients on the flow dynamics in wetting, partially wetting and non-wetting droplets are studied in detail. It is observed that the effects of surfactants are more in wetting droplets than in the non-wetting droplets. Further, the presence of surfactants at the contact line reduces the equilibrium contact angle further when theta(0)(e) is less than 90 degrees, and increases it further when theta(0)(e) is greater than 90 degrees. Nevertheless, the presence of surfactants has no effect on the contact angle when theta(0)(e) = 90 degrees. The numerical study clearly demonstrates that the surfactant-dependent contact angle has to be considered, in addition to the Marangoni effect, in order to study the flow dynamics and the equilibrium states of surfactant droplet impingement accurately. The proposed numerical scheme guarantees the conservation of fluid mass and of the surfactant mass accurately. (C) 2015 Elsevier Inc. All rights reserved.

Cyclic Cationic Peptides Containing Sugar Amino Acids Selectively Distinguishes and Inhibits Maturation of Pre-miRNAs of the Same Family

The discovery of microRNAs (miRNAs) has added a new dimension to the gene regulatory networks, making aberrantly expressed miRNAs as therapeutically important targets. Small molecules that can selectively target and modulate miRNA levels can thus serve as lead structures. Cationic cyclic peptides containing sugar amino acids represent a new class of small molecules that can target miRNA selectively. Upon treatment of these small molecules in breast cancer cell line, we profiled 96 therapeutically important miRNAs associated with cancer and observed that these peptides can selectively target paralogous miRNAs of the same seed family. This selective inhibition is of prime significance in cases when miRNAs of the same family have tissue-specific expression and perform different functions. During these conditions, targeting an entire miRNA family could lead to undesired adverse effects. The selective targeting is attributable to the difference in the three-dimensional structures of precursor miRNAs. Hence, the core structure of these peptides can be used as a scaffold for designing more potent inhibitors of miRNA maturation and hence function.

Synthesis of Graphene from a Used Battery Electrode

Graphene was produced by electrochemical exfoliation of a used battery electrode. Aqueous solutions of cationic (cetyltrimethylammonium bromide), anionic (sodium dodecyl sulphate), and nonionic (poly vinyl pyrrolidone) surfactants, along with NaCl and combinations of these surfactants with NaCl, were used as the electrolyte. The following observations were made: (I) up to several micrometer sized graphene sheets were produced, (II) the addition of NaCl into the electrolytes significantly enhanced the yield of the exfoliated graphene, (III) the type of surfactant affected the defect density of the exfoliated product, and (IV) electrochemical impedance spectroscopy provided insight into the reason for the changes in the defect density ratio between the graphene samples.

Role of spacer length in interaction between novel gemini imidazolium surfactants and Rhizopus oryzae lipase

An insight into the effects of new ionic liquid-type gemini imidazolium cationic surfactants on the structure and function of the lipases is of prime importance for their potential application. Changes in the activity, stability and structure of Rhizopus ouzae lipase in the presence of novel gemini surfactants, C-16-3-C(16)im]Br-2 and C-16-12-C(16)im]Br-2 were probed in the present study. Surfactant with shorter spacer length, C-16-3-C(i6)im]Br-2 was found to be better in improving the hydrolytic activity and thermal stability of the lipase. For both the surfactants, activation was concentration dependent. CD spectroscopy results showed a decrease in a-helix and an increase in beta-sheet content in the presence of these surfactants. A higher structural change observed in presence of C-16-12-C(16)im]Br-2 correlated with lower enzyme activity. Isothermal titration calorimetric studies showed the binding to be spontaneous in nature based on sequential two site binding model. The forces involved in binding were found to differ for the two surfactants proving that the spacer length is an important factor which governs the interaction. These surfactants could be used as promising components both in enzyme modification and media engineering for attaining the desired goals in biocatalytic reactions. (C) 2015 Elsevier B.V. All rights reserved.

Studies on the phase diagram of the surfactant/1-pentanol water ternary system I: The isotropic phases

The phase diagram of the dodecyl dimethyl ammonium hydroxyl propyl sulfonate(DDAHPS)/1-pentanol(C5H11OH)/water ternary system has been established. It contains two isotropic monophase regions (L-1 and L-2) and a liquid crystalline region (L.C.). The isotropic phase regions have been investigated by means of Raman spectroscopy and conductivity.

The effect of an insoluble surfactant on the skin friction of a bubble

In this paper, we develop a novel moving mesh method suitable for solving axisymmetric free-boundary problems, including the Marangoni effect induced by surfactant or temperature variation. This method employs a body-fitted grid system where the gas-liquid interface is one line of the grid system. We model the surfactant equation of state with a non-linear Langmuir law, and, for simplicity, we limit ourselves to the situation of an insoluble surfactant. We solve complicated dynamic boundary conditions accurately on the gas-liquid interface in the framework of finite-volume methods. Our method is used to study the effect of a surfactant on the skin friction of a bubble in a uniaxial flow. For the limiting case where the surface diffusivity is zero, the effect of a tangential stress generated by the surface tension gradient, allows us to explain a new phenomenon in high concentration regimes: larger surface tension, but also larger deformation. Furthermore, this condition leads to the formation of boundary layers and flow separation at high Reynolds numbers. The influence of these complex flow patterns is examined. © 2005 Elsevier SAS. All rights reserved.

Influence of insoluble surfactant on the deformation and breakup of a bubble or thread in a viscous fluid

The influence of surfactant on the breakup of a prestretched bubble in a quiescent viscous surrounding is studied by a combination of direct numerical simulation and the solution of a long-wave asymptotic model. The direct numerical simulations describe the evolution toward breakup of an inviscid bubble, while the effects of small but non-zero interior viscosity are readily included in the long-wave model for a fluid thread in the Stokes flow limit. The direct numerical simulations use a specific but realizable and representative initial bubble shape to compare the evolution toward breakup of a clean or surfactant-free bubble and a bubble that is coated with insoluble surfactant. A distinguishing feature of the evolution in the presence of surfactant is the interruption of bubble breakup by formation of a slender quasi-steady thread of the interior fluid. This forms because the decrease in surface area causes a decrease in the surface tension and capillary pressure, until at a small but non-zero radius, equilibrium occurs between the capillary pressure and interior fluid pressure. The long-wave asymptotic model, for a thread with periodic boundary conditions, explains the principal mechanism of the slender thread's formation and confirms, for example, the relatively minor role played by the Marangoni stress. The large-time evolution of the slender thread and the precise location of its breakup are, however, influenced by effects such as the Marangoni stress and surface diffusion of surfactant. © 2008 Cambridge University Press.