Sample records for micellar aggregation number

  1. Determination of micellar aggregation numbers of Gemini surfactants%Gemini阳离子表面活性剂胶束聚集数的测定

    倪人捷; 黄煜; 姚成


    以芘为荧光探针,十六烷基氯化吡啶为猝灭剂,用芘饱和水溶液配制浓度范围为0.10 ~2.40 mmol/L的系列Gemini阳离子表面活性剂溶液,用稳态荧光探针法测定了该系列表面活性剂的临界胶束浓度CMC与胶束聚集数N_m.实验结果表明:该方法测定的CMC值与电导率法测定的CMC值相当;选择猝灭剂浓度为0.20~0.50 mmol/L时,所测得的表面活性剂胶束聚集数基本不变;当表面活性剂16-X-16浓度为4~9倍CMC时,胶束聚集数随表面活性剂浓度增大而线性增大;利用外推法得到的该表面活性剂临界胶束聚集数约为亲油基同碳数的CTAB临界胶束聚集数的一半.%The critical micelle concentration (CMC) and micellar aggregation numbers of series of cationic Gemini surfactants are determined by steady-state fluorescence probe method in which py-rene was used as a fluorescence probe and cetylpyridinium chloride as a quencher. The experimental results indicate that the CMC values are basically in agreement with the values determined by conductivity method, the aggregation numbers of this series cationic Gemini surfactants are essentially constant when the concentrations of the quencher are in 0. 20 to 0. 50 mmol/L. The aggregation numbers of the Gemini surfactant(16-X-16) increases linearly with the increase of surfactant concentration in the range of 4 to 9 times of CMC. The critical micellar aggregation numbers obtained by extrapolation method are half of the CTAB's(cetyltrimethylammonium bromide) which is hydropho-bic with the same carbon number.

  2. Deracemization of bilirubin as the marker of the chirality of micellar aggregates.

    Sorrenti, Alessandro; Altieri, Barbara; Ceccacci, Francesca; Di Profio, Pietro; Germani, Raimondo; Giansanti, Luisa; Savelli, Gianfranco; Mancini, Giovanna


    The deracemization of bilirubin in micellar aggregates of structurally correlated chiral surfactants was studied by circular dichroism experiments and exploited as the marker of the expression of chirality of the aggregates. The obtained results suggest that the hydrophobic interactions control the transfer of chirality from the monomers to the aggregates, and that different regions of the same aggregate might feature opposite enantiorecognition capabilities.

  3. Inhibitory effect of post-micellar SDS concentration on thermal aggregation and activity of papain.

    Qadeer, A; Zaman, M; Khan, R H


    Papain, a cysteine protease isolated from the latex of Carica papaya, is known to undergo irreversible thermal unfolding. In this study, we found that thermal unfolding of papain is accompanied by a simultaneous self-assembly process where this protein is observed to aggregate above 50°C. The extent of aggregation increased with increasing protein concentration from 3-40 µM. The aggregation was confirmed by enhanced turbidity, light scattering intensity, 1-anilino-8-naphthalene sulfonate (ANS) fluorescence intensity and by transmission electron microscopy. Furthermore, we noted that post-micellar concentration of sodium dodecyl sulfate (SDS) remarkably suppresses the thermal aggregation of papain. Far-UV circular dichroism studies revealed that SDS significantly enhances α-helical content of the protein and also tends to prevent its unfolding, and thus inhibits aggregation. Additionally, papain showed maximal activity at 65°C in neutral buffer. However, in the presence of 6 mM SDS (above its critical micellar concentration), the enzyme lost activity by about 10-fold. Thus, promoting the helical propensity of the protein does not appear to be a suitable strategy to overcome the aggregation related problems of industrially important proteins such as papain, which are not only required to be protected against aggregation but also need to remain functionally active in the presence of aggregation inhibitors.

  4. Amplification of Chirality through Self-Replication of Micellar Aggregates in Water

    Bukhriakov, Konstantin


    We describe a system in which the self-replication of micellar aggregates results in a spontaneous amplification of chirality in the reaction products. In this system, amphiphiles are synthesized from two "clickable" fragments: a water-soluble "head" and a hydrophobic "tail". Under biphasic conditions, the reaction is autocatalytic, as aggregates facilitate the transfer of hydrophobic molecules to the aqueous phase. When chiral, partially enantioenriched surfactant heads are used, a strong nonlinear induction of chirality in the reaction products is observed. Preseeding the reaction mixture with an amphiphile of one chirality results in the amplification of this product and therefore information transfer between generations of self-replicating aggregates. Because our amphiphiles are capable of catalysis, information transfer, and self-assembly into bounded structures, they present a plausible model for prenucleic acid "lipid world" entities. © 2015 American Chemical Society.

  5. DNA packaging induced by micellar aggregates: a novel in vitro DNA condensation system.

    Ghirlando, R; Wachtel, E J; Arad, T; Minsky, A


    Evidence for a conceptually novel DNA packaging process is presented. X-ray scattering, electron microscopy, and circular dichroism measurements indicate that in the presence of positively charged micellar aggregates and flexible anionic polymers, such as negatively charged polypeptides or single-stranded RNA species, a complex is formed in which DNA molecules are partially embedded within a micellar scaffold and partially condensed into highly packed chiral structures. Based on studies of micelle-DNA and micelle-flexible anionic polymer systems, as well as on the known effects of a high charge density upon the micellar organization, a DNA packaging model is proposed. According to this model, the DNA induces the elongation of the micelles into rodlike aggregates, forming a closely packed matrix in which the DNA molecules are immobilized. In contrast, the flexible anionic polymers stabilize clusters of spherical micelles which are proposed to effect a capping of the rodlike micelles, thus arresting their elongation and creating surfactant-free segments of the DNA that are able to converge and collapse. Thus, unlike other in vitro DNA packaging systems, in which condensation follows encounters between charge-neutralized DNA molecules, a prepackaging phase where the DNA is immobilized within a matrix is proposed in this case. Cellular and nuclear membranes have been implicated in DNA packaging processes in vivo, and negatively charged polyelectrolytes were shown to be involved in the processes. These observations, combined with the basic tenets of the DNA condensation system described here, allow for the progression to the study of more elaborate model systems and thus might lead to insights into the nature and roles of the intricate in vivo DNA-membrane complexes.

  6. Triblock polyphiles through click chemistry: self-assembled thermotropic cubic phases formed by micellar and monolayer vesicular aggregates.

    Tan, Xiaoping; Kong, Leiyang; Dai, Heng; Cheng, Xiaohong; Liu, Feng; Tschierske, Carsten


    Three series of triblock polyphiles consisting of a rigid 4-phenyl-1,2,3-triazole or 1,4-diphenyl-1,2,3-triazole core with three lipophilic and flexible alkoxyl chains at one end and a polar glycerol group at the opposite end were synthesized by copper-catalyzed azide-alkyne click reactions. Their mesophase behavior was studied by polarizing optical microscopy, differential scanning calorimetry, and XRD. Depending on alkyl chain length and core length, a transition from hexagonal columnar to Pm3n-type cubic phases was observed. In the cubic phases, the molecules are organized as spherical objects. Remarkably, compounds with a longer core unit have a higher tendency to form these cubic phases, and their stability is strongly enhanced over those of the compounds with a shorter core, despite longer cores having a smaller cone angle and therefore being expected to disfavor the formation of spherical objects. There is a large difference in the number of molecules involved in the spherical aggregates formed by compounds with long and short cores. Whereas the aggregates in the cubic phases of the compounds with short rod units are small and could be regarded as micellar, the long-core compounds form much larger aggregates which are regarded as a kind of monolayer vesicular aggregate.

  7. LPS-protein aggregation influences protein partitioning in aqueous two-phase micellar systems.

    Lopes, André Moreni; Santos-Ebinuma, Valéria de Carvalho; Novaes, Leticia Celia de Lencastre; Molino, João Vitor Dutra; Barbosa, Leandro Ramos Souza; Pessoa, Adalberto; Rangel-Yagui, Carlota de Oliveira


    Lipopolysaccharide endotoxins (LPS) are the most common pyrogenic substances in recombinant peptides and proteins purified from Gram-negative bacteria, such as Escherichia coli. In this respect, aqueous two-phase micellar systems (ATPMS) have already proven to be a good strategy to purify recombinant proteins of pharmaceutical interest and remove high LPS concentrations. In this paper, we review our recent experimental work in protein partitioning in Triton X-114 ATPMS altogether with some new results and show that LPS-protein aggregation can influence both protein and LPS partitioning. Green fluorescent protein (GFPuv) was employed as a model protein. The ATPMS technology proved to be effective for high loads of LPS removal into the micelle-rich phase (%REM(LPS) > 98 %) while GFPuv partitioned preferentially to the micelle-poor phase (K GFP(uv) system. Nonetheless, ATPMS can still be considered as an efficient strategy for high loads of LPS removal, but being aware that the excluded-volume partitioning theory available might overestimate partition coefficient values due to the presence of protein-LPS aggregation.

  8. Micellar aggregates of saponins from Chenopodium quinoa: characterization by dynamic light scattering and transmission electron microscopy.

    Verza, S G; de Resende, P E; Kaiser, S; Quirici, L; Teixeira, H F; Gosmann, G; Ferreira, F; Ortega, G G


    Entire seeds of Chenopodium quinoa Willd are a rich protein source and are also well-known for their high saponin content. Due to their amphiphily quinoa saponins are able to form intricate micellar aggregates in aqueous media. In this paper we study the aggregates formed by self-association of these compounds from two quinoa saponin fractions (FQ70 and FQ90) as well as several distinctive nanostructures obtained after their complexation with different ratios of cholesterol (CHOL) and phosphatidylcholine (PC). The FQ70 and FQ90 fractions were obtained by reversed-phase preparative chromatography. The structural features of their resulting aggregates were determined by Dynamic Light Scattering (DLS) and Transmission Electron Microscopy (TEM). Novel nanosized spherical vesicles formed by self-association with mean diameter about 100-200 nm were observed in FQ70 aqueous solutions whereas worm-like micelles an approximate width of 20 nm were detected in FQ90 aqueous solutions. Under experimental conditions similar to those reported for the preparation of Quillaja saponaria ISCOM matrices, tubular and ring-like micelles arose from FQ70:CHOL:PC and FQ90:CHOL:PC formulations, respectively. However, under these conditions no cage-like ISCOM matrices were observed. The saponin composition of FQ70 and FQ90 seems to determine the nanosized structures viewed by TEM. Phytolaccagenic acid, predominant in FQ70 and FQ90 fractions, is accountable for the formation of the nanosized vesicles and tubular structures observed by TEM in the aqueous solutions of both samples. Conversely, ring-like micelles observed in FQ90:CHOL:PC complexes can be attributed to the presence of less polar saponins present in FQ90, in particular those derived from oleanolic acid.

  9. The membrane protein LeuT in micellar systems: aggregation dynamics and detergent binding to the S2 site.

    Khelashvili, George; LeVine, Michael V; Shi, Lei; Quick, Matthias; Javitch, Jonathan A; Weinstein, Harel


    Structural and functional properties of integral membrane proteins are often studied in detergent micellar environments (proteomicelles), but how such proteomicelles form and organize is not well understood. This makes it difficult to evaluate the relationship between the properties of the proteins measured in such a detergent-solubilized form and under native conditions. To obtain mechanistic information about this relationship for the leucine transporter (LeuT), a prokaryotic homologue of the mammalian neurotransmitter/sodium symporters (NSSs), we studied the properties of proteomicelles formed by n-dodecyl-β,D-maltopyranoside (DDM) detergent. Extensive atomistic molecular dynamics simulations of different protein/detergent/water number ratios revealed the formation of a proteomicelle characterized by a constant-sized shell of detergents surrounding LeuT protecting its transmembrane segments from unfavorable hydrophobic/hydrophilic exposure. Regardless of the DDM content in the simulated system, this shell consisted of a constant number of DDM molecules (∼120 measured at a 4 Å cutoff distance from LeuT). In contrast, the overall number of DDMs in the proteomicelle (aggregation number) was found to depend on the detergent concentration, reaching a saturation value of 226±17 DDMs in the highest concentration regime simulated. Remarkably, we found that at high detergent-to-protein ratios we observed two independent ways of DDM penetration into LeuT, both leading to a positioning of the DDM molecule in the second substrate (S2) binding site of LeuT. Consonant with several recent experimental studies demonstrating changes in functional properties of membrane proteins due to detergent, our findings highlight how the environment in which the membrane proteins are examined may affect the outcome and interpretation of their mechanistic features.

  10. Multicompartment micellar aggregates of linear ABC amphiphiles in solvents selective for the C block: A Monte Carlo simulation

    Zhu, Yutian


    In the current study, we applied the Monte Carlo method to study the self-assembly of linear ABC amphiphiles composed of two solvophobic A and B blocks and a solvophilic C block. A great number of multicompartment micelles are discovered from the simulations and the detailed phase diagrams for the ABC amphiphiles with different block lengths are obtained. The simulation results reveal that the micellar structure is largely controlled by block length, solvent quality, and incompatibility between the different block types. When the B block is longer than or as same as the terminal A block, a rich variety of micellar structures can be formed from ABC amphiphiles. By adjusting the solvent quality or incompatibility between the different block types, multiple morphological transitions are observed. These morphological sequences are well explained and consistent with all the previous experimental and theoretical studies. Despite the complexity of the micellar structures and morphological transitions observed for the self-assembly of ABC amphiphiles, two important common features of the phase behavior are obtained. In general, the micellar structures obtained in the current study can be divided into zero-dimensional (sphere-like structures, including bumpy-surfaced spheres and sphere-on-sphere structures), one-dimensional (cylinder-like structures, including rod and ring structures), two-dimensional (layer-like structures, including disk, lamella and worm-like and hamburger structures) and three-dimensional (vesicle) structures. It is found that the micellar structures transform from low- to high- dimensional structures when the solvent quality for the solvophobic blocks is decreased. In contrast, the micellar structures transform from high- to low-dimensional structures as the incompatibility between different block types increases. Furthermore, several novel micellar structures, such as the CBABC five-layer vesicle, hamburger, CBA three-layer ring, wormlike shape with

  11. Aggregation of phosphate and 1-tetradecyl-3-methylimidazolium chloride background electrolytes during micellar electrokinetic chromatography.

    Kazarjan, Jana; Vaher, Merike; Kaljurand, Mihkel


    We report the possible aggregation of phosphate and ionic liquid (1-tetradecyl-3-methylimidazolium chloride) based BGEs during MEKC. After a certain transit period, the aggregates appear as a random sequence of spikes on a UV detector signal. Root mean square values of the spikes and aggregation time (Ta ) were plotted against BGE concentrations. The observation suggests that MEKC is a simple and easy technique for micelle aggregation studies.

  12. Relaxation times and modes of disturbed aggregate distribution in micellar solutions with fusion and fission of micelles

    Zakharov, Anatoly I.; Adzhemyan, Loran Ts.; Shchekin, Alexander K., E-mail: [Department of Statistical Physics, Faculty of Physics, St. Petersburg State University, Ulyanovskaya 1, Petrodvoretz, St. Petersburg 198504 (Russian Federation)


    We have performed direct numerical calculations of the kinetics of relaxation in the system of surfactant spherical micelles under joint action of the molecular mechanism with capture and emission of individual surfactant molecules by molecular aggregates and the mechanism of fusion and fission of the aggregates. As a basis, we have taken the difference equations of aggregation and fragmentation in the form of the generalized kinetic Smoluchowski equations for aggregate concentrations. The calculations have been made with using the droplet model of molecular surfactant aggregates and two modified Smoluchowski models for the coefficients of aggregate-monomer and aggregate-aggregate fusions which take into account the effects of the aggregate size and presence of hydrophobic spots on the aggregate surface. A full set of relaxation times and corresponding relaxation modes for nonequilibrium aggregate distribution in the aggregation number has been found. The dependencies of these relaxation times and modes on the total concentration of surfactant in the solution and the special parameter controlling the probability of fusion in collisions of micelles with other micelles have been studied.

  13. Thermodynamics of Micellization of Surfactants of Low Aggregation Number: The Aggregation of Propranolol Hydrochloride.

    Mosquera; Ruso; Attwood; Jones; Prieto; Sarmiento


    The self-association of propranolol hydrochloride in aqueous solution has been studied as a function of temperature. The critical concentration (C*) and the degree of ionization (alpha) were determined by conductivity measurements at temperatures over the range 298.15 to 313.15 K. The enthalpy change on aggregation in water was measured by microcalorimetry. To calculate changes in the thermodynamic properties of aggregation the mass action model for high and low aggregation numbers was applied, the latter model giving better agreement between experimental and theoretical enthalpy changes. Copyright 1999 Academic Press.

  14. Compartmentalization of amino acids in surfactant aggregates - Partitioning between water and aqueous micellar sodium dodecanoate and between hexane and dodecylammonium propionate trapped water in hexane

    Fendler, J. H.; Nome, F.; Nagyvary, J.


    The partitioning of amino acids (glycine, alanine, leucine, phenylalanine, histidine, aspartic acid, glutamic acid, lysine, isoleucine, threonine, serine, valine, proline, arginine) in aqueous and nonaqueous micellar systems was studied experimentally. Partitioning from neat hexane into dodecylammonium propionate trapped water in hexane was found to be dependent on both electrostatic and hydrophobic interactions, which implies that the interior of dodecylammonium propionate aggregates is negatively charged and is capable of hydrogen bonding in addition to providing a hydrophobic environment. Unitary free energies of transfer of amino acid side chains from hexane to water were determined and solubilities of amino acids in neat hexane substantiated the amino acid hydrophobicity scale. The relevance of the experiments to prebiotic chemistry was examined.

  15. Phenothiazines solution complexity - Determination of pKa and solubility-pH profiles exhibiting sub-micellar aggregation at 25 and 37°C.

    Pobudkowska, Aneta; Ràfols, Clara; Subirats, Xavier; Bosch, Elisabeth; Avdeef, Alex


    The ionization constants (pKa) and the pH-dependent solubility (log S-pH) of six phenothiazine derivatives (promazine hydrochloride, chlorpromazine hydrochloride, triflupromazine hydrochloride, fluphenazine dihydrochloride, perphenazine free base, and trifluoperazine dihydrochloride) were determined at 25 and 37°C. The pKa values of these low-soluble surface active molecules were determined by the cosolvent method (n-propanol/water at 37°C and methanol/water at 25°C). The log S-pH profiles were measured at 24h incubation time in 0.15M phosphate buffers. The log S-pH "shape-template" method, which critically depends on accurate pKa values (determined independently of solubility data), was used to propose speciation models, which were subsequently refined by rigorous mass-action weighted regression procedure described recently. Differential scanning calorimetry (DSC), UV-visible spectrophotometry, potentiometric, and high performance liquid chromatography (HPLC) measurements were used to characterize the compounds. The intrinsic solubility (S0) values of the three least-soluble drugs (chlorpromazine·HCl, triflupromazine·HCl, and trifluoperazine·2HCl) at 25°C were 0.5, 1.1, and 2.7μg/mL (resp.). These values increased to 5.5, 9.2, and 8.7μg/mL (resp.) at the physiological temperature. The enthalpies of solution for the latter compounds were exceptionally high positive (endothermic) values (99-152kJ·mol(-1)). Cationic sub-micellar aggregates were evident (from the distortions in the log S-pH profiles) for chlorpromazine, fluphenazine, perphenazine, and trifluoperazine at 25°C. The effects persisted at 37°C for chlorpromazine and trifluoperazine. The solids in suspension were apparently amorphous in cases where the drugs were introduced as the chloride salts.

  16. An Asymptotic Theory for the Re-Equilibration of a Micellar Surfactant Solution

    Griffiths, I. M.


    Micellar surfactant solutions are characterized by a distribution of aggregates made up predominantly of premicellar aggregates (monomers, dimers, trimers, etc.) and a region of proper micelles close to the peak aggregation number, connected by an intermediate region containing a very low concentration of aggregates. Such a distribution gives rise to a distinct two-timescale reequilibration following a system dilution, known as the t1 and t2 processes, whose dynamics may be described by the Becker-Döring equations. We use a continuum version of these equations to develop a reduced asymptotic description that elucidates the behavior during each of these processes.© 2012 Society for Industrial and Applied Mathematics.

  17. Pressure-induced melting of micellar crystal

    Mortensen, K.; Schwahn, D.; Janssen, S.


    Aqueous solutions of triblock copolymers of poly(ethylene oxide) and poly(propylene oxide) aggregate at elevated temperatures into micelles which for polymer concentrations greater-than-or-equal-to 20% make a hard sphere crystallization to a cubic micellar crystal. Structural studies show...... that pressure improves the solvent quality of water, thus resulting in decomposition of the micelles and consequent melting of the micellar crystal. The combined pressure and temperature dependence reveals that in spite of the apparent increase of order on the 100 angstrom length scale upon increasing...... temperature (decreasing pressure) the overall entropy increases through the inverted micellar crystallization characteristic....

  18. Determination of the aggregation number for micelles by isothermal titration calorimetry

    Olesen, Niels Erik; Holm, Rene; Westh, Peter


    Isothermal titration calorimetry (ITC) has previously been applied to estimate the aggregation number (n), Gibbs free energy (ΔG), enthalpy (ΔH) and entropy (ΔS) of micellization. However, some difficulties of micelle characterization by ITC still remain; most micelles have aggregation numbers...... > 4 and its mathematical implementation is therefore not straight-forward. It seems as if all of these difficulties can be traced back to the aggregation number. In this work a new principle of data quantification is derived which is easy to apply, interpret and will provide statistical reliable...... insight into optimal design of titration protocols for micelle characterization. By applying the new method, the aggregation number of sodium dodecyl sulphate and glycochenodeoxycholate was determined at concentrations around their critical micelle concentration (CMC)...

  19. Small-angle neutron scattering from micellar solutions

    V K Aswal; P S Goyal


    Micellar solutions are the suspension of the colloidal aggregates of the surfactant molecules in aqueous solutions. The structure (shape and size) and the interaction of these aggregates, referred to as micelles, depend on the molecular architecture of the surfactant molecule, presence of additives and the solution conditions such as temperature, concentration etc. This paper gives the usefulness of small-angle neutron scattering to the study of micellar solutions with some of our recent results.

  20. Flow-induced gelation of living (micellar) polymers

    Bruinsma, Robijn; Gelbart, William M.; Ben-Shaul, Avinoam


    The effect of shear velocity gradients on the size (L) of rodlike micelles in dilute and semidilute solution is considered. A kinetic equation is introduced for the time-dependent concentration of aggregates of length L, consisting of 'bimolecular' combination processes L + L-prime yield (L + L-prime) and unimolecular fragmentations L yield L + (L - L-prime). The former are described by a generalization (from spheres to rods) of the Smoluchowski mechanism for shear-induced coalesence of emulsions, and the latter by incorporating the tension-deformation effects due to flow. Steady-state solutions to the kinetic equation are obtained, with the corresponding mean micellar size evaluated as a function of the Peclet number P (i.e., the dimensionless ratio of the flow rate and the rotational diffusion coefficient). For sufficiently dilute solutions, only a weak dependence of the micellar size on P is found. In the semidilute regime, however, an apparent divergence in the micellar size at P of about 1 suggests a flow-induced first-order gelation phenomenon.

  1. Solubilization of benzene, toluene, and xylene (BTX) in aqueous micellar solutions of amphiphilic imidazolium ionic liquids.

    Łuczak, Justyna; Jungnickel, Christian; Markiewicz, Marta; Hupka, Jan


    Water-soluble ionic liquids may be considered analogues to cationic surfactants with a corresponding surface activity and ability to create organized structures in aqueous solutions. For the first time, the enhanced solubility of the aromatic hydrocarbons, benzene, toluene, and xylene, in aqueous micellar systems of 1-alkyl-3-methylimidazolium chlorides was investigated. Above a critical micelle concentration, a gradual increase in the concentration of aromatic hydrocarbons in the miceller solution was observed. This phenomenon was followed by means of the molar solubilization ratio, the micellar/water partition coefficient, and the number of solubilizate molecules per IL micelle. The molar solubilization ratio for ionic liquid micelles was found to be significantly higher when compared to that of ionic surfactants of similar chain length. The incorporation of the hydrocarbon into the micelle affects also an increase of the aggregation number.

  2. Enhanced Micellar Catalysis LDRD.

    Betty, Rita G.; Tucker, Mark D; Taggart, Gretchen; Kinnan, Mark K.; Glen, Crystal Chanea; Rivera, Danielle; Sanchez, Andres; Alam, Todd Michael


    The primary goals of the Enhanced Micellar Catalysis project were to gain an understanding of the micellar environment of DF-200, or similar liquid CBW surfactant-based decontaminants, as well as characterize the aerosolized DF-200 droplet distribution and droplet chemistry under baseline ITW rotary atomization conditions. Micellar characterization of limited surfactant solutions was performed externally through the collection and measurement of Small Angle X-Ray Scattering (SAXS) images and Cryo-Transmission Electron Microscopy (cryo-TEM) images. Micellar characterization was performed externally at the University of Minnesotas Characterization Facility Center, and at the Argonne National Laboratory Advanced Photon Source facility. A micellar diffusion study was conducted internally at Sandia to measure diffusion constants of surfactants over a concentration range, to estimate the effective micelle diameter, to determine the impact of individual components to the micellar environment in solution, and the impact of combined components to surfactant phase behavior. Aerosolized DF-200 sprays were characterized for particle size and distribution and limited chemical composition. Evaporation rates of aerosolized DF-200 sprays were estimated under a set of baseline ITW nozzle test system parameters.

  3. Passage number affects the pluripotency of mouse embryonic stem cells as judged by tetraploid embryo aggregation.

    Li, Xiang-Yun; Jia, Qing; Di, Ke-Qian; Gao, Shu-Min; Wen, Xiao-Hui; Zhou, Rong-Yan; Wei, Wei; Wang, Li-Ze


    The aim of this study was to determine whether the number of passages affected the developmental pluripotency of embryonic stem (ES) cells as measured by the attainment of adult fertile mice derived from embryonic stem (ES) cell/tetraploid embryo complementation. Thirty-six newborns were produced by the aggregation of tetraploid embryos and hybrid ES cells after various numbers of passages. These newborns were entirely derived from ES cells as judged by microsatellite DNA, coat-color phenotype, and germline transmission. Although 15 survived to adulthood, 17 died of respiratory failure, and four were eaten by their foster mother. From the 15 mice that reached adulthood and that could reproduce, none arose from ES cells at passage level 15 or more. All 15 arose from cells at passages 3-11. Our results demonstrate that the number of passages affects the developmental pluripotency of ES cells.

  4. Location of ethanol in sodium dodecyl sulfate aggregates

    LIU, Tian-Qing; YU, Wei-Li; GUO, Rong


    The hexagonal liquid crystalline phase of SDS ( Sodium dodecyl sulfate)/H2O system changes into lamellar liquid crystal and the effective length of surfactant molecule d0/2 in the lamellar liquid crystal decreases with the addition of ethanol.The micellar aggregation number N of SDS decreases and the micellar diffusion coefficient increases with the added ethanol.Under a constant concentration of SDS, the molecule number ratio of ethanol to SDS in the micelle increases with the concentration of ethanol and even exceeds 10 when ethanol concentration is 1.085 mol/L. All these results show that ethanol, even though a short chain alcohol and soluble in water, can partly exist in the interphase of the amphiphilic aggregates showing some properties of co-surfactant.

  5. Micellar Electrokinetic Chromatography

    Bald, Edward; Kubalczyk, Paweł

    Since the introduction of micellar electrokinetic chromatography by Terabe, several authors have paid attention to the fundamental characteristics of this separation method. In this chapter the theoretical and practical aspects of resolution optimization, as well as the effect of different separation parameters on the migration behavior are discussed. These among others include fundamentals of separation, retention factor and resolution equation, efficiency, selectivity, and various surfactants and additives. Initial conditions for method development and instrumental approaches such as mass spectrometry detection are also mentioned covering the proposals for overcoming the difficulties arising from the coupling micellar electrokinetic chromatography with mass spectrometry detection.

  6. Aggregation of sulfosuccinate surfactants in water

    Magid, L.J.; Daus, K.A.; Butler, P.D.; Quincy, R.B.


    The aggregation of sodium di-n-alkyl sulfosuccinates in water (H/sub 2/O and D/sub 2/O at 45/sup 0/C) has been investigated. A self-consistent picture of the dependence of sodium ion binding on surfactant concentration is obtained from emf measurements, conductimetry, and small-angle neutron scattering (SANS) measurements. The concentration dependence of the micellar agregation number for the sulfosuccinates and related double-tailed surfactants depends markedly on surfactant solubility. A sphere-to-disk transition in micellar shape, which might have been expected as a precursor to formation of a lamellar mesophase, was not observed as the surfactant concentration was increased. 8 figures, 2 tables.

  7. Aggregation number-based degrees of counterion dissociation in sodium n-alkyl sulfate micelles.

    Lebedeva, Nataly V; Shahine, Antoine; Bales, Barney L


    Values of the degree of counterion dissociation, alpha, for sodium n-alkyl sulfate micelles, denoted by SN(c)S, where N(c) is the number of carbon atoms in the alkyl chain, are defined by asserting that the aggregation number, N, is dependent only on the concentration, C(aq), of counterions in the aqueous pseudophase. By using different combinations of surfactant and added salt concentrations to yield the same value of N, alpha can be determined, independent of the experimental method. Electron paramagnetic resonance measurements of the hyperfine spacings of two nitroxide spin probes, 16- and 5-doxylstearic acid methyl ester (16DSE and 5DSE, respectively), are employed to determine whether micelles from two samples have the same value of N to high precision. The EPR spectra are different for the two spin probes, but the values of alpha are the same, within experimental error, as they must be. In agreement with recent work on S12S and with prevailing thought in the literature, values of alpha are constant as a function of N. This implies that the value of alpha is constant whether the surfactant or added electrolyte concentrations are varied. Interestingly, alpha varies with chain length as follows: N(c) = 8, alpha = 0.42 +/- 0.03; N(c) = 9, alpha = 0.41 +/- 0.03; N(c) = 10, alpha = 0.35 +/- 0.02; N(c) = 11, alpha = 0.30 +/- 0.02 at 25 degrees C and N(c) = 13, alpha = 0.22 +/- 0.02; and N(c) = 14, alpha = 0.19 +/- 0.01 at 40 degrees C. A simple electrostatic theoretical description, based on the nonlinear Poisson-Boltzmann equation for the ion distribution around a charged sphere, was compared with the experimental results. The theory predicts values of alpha that are in reasonable agreement with experiment, nicely predicting the decrease of alpha as N(c) increases. However, the theory also predicts that, for a given value of N(c), alpha decreases as N increases. Moreover, this decrease is predicted to be different if N is increased by adding salt or by increasing

  8. Aggregation operators on intuitionistic trapezoidal fuzzy number and its application to multi-criteria decision making problems

    Wang Jianqiang; Zhang Zhong


    Intuitionistic trapezoidal fuzzy numbers and their operational laws are defined. Based on these op-erational laws, some aggregation operators, including intuitionistic trapezoidal fuzzy weighted arithmetic averaging operator and weighted geometric averaging operator are proposed. Expected values, score function, and accuracy function of intuitionitsic trapezoidal fuzzy numbers are defined. Based on these, a kind of intuitionistic trapezoidal fuzzy multi-criteria decision making method is proposed. By using these aggregation operators, criteria values are aggregated and integrated intuitionistic trapezoidal fuzzy numbers of alternatives are attained. By comparing score function and accuracy function values of integrated fuzzy numbers, a ranking of the whole alternative set can be attained. An example is given to show the feasibility and availability of the method.

  9. Aggregation Operators on Triangular Intuitionistic Fuzzy Numbers and its Application to Multi-Criteria Decision Making Problems

    Liang Changyong


    Full Text Available The aim of this work is to present some aggregation operators with triangular intuitionistic fuzzy numbers and study their desirable properties. Firstly, the score function and the accuracy function of triangular intuitionistic fuzzy number are given, the method for ranking triangular intuitionistic fuzzy numbers are developed. Then, some geometric aggregation operators for aggregating triangular intuitionistic fuzzy numbers are developed, such as triangular intuitionistic fuzzy weighted geometric (TIFWG operator, the triangular intuitionistic fuzzy ordered weighted geometric (TIFOWG operator and the triangular intuitionistic fuzzy hybrid geometric (TIFHG operator. Moreover, an application of the new approach to multi-criteria decision making method was proposed based on the geometric average operator of TIFNs, and the new ranking method for TIFNs is used to rank the alternatives. Finally, an example analysis is given to verify and demonstrate the practicality and effectiveness of the proposed method.

  10. Effect of the interaction of heat-processing style and fat type on the micellarization of lipid-soluble pigments from green and red pungent peppers (Capsicum annuum).

    Victoria-Campos, Claudia I; Ornelas-Paz, José de Jesús; Yahia, Elhadi M; Failla, Mark L


    The high diversity of carotenoids and chlorophylls in foods contrasts with the reduced number of pigments that typically are investigated in micellarization studies. In this study, pepper samples (raw and heat-treated) contained 68 individual pigments, but only 38 of them were micellarized after in vitro digestion. The micellarization of pigments was majorly determined by the interaction effect of processing style (food matrix effect) and fat type (saturated and unsaturated). The highest micellarization was observed with raw peppers. Unsaturated fat increased the micellarization of carotenoid esters, while the impact of fat on the micellarization of free carotenoids seemed to be dependent on pigment structure. The micellarization efficiency was diminished as the esterification level of carotenoids increased. The type of fatty acid moiety and the polarity of the carotenoids modulated their micellarization. Chlorophylls were transformed into pheophytins by heat-processing and digestion, with the pheophytins being stable under gastrointestinal conditions. Micellarization of pheophytins was improved by fat.

  11. Rheological Properties of Hydrophobically Associative Copolymers Prepared in a Mixed Micellar Method Based on Methacryloxyethyl-dimethyl Cetyl Ammonium Chloride as Surfmer

    Rui Liu


    Full Text Available A novel cationic surfmer, methacryloxyethyl-dimethyl cetyl ammonium chloride (DMDCC, is synthesized. The micellar properties, including critical micelle concentration and aggregation number, of DMDCC-SDS mixed micelle system are studied using conductivity measurement and a steady-state fluorescence technique. A series of water-soluble associative copolymers with acrylamide and DMDCC are prepared using the mixed micellar polymerization. Compared to conventional micellar polymerization, this new method could not only reasonably adjust the length of the hydrophobic microblock, that is, NH, but also sharply reduce the amount of surfactant. Their rheological properties related to hydrophobic microblock and stickers are studied by the combination of steady flow and linear viscoelasticity experiments. The results indicate that both the hydrophobic content and, especially the length of the hydrophobic microblock are the dominating factors effecting the intermolecular hydrophobic association. The presence of salt influences the dynamics of copolymers, resulting in the variation of solution characters. Viscosity measurement indicates that mixed micelles between the copolymer chain and SDS molecules serving as junction bridges for transitional network remarkably enhance the viscosity. Moreover, the microscopic structures of copolymers at different experimental conditions are conducted by ESEM. This method gives us an insight into the preparation of hydrophobically associative water-soluble copolymers by cationic surfmer-anionic surfactant mixed micellar polymerization with good performance.

  12. On the predictions and limitations of the Becker–Döring model for reaction kinetics in micellar surfactant solutions

    Griffiths, I.M.


    We investigate the breakdown of a system of micellar aggregates in a surfactant solution following an order-one dilution. We derive a mathematical model based on the Becker-Döring system of equations, using realistic expressions for the reaction constants fit to results from Molecular Dynamics simulations. We exploit the largeness of typical aggregation numbers to derive a continuum model, substituting a large system of ordinary differential equations for a partial differential equation in two independent variables: time and aggregate size. Numerical solutions demonstrate that re-equilibration occurs in two distinct stages over well-separated timescales, in agreement with experiment and with previous theories. We conclude by exposing a limitation in the Becker-Döring theory for re-equilibration of surfactant solutions. © 2011 Elsevier Inc.

  13. Micellar liquid chromatography

    Basova, Elena M.; Ivanov, Vadim M.; Shpigun, Oleg A.


    Background and possibilities of practical applications of micellar liquid chromatography (MLC) are considered. Various retention models in MLC, the effects of the nature and concentration of surfactants and organic modifiers, pH, temperature and ionic strength on the MLC efficiency and selectivity are discussed. The advantages and limitations of MLC are demonstrated. The performance of MLC is critically evaluated in relationship to the reversed-phase HPLC and ion-pair chromatography. The potential of application of MLC for the analysis of pharmaceuticals including that in biological fluids and separation of inorganic anions, transition metal cations, metal chelates and heteropoly compounds is described. The bibliography includes 146 references.

  14. A micellar solution

    Jewulski, J.


    The subject of the invention is a micellar solution used in oil extraction when flooding a deposit and washing out the critical zone. It contains ethanolamine salt of alkylobenzolsulfonic acid (10 to 56 percent by mass), higher alcohol (4 to 56 percent) an organic solvent and water (2.4 to 57.2 percent) and is distinguished by the fact that an amyl alcohol of the third series is used as the higher alcohol, while oil in a volume of 19 to 71 percent or gasoline in a volume of 6 to 16 percent) is used as the solvent.

  15. Determination of thermodynamic potentials and the aggregation number for micelles with the mass-action model by isothermal titration calorimetry

    Olesen, Niels Erik; Westh, Peter; Holm, René


    The aggregation number (n), thermodynamic potentials (ΔG, ΔH, ΔS) and critical micelle concentration (CMC) for 6 natural bile salts were determined on the basis of both original and previously published isothermal titration calorimetry (ITC) data. Different procedures to estimate parameters...

  16. Generalized Einstein Aggregation Operators Based on the Interval Neutrosophic Numbers and Their Application to Multi-attribute Group Decision Making

    Don Hass


    Based on the Einstein operator, the operational rules of interval neutrosophic numbers are defined, according to the combination of Einstein operations and generalized aggregation operators, the interval neutrosophic generalized weighted Einstein average (INGWEA) operator, interval neutrosophic generalized ordered weighted Einstein average (INGOWEA) operator and interval neutrosophic generalized hybrid weighted Einstein average (INGHWEA) operator are proposed .

  17. Surface-active ionic liquids in micellar catalysis: impact of anion selection on reaction rates in nucleophilic substitutions† †Electronic supplementary information (ESI) available: Formulae for calculating aggregation parameters and fitting of kinetic constants and copies of NMR spectra. See DOI: 10.1039/c6cp00493h Click here for additional data file.

    Cognigni, Alice; Gaertner, Peter; Zirbs, Ronald; Peterlik, Herwig; Prochazka, Katharina; Schröder, Christian


    A series of surface-active ionic liquids based on the 1-dodecyl-3-methylimidazolium cation and different anions such as halides and alkylsulfates was synthesized. The aggregation behavior of these ionic liquids in water was characterized by surface tension, conductivity measurements and UV-Vis spectroscopy in order to determine the critical micelle concentration (CMC) and to provide aggregation parameters. The determination of surface activity and aggregation properties of amphiphilic ionic liquids was accompanied by SAXS studies on selected surface-active ionic liquids. The application of these surface-active ionic liquids with different anions was tested in nucleophilic substitution reactions for the degradation of organophosphorus compounds. Kinetic studies via UV-Vis spectrophotometry showed a strong acceleration of the reaction in the micellar system compared to pure water. In addition, an influence of the anion was observed, resulting in a correlation between the anion binding to the micelle and the reaction rate constants, indicating that the careful choice of the surface-active ionic liquid can considerably affect the outcome of reactions. PMID:27121134

  18. Effects of divalent ions on displacement of oil from porous media by micellar solutions

    Mobarak, S.A.M.


    Micellar solutions are currently being investigated by a number of oil companies and research institutes as potential candidates for tertiary oil recovery processes. Micellar solutions can be used in either secondary or tertiary recovery operations. The process is being tested in some fields, but the results are inconclusive. In general, the limited field trials indicate that micellar solutions do not work as effectively as predicted from laboratory data. This research was to investigate the effect of presence of calcium ions in formation water on oil recovery using micellar solutions. Adsorption of surfactant on sand grain surfaces as a function of calcium ions concentrations also was investigated. A series of laboratory experiments was conducted in which oil was displaced from porous media by micellar solution (Amoco Floodaid 131) driven by viscous water and plain water, respectively. Based on the experimental results, micellar solutions proved to be very effective in displacing oil from porous media. The recovery of oil from porous media by micellar solution in the presence of calcium ions in formation water was improved when ethylene diamene tetracetic acid was added to the micellar solution. (Longer abstract available)

  19. Bending energetics of tablet-shaped micelles: a novel approach to rationalize micellar systems.

    Bergström, L Magnus


    A novel approach to rationalize micellar systems is expounded in which the structural behavior of tablet-shaped micelles is theoretically investigated as a function of the three bending elasticity constants: spontaneous curvature (H0), bending rigidity (k(c)), and saddle-splay constant (k(c)). As a result, experimentally accessible micellar properties, such as aggregation number, length-to-width ratio, and polydispersity, may be related to the different bending elasticity constants. It is demonstrated that discrete micelles or connected cylinders form when H0 > 1/4xi, where xi is the thickness of a surfactant monolayer, whereas various bilayer structures are expected to predominate when H0 bending rigidity is lowered, approaching the critical point at k(c) = 0, whereas monodisperse globular micelles (small length-to-width ratio) are expected to be present at large k(c) values. The spontaneous curvature mainly determines the width of tablet-shaped or ribbonlike micelles, or the radius of disklike micelles, whereas the saddle-splay constant primarily influences the size but not the shape of the micelles.

  20. Determination of thermodynamic potentials and the aggregation number for micelles with the mass-action model by isothermal titration calorimetry: A case study on bile salts.

    Olesen, Niels Erik; Westh, Peter; Holm, René


    The aggregation number (n), thermodynamic potentials (ΔG, ΔH, ΔS) and critical micelle concentration (CMC) for 6 natural bile salts were determined on the basis of both original and previously published isothermal titration calorimetry (ITC) data. Different procedures to estimate parameters of micelles with ITC were compared to a mass-action model (MAM) of reaction type: n⋅S⇌Mn. This analysis can provide guidelines for future ITC studies of systems behaving in accordance with this model such as micelles and proteins that undergo self-association to oligomers. Micelles with small aggregation numbers, as those of bile salts, are interesting because such small aggregates cannot be characterized as a separate macroscopic phase and the widely applied pseudo-phase model (PPM) is inaccurate. In the present work it was demonstrated that the aggregation number of micelles was constant at low concentrations enabling determination of the thermodynamic potentials by the MAM. A correlation between the aggregation number and the heat capacity was found, which implies that the dehydrated surface area of bile salts increases with the aggregation number. This is in accordance with Tanford's principles of opposing forces where neighbouring molecules in the aggregate are better able to shield from the surrounding hydrophilic environment when the aggregation number increases. Copyright © 2015 Elsevier Inc. All rights reserved.

  1. Tannin-assisted aggregation of natively unfolded proteins

    Zanchi, D.; Narayanan, T.; Hagenmuller, D.; Baron, A.; Guyot, S.; Cabane, B.; Bouhallab, S.


    Tannin-protein interactions are essentially physical: hydrophobic and hydrogen-bond-mediated. We explored the tannin-assisted protein aggregation on the case of β-casein, which is a natively unfolded protein known for its ability to form micellar aggregates. We used several tannins with specified length. Our SAXS results show that small tannins increase the number of proteins per micelle, but keeping their size constant. It leads to a tannin-assisted compactization of micelles. Larger tannins, with linear dimensions greater than the crown width of micelles, lead to the aggregation of micelles by a bridging effect. Experimental results can be understood within a model where tannins are treated as effective enhancers of hydrophobic attraction between specific sites in proteins.

  2. Effect of compressed CO2 on the critical micelle concentration and aggregation number of AOT reverse micelles in isooctane.

    Chen, Jing; Zhang, Jianling; Han, Buxing; Feng, Xiaoying; Hou, Minqiang; Li, Wenjing; Zhang, Zhaofu


    The effect of compressed CO2 on the critical micelle concentration (cmc) and aggregation number of sodium bis-2-ethylhexylsulfosuccinate (AOT) reverse micelles in isooctane solution was studied by UV/Vis and fluorescence spectroscopy methods in the temperature range of 303.2-318.2 K and at different pressures or mole fractions of CO2 (X(CO2)). The capacity of the reverse micelles to solubilize water was also determined by direct observation. The standard Gibbs free energy (DeltaGo(m)), standard enthalpy (DeltaHo(m)), and standard entropy (DeltaSo(m)) for the formation of the reverse micelles were calculated by using the cmc data determined. It was discovered that the cmc versus X(CO2) curve and the DeltaGo(m) versus X(CO2) curve for a fixed temperature have a minimum, and the aggregation number and water-solubilization capacity of the reverse micelles reach a maximum at the X(CO2) value corresponding to that minimum. These results indicate that CO2 at a suitable concentration favors the formation of and can stabilize AOT reverse micelles. A detailed thermodynamic study showed that the driving force for the formation of the reverse micelles is entropy.

  3. Small angle neutron scattering study on the aggregation behaviour of PEO–PPO–PEO copolymers in the presence of a hydrophobic diol

    B Bharatiya; V K Aswal; P Bahadur


    Small angle neutron scattering (SANS) measurements on aqueous solutions of four polyethylene oxide–polypropylene oxide–polyethylene oxide block copolymers (commercially known as Pluronic®)F88, P85, F127 and P123 in the presence of hydrophobic C14Diol (also known as Surfynol® 104) reveal information on micellization, micellar size and micellar transitions. While most hydrophilic F88 (with least PPO/PEO ratio) remained unimers in water at 30◦ C, other copolymers formed micellar solutions. Surfynol® 104 is sparingly soluble in water to only about ∼ 0.1 wt%, but on addition to pluronic solution, it gets incorporated in the micellar region of block copolymer which leads to increase in aggregation number and transformation of spherical to ellipsoidal micelles. The added diol-induced micellization in F88, though hydrophilic copolymers F88 and F127 did not show any appreciable micellar growth or shape changes as observed for P85 and P123 (which are comparatively more hydrophobic). The SANS results on copolymer pairs with same molecular weight PPO but different % PEO (viz. F88 and P85, F127 and P123) and with same molecular weight PEO but different PPO (F88 and F127) reveal that the copolymer with large PPO/PEO ratio facilitate micellar transition in the presence of diol. An increase in temperature and presence of added electrolyte (sodium chloride) in the solution further enhances these effects. The micellar parameters for these systems were found out using available software and are reported.

  4. Hydrogels with micellar hydrophobic (nanodomains

    Miloslav ePekař


    Full Text Available Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  5. The Aggregate behavior of branch points--measuring the number and velocity of atmospheric turbulence layers.

    Oesch, Denis W; Sanchez, Darryl J; Matson, Charles L


    Optical waves propagating through atmospheric turbulence develop spatial and temporal variations in their phase. For sufficiently strong turbulence, these phase differences can lead to interference in the propagating wave and the formation of branch points; positions of zero amplitude. Under the assumption of a layered turbulence model, we show that these branch points can be used to estimate the number and velocities of atmospheric layers. We describe how to carry out this estimation process and demonstrate its robustness in the presence of sensor noise.

  6. Extension of the analytical kinetics of micellar relaxation: Improving a relation between the Becker-Döring difference equations and their Fokker-Planck approximation

    Babintsev, I. A.; Adzhemyan, L. Ts.; Shchekin, A. K.


    Relaxation of micellar systems can be described with the help of the Becker-Döring kinetic difference equations for aggregate concentrations. Passing in these equations to continual description, when the aggregation number is considered as continuous variable and the concentration difference is replaced by the concentration differential, allows one to find analytically the eigenvalues (to whom the inverse times of micellar relaxation are related) and eigenfunctions (or the modes of fast relaxation) of the linearized differential operator of the kinetic equation corresponding to the Fokker-Planck approximation. At this the spectrum of eigenvalues appears to be degenerated at some surfactant concentrations. However, as has been recently found by us, there is no such a degeneracy at numerical determination of the eigenvalues of the matrix of coefficients for the linearized difference Becker-Döring equations. It is shown in this work in the frameworks of the perturbation theory, that taking into account the corrections to the kinetic equation produced by second derivatives at transition from differences to differentials and by deviation of the aggregation work from a parabolic form in the vicinity of the work minimum, lifts the degeneracy of eigenvalues and improves markedly the agreement of concentration-dependent fast relaxation time with the results of the numerical solution of the linearized Becker-Döring difference equations.

  7. Micellar systems: Novel family for drug carriers

    Rana, Meenakshi; Chowdhury, Papia


    Micellar systems have attracted a great deal of interest, especially in the field of biomedical sciences. The paper deals with the encapsulation behavior of Pyrrole-2-carboxyldehyde (PCL) an anti-cancer drug in different micellar systems. The inculsion capability of PCL is verified experimentally (UV-Vis, Photoluminescence and Raman spectroscopy) in polymer matrix. Two-micellar systems sodium dodecyl sulfate (SDS) and Polysorbate 80 (TWEEN 80) have been studied with a poorly water soluble PCL. The present work provides the effects of biocompatible organic PCL molecule entrap in micellar system in polymer phase due to its vast applicability in drug industry.


    Noor Rehman; Abbas Khan; Iram Bibi; Mohammad Siddiq


    The interactions of non-ionic amphiphilic diblock copolymer poly(oxyethylene/oxybutylene) (E39B18) with anionic surfactant sodium dodecyl sulphate (SDS) and cationic surfactant hexadecyltrimethylammonium bromide (CTAB) were studied by using various techniques such as surface tension,conductivity,steady-state fluorescence and dynamic light scattering.Surface tension measurements were used to determine the critical micelle concentration (CMC) and thereby the free energy of micellization (AGmic),free energy of adsorption (AGads),surface excess concentration (F) and minimum area per molecule (A).Conductivity measurements were used to determine the critical micelle concentration (CMC),critical aggregation concentration (CAC),polymer saturation point (PSP),degree of ionization (α) and counter ion binding (β).Dynamic light scattering experiments were performed to check the changes in physiochemical properties of the block copolymer micelles taken place due to the interactions of diblock copolymers with ionic surfactants.The ratio of the first and third vibronic peaks (I1/I13) indicated the polarity of the pyrene micro environment and was used for the detection of micelle as well as polymer-surfactant interactions.Aggregation number (N),number of binding sites (n) and free energy of binding (AGb) for pure surfactants as well as for polymer-surfactant mixed micellar systems were determined by the fluorescence quenching method.

  9. Aggregation of estimated numbers of undiscovered deposits: an R-script with an example from the Chu Sarysu Basin, Kazakhtan: Chapter B in Global mineral resource assessment

    Schuenemeyer, John H.; Zientek, Michael L.; Box, Stephen E.


    Mineral resource assessments completed by the U.S. Geological Survey during the past three decades express geologically based estimates of numbers of undiscovered mineral deposits as probability distributions. Numbers of undiscovered deposits of a given type are estimated in geologically defined regions. Using Monte Carlo simulations, these undiscovered deposit estimates are combined with tonnage and grade models to derive a probability distribution describing amounts of commodities and rock that could be present in undiscovered deposits within a study area. In some situations, it is desirable to aggregate the assessment results from several study areas. This report provides a script developed in open-source statistical software, R, that aggregates undiscovered deposit estimates of a given type, assuming independence, total dependence, or some degree of correlation among aggregated areas, given a user-specified correlation matrix.

  10. Micellar electrokinetic chromatography on microchips.

    Kitagawa, Fumihiko; Otsuka, Koji


    This review highlights the methodological and instrumental developments in microchip micellar EKC (MCMEKC) from 1995. The combination of higher separation efficiencies in micellar EKC (MEKC) with high-speed separation in microchip electrophoresis (MCE) should provide high-throughput and high-performance analytical systems. The chip-based separation technique has received considerable attention due to its integration ability without any connector. This advantage allows the development of a multidimensional separation system. Several types of 2-D separation microchips are described in the review. Since complicated channel configurations can easily be fabricated on planar substrates, various sample manipulations can be carried out prior to MCMEKC separations. For example, mixing for on-chip reactions, on-line sample preconcentration, on-chip assay, etc., have been integrated on MEKC microchips. The application of on-line sample preconcentration to MCMEKC can provide not only sensitivity enhancement but also the elucidation of the preconcentration mechanism due to the visualization ability of MCE. The characteristics of these sample manipulations on MEKC microchips are presented in this review. The scope of applications in MCMEKC covers mainly biogenic compounds such as amino acids, peptides, proteins, biogenic amines, DNA, and oestrogens. This review provides a comprehensive table listing the applications in MCMEKC in relation to detection methods.

  11. Molecular thermodynamics for micellar branching in solutions of ionic surfactants.

    Andreev, Vasily A; Victorov, Alexey I


    We develop an analytical molecular-thermodynamic model for the aggregation free energy of branching portions of wormlike ionic micelles in 1:1 salt solution. The junction of three cylindrical aggregates is represented by a combination of pieces of the torus and bilayer. A geometry-dependent analytical solution is obtained for the linearized Poisson-Boltzmann equation. This analytical solution is applicable to saddle-like structures and reduces to the solutions known previously for planar, cylindrical, and spherical aggregates. For micellar junctions, our new analytical solution is in excellent agreement with numerical results over the range of parameters typical of ionic surfactant systems with branching micelles. Our model correctly predicts the sequence of stable aggregate morphologies, including a narrow bicontinuous zone, in dependence of hydrocarbon tail length, head size, and solution salinity. For predicting properties of a spatial network of wormlike micelles, our aggregation free energy is used in the Zilman-Safran theory. Our predictions are compared with experimental data for branching micelles of ionic surfactants.

  12. Capillary Separation: Micellar Electrokinetic Chromatography

    Terabe, Shigeru


    Micellar electrokinetic chromatography (MEKC), a separation mode of capillary electrophoresis (CE), has enabled the separation of electrically neutral analytes. MEKC can be performed by adding an ionic micelle to the running solution of CE without modifying the instrument. Its separation principle is based on the differential migration of the ionic micelles and the bulk running buffer under electrophoresis conditions and on the interaction between the analyte and the micelle. Hence, MEKC's separation principle is similar to that of chromatography. MEKC is a useful technique particularly for the separation of small molecules, both neutral and charged, and yields high-efficiency separation in a short time with minimum amounts of sample and reagents. To improve the concentration sensitivity of detection, several on-line sample preconcentration techniques such as sweeping have been developed.

  13. Catalysis in micellar and macromoleular systems

    Fendler, Janos


    Catalysis in Micellar and Macromolecular Systems provides a comprehensive monograph on the catalyses elicited by aqueous and nonaqueous micelles, synthetic and naturally occurring polymers, and phase-transfer catalysts. It delineates the principles involved in designing appropriate catalytic systems throughout. Additionally, an attempt has been made to tabulate the available data exhaustively. The book discusses the preparation and purification of surfactants; the physical and chemical properties of surfactants and micelles; solubilization in aqueous micellar systems; and the principles of

  14. 稳态荧光猝灭法确定胶束聚合合成条件%Determination of the synthesis condition of micellar polymerization by steady-state fluorescence quenching method

    钟金杭; 郭拥军; 柳建新; 杨雪杉; 杨红苹; 冯茹森; 祝仰文


    以芘(Py)为荧光探针,十六烷基氯化吡啶(CPC)为猝灭剂,用稳态荧光猝灭法研究十二烷基硫酸钠(SDS)浓度和溶液极性对其胶束聚集数的影响.结果表明,当SDS浓度在5~42倍cmc时,胶束聚集数Nagg随SDS的浓度增大而增大,并且趋势逐渐变缓.当SDS浓度为11.3倍cmc时,胶束聚集数随NaCl浓度增大而明显增大,I1/I3值逐渐减小.以上两种条件下聚集数的增大引起疏水微嵌段长度较大的变化,而微嵌段长度又是胶束聚合中最重要的参数之一.因此,胶束聚合合成微嵌段缔合聚合物中,SDS浓度和溶液极性对其胶束聚集数的影响不能忽略.%The micellar aggregation numbers of SDS with different concentrations of SDS or polarity were determined by steady-state fluorescence quenching method in which pyrene was used as a fluorescence probe and cetylpyridinium chloride as a quencher. The results showed that /Vagg increased with increasing the SDS concentration in a range of 5 -42 times cmc and the increased value became more and more slowly. When the concentration of SDS was 11.3 times cmc,the ./Vagg increased significantly with increasing the NaCl concentration and /,//3 decreased gradually. Under these two conditions, the increase numbers of aggregation caused a great change in hydrophobe micro-block length, and the micro-block length was one of the most important parameter in micellar polymerization. Therefore,in the synthesis of the micro-block' associative polymers by micellar polymerization, the effect of concentrations of SDS or polarity on micellar aggregation numbers can not be ignored.

  15. Removal of Pyrethrin from Aqueous Effluents by Adsorptive Micellar Flocculation

    Pardon K. Kuipa


    Full Text Available The equilibrium adsorption of pyrethrin onto aggregates formed by the flocculation of micelles of the surfactant sodium dodecyl sulphate (SDS with aluminium sulphate is reported. The experimental results were analysed using different adsorption isotherms (Langmuir, Freundlich, Redlich-Peterson, Sips, Radke-Prausnitz, Temkin, linear equilibrium, and the Dubin-Radushkevich isotherms. The Freundlich and linear equilibrium isotherms best describe the adsorption of pyrethrin onto SDS micellar flocs, with the Freundlich adsorption constant, KF, and the mass distribution coefficient, KD, of 64.266 ((mg/g(L/mg1/n and 119.65 L/g, respectively. Applicability of the Freundlich adsorption model suggests that heterogeneous surface adsorption affects the adsorption. The mean free energy value estimated using the Dubinin-Radushkevich isotherm was 0.136 kJ/mol indicating that physisorption may be predominant in the adsorption process.

  16. Influence of solvent on micellar morphologies of semifluorinated block copolymers.

    Lee, Min Young; Kim, Sang Jae; Jeong, Yeon Tae; Kim, Joo Hyun; Gal, Yeong-Soon; Lim, Kwon Taek


    The influence of solvents on micellar architectures of block copolymers composed of poly(1H,1H-dihydroperfluorooctyl methacrylate) and poly(ethylene oxide) was investigated. In this study, binary solvents with desired proportions were chosen, which had remarkable influence on the morphology of the resulting micelles. With simple adjusting the composition of the binary solvent of chloroform and trichlorofluoromethane, interesting shapes of micelle-like aggregates, such as core-shell, cylinder, worm-like and inverted micelles were formed with sizes of 15, 70, 30 and 250 nm, respectively. In the case of methanol/water system, core-shell spheres and vesicles were produced by varying the proportion of the contents. The morphologies were also tuned to honeycomb-like and bowl-shaped micelles as well as large planar lamellae with holes in DMF and water binary solvent.

  17. Preparation of PEO/Clay Nanocomposites Using Organoclay Produced via Micellar Adsorption of CTAB

    Ahmet Gürses


    Full Text Available The aim of this study was the preparation of polyethylene oxide (PEO/clay nanocomposites using organoclay produced via micellar adsorption of cethyltrimethyl ammonium bromide (CTAB and their characterisation by X-ray diffraction (XRD, and Fourier transform infrared (FT-IR spectra, and the investigation of certain mechanical properties of the composites. The results show that the basal distance between the layers increased with the increasing CTAB/clay ratio as parallel with the zeta potential values of particles. By considering the aggregation number of CTAB micelles and interlayer distances of organo-clay, it could be suggested that the predominant micelle geometry at lower CTAB/clay ratios is an ellipsoidal oblate, whereas, at higher CTAB/clay ratios, sphere-ellipsoid transition occurs. The increasing tendency of the exfoliation degree with an increase in clay content may be attributed to easier diffusion of PEO chains to interlayer regions. FT-IR spectra show that the intensity of Si-O stretching vibrations of the organoclays (1050 cm−1 increased, especially in the ratios of 1.0 g/g clay and 1.5 g/g clay with the increasing CTAB content. It was observed that the mechanical properties of the composites are dependent on both the CTAB/clay ratios and clay content of the composites.

  18. Micellar copolymerization of associative polymers: study of the effect of acrylamide on sodium dodecyl sulfate-poly(propylene oxide) methacrylate mixed micelles.

    Bastiat, Guillaume; Grassl, Bruno; François, Jeanne


    Mixed micelles of sodium dodecyl sulfate (SDS) and poly(propylene oxide) methacrylate (PPOMA) have been studied in the presence of acrylamide using conductimetry, fluorescence spectroscopy, and small-angle neutron scattering (SANS) under the following conditions: (i) the SDS-acrylamide binary system in water; (ii) the SDS-acrylamide-PPOMA ternary system in water. The addition of acrylamide in SDS solutions perturbs the micellization of the surfactant by decreasing the aggregation number of the micelles and increasing their ionization degree. The variations of the various micellar parameters versus the weight ratio R=PPOMA/SDS are different in the presence of acrylamide or in pure water. These differences are much more pronounced for the lower than for the higher PPOMA concentrations. There is competition between acrylamide and PPOMA and at higher PPOMA concentration, acrylamide tends to be released from SDS micelles and is completely replaced by PPOMA.

  19. An improvement of a beam search method for warehouse storage allocation planning problems minimizing the number of operations and the aggregated number of products for each customer

    Nishi, Tatsushi; Yamamoto, Shinichiro; Konishi, Masami

    The storage allocation planning problem in warehouse management is to determine the allocation of products to the storage space and intermediate operations for retrieving products so as to minimize the number of operations, and maximize the collected number of products for each customer when the sequence of requests for inlet and retrieval operations are given. In this paper, we propose an efficient beam search method for generating a near optimal solution with a reasonable computation time. A heuristic procedure is also proposed in order to reduce a search space in the beam search method by using the information of subsequent inlet and retrieving requests. The validity of the proposed method is confirmed by comparing the results with the optimal solution derived by solving an MILP problem. The effectiveness of the proposed method is demonstrated by solving an actual large-sized problem consisting of more than 3000 operations.

  20. Hydrogels with Micellar Hydrophobic (Nano)Domains

    Pekař, Miloslav


    Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  1. Hydrogels with micellar hydrophobic (nano)domains

    Miloslav ePekař


    Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.

  2. Hydrogels with micellar hydrophobic (nano)domains

    Pekař, Miloslav


    Hydrogels containing hydrophobic domains or nanodomains, especially of the micellar type, are reviewed. Examples of the reasons for introducing hydrophobic domains into hydrophilic gels are given; typology of these materials is introduced. Synthesis routes are exemplified and properties of a variety of such hydrogels in relation with their intended applications are described. Future research needs are identified briefly.




    Catalysis of organic reactions by unfunctionalized surfactant aggregates (micelles, vesicles) in aqueous solution is largely determined by medium effects induced at the micellar binding sites and by entropy effects due to compartimentalization. The efficiency of these catalytic effects responds to c

  4. Study of the micellization and micellar growth in pure alkanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide and MEGA10 surfactant solutions and their mixtures. Influence of the spacer on the enthalpy change accompanying sphere-to-rod transitions.

    Martín, Victoria Isabel; Rodríguez, Amalia; Graciani, María del Mar; Robina, Inmaculada; Moyá, María Luisa


    The micellization and micellar growth in pure aqueous alkanediyl-alpha-omega-bis(dodecyldimethylammonium) bromide, 12-s-12,2Br(-) (with s = 2,5,6,8,10,12), and N-decanoyl-N-methylglucamide MEGA10 solutions and their mixtures are investigated at 303 K. Application of different theoretical approaches to the binary mixtures shows a nonideal behavior. It also shows that the spacer length does not play an important role in the attractive interactions shown by the mixed systems. The sphere-to-rod morphological transition in the pure dimeric micellar solutions is studied at 303 K. From comparison of these results with those at 298 K the key role played by the spacer in the micellar growth is shown. The spacer length controls not only the surfactant concentration at which the morphological transition happens but also the sign of the enthalpy change accompanying the sphere-to-rod equilibrium. Spacers with an even number of methylenes show smaller C* values than those with an odd number of -CH(2)- units. An endothermic enthalpy change is found for even spacers whereas an exothermic enthalpy change is found for odd spacers. To the authors knowledge, this is the first time this experimental trend has been shown. Addition of MEGA10 diminishes the tendency of the aggregates to grow. An increment in the solution mole fraction of MEGA10 makes the formation of elongated micelles difficult. Microviscosity measurements provide additional information about the influence of the MEGA10 content on the sphere-to-rod transition.

  5. A new insight on the dynamics of sodium dodecyl sulfate aqueous micellar solutions by dielectric spectroscopy.

    Lanzi, Leandro; Carlà, Marcello; Lanzi, Leonardo; Gambi, Cecilia M C


    Aqueous sodium dodecyl sulfate micellar solutions were investigated by a recently developed double-differential dielectric spectroscopy technique in the frequency range 100 MHz-3 GHz at 22 degrees C, in the surfactant concentration range 29.8-524 mM, explored for the first time above 104 mM. The micellar contribution to dielectric spectra was analyzed according to three models containing, respectively, a single Debye relaxation, a Cole-Cole relaxation and a double Debye relaxation. The single Debye model is not accurate enough. Both Cole-Cole and double Debye models fit well the experimental dielectric spectra. With the double Debye model, two characteristic relaxation times were identified: the slower one, in the range 400-900 ps, is due to the motion of counterions bound to the micellar surface (lateral motion); the faster one, in the range 100-130 ps, is due to interfacial bound water. Time constants and amplitudes of both processes are in fair agreement with Grosse's theoretical model, except at the largest concentration values, where interactions between micelles increase. For each sample, the volume fraction of bulk water and the effect of bound water as well as the conductivity in the low frequency limit were computed. The bound water increases as the surfactant concentration increases, in quantitative agreement with the micellar properties. The number of water molecules per surfactant molecule was also computed. The conductivity values are in agreement with Kallay's model over the whole surfactant concentration range.

  6. Accelerating Strain-Promoted Azide-Alkyne Cycloaddition Using Micellar Catalysis.

    Anderton, Grant I; Bangerter, Alyssa S; Davis, Tyson C; Feng, Zhiyuan; Furtak, Aric J; Larsen, Jared O; Scroggin, Triniti L; Heemstra, Jennifer M


    Bioorthogonal conjugation reactions such as strain-promoted azide-alkyne cycloaddition (SPAAC) have become increasingly popular in recent years, as they enable site-specific labeling of complex biomolecules. However, despite a number of improvements to cyclooctyne design, reaction rates for SPAAC remain significantly lower than those of the related copper-catalyzed azide-alkyne cycloaddition (CuAAC) reaction. Here we explore micellar catalysis as a means to increase reaction rate between a cyclooctyne and hydrophobic azide. We find that anionic and cationic surfactants provide the most efficient catalysis, with rate enhancements of up to 179-fold for reaction of benzyl azide with DIBAC cyclooctyne. Additionally, we find that the presence of surfactant can provide up to 51-fold selectivity for reaction with a hydrophobic over hydrophilic azide. A more modest, but still substantial, 11-fold rate enhancement is observed for micellar catalysis of the reaction between benzyl azide and a DIBAC-functionalized DNA sequence, demonstrating that micellar catalysis can be successfully applied to hydrophilic biomolecules. Together, these results demonstrate that micellar catalysis can provide higher conjugation yields in reduced time when using hydrophobic SPAAC reagents.

  7. Study of monoprotic acid-base equilibria in aqueous micellar solutions of nonionic surfactants using spectrophotometry and chemometrics.

    Babamoradi, Hamid; Abdollahi, Hamid


    Many studies have shown the distribution of solutes between aqueous phase and micellar pseudo-phase in aqueous micellar solutions. However, spectrophotometric studies of acid-base equilibria in these media do not confirm such distribution because of the collinearity between concentrations of chemical species in the two phases. The collinearity causes the number of detected species to be equal to the number of species in a homogenous solution that automatically misinterpreted as homogeneity of micellar solutions, therefore the collinearity is often neglected. This interpretation is in contradiction to the distribution theory in micellar media that must be avoided. Acid-base equilibrium of an indicator was studied in aqueous micellar solutions of a nonionic surfactant to address the collinearity using UV/Visible spectrophotometry. Simultaneous analysis (matrix augmentation) of the equilibrium and solvation data was applied to eliminate the collinearity from the equilibrium data. A model was then suggested for the equilibrium that was fitted to the augmented data to estimate distribution coefficients of the species between the two phases. Moreover, complete resolution of concentration and spectral profiles of species in each phase was achieved.

  8. Multiscale Modeling of the Effects of Salt and Perfume Raw Materials on the Rheological Properties of Commercial Threadlike Micellar Solutions.

    Tang, Xueming; Zou, Weizhong; Koenig, Peter H; McConaughy, Shawn D; Weaver, Mike R; Eike, David M; Schmidt, Michael J; Larson, Ronald G


    We link micellar structures to their rheological properties for two surfactant body-wash formulations at various concentrations of salts and perfume raw materials (PRMs) using molecular simulations and micellar-scale modeling, as well as traditional surfactant packing arguments. The two body washes, namely, BW-1EO and BW-3EO, are composed of sodium lauryl ethylene glycol ether sulfate (SLEnS, where n is the average number of ethylene glycol repeat units), cocamidopropyl betaine (CAPB), ACCORD (which is a mixture of six PRMs), and NaCl salt. BW-3EO is an SLE3S-based body wash, whereas BW-1EO is an SLE1S-based body wash. Additional PRMs are also added into the body washes. The effects of temperature, salt, and added PRMs on micellar lengths, breakage times, end-cap free energies, and other properties are obtained from fits of the rheological data to predictions of the "Pointer Algorithm" [ Zou , W. ; Larson , R.G. J. Rheol. 2014 , 58 , 1 - 41 ], which is a simulation method based on the Cates model of micellar dynamics. Changes in these micellar properties are interpreted using the Israelachvili surfactant packing argument. From coarse-grained molecular simulations, we infer how salt modifies the micellar properties by changing the packing between the surfactant head groups, with the micellar radius remaining nearly constant. PRMs do so by partitioning to different locations within the micelles according to their octanol/water partition coefficient POW and chemical structures, adjusting the packing of the head and/or tail groups, and by changing the micelle radius, in the case of a large hydrophobic PRM. We find that relatively hydrophilic PRMs with log POW 4, are isolated deep inside the micelle, separating from the tails and swelling the radius of the micelle, leading to shorter micelles and much lower viscosities, leading eventually to swollen-droplet micelles.

  9. Micellar Enzymology for Thermal, pH, and Solvent Stability.

    Minteer, Shelley D


    This chapter describes methods for enzyme stabilization using micellar solutions. Micellar solutions have been shown to increase the thermal stability, as well as the pH and solvent tolerance of enzymes. This field is traditionally referred to as micellar enzymology. This chapter details the use of ionic and nonionic micelles for the stabilization of polyphenol oxidase, lipase, and catalase, although this method could be used with any enzymatic system or enzyme cascade system.

  10. Effect of the salt-induced micellar microstructure on the nonlinear shear flow behavior of ionic cetylpyridinium chloride surfactant solutions

    Gaudino, D.; Pasquino, R.; Kriegs, H.; Szekely, N.; Pyckhout-Hintzen, W.; Lettinga, M. P.; Grizzuti, N.


    The shear flow dynamics of linear and branched wormlike micellar systems based on cetylpyridinium chloride and sodium salicylate in brine solution is investigated through rheometric and scattering techniques. In particular, the flow and the structural flow response are explored via velocimetry measurements and rheological and rheometric small-angle neutron scattering (SANS) experiments, respectively. Although all micellar solutions display a similar shear thinning behavior in the nonlinear regime, the experimental results show that shear banding sets in only when the micelle contour length L ¯ is sufficiently long, independent of the nature of the micellar connections (either linear or branched micelles). Using rheometric SANS, we observe that the shear banding systems both show very similar orientational ordering as a function of Weissenberg number, while the short branched micelles manifest an unexpected increase of ordering at very low Weissenberg numbers. This suggests the presence of an additional flow-induced relaxation process that is peculiar for branched systems.

  11. Solubilization of parabens in aqueous Pluronic solutions: investigating the micellar growth and interaction as a function of paraben composition.

    Khimani, M; Ganguly, R; Aswal, V K; Nath, S; Bahadur, P


    The influence of methyl paraben (MP) and butyl paraben (BP) on the aggregation characteristics of Pluronics in an aqueous medium has been investigated by DLS, SANS, viscometry, and fluorescence measurement techniques. Parabens are extensively used as preservatives in cosmetic, pharmaceutical, and food products. In this paper, we show that their influence on the restructuring and growth of Pluronics micelles vary quite significantly with their aqueous solubility and with the composition of Pluronics. In the case of P105 and P104, MP reduces the sphere-to-rod transition temperature down to room temperature, but BP with significantly less aqueous solubility than MP suppresses such micellar transition and leads to the formation of micellar clusters due to the onset of intermicellar attractive interaction. In the case of more hydrophobic Pluronic P103, on the other hand, both MP and BP are able to induce rapid room temperature sphere-to-rod micellar growth, which is not observed in the presence of water structure making salts like NaCl and Na(3)PO(4). These observations have been attributed to modulation of growth and restructuring processes of the Pluronic micelles arising due to different locations of parabens within the micellar corona as determined by their aqueous solubility and the hydrophobicity of the Pluronics.

  12. A theory of phase separation in asphaltene-micellar solutions

    Pacheco Sanchez, Juan H. [Instituto Mexicano del Petroleo, Mexico D.F. (Mexico)


    A theory of phase separation in micellar solutions of asphaltene in aromatic hydrocarbons was reported in this paper, based on both the approach of the phase behavior of amphiphile/water micelles, and the self-association of asphaltene in aromatic core. Several experimental techniques have been used by different investigators showing the existence of some kind of critical micellar concentration (CMC) on asphaltenes in aromatic solutions. So, at least asphaltene-monomer and asphaltene-micellar phases are experimentally demonstrated facts. These two phases are the main purpose in this report on a theoretical model. Some results show the temperature versus asphaltene concentration phase diagram. The phase diagram is examined against the limited critical micelle concentration data for asphaltenes-in-toluene systems. Such phase diagram is also qualitatively examined against an experimental demonstration of phase separation. The asphaltene-micelle growth depends on the parameter K responsible for the shape and size of it. At the same time, parameter K depends on both the number of asphaltene-monomer associated in the asphaltene-micelle, and the chemical potentials in the interior and in the periphery of the micelle. An expression for getting the number of asphaltene-monomers self-associated in the asphaltene-micelle was obtained. [Spanish] Se reporta una teoria de separacion de fases en soluciones micelares de asfalteno en hidrocarburos aromaticos, basada tanto en la conducta de fase de micelas formadas por anififilos en agua como en la autoasociacion de asfaltenos en nucleos aromaticos. Se han usado diversas tecnicas experimentales por diferentes investigadores que demuestran la existancia de algun tipo de concentracion micelar critica (CMC) de soluciones de asfaltenos en aromaticos. Entonces, al menos las fases de asfalteno-monomerico y de asfalteno-micelar son hechos experimentalmente demostrados. Esta dos fases son el principal proposito de este reporte en un modelo

  13. Separation of cationic analytes by nonionic micellar electrokinetic chromatography using polyoxyethylene lauryl ether surfactants with different polyoxyethylene length.

    Quirino, Joselito P; Kato, Masaru


    Although nonionic micellar electrokinetic chromatography is used for the separation of charged compounds that are not easily separated by capillary zone electrophoresis, the effect of the hydrophilic moiety of the nonionic surfactant has not been studied well. In this study, the separation of ultraviolet-absorbing amino acids was studied in electrokinetic chromatography using neutral polyoxyethylene lauryl ether surfactants (Adekatol) in the separation solution. The effect of the polyethylene moiety (the number of repeating units was from 6.5 to 50) of the hydrophobic test amino acids (methionine, tryptophan, and tysorine) was studied using a 10 cm effective length capillary. The separation mechanism was based on hydrophobic as well as hydrogen bonding interactions at the micellar surface, which was made of the polyoxyethylene moiety. The length of the polyoxyethylene moiety of the surfactants was not important in nonionic micellar electrokinetic chromatography mode.

  14. Surface Attachment of Gold Nanoparticles Guided by Block Copolymer Micellar Films and Its Application in Silicon Etching

    Mingjie Wei


    Full Text Available Patterning metallic nanoparticles on substrate surfaces is important in a number of applications. However, it remains challenging to fabricate such patterned nanoparticles with easily controlled structural parameters, including particle sizes and densities, from simple methods. We report on a new route to directly pattern pre-formed gold nanoparticles with different diameters on block copolymer micellar monolayers coated on silicon substrates. Due to the synergetic effect of complexation and electrostatic interactions between the micellar cores and the gold particles, incubating the copolymer-coated silicon in a gold nanoparticles suspension leads to a monolayer of gold particles attached on the coated silicon. The intermediate micellar film was then removed using oxygen plasma treatment, allowing the direct contact of the gold particles with the Si substrate. We further demonstrate that the gold nanoparticles can serve as catalysts for the localized etching of the silicon substrate, resulting in nanoporous Si with a top layer of straight pores.

  15. Glassy states in attractive micellar systems

    Mallamace, F.; Broccio, M.; Faraone, A.; Chen, W. R.; Chen, S.-H.


    Recent mode coupling theory (MCT) calculations show that in attractive colloids one may observe a new type of glass originating from clustering effects, as a result of the attractive interaction. This happens in addition to the known glass-forming mechanism due to cage effects in the hard sphere system. MCT also indicates that, within a certain volume fraction range, varying the external control parameter, the effective temperature, makes the glass-to-liquid-to-glass re-entrance and the glass-to-glass transitions possible. Here we present experimental evidence and details on this complex phase behavior in a three-block copolymer micellar system.

  16. Stratification of a Foam Film Formed from a Nonionic Micellar Solution: Experiments and Modeling.

    Lee, Jongju; Nikolov, Alex; Wasan, Darsh


    Thin liquid films containing surfactant micelles or other nanocolloidal particles are considered to be the key structural elements of foams containing gas and liquid. We report here the experimental results and theoretical modeling for the phenomenon of the stratification (stepwise thinning) of a foam film formed from a nonionic micellar solution. The film stratification phenomenon was experimentally observed by reflected light microinterferometry. We observed that the stepwise layer-by-layer decrease of the film thickness is due to the appearance and growth of a dark spot of one layer less than the film thickness in the film. The dark spot expansion is driven by the diffusion of the dislocation (or vacancy) in the micellar lattice. The vacancies from the meniscus diffuse and condense into the dark spot, leading to its expansion inside the film. We experimentally observed the expansion of the dark spot at various film thicknesses (i.e., the number of micellar layers) and at different film sizes. We also measured the contact angle between the film and the meniscus; we used the data to estimate the structural film interaction energy barrier and the apparent diffusion coefficient. We used the two-dimensional diffusion model to model the dynamics of the dark spot expansion with consideration to the apparent diffusion coefficient and the film size. The model predictions are in good agreement with the experimental observations. On the basis of this model, we carried out a parametric study depicting the effects of the film thickness (or the number of micellar layers) and film area on the rate of the dark spot expansion. We also generalized the model previously proposed by Kralchevsky et al. [ Langmuir 1990 , 6 , 1180 - 1189 ], incorporating the effects of the film size, film thickness, and apparent diffusion coefficient to predict the dark spot expansion rate.

  17. Effects of environmental factors on MSP21-25 aggregation indicate the roles of hydrophobic and electrostatic interactions in the aggregation process.

    Zhang, Xuecheng; Dong, Yuanqiu; Yu, Jigang; Tu, Xiaoming


    Merozoite surface protein 2 (MSP2), one of the most abundant proteins on the merozoite surface of Plasmodium falciparum, is recognized to be important for the parasite's invasion into the host cell and is thus a promising malaria vaccine candidate. However, mediated mainly by its conserved N-terminal 25 residues (MSP21-25), MSP2 readily forms amyloid fibril-like aggregates under physiological conditions in vitro, which impairs its potential as a vaccine component. In addition, there is evidence that MSP2 exists in aggregated forms on the merozoite surface in vivo. To elucidate the aggregation mechanism of MSP21-25 and thereby understand the behavior of MSP2 in vivo and find ways to avoid the aggregation of relevant vaccine in vitro, we investigated the effects of agitation, pH, salts, 1-anilinonaphthalene-8-sulfonic acid (ANS), trimethylamine N-oxide dihydrate (TMAO), urea, and sub-micellar sodium dodecyl sulfate (SDS) on the aggregation kinetics of MSP21-25 using thioflavin T (ThT) fluorescence. The results showed that MSP21-25 aggregation was accelerated by agitation, while repressed by acidic pHs. The salts promoted the aggregation in an anion nature-dependent pattern. Hydrophobic surface-binding agent ANS and detergent urea repressed MSP21-25 aggregation, in contrast to hydrophobic interaction strengthener TMAO, which enhanced the aggregation. Notably, sub-micellar SDS, contrary to its micellar form, promoted MSP21-25 aggregation significantly. Our data indicated that hydrophobic interactions are the predominant driving force of the nucleation of MSP21-25 aggregation, while the elongation is controlled mainly by electrostatic interactions. A kinetic model of MSP21-25 aggregation and its implication were also discussed.

  18. Glutathione transferase mimics : Micellar catalysis of an enzymic reaction

    Lindkvist, Björn; Weinander, Rolf; Engman, Lars; Koetse, Marc; Engberts, Jan B.F.N.; Morgenstern, Ralf


    Substances that mimic the enzyme action of glutathione transferases (which serve in detoxification) are described. These micellar catalysts enhance the reaction rate between thiols and activated halogenated nitroarenes as well as alpha,beta-unsaturated carbonyls. The nucleophilic aromatic substituti

  19. Determination of the hydrolysis kinetics of alpha-naphthyl acetate in micellar systems and the effect of HPMC (catalyst present).

    Werawatganone, Pornpen; Wurster, Dale Eric


    The change in the hexadecyltrimethylammonium bromide (CTAB) critical aggregation concentration (CAC) was studied in the presence of various concentrations and grades of hydroxypropylmethyl cellulose (HPMC) using surface tension measurement (duNoüy ring and Wilhelmy plate) and oil red O solubilization. According to the surface tension methods, the CAC was higher than the CTAB critical micelle concentration (CMC). CAC and CMC were not different when the solubilization method was used. Micellar solutions of CTAB have been found to accelerate the hydrolysis of alpha-naphthyl acetate (alpha-NA) by o-iodosobenzoic acid (IBA), a strong nucleophile. Pseudo-first-order kinetics were utilized for rate constant determination. The observed rate constants for the degradation of alpha-NA in the presence of varying CTAB concentrations with and without HPMC were analyzed according to the pseudophase model. The micellar rate constants and the micellar binding constants for the substrates were obtained. The presence of HPMC retarded the reaction rate, and the rate constant decreased as the polymer concentration increased. However, there was no obvious difference in the observed rate constants among the different grades of HPMC (Methocel E5, Methocel E15, Methocel E50). The decrease in the rate constant was likely due to the polymer-micelle interaction interfering with substrate binding to the CTAB micelles.

  20. Modeling and simulation of aggregation of membrane protein LAT with molecular variability in the number of binding sites for cytosolic Grb2-SOS1-Grb2.

    Ambarish Nag

    Full Text Available The linker for activation of T cells (LAT, the linker for activation of B cells (LAB, and the linker for activation of X cells (LAX form a family of transmembrane adaptor proteins widely expressed in lymphocytes. These scaffolding proteins have multiple binding motifs that, when phosphorylated, bind the SH2 domain of the cytosolic adaptor Grb2. Thus, the valence of LAT, LAB and LAX for Grb2 is variable, depending on the strength of receptor activation that initiates phosphorylation. During signaling, the LAT population will exhibit a time-varying distribution of Grb2 valences from zero to three. In the cytosol, Grb2 forms 1:1 and 2:1 complexes with the guanine nucleotide exchange factor SOS1. The 2:1 complex can bridge two LAT molecules when each Grb2, through their SH2 domains, binds to a phosphorylated site on a separate LAT. In T cells and mast cells, after receptor engagement, receptor phosphoyrlation is rapidly followed by LAT phosphorylation and aggregation. In mast cells, aggregates containing more than one hundred LAT molecules have been detected. Previously we considered a homogeneous population of trivalent LAT molecules and showed that for a range of Grb2, SOS1 and LAT concentrations, an equilibrium theory for LAT aggregation predicts the formation of a gel-like phase comprising a very large aggregate (superaggregate. We now extend this theory to investigate the effects of a distribution of Grb2 valence in the LAT population on the formation of LAT aggregates and superaggregate and use stochastic simulations to calculate the fraction of the total LAT population in the superaggregate.

  1. The Chiral Bilayer Effect Stabilizes Micellar Fibers

    Fuhrhop, Jürgen-Hinrich; Schnieder, Peter; Rosenberg, Jörg; Boekema, Egbert


    Dihelical fibers several micrometers in length and gels were obtained by spontaneous aggregation of octyl L- and D-gluconamides. The single strands have the thickness of a bimolecular layer. No fibers are formed from the racemate. The tendency of the chiral amphiphiles to aggregate to very long fibe

  2. The Chiral Bilayer Effect Stabilizes Micellar Fibers

    Fuhrhop, Jürgen-Hinrich; Schnieder, Peter; Rosenberg, Jörg; Boekema, Egbert


    Dihelical fibers several micrometers in length and gels were obtained by spontaneous aggregation of octyl L- and D-gluconamides. The single strands have the thickness of a bimolecular layer. No fibers are formed from the racemate. The tendency of the chiral amphiphiles to aggregate to very long

  3. Micellar Copolymerization:the State of the Arts

    FENG Yu-jun


    Over the past two decades, hydrophobically modified water-soluble polymers (HMWSPs),particularly hydrophobically associating polyacrylamides (HAPAMs), have attracted increased interest owing to their practical and fundamental importance[1]. This system usually consists of a hydrophilic backbone with a small proportion (generally less than 2 mol %) of hydrophobic pendent groups. When dissolved in aqueous solutions, the apolar moieties tend to exclude water and are held together by intra- and intermolecular hydrophobic associations. This leads to a transitional network structure that induces a substantial increase in solution viscosity. Such viscosity-building ability is further elevated upon adding salt or increasing temperature due to the enhanced polarity.Additionally, the dynamic associating junctions can be ruptured upon high shear stress, but re-formed when the force ceases. All these unique properties enable HAPAMs attractiveness to various industrial uses in which the control of fluid theology is required.However, it is a great challenge to synthesize HAPAMs since acrylamide and hydrophobic comonomers are mutually incompatible. After attempts using heterogeneous, inverse emulsion,microemulsion, and precipitation copolymerization processes, the commonly accepted method is micellar free radical copolymerization in which an appropriate surfactant is used to solubilize the hydrophobic comonomer[2].In this paper, the sate of the arts for micellar copolymerization is comprehensively reviewed:1. the mechanism of micellar copolymerization;2. parameters affecting micellar copolymerization, including:(1) nature and level of hydrophobic comonomer;(2) nature and content of surfactant used;(3) initiator and temperature.3. structural characteristics of HAPAMs prepared via micellar copolymerization;4. properties of HAPAMs prepared via micellar copolymerization:(1) dilute solution properties;(2) semi-dilute solution properties.5. applications of micellar copolymerization

  4. Multiple criteria group decision making method based on binary connection number aggregation operators%基于二元联系数集结算子的多准则群决策方法

    汪新凡; 王坚强; 杨恶恶


    定义了二元联系数的加性运算法则,给出了几种新的算术集结算子,即二元联系数加权算术平均(BCNWAA)算子、二元联系数有序加权平均(BCNOWA)算子和二元联系数混合集结(BCNHA)算子,提出了一种基于二元联系数的准则权重信息不完全确定的群决策方法。该方法利用BCNWAA算子和BCNHA算子对二元联系数准则值进行集结;利用二元联系数准则值的方差和准则权重的随机性,通过构建优化模型确定最优准则权重。最后,通过实例分析表明了该方法的可行性和有效性。%Some additive operational laws of binary connection numbers are defined, and several new arithmetic aggregation operators, such as the binary connection number weighted arithmetic averaging(BCNWAA) operator, the binary connection number ordered weighted averaging(BCNOWA) operator and the binary connection number hybrid aggregation(BCNHA) operator, are proposed. Then an approach is developed for solving multiple criterion group decision making based on binary connection numbers with incomplete uncertain information. In this method, binary connection number criterion values are aggregated using the BCNWAA operator and the BCNHA operator, some optimal models are constructed to determine the optimal criterion weights using the variance of binary connection number criterion values and the randomness of criterion weights. Finally, an example is given to illustrate the feasibility and effectiveness of the developed method.

  5. Marine Synechococcus Aggregation

    Neuer, S.; Deng, W.; Cruz, B. N.; Monks, L.


    Cyanobacteria are considered to play an important role in the oceanic biological carbon pump, especially in oligotrophic regions. But as single cells are too small to sink, their carbon export has to be mediated by aggregate formation and possible consumption by zooplankton producing sinking fecal pellets. Here we report results on the aggregation of the ubiquitous marine pico-cyanobacterium Synechococcus as a model organism. We first investigated the mechanism behind such aggregation by studying the potential role of transparent exopolymeric particles (TEP) and the effects of nutrient (nitrogen or phosphorus) limitation on the TEP production and aggregate formation of these pico-cyanobacteria. We further studied the aggregation and subsequent settling in roller tanks and investigated the effects of the clays kaolinite and bentonite in a series of concentrations. Our results show that despite of the lowered growth rates, Synechococcus in nutrient limited cultures had larger cell-normalized TEP production, formed a greater volume of aggregates, and resulted in higher settling velocities compared to results from replete cultures. In addition, we found that despite their small size and lack of natural ballasting minerals, Synechococcus cells could still form aggregates and sink at measureable velocities in seawater. Clay minerals increased the number and reduced the size of aggregates, and their ballasting effects increased the sinking velocity and carbon export potential of aggregates. In comparison with the Synechococcus, we will also present results of the aggregation of the pico-cyanobacterium Prochlorococcus in roller tanks. These results contribute to our understanding in the physiology of marine Synechococcus as well as their role in the ecology and biogeochemistry in oligotrophic oceans.

  6. Principles of micellar electrokinetic capillary chromatography applied in pharmaceutical analysis.

    Hancu, Gabriel; Simon, Brigitta; Rusu, Aura; Mircia, Eleonora; Gyéresi, Arpád


    Since its introduction capillary electrophoresis has shown great potential in areas where electrophoretic techniques have rarely been used before, including here the analysis of pharmaceutical substances. The large majority of pharmaceutical substances are neutral from electrophoretic point of view, consequently separations by the classic capillary zone electrophoresis; where separation is based on the differences between the own electrophoretic mobilities of the analytes; are hard to achieve. Micellar electrokinetic capillary chromatography, a hybrid method that combines chromatographic and electrophoretic separation principles, extends the applicability of capillary electrophoretic methods to neutral analytes. In micellar electrokinetic capillary chromatography, surfactants are added to the buffer solution in concentration above their critical micellar concentrations, consequently micelles are formed; micelles that undergo electrophoretic migration like any other charged particle. The separation is based on the differential partitioning of an analyte between the two-phase system: the mobile aqueous phase and micellar pseudostationary phase. The present paper aims to summarize the basic aspects regarding separation principles and practical applications of micellar electrokinetic capillary chromatography, with particular attention to those relevant in pharmaceutical analysis.

  7. Flow-induced structured phase in nonionic micellar solutions.

    Cardiel, Joshua J; Tonggu, Lige; de la Iglesia, Pablo; Zhao, Ya; Pozzo, Danilo C; Wang, Liguo; Shen, Amy Q


    In this work, we consider the flow of a nonionic micellar solution (precursor) through an array of microposts, with focus on its microstructural and rheological evolution. The precursor contains polyoxyethylene(20) sorbitan monooleate (Tween-80) and cosurfactant monolaurin (ML). An irreversible flow-induced structured phase (NI-FISP) emerges after the nonionic precursor flows through the hexagonal micropost arrays, when subjected to strain rates ~10(4) s(-1) and strain ~10(3). NI-FISP consists of close-looped micellar bundles and multiconnected micellar networks as evidenced by transmission electron microscopy (TEM) and cryo-electron microscopy (cryo-EM). We also conduct small-angle neutron scattering (SANS) measurements in both precursor and NI-FISP to illustrate the structural transition. We propose a potential mechanism for the NI-FISP formation that relies on the micropost arrays and the flow kinematics in the microdevice to induce entropic fluctuations in the micellar solution. Finally, we show that the rheological variation from a viscous precursor solution to a viscoelastic micellar structured phase is associated with the structural evolution from the precursor to NI-FISP.

  8. Principles of Micellar Electrokinetic Capillary Chromatography Applied in Pharmaceutical Analysis

    Árpád Gyéresi


    Full Text Available Since its introduction capillary electrophoresis has shown great potential in areas where electrophoretic techniques have rarely been used before, including here the analysis of pharmaceutical substances. The large majority of pharmaceutical substances are neutral from electrophoretic point of view, consequently separations by the classic capillary zone electrophoresis; where separation is based on the differences between the own electrophoretic mobilities of the analytes; are hard to achieve. Micellar electrokinetic capillary chromatography, a hybrid method that combines chromatographic and electrophoretic separation principles, extends the applicability of capillary electrophoretic methods to neutral analytes. In micellar electrokinetic capillary chromatography, surfactants are added to the buffer solution in concentration above their critical micellar concentrations, consequently micelles are formed; micelles that undergo electrophoretic migration like any other charged particle. The separation is based on the differential partitioning of an analyte between the two-phase system: the mobile aqueous phase and micellar pseudostationary phase. The present paper aims to summarize the basic aspects regarding separation principles and practical applications of micellar electrokinetic capillary chromatography, with particular attention to those relevant in pharmaceutical analysis.

  9. 基于改进区间数密度集结算子指标群赋权方法%Research on Obtaining the Weights of Index Group Based on Modified Interval Number Density Aggregation Operator



    A decision-making method with a modified interval number density aggregation operator is proposed to solve the group weights problems with index data known and weights unknown .First, the several concepts of in-terval number and interval number density aggregation operator are introduced , the method of interval number clustering is improved , the direct algorithm is applied to cluster the one-dimensional data , and fuzzy statistics variables are defined to make sure which is the best way to clustering .Then based on a modified interval number density aggregation operator the group weights problems with index data known and weights unknown are solved . Finally it is shown that the method is feasible and effective with an example .%针对指标数据已知,而权重数据未知的群组赋权问题,给出了一种基于改进的区间数密度集结算子来进行指标群组赋权的决策方法。首先给出了区间数和区间数密度集结算子( IDM)的定义及性质,改进了以前区间数聚类的方法,应用直接法对一维区间数据组进行聚类,并定义了模糊统计量,以确定最为合理的一种聚类方式。然后基于改进的区间数密度集结算子这种数学模型,来解决指标值数据已知,而权重未知的群组赋权问题。最后举例说明该方法的可行性和实用性。

  10. Chloromethylation of 2-chloroethylbenzene catalyzed by micellar catalysis

    LIU QiFa; LU Ming; WEI Wei


    The chloromethylation reaction of 2-chloroethylbenzene was performed successfully by micellar catalysis in the biphasic oil/water system.The effects of anionic,cationic and non-ionic surfactants on the reaction were compared.The mechanism of chloromethyiation reaction and the mechanism of micellar catalysis were investigated.The results show that the micellar catalysis is an effective way to realize the chloromethylation of 2-chloroethylbenzene,and the cationic surfactant shows the most effectiveness.The longer the hydrophobic chain of the cationic surfactant is,the better the catalysis effect will be,and the addition of inorganic electrolyte into the aqueous phase can markedly promote the catalysis effect.

  11. Micellar kinetics of a fluorosurfactant through stopped-flow NMR.

    Yushmanov, Pavel V; Furó, István; Stilbs, Peter


    19F NMR chemical shifts and transverse relaxation times T2 were measured as a function of time after quick stopped-flow dilution of aqueous solutions of sodium perfluorooctanoate (NaPFO) with water. Different initial concentrations of micellar solution and different proportions of mixing were tested. Previous stopped-flow studies by time-resolved small-angle X-ray scattering (TR-SAXS) detection indicated a slow (approximately 10 s) micellar relaxation kinetics in NaPFO solutions. In contrast, no evidence of any comparable slow (>100 ms) relaxation process was found in our NMR studies. Possible artifacts of stopped-flow experiments are discussed as well as differences between NMR and SAXS detection methods. Upper bounds on the relative weight of a slow relaxation process are given within existing kinetic theories of micellar dissolution.

  12. Propagation of Tau aggregates.

    Goedert, Michel; Spillantini, Maria Grazia


    Since 2009, evidence has accumulated to suggest that Tau aggregates form first in a small number of brain cells, from where they propagate to other regions, resulting in neurodegeneration and disease. Propagation of Tau aggregates is often called prion-like, which refers to the capacity of an assembled protein to induce the same abnormal conformation in a protein of the same kind, initiating a self-amplifying cascade. In addition, prion-like encompasses the release of protein aggregates from brain cells and their uptake by neighbouring cells. In mice, the intracerebral injection of Tau inclusions induced the ordered assembly of monomeric Tau, followed by its spreading to distant brain regions. Short fibrils constituted the major species of seed-competent Tau. The existence of several human Tauopathies with distinct fibril morphologies has led to the suggestion that different molecular conformers (or strains) of aggregated Tau exist.

  13. Micellar liquid chromatography of terephthalic acid impurities.

    Richardson, Ashley E; McPherson, Shakeela D; Fasciano, Jennifer M; Pauls, Richard E; Danielson, Neil D


    The production of terephthalic acid (TPA) by oxidation of p-xylene is an important industrial process because high purity TPA is required for the synthesis of polyethylene terephthalate, the primary polymer used to make plastic beverage bottles. Few separation methods have been published that aim to separate TPA from eight major aromatic acid impurities. This work describes a "green" micellar liquid chromatography (MLC) method using a C18 column (100×2.1mm, 3.5μm), an acidic 1% sodium dodecyl sulfate (SDS) mobile phase, and a simple step flow rate gradient to separate TPA and eight impurities in less than 20min. The resulting chromatogram shows excellent peak shape and baseline resolution of all nine acids, in which there are two sets of isomers. Partition coefficients and equilibrium constants have been calculated for the two sets of isomers by plotting the reciprocal of the retention factor versus micelle concentration. Quantitation of the nine analytes in an actual industrial TPA sample is possible. Limits of detection for all nine acids range from 0.180 to 1.53ppm (2.16-19.3 pmoles) and limits of quantitation range from 0.549 to 3.45ppm (6.48-43.0 pmoles). In addition, the method was tested on two other reversed phase C18 columns of similar dimensions and particle diameter from different companies. Neither column showed quite the same peak resolution as the original column, however slight modifications to the mobile phase could improve the separation. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Evolution of mixed surfactant aggregates in solutions and at solid/solution interfaces

    Zhang, Rui

    Surfactant systems have been widely used in such as enhanced oil recovery, waste treatment and metallurgy, etc., in order to solve the problem of global energy crisis, to remove the pollutants and to generate novel energy resources. Almost all surfactant systems are invariably mixtures due to beneficial and economic considerations. The sizes and shapes of aggregates in solutions and at solid/solution interfaces become important, since the nanostructures of mixed aggregates determine solution and adsorption properties. A major hurdle in science is the lack of information on the type of complexes and aggregates formed by mixtures and the lack of techniques for deriving such information. Using techniques such as analytical ultracentrifuge, small angle neutron scattering, surface tension, fluorescence, cryo-TEM, light scattering and ultrafiltration, the nanostructures of aggregates of sugar based n-dodecyl-beta-D-maltoside (DM) and nonionic pentaethyleneglycol monododecyl ether or nonyl phenol ethoxylated decyl ether (NP-10) and their mixtures have been investigated to prove the hypothesis that the aggregation behavior is linked to packing of the surfactant governed by the molecular interactions as well as the molecular structures. The results from both sedimentation velocity and sedimentation equilibrium experiments suggest coexistence of two types of micelles in nonyl phenol ethoxylated decyl ether solutions and its mixtures with n-dodecyl-beta-D-maltoside while only one micellar species is present in n-dodecyl-beta-D-maltoside solutions, in good agreement with those from small angle neutron scattering, cryo-TEM, light scattering and ultrafiltration. Type I micelles were primary micelles at cmc while type II micelles were elongated micelles. On the other hand, the nanostructures of mixed surface aggregates have been quantitatively predicted for the first time using a modified packing index. As a continuation of the Somasundaran-Fuersteneau adsorption model, a

  15. Ordering fluctuations in a shear-banding wormlike micellar system

    Angelico, R.; Rossi, C. Oliviero; Ambrosone, L.;


    We present a first investigation about the non-linear flow properties and transient orientational-order fluctuations observed in the shear-thinning lecithin–water–cyclohexane wormlike micellar system at a concentration near to the zero-shear isotropic–nematic phase transition. From rheological...


    The combination of micellar electrokinetic chromatography (MEKC) with mass spectrometry (MS) is very attractive for the direct identification of analyte molecules, for the possibility of selectivity enhancement, and for the structure confirmation and analysis in a MS-MS mode. The...

  17. Use of a fluorosurfactant in micellar electrokinetic capillary chromatography.

    de Ridder, R; Damin, F; Reijenga, J; Chiari, M


    A fluorosurfactant, the anionic N-ethyl-N-[(heptadecafluorooctyl)sulfonyl]glycine potassium salt, trade name FC-129 [CAS 2991-51-7] was investigated for possible application in micellar electrokinetic capillary chromatography (MEKC). The surfactant was characterized with conductometric titration and test sample mixtures were investigated in MEKC systems, and compared with sodium dodecylsulphate. An increased efficiency and interesting selectivity differences were observed.

  18. Analysis of Some Biogenic Amines by Micellar Liquid Chromatography

    Irena Malinowska


    Full Text Available Micellar liquid chromatography (MLC with the use of high performance liquid chromatography (HPLC was used to determine some physicochemical parameters of six biogenic amines: adrenaline, dopamine, octopamine, histamine, 2-phenylethylamine, and tyramine. In this paper, an influence of surfactant’s concentration and pH of the micellar mobile phase on the retention of the tested substances was examined. To determine the influence of surfactant’s concentration on the retention of the tested amines, buffered solutions (at pH 7.4 of ionic surfactant—sodium dodecyl sulfate SDS (at different concentrations with acetonitrile as an organic modifier (0.8/0.2 v/v were used as the micellar mobile phases. To determine the influence of pH of the micellar mobile phase on the retention, mobile phases contained buffered solutions (at different pH values of sodium dodecyl sulfate SDS (at 0.1 M with acetonitrile (0.8/0.2 v/v. The inverse of value of retention factor (1/ versus concentration of micelles ( relationships were examined. Other physicochemical parameters of solutes such as an association constant analyte—micelle (ma—and partition coefficient of analyte between stationary phase and water (hydrophobicity descriptor (swΦ were determined by the use of Foley’s equation.

  19. Polymeric micellar drug carriers with fluorescent properties

    Abreu, Ana Sofia Lemos Machado; Sá, Arsénio Vasconcelos; Oliveira, Manuel; Moura, I; Machado, A.V.


    Self-assembling polymeric surfactants, based on amphiphilic block copolymers into nanosized aggregates in aqueous solution, are of great interest in the biomedical fields as one class of promising carrier systems, for drug delivery, gene therapy and diagnostic biosensors.[1] The incorporation of fluorescent probes into polymeric micelles has been fulfilled either by physically encapsulation or chemically attachment of fluorophores. [2] These micelle-based fluorescent probes not only facili...

  20. Construction aggregates

    Nelson, T.I.; Bolen, W.P.


    Construction aggregates, primarily stone, sand and gravel, are recovered from widespread naturally occurring mineral deposits and processed for use primarily in the construction industry. They are mined, crushed, sorted by size and sold loose or combined with portland cement or asphaltic cement to make concrete products to build roads, houses, buildings, and other structures. Much smaller quantities are used in agriculture, cement manufacture, chemical and metallurgical processes, glass production and many other products.

  1. A novel, rapid and automated conductometric method to evaluate surfactant-cells interactions by means of critical micellar concentration analysis.

    Tiecco, Matteo; Corte, Laura; Roscini, Luca; Colabella, Claudia; Germani, Raimondo; Cardinali, Gianluigi


    Conductometry is widely used to determine critical micellar concentration and micellar aggregates surface properties of amphiphiles. Current conductivity experiments of surfactant solutions are typically carried out by manual pipetting, yielding some tens reading points within a couple of hours. In order to study the properties of surfactant-cells interactions, each amphiphile must be tested in different conditions against several types of cells. This calls for complex experimental designs making the application of current methods seriously time consuming, especially because long experiments risk to determine alterations of cells, independently of the surfactant action. In this paper we present a novel, accurate and rapid automated procedure to obtain conductometric curves with several hundreds reading points within tens of minutes. The method was validated with surfactant solutions alone and in combination with Saccharomyces cerevisiae cells. An easy-to use R script, calculates conductometric parameters and their statistical significance with a graphic interface to visualize data and results. The validations showed that indeed the procedure works in the same manner with surfactant alone or in combination with cells, yielding around 1000 reading points within 20 min and with high accuracy, as determined by the regression analysis.

  2. SAAS-CNV: A Joint Segmentation Approach on Aggregated and Allele Specific Signals for the Identification of Somatic Copy Number Alterations with Next-Generation Sequencing Data.

    Zhongyang Zhang


    Full Text Available Cancer genomes exhibit profound somatic copy number alterations (SCNAs. Studying tumor SCNAs using massively parallel sequencing provides unprecedented resolution and meanwhile gives rise to new challenges in data analysis, complicated by tumor aneuploidy and heterogeneity as well as normal cell contamination. While the majority of read depth based methods utilize total sequencing depth alone for SCNA inference, the allele specific signals are undervalued. We proposed a joint segmentation and inference approach using both signals to meet some of the challenges. Our method consists of four major steps: 1 extracting read depth supporting reference and alternative alleles at each SNP/Indel locus and comparing the total read depth and alternative allele proportion between tumor and matched normal sample; 2 performing joint segmentation on the two signal dimensions; 3 correcting the copy number baseline from which the SCNA state is determined; 4 calling SCNA state for each segment based on both signal dimensions. The method is applicable to whole exome/genome sequencing (WES/WGS as well as SNP array data in a tumor-control study. We applied the method to a dataset containing no SCNAs to test the specificity, created by pairing sequencing replicates of a single HapMap sample as normal/tumor pairs, as well as a large-scale WGS dataset consisting of 88 liver tumors along with adjacent normal tissues. Compared with representative methods, our method demonstrated improved accuracy, scalability to large cancer studies, capability in handling both sequencing and SNP array data, and the potential to improve the estimation of tumor ploidy and purity.

  3. SAAS-CNV: A Joint Segmentation Approach on Aggregated and Allele Specific Signals for the Identification of Somatic Copy Number Alterations with Next-Generation Sequencing Data.

    Zhang, Zhongyang; Hao, Ke


    Cancer genomes exhibit profound somatic copy number alterations (SCNAs). Studying tumor SCNAs using massively parallel sequencing provides unprecedented resolution and meanwhile gives rise to new challenges in data analysis, complicated by tumor aneuploidy and heterogeneity as well as normal cell contamination. While the majority of read depth based methods utilize total sequencing depth alone for SCNA inference, the allele specific signals are undervalued. We proposed a joint segmentation and inference approach using both signals to meet some of the challenges. Our method consists of four major steps: 1) extracting read depth supporting reference and alternative alleles at each SNP/Indel locus and comparing the total read depth and alternative allele proportion between tumor and matched normal sample; 2) performing joint segmentation on the two signal dimensions; 3) correcting the copy number baseline from which the SCNA state is determined; 4) calling SCNA state for each segment based on both signal dimensions. The method is applicable to whole exome/genome sequencing (WES/WGS) as well as SNP array data in a tumor-control study. We applied the method to a dataset containing no SCNAs to test the specificity, created by pairing sequencing replicates of a single HapMap sample as normal/tumor pairs, as well as a large-scale WGS dataset consisting of 88 liver tumors along with adjacent normal tissues. Compared with representative methods, our method demonstrated improved accuracy, scalability to large cancer studies, capability in handling both sequencing and SNP array data, and the potential to improve the estimation of tumor ploidy and purity.

  4. Polymeric micelles based on poly(ethylene oxide) and α-carbon substituted poly(ɛ-caprolactone): An in vitro study on the effect of core forming block on polymeric micellar stability, biocompatibility, and immunogenicity.

    Garg, Shyam M; Vakili, Mohammad Reza; Lavasanifar, Afsaneh


    A series of block copolymers based on methoxy poly(ethylene oxide)-block-poly(ɛ-caprolactone) (PEO-b-PCL), PEO-b-PCL bearing side groups of benzyl carboxylate (PEO-b-PBCL), or free carboxyl (PEO-b-PCCL) on the PCL backbone with increasing degrees of polymerization of the PCL backbone were synthesized. Prepared block copolymers assembled to polymeric micelles by co-solvent evaporation. The physical stability of prepared micelles was assessed by measuring their tendency toward aggregation over time using dynamic light scattering (DLS). The resistance of micelles against dissociation in the presence of a micelle destabilizing agent, i.e., sodium dodecyl sulfate (SDS), was also investigated using DLS. The rate of micellar core degradation was determined using (1)H NMR for polymer molecular weight measurement upon incubation of micelles in PBS (pH=7.4) at 37°C followed by dialysis of the remaining polymer at different time intervals. The effect of pendent group chemistry in the micellar core on the adsorption of serum proteins to micellar structure was then evaluated using Bradford Protein assay kit. Finally, the effect of micellar core structure on the induction of bone marrow derived dendritic cell (BMDC) maturation and secretion of IL-12 was studied as a measure of micellar immunogenicity. The results showed micelle structures from polymers with higher degree of polymerization in the hydrophobic block and/or those with more hydrophobic substituents on the core-forming block, to be more stable. This was reflected by a decreased tendency for micellar aggregation, reduced dissociation of micelles in the presence of SDS, and diminished core degradation. All micelles were shown to have insignificant adsorption of serum protein suggesting that the hydrophilic PEO shell provided sufficient protection of the core. However, the protein adsorption increased with increase in the hydrophobicity and molecular weight of the core-forming block. Irrespective of the micellar core

  5. Discrepancies over the onset of surfactant monomer aggregation interpreted by fluorescence, conductivity and surface tension methods

    Maria de Fátima Carvalho Costa


    Full Text Available Molecular probe techniques have made important contributions to the determination of microstructure of surfactant assemblies such as size, stability, micropolarity and conformation. Conductivity and surface tension were used to determine the critical aggregation concentration (cac of polymer-surfactant complexes and the critical micellar concentration (cmc of aqueous micellar aggregates. The results are compared with those of fluorescent techniques. Several surfactant systems were examined, 1-butanol-sodium dodecylsulfate (SDS mixtures, solutions containing poly(ethylene oxide-SDS, poly(vinylpyrrolidone-SDS and poly(acrylic acid-alkyltrimethylammonium bromide complexes. We found differences between the cac and cmc values obtained by conductivity or surface tension and those obtained by techniques which use hydrophobic probe.

  6. Photodegradation in Micellar Aqueous Solutions of Erythrosin Esters Derivatives.

    Herculano, Leandro Silva; Lukasievicz, Gustavo Vinicius Bassi; Sehn, Elizandra; Caetano, Wilker; Pellosi, Diogo Silva; Hioka, Noboru; Astrath, Nelson Guilherme Castelli; Malacarne, Luis Carlos


    Strong light absorption and high levels of singlet oxygen production indicate erythrosin B as a viable candidate as a photosensitizer in photodynamic therapy or photodynamic inactivation of microorganisms. Under light irradiation, erythrosin B undergoes a photobleaching process that can decrease the production of singlet oxygen. In this paper, we use thermal lens spectroscopy to investigate photobleaching in micellar solutions of erythrosin ester derivatives: methyl, butyl, and decyl esters in low concentrations of non-ionic micellar aqueous solutions. Using a previously developed thermal lens model, it was possible to determine the photobleaching rate and fluorescence quantum efficiency for dye-micelle solutions. The results suggest that photobleaching is related to the intensity of the dye-micelle interaction and demonstrate that the thermal lens technique can be used as a sensitive tool for quantitative measurement of photochemical properties in very diluted solutions.

  7. Terahertz absorption spectroscopy of protein-containing reverse micellar solution

    Murakami, H.; Toyota, Y.; Nishi, T.; Nashima, S.


    Terahertz time-domain spectroscopy has been carried out for AOT/isooctane reverse micellar solution with myoglobin at the water-to-surfactant molar ratios ( w0) of 0.2 and 4.4. The amplitude of the absorption spectrum increases with increasing the protein concentration at w0 = 0.2, whereas it decreases at w0 = 4.4. The molar extinction coefficients of the protein-filled reverse micelle, and the constituents, i.e., myoglobin, water, and AOT, have been derived by use of the structural parameters of the micellar solution. The experimental results are interpreted in terms of hydration onto the protein and surfactant in the reverse micelle.

  8. Phosphatidylcholine embedded micellar systems: enhanced permeability through rat skin.

    Spernath, Aviram; Aserin, Abraham; Sintov, Amnon C; Garti, Nissim


    Micellar and microemulsion systems are excellent potential vehicles for delivery of drugs because of their high solubilization capacity and improved transmembrane bioavailability. Mixtures of propylene glycol (PG) and nonionic surfactants with sodium diclofenac (DFC) were prepared in the presence of phosphatidylcholine (PC) as transmembrane transport enhancers. Fully dilutable systems with maximum DFC solubilization capacity (SC) at pH 7 are presented. It was demonstrated that the concentrates underwent phase transitions from reverse micelles to swollen reverse micelles and, via the bicontinuous transitional mesophase, into inverted O/W microstructures. The SC decreases as a function of dilution. DFC transdermal penetration using rat skin in vitro correlated with SC, water content, effect of phospholipid content, presence of an oil phase, and ethanol. Skin penetration from the inverted bicontinuous mesophase and the skin penetration from the O/W-like microstructure were higher than that measured from the W/O-like droplets, especially when the micellar system containing the nonionic surfactant, sugar ester L-1695, and hexaglycerol laurate. PC embedded within the micelle interface significantly increased the penetration flux across the skin compared to micellar systems without the embedded PC at their interface. Moreover, the combination of PC with HECO40 improved the permeation rate (P) and shortened the lag-time (T(L)).

  9. Factors that influence the membrane area of a multistage microfiltration process required to produce a micellar casein concentrate.

    Hurt, Emily E; Barbano, David M


    The objective of the work reported in this paper was to develop a theoretical model to determine the effect of type of microfiltration (MF)-process feed, number of stages, and flux on the minimization of the MF membrane area required to produce a 95% serum protein-reduced micellar casein concentrate. The MF feed, number of stages, and flux were all factors that had an effect on the MF membrane area and should be taken into consideration when designing a MF system to produce a 95% serum protein-reduced micellar casein concentrate. Feeding the MF process with a diluted ultrafiltration retentate (DUR) diluted to the protein concentration of skim milk, as opposed to skim milk, reduced the required membrane area by 36% for a 5-stage process. When DUR was the MF feed, feed protein concentration, which depended on the number of MF stages, was optimized. The DUR protein concentration that minimized the required MF membrane area was 2.47, 3.85, 4.77, and 5.41% for a 2-, 3-, 4-, or 5-stage MF process, respectively. For a 5-stage process, increasing the protein concentration of the feed from 3.2 to 5.4% decreased the required MF membrane area by 10%. It was also found that as the number of stages increased from 2 to 5, the required MF membrane area decreased by 39%, when the MF feed was DUR at the optimal feed protein concentration. Finally, increasing the flux from 50 to 60 kg/m(2) per hour decreased the required MF membrane area by 17% when the MF feed was DUR at the optimal MF feed protein concentration. Overall, using DUR as a feed for MF could reduce the amount of MF membrane area required to make a 95% serum protein-reduced micellar casein concentrate.

  10. Determination of the macromolecular dimensions of hydrophobically modified polymers by micellar size exclusion chromatography coupled with multiangle light scattering.

    Dupuis, Guillaume; Rigolini, Julien; Clisson, Gérald; Rousseau, David; Tabary, René; Grassl, Bruno


    The present work demonstrates that the use of a nonionic surfactant in the mobile phase together with light scattering coupled to size exclusion chromatography (SEC) provides an accurate determination of macromolecular dimensions of hydrophobically modified water-soluble polymer and polyelectrolyte, i.e., weight-average molar mass M(w) and polydispersity I(p). This method, called micellar SEC, is based on the dissociation of the aggregates in aqueous solution and the formation of mixed micelles between the surfactant and the polymer hydrophobic groups. The methodology and its application are presented for synthetic sulfonated polyacrylamides (5 and 20 mol %) modified with three hydrophobic alkyl side groups (C8, C12, and C18) and with Triton X-100 as a nonionic surfactant and are discussed according to the associativity of polymers. The results are compared to those obtained by classical SEC in 0.1 M NaNO(3) and by static light scattering in formamide solution.

  11. Sequence-dependent internalization of aggregating peptides.

    Couceiro, José R; Gallardo, Rodrigo; De Smet, Frederik; De Baets, Greet; Baatsen, Pieter; Annaert, Wim; Roose, Kenny; Saelens, Xavier; Schymkowitz, Joost; Rousseau, Frederic


    Recently, a number of aggregation disease polypeptides have been shown to spread from cell to cell, thereby displaying prionoid behavior. Studying aggregate internalization, however, is often hampered by the complex kinetics of the aggregation process, resulting in the concomitant uptake of aggregates of different sizes by competing mechanisms, which makes it difficult to isolate pathway-specific responses to aggregates. We designed synthetic aggregating peptides bearing different aggregation propensities with the aim of producing modes of uptake that are sufficiently distinct to differentially analyze the cellular response to internalization. We found that small acidic aggregates (≤500 nm in diameter) were taken up by nonspecific endocytosis as part of the fluid phase and traveled through the endosomal compartment to lysosomes. By contrast, bigger basic aggregates (>1 μm) were taken up through a mechanism dependent on cytoskeletal reorganization and membrane remodeling with the morphological hallmarks of phagocytosis. Importantly, the properties of these aggregates determined not only the mechanism of internalization but also the involvement of the proteostatic machinery (the assembly of interconnected networks that control the biogenesis, folding, trafficking, and degradation of proteins) in the process; whereas the internalization of small acidic aggregates is HSF1-independent, the uptake of larger basic aggregates was HSF1-dependent, requiring Hsp70. Our results show that the biophysical properties of aggregates determine both their mechanism of internalization and proteostatic response. It remains to be seen whether these differences in cellular response contribute to the particular role of specific aggregated proteins in disease.

  12. Glycerol in micellar confinement with tunable rigidity

    Lannert, Michael; Müller, Allyn; Gouirand, Emmanuel; Talluto, Vincenzo; Rosenstihl, Markus; Walther, Thomas; Stühn, Bernd; Blochowicz, Thomas; Vogel, Michael


    We investigate the glassy dynamics of glycerol in the confinement of a microemulsion system, which is stable on cooling down to the glass transition of its components. By changing the composition, we vary the viscosity of the matrix, while keeping the confining geometry intact, as is demonstrated by small angle X-ray scattering. By means of 2H NMR, differential scanning calorimetry, and triplet solvation dynamics we, thus, probe the dynamics of glycerol in confinements of varying rigidity. 2H NMR results show that, at higher temperatures, the dynamics of confined glycerol is unchanged compared to bulk behavior, while the reorientation of glycerol molecules becomes significantly faster than in the bulk in the deeply supercooled regime. However, comparison of different 2H NMR findings with data from calorimetry and solvation dynamics reveals that this acceleration is not due to the changed structural relaxation of glycerol, but rather due to the rotational motion of essentially rigid glycerol droplets or of aggregates of such droplets in a more fluid matrix. Thus, independent of the matrix mobility, the glycerol dynamics remains unchanged except for the smallest droplets, where an increase of Tg and, thus, a slowdown of the structural relaxation is observed even in a fluid matrix.

  13. Microemulsions and Aggregation Formation in Extraction Processes for Used Nuclear Fuel: Thermodynamic and Structural Studies

    Nilsson, Mikael [Univ. of California, Irvine, CA (United States)


    Advanced nuclear fuel cycles rely on successful chemical separation of various elements in the used fuel. Numerous solvent extraction (SX) processes have been developed for the recovery and purification of metal ions from this used material. However, the predictability of process operations has been challenged by the lack of a fundamental understanding of the chemical interactions in several of these separation systems. For example, gaps in the thermodynamic description of the mechanism and the complexes formed will make predictions very challenging. Recent studies of certain extraction systems under development and a number of more established SX processes have suggested that aggregate formation in the organic phase results in a transformation of its selectivity and efficiency. Aggregation phenomena have consistently been interfering in SX process development, and have, over the years, become synonymous with an undesirable effect that must be prevented. This multiyear, multicollaborative research effort was carried out to study solvation and self-organization in non-aqueous solutions at conditions promoting aggregation phenomena. Our approach to this challenging topic was to investigate extraction systems comprising more than one extraction reagent where synergy of the metal ion could be observed. These systems were probed for the existence of stable microemulsions in the organic phase, and a number of high-end characterization tools were employed to elucidate the role of the aggregates in metal ion extraction. The ultimate goal was to find connections between synergy of metal ion extraction and reverse micellar formation. Our main accomplishment for this project was the expansion of the understanding of metal ion complexation in the extraction system combining tributyl phosphate (TBP) and dibutyl phosphoric acid (HDBP). We have found that for this system no direct correlation exists for the metal ion extraction and the formation of aggregates, meaning that the

  14. Dynamic fluorescence quenching of quinine sulfate dication by chloride ion in ionic and neutral micellar environments

    Joshi, Sunita; Varma Y, Tej Varma; Pant, Debi D.


    Fluorescence quenching of Quinine sulfate dication (QSD) by chloride-ion (Cl-) in micellar environments of anionic, sodium dodecyl sulfate (SDS), cationic, cetyltrimethylammonium bromide (CTAB) and neutral, triton X-100 (TX-100) in aqueous phase has been investigated by time-resolved and steady- state fluorescence measurements. The quenching follows linear Stern-Volmer relation in micellar solutions and is dynamic in nature.

  15. Characterisation of aggregation of tributylphosphate molecules in organic solvent; Caracterisation de l'auto-organisation du phosphate de tributyle en solvant organique

    Mandin, C.; Martinet, L.; Zemb, Th.; Berthon, L.; Madic, Ch


    This report presents a structural study of the aggregates formed with the organic phases of the extractant tri-n-butyl phosphate, used in the industrial PUREX process (Plutonium and Uranium Extraction; liquid-liquid solvent extraction) for the treatment of high radioactive waste. Combined Small Angle X-ray Scattering and Small Angle Neutron Scattering show that organic TBP solutions (in equilibrium with acid solutions) are organised in oligomeric aggregates. The influence of various parameters such as HNO{sub 3} or TBP concentrations, diluent or acid natures, does not seem to modify the aggregate shape and size, whereas the interactions are modified. Moreover the aggregates disappear under high temperatures, whereas the attractive interactions between them increase at low temperatures. The 'drop weight' method gives the critical micellar concentration values of TBP in case of H{sub 2}O or HNO{sub 3} extractions (H{sub 2}O: 0.48 M; HNO{sub 3} 2M: 0.65 M; at 21 deg C). Furthermore, the measures at different acid concentrations show that the c.m.c. varies with the acidity. The more acid the aqueous phase is, the smaller is the entropy in the system because of the numerous negative charges, i.e. the harder the micellization occurs, so the higher the c.m.c. value is. The sticky sphere model proposed by Baxter, can be used to model successfully small reverse micelles of the organic TBP phases. The aggregation number would be 4{+-}1 (water extraction) and 5{+-}1(HNO{sub 3}2M extraction). These values are also given by vapor pressure measurements. (authors)

  16. Characterisation of aggregation of tributylphosphate molecules in organic solvent; Caracterisation de l'auto-organisation du phosphate de tributyle en solvant organique

    Mandin, C.; Martinet, L.; Zemb, Th.; Berthon, L.; Madic, Ch


    This report presents a structural study of the aggregates formed with the organic phases of the extractant tri-n-butyl phosphate, used in the industrial PUREX process (Plutonium and Uranium Extraction; liquid-liquid solvent extraction) for the treatment of high radioactive waste. Combined Small Angle X-ray Scattering and Small Angle Neutron Scattering show that organic TBP solutions (in equilibrium with acid solutions) are organised in oligomeric aggregates. The influence of various parameters such as HNO{sub 3} or TBP concentrations, diluent or acid natures, does not seem to modify the aggregate shape and size, whereas the interactions are modified. Moreover the aggregates disappear under high temperatures, whereas the attractive interactions between them increase at low temperatures. The 'drop weight' method gives the critical micellar concentration values of TBP in case of H{sub 2}O or HNO{sub 3} extractions (H{sub 2}O: 0.48 M; HNO{sub 3} 2M: 0.65 M; at 21 deg C). Furthermore, the measures at different acid concentrations show that the c.m.c. varies with the acidity. The more acid the aqueous phase is, the smaller is the entropy in the system because of the numerous negative charges, i.e. the harder the micellization occurs, so the higher the c.m.c. value is. The sticky sphere model proposed by Baxter, can be used to model successfully small reverse micelles of the organic TBP phases. The aggregation number would be 4{+-}1 (water extraction) and 5{+-}1(HNO{sub 3}2M extraction). These values are also given by vapor pressure measurements. (authors)

  17. Separation of Aniline Derivatives by Micellar Electrokinetic Capillary Chromatography

    Jun LI; Zhuo Bin YUAN


    A micellar electrokinetic capillary chromatography (MECC) was developed for the determination of aniline and 6 substituted anilines.The seven components were separated within 25 min in the buffer solution of 40 mmol/L sodium borate and 100 mmol/L SDS.It was found that the separation was dependent on operating voltage, pH value, borate and SDS concentrations.The analytical performance was examined in terms of linear response and reproducibility.Wastewater was determined by the established method.

  18. Analysis of anthraquinones in Rumex crispus by micellar electrokinetic chromatography.

    Başkan, Selda; Daut-Ozdemir, Ayşe; Günaydin, Keriman; Erim, F Bedia


    A micellar electrochromatographic method was performed for the analysis of the pharmaceutically important anthraquinones from the root of Rumex crispus. The separation of 1,5-dihydroxy-3-methylanthraquinone (1); 1,3,5-trihydroxy-6-hydroxymethylanthraquinone (2); 1,5-dihydroxy-3-methoxy-7-methylanthraquinone (3) was achieved in 6min using a running buffer containing 10mmol/l sodium borate, 50mmol/l sodium dodecylsulfate, and 25% acetonitrile at pH 10.6. The method is simple, rapid, and reproducible.

  19. Two-phase aqueous micellar systems: an alternative method for protein purification

    Rangel-Yagui C. O.


    Full Text Available Two-phase aqueous micellar systems can be exploited in separation science for the extraction/purification of desired biomolecules. This article reviews recent experimental and theoretical work by Blankschtein and co-workers on the use of two-phase aqueous micellar systems for the separation of hydrophilic proteins. The experimental partitioning behavior of the enzyme glucose-6-phosphate dehydrogenase (G6PD in two-phase aqueous micellar systems is also reviewed and new results are presented. Specifically, we discuss very recent work on the purification of G6PD using: i a two-phase aqueous micellar system composed of the nonionic surfactant n-decyl tetra(ethylene oxide (C10E4, and (ii a two-phase aqueous mixed micellar system composed of C10E4 and the cationic surfactant decyltrimethylammonium bromide (C10TAB. Our results indicate that the two-phase aqueous mixed (C10E4/C10TAB micellar system can improve significantly the partitioning behavior of G6PD relative to that observed in the two-phase aqueous C10E4 micellar system.

  20. Worming Their Way into Shape: Toroidal Formations in Micellar Solutions

    Cardiel Rivera, Joshua J.; Tonggu, Lige; Dohnalkova, Alice; de la Iglesia, Pablo; Pozzo, Danilo C.; Shen, Amy


    We report the formation of nanostructured toroidal micellar bundles (nTMB) from a semidilute wormlike micellar solution, evidenced by both cryogenicelectron microscopy and transmission electron microscopy images. Our strategy for creating nTMB involves a two-step protocol consisting of a simple prestraining process followed by flow through a microfluidic device containing an array of microposts, producing strain rates in the wormlike micelles on the order of 105 s^1. In combination with microfluidic confinement, these unusually large strain rates allow for the formation of stable nTMB. Electron microscopy images reveal a variety of nTMB morphologies and provide the size distribution of the nTMB. Small-angle neutron scattering indicates the underlying microstructural transition from wormlike micelles to nTMB. We also show that other flow-induced approaches such as sonication can induce and control the emergence of onion-like and nTMB structures, which may provide a useful tool for nanotemplating.

  1. The use of micellar solutions for novel separation techniques

    Roberts, Bruce Lynn [Univ. of Oklahoma, Norman, OK (United States)


    Surfactant based separation techniques based on the solubilization of organic compounds into the nonpolar interior of a micelle or electrostatic attraction of ionized metals and metal complexes to the charged surface of a micelle were studied in this work. Micellar solutions were used to recover two model volatile organic compounds emitted by the printing and painting industries (toluene and amyl acetate) and to investigate the effect of the most important variables in the surfactant enhanced carbon regeneration (SECR) process. SECR for liquid phase applications was also investigated in which the equilibrium adsorption of cetyl pyridinium chloride (CPC) and sodium dodecyl sulfate (SDS) on activated carbon were measured. Micellar-enhanced ultrafiltration (MEUF) was investigated using spiral wound membranes for the simultaneous removal of organic compounds, metals and metal complexes dissolved in water, with emphasis on pollution control applications. Investigations of MEUF to remove 99+ per cent of trichloroethylene (TCE) from contaminated groundwater using criteria such as: membrane flux, solubilization equilibrium constant, surfactant molecular weight, and Krafft temperature led to the selection of an anionic disulfonate with a molecular weight of 642 (DOWFAX 8390). These data and results from supporting experiments were used to design a system which could clean-up water in a 100,000 gallon/day operation. A four stage process was found to be an effective design and estimated cost for such an operation were found to be in the range of the cost of mature competitive technologies.

  2. Conductivity measurements in a shear-banding wormlike micellar system.

    Photinos, Panos J; López-González, M R; Hoven, Corey V; Callaghan, Paul T


    Shear banding in the cetylpyridinium chloride/sodium salicylate micellar system is investigated using electrical conductivity measurements parallel to the velocity and parallel to the vorticity in a cylindrical Couette cell. The measurements show that the conductivity parallel to the velocity (vorticity) increases (decreases) monotonically with applied shear rate. The shear-induced anisotropy is over one order of magnitude lower than the anisotropy of the N(c) nematic phase. The steady-state conductivity measurements indicate that the anisotropy of the shear induced low-viscosity (high shear rate) phase is not significantly larger than the anisotropy of the high viscosity (low shear rate) phase. We estimate that the micelles in the shear induced low viscosity band are relatively short, with a characteristic length to diameter ratio of 5-15. The relaxation behavior following the onset of shear is markedly different above and below the first critical value γ1, in agreement with results obtained by other methods. The transient measurements show that the overall anisotropy of the sample decreases as the steady state is approached, i.e., the micellar length/the degree of order decrease.

  3. Percolation and Critical Phenomena of AN Attractive Micellar System

    Mallamace, F.; Chen, S. H.; Gambadauro, P.; Lombardo, D.; Faraone, A.; Tartaglia, P.

    In this work we study an attractive micellar system for which the percolation curve terminates near the critical point. We have studied such an intriguing situation by means of scattering (elastic and dynamical) and viscoelasticity experiments. Obtained data are accounted by considering in a proper way the fractal clustering processes typical of percolating systems and the related scaling concepts. We observe that the main role in the system structure and dynamics it is played by the cluster's partial screening of hydrodynamic interaction. This behaves on approaching the percolation threshold dramatic effects on the system rheological properties and on the density decay relaxations. The measured correlation functions assume a stretched exponential form and the system becomes strongly viscoelastic. The overall behavior of the measured dynamical and structural parameters indicates, that in the present micellar system, the clustering process originates dilute, poly-disperse and swelling structures. Finally, this originates an interesting situation observed in the present experiment. As it has been previously, proposed by A. Coniglio et al., percolation clusters can be considered to be "Ising clusters" with the same properties as the Fisher's critical droplets. Therefore at the critical point the percolation connectedness length (ξp) can be assumed as the diverging correlation length (ξp ≡ ξ) and the mean cluster size diverges as the susceptibility.

  4. The use of micellar solutions for novel separation techniques

    Roberts, B.L.


    Surfactant based separation techniques based on the solubilization of organic compounds into the nonpolar interior of a micelle or electrostatic attraction of ionized metals and metal complexes to the charged surface of a micelle were studied in this work. Micellar solutions were used to recover two model volatile organic compounds emitted by the printing and painting industries (toluene and amyl acetate) and to investigate the effect of the most important variables in the surfactant enhanced carbon regeneration (SECR) process. SECR for liquid phase applications was also investigated in which the equilibrium adsorption of cetyl pyridinium chloride (CPC) and sodium dodecyl sulfate (SDS) on activated carbon were measured. Micellar-enhanced ultrafiltration (MEUF) was investigated using spiral wound membranes for the simultaneous removal of organic compounds, metals and metal complexes dissolved in water, with emphasis on pollution control applications. Investigations of MEUF to remove 99+ per cent of trichloroethylene (TCE) from contaminated groundwater using criteria such as: membrane flux, solubilization equilibrium constant, surfactant molecular weight, and Krafft temperature led to the selection of an anionic disulfonate with a molecular weight of 642 (DOWFAX 8390). These data and results from supporting experiments were used to design a system which could clean-up water in a 100,000 gallon/day operation. A four stage process was found to be an effective design and estimated cost for such an operation were found to be in the range of the cost of mature competitive technologies.

  5. Utilization of micellar electrokinetic chromatography-tandem mass spectrometry employed volatile micellar phase in the analysis of cathinone designer drugs.

    Švidrnoch, Martin; Lněníčková, Ludmila; Válka, Ivo; Ondra, Peter; Maier, Vítězslav


    A micellar electrokinetic chromatography method with tandem mass spectrometry has been developed for the selective separation, identification and determination of twelve new designer drugs from the group of synthetic cathinones. Ammonium salt of perfluorooctanoic acid at various concentrations as a volatile background electrolyte (BGE) to create micellar phase was studied for separation of selected synthetic cathinones with direct tandem mass spectrometry without significant loss of detection sensitivity. The optimized BGE contained 100 mM perfluorooctanoic acid with 200 mM ammonium hydroxide providing acceptable resolution of studied drugs in the MEKC step. In order to minimize interferences with matrix components and to preconcentrate target analytes, solid phase extraction was introduced as a clean-up step. The method was linear in the concentration range of 10-5000 ng mL(-1) and the limits of detection were in the range of 10-78 ng mL(-1). The method was demonstrated to be specific, sensitive, and reliable for the systematic toxicological analysis of these derivatives in urine samples.

  6. Prediction of retention in micellar electrokinetic chromatography based on molecular structural descriptors by using the heuristic method

    Liu Huanxiang [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Yao Xiaojun [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China)]. E-mail:; Liu Mancang [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Hu Zhide [Department of Chemistry, Lanzhou University, Lanzhou 730000 (China); Fan Botao [Universite Paris 7-Denis Diderot, ITODYS 1, rue Guy de la Brosse, 75005 Paris (France)


    Based on calculated molecular descriptors from the solutes' structure alone, the micelle-water partition coefficients of 103 solutes in micellar electrokinetic chromatography (MEKC) were predicted using the heuristic method (HM). At the same time, in order to show the influence of different molecular descriptors on the micelle-water partition of solute and to well understand the retention mechanism in MEKC, HM was used to build several multivariable linear models using different numbers of molecular descriptors. The best 6-parameter model gave the following results: the square of correlation coefficient R {sup 2} was 0.958 and the mean relative error was 3.98%, which proved that the predictive values were in good agreement with the experimental results. From the built model, it can be concluded that the hydrophobic, H-bond, polar interactions of solutes with the micellar and aqueous phases are the main factors that determine their partitioning behavior. In addition, this paper provided a simple, fast and effective method for predicting the retention of the solutes in MEKC from their structures and gave some insight into structural features related to the retention of the solutes.

  7. Effect of calcium chelators on physical changes in casein micelles in concentrated micellar casein solutions

    Kort, de E.J.P.; Minor, M.; Snoeren, T.H.M.; Hooijdonk, van A.C.M.; Linden, van der E.


    The effect of calcium chelators on physical changes of casein micelles in concentrated micellar casein solutions was investigated by measuring calcium-ion activity, viscosity and turbidity, and performing ultracentrifugation. The highest viscosities were measured on addition of sodium

  8. Application of micellar liquid chromatography for the determination of antitumoral and antiretroviral drugs in plasma.

    Peris-Vicente, Juan; Casas-Breva, Inmaculada; Roca-Genovés, Pasqual; Esteve-Romero, Josep


    In micellar liquid chromatography, the mobile phase is made of a surfactant and, eventually, an alcohol. This article describes several methods to measure the concentration of antitumoral and antiretroviral drugs in plasma, utilizing micellar liquid chromatography. Samples can be injected after dilution with a micellar solution and filtration, because proteins and other endogenous compounds are solubilized in micellar medium. We will discuss the following optimized parameters: dilution ratio, type of column, detection conditions and mobile phase composition. This article will also cover the validation performed following the International Conference on Harmonization guidelines and the results reported in the literature, indicating that the methods are useful for the routine analysis of plasma samples for clinical purposes.


    Although surfactants have received considerable attention as a potential means for enhancing the recovery of organic compounds from the subsurface, only limited information is available regarding the micellar solubilization of common groundwater contaminants by nonionic surfactan...

  10. Surfactant aggregation and its application to drag reduction

    Harwigsson, I.


    A number of different drag-reducing (DR) surfactants: nonionics, zwitterionics and ampholytics suitable for use in both cool and hot water solution are described. These surfactants have been tested under various conditions common in district energy distribution. The surfactants described are environmentally more acceptable than the organic salts of quaternary ammonium compounds which have so far dominated as DR surfactants. The micellar phase formed in water by the surfactant system cetylpyridinium chloride/sodium salicylate has been investigated with surfactant self-diffusion (NMR) measurements and cryo-transmission electron microscopy. Results from this study support the hypothesis that worm-like micellar systems form a network before the phase boundary, when the first liquid crystalline phase formed is a bicontinuous cubic phase. A series of surfactants similar to the one used in the DR experiments has been examined in dilute solutions. Critical micellar concentration and the size of these micelles are investigated as a function of the amphiphile concentration, the pH and salt concentration. Adsorption properties on silica of zwitterionic dodecyl-N,N-dimethylammonio alkanoates, with polymethylene interchange arms of different lengths, have been investigated with an in situ ellipsometry technique. The use of two-tone frequency modulation spectroscopy as a general method for the determination of water activity has been initiated. 173 refs, 6 figs

  11. Micellar electrokinetic chromatography (MEKC) separation of furanonaphthoquinones from Tabebuia impetiginosa.

    Koyama, J; Morita, I; Kino, A; Tagahara, K


    The separation of nine furanonaphthoquinones by micellar electrokinetic chromatography (MEKC) is described. The running electrolytes used in this method were 0.03 M sodium dodecyl sulphate (SDS) in 0.09 M borate buffer (pH 9) containing 10% methanol, with an applied voltage of 20 kV. Application of this technique in the determination of the main furanonaphthoquinones, 5-hydroxy-2-(1-hydroxyethyl)naphtho[2,3-b]furan-4,9-dione, 8-hydroxy-2-(1-hydroxyethyl)naphtho[2,3-b]furan-4,9-dione, and 2-(1-hydroxyethyl)naphtho[2,3-b]furan-4,9-dione, of Tabebuia impetiginosa is demonstrated in this paper.

  12. Separation of bisbenzylisoquinoline alkaloids by micellar electrokinetic chromatography.

    Kuo, Ching-Hua; Sun, Shao-Wen


    The micellar electrokinetic chromatographic (MEKC) separation of seven bisbenzylisoquinoline alkaloids has been developed. The effects of various separating factors were studied. Optimum separation was achieved using a buffer (pH 9.2) of 20 mM sodium borate and 20 mM sodium dihydrogen phosphate buffer containing 55 mM sodium cholate; the optimum voltage and injection time were 21 kV and 0.05 min, respectively. Highest peak efficiency was obtained when the analytes were dissolved in 10 mM sodium dodecyl sulphate as sample matrix for injection. The elution order of the bisbenzylisoquinoline alkaloids was related to their lipophilicity. The resolution, run time and detection limits of the MEKC method were compared with those of an HPLC method developed previously.

  13. SANS study of three-layer micellar particles

    Plestil, J; Kuklin, A I; Cubitt, R


    Three-layer nanoparticles were prepared by polymerization of methyl methacrylate (MMA) in aqueous micellar solutions of poly(methyl methacrylate)-block-poly(methacrylic acid) (PMMA-b-PMA) and polystyrene-block-poly(methacrylic acid) (PS-b-PMA). The resulting polymer forms a layer on the core surface of the original micelles. SANS curves were fitted using an ellipsoidal (PMMA/PMMA/PMA) or spherical (PS/PMMA/PMA) model for the particle core. The particle size (for the presented series of the PMMA/PMMA/PMA particles, the core semiaxes ranged from 87 to 187 A and the axis ratio was about 6) can be finely tuned by variation of monomer concentration. Time-resolved SANS experiments were carried out to describe the growth of the PS/PMMA/PMA particles during polymerization. (orig.)

  14. Effect of Micelle Composition on Acidic Drugs Separation Behavior by Micellar Electrokinetic Capillary Chromatography


    Micellar electrokinetic capillary chromatography (MECC) separation of four acidic drugs similar in structure was studied. Both anionic surfactant sodium dodecyl sulfate (SDS) and nonionic surfactant Tween 20 were used to form single micelles and mixed micelles as pseudostationary phases. The effects of the composition of micellar solution on retention behaviors were studied. The results indicate that there is markedly different selectivity among SDS, Tween 20 and the mixed micelles systems.

  15. Separation of Six Pyridoncarboylxic Acid Derivatives by Micellar and Microemulsion Electrokinetic Chromatography


    Micellar and microemulsion electrokinetic chromatography (MEKC & MEEKC) separation of six closely structural pyridoncarboylxic acid derivatives were studied and compared. Both anionic surfactant sodium dodecyl sulfate (SDS) and cationic surfactant hexadecyl-trimethyl ammonium bromide (CTAB) were used to form micellar and microemulsion as pseudostation phases, respectively. The effects of the separation conditions on retention time and selectivity were studied. Good resolutions were obtained in selected systems, indicating that there is markably different selectivity between SDS and CTAB systems.

  16. Jet A fuel recovery using micellar flooding: Design and implementation.

    Kostarelos, Konstantinos; Lenschow, Søren R; Stylianou, Marinos A; de Blanc, Phillip C; Mygind, Mette Marie; Christensen, Anders G


    Surfactants offer two mechanisms for recovering NAPLs: 1) to mobilize NAPL by reducing NAPL/water interfacial tension, and; 2) to increase the NAPL's aqueous solubility-called solubilization-as an enhancement to pump & treat. The second approach has been well-studied and applied successfully in several pilot-scale and a few full-scale tests within the last 15years, known as Surfactant Enhanced Aquifer Remediation (SEAR). A useful source of information for this second approach is the "Surfactant-enhanced aquifer remediation (SEAR) design manual" from the U.S. Navy Facilities Engineering Command. Few attempts, however, have been made at recovering NAPLs using the mobilization approach presented in this paper. Now, a full-scale field implementation of the mobilization approach is planned to recover an LNAPL (Jet A fuel) from a surficial sand aquifer located in Denmark using a smaller amount of surfactant solution and fewer PVs of throughput compared with the SEAR approach. The approach will rely on mobilizing the LNAPL so that it is recovered ahead of the surfactant microemulsion, also known as a micellar flood. This paper will review the laboratory work performed as part of the design for a full-scale implementation of a micellar flood. Completed lab work includes screening of surfactants, phase behavior and detailed salinity scans of the most promising formulations, and generating a ternary diagram to be used for the numerical simulations of the field application. The site owners and regulators were able to make crucial decisions such as the anticipated field results based on this work.

  17. Bell Creek field micellar-polymer pilot demonstration. Third annual report, October 1978-September 1979

    Goldburg, A.


    Gary Energy Corporation is conducting a DOE Demonstration Pilot to determine if micellar-polymer flooding is an economically feasible technique to enhance oil recovery from the Bell Creek Field, Powder River County, southeastern Montana. The pilot is a contained 40-acre 5-spot located in a representative watered-out portion of Unit A Reservoir. The pay is sandstone with an average net pay of 6.4 feet, air permeability of 1050 md, and water TDS of 4000 ppM. The current average remaining oil saturation in the 40-acre pilot area is estimated to be 28%. The pilot has four injectors (Wells MPP-1, MPP-2, MPP-3, and MPP-4) and one producer (Well 12-1). The overall micellar-polymer oil recovery is estimated at 47% of the remaining oil at the initiation of the micellar-polymer flood. In the third contract year (October 1978 to September 1979), all tasks including the initiation of soluble oil/micellar injection were completed. Test site development included completion of: (1) radioactive tracer survey and analysis, (2) core analysis, (3) pressure pulse tests and analysis, (4) reservoir description, and (5) test site facilities. Based on test site development data, soluble oil/micellar formulation was finalized and mathematical simulation work by Intercomp completed. The preflush injection phase of the demonstration program was completed, and the soluble oil/micellar injection was initiated at the end of the contract year. The pilot demonstration project has progressed as scheduled.

  18. Aliphatic carboxylic acids as new modifiers for separation of 2,4-dinitrophenyl amino acids by micellar liquid chromatography.

    Boichenko, Alexander P; Kulikov, Artem U; Loginova, Lidia P; Iwashchenko, Anna L


    The possibilities of isocratic separation of 2,4-dinitrophenyl derivatives of 12 amino acids that considerably differ in hydrophobicity by micellar mobile phases with different organic modifiers have been discussed. For the first time aliphatic carboxylic acids have been used as modifiers of micellar eluent in micellar liquid chromatography with C18 columns. Elution strength of hybrid micellar phases on the basis of sodium dodecylsulfate and aliphatic carboxylic acids increases in sequence: aceticacid. The effect of sodium dodecylsulfate micelles on aliphatic carboxylic acids has been characterized by their micellar-induced shifts of ionization constants. The use of aliphatic carboxylic acids as modifiers of SDS micellar eluents provides better overall resolution of 2,4-dinitrophenyl-amino acids in comparison with aliphatic alcohols.

  19. Adsorption of the anionic surfactant sodium dodecyl sulfate on a C18 column under micellar and high submicellar conditions in reversed-phase liquid chromatography.

    Ortiz-Bolsico, C; Ruiz-Angel, M J; García-Alvarez-Coque, M C


    Micellar liquid chromatography makes use of aqueous solutions or aqueous-organic solutions containing a surfactant, at a concentration above its critical micelle concentration. In the mobile phase, the surfactant monomers aggregate to form micelles, whereas on the surface of the nonpolar alkyl-bonded stationary phases they are significantly adsorbed. If the mobile phase contains a high concentration of organic solvent, micelles break down, and the amount of surfactant adsorbed on the stationary phase is reduced, giving rise to another chromatographic mode named high submicellar liquid chromatography. The presence of a thinner coating of surfactant enhances the selectivity and peak shape, especially for basic compounds. However, the risk of full desorption of surfactant is the main limitation in the high submicellar mode. This study examines the adsorption of the anionic surfactant sodium dodecyl sulfate under micellar and high submicellar conditions on a C18 column, applying two methods. One of them uses a refractive index detector to obtain direct measurements of the adsorbed amount of sodium dodecyl sulfate, whereas the second method is based on the retention and peak shape for a set of cationic basic compounds that indirectly reveal the presence of adsorbed monomers of surfactant on the stationary phase.

  20. Direct Injection of Seawater for the Analysis of Nitroaromatic Explosives and their Degradation Products by Micellar Electrokinetic Chromatography


    micellar electrokinetic chromatography Braden C. Giordanoa,∗, Dean S. Burgib, Greg E. Collinsa a Uanited States Naval Research Laboratory, Chemistry...threats to our coastal regions. Micellar electrokinetic chromatography (MEKC) has been demonstrated to be a useful analytical tool in the anal- ysis of...injection of seawater for the analysis of nitroaromatic explosives and their degradation products by micellar electrokinetic chromatography 5a. CONTRACT

  1. Balancing energy flexibilities through aggregation

    Valsomatzis, Emmanouil; Hose, Katja; Pedersen, Torben Bach


    One of the main goals of recent developments in the Smart Grid area is to increase the use of renewable energy sources. These sources are characterized by energy fluctuations that might lead to energy imbalances and congestions in the electricity grid. Exploiting inherent flexibilities, which exist...... in both energy production and consumption, is the key to solving these problems. Flexibilities can be expressed as flex-offers, which due to their high number need to be aggregated to reduce the complexity of energy scheduling. In this paper, we discuss balance aggregation techniques that already during...

  2. Aggregation kinetics of a simulated telechelic polymer

    Wilson, Mark; Rabinovitch, Avinoam; Baljon, Arlette R. C.


    We investigate the aggregation kinetics of a simulated telechelic polymer gel. In the hybrid molecular dynamics (MD)/Monte Carlo (MC) algorithm, aggregates of associating end groups form and break according to MC rules, while the position of the polymers in space is dictated by MD. As a result, the aggregate sizes change over time. In order to describe this aggregation process, we employ master equations. They define changes in the number of aggregates of a certain size in terms of reaction rates. These reaction rates indicate the likelihood that two aggregates combine to form a large one, or that a large aggregate splits into two smaller parts. The reaction rates are obtained from the simulations for a range of temperatures. Our results indicate that the rates are not only temperature dependent, but also a function of the sizes of the aggregates involved in the reaction. Using the measured rates, solutions to the master equations are shown to be stable and in agreement with the aggregate size distribution, as obtained directly from simulation data. Furthermore, we show how temperature-induced variations in these rates give rise to the observed changes in the aggregate distribution that characterizes the sol-gel transition.

  3. A vertically resolved model for phytoplankton aggregation

    Iris Kriest; Geoffrey T Evans


    This work presents models of the vertical distribution and flux of phytoplankton aggregates, including changes with time in the distribution of aggregate sizes and sinking speeds. The distribution of sizes is described by two parameters, the mass and number of aggregates, which greatly reduces the computational cost of the models. Simple experiments demonstrate the effects of aggregation on the timing and depth distribution of primary production and export. A more detailed ecological model is applied to sites in the Arabian Sea; it demonstrates that aggregation can be important for deep sedimentation even when its effect on surface concentrations is small, and it presents the difference in timing between settlement of aggregates and fecal pellets.

  4. Production efficiency of micellar casein concentrate using polymeric spiral-wound microfiltration membranes.

    Beckman, S L; Zulewska, J; Newbold, M; Barbano, D M


    Most current research has focused on using ceramic microfiltration (MF) membranes for micellar casein concentrate production, but little research has focused on the use of polymeric spiral-wound (SW) MF membranes. A method for the production of a serum protein (SP)-reduced micellar casein concentrate using SW MF was compared with a ceramic MF membrane. Pasteurized (79°C, 18s) skim milk (1,100 kg) was microfiltered at 50°C [about 3 × concentration] using a 0.3-μm polyvinylidene fluoride spiral-wound membrane, bleed-and-feed, 3-stage process, using 2 diafiltration stages, where the retentate was diluted 1:2 with reverse osmosis water. Skim milk, permeate, and retentate were analyzed for SP content, and the reduction of SP from skim milk was determined. Theoretically, 68% of the SP content of skim milk can be removed using a single-stage 3× MF. If 2 subsequent water diafiltration stages are used, an additional 22% and 7% of the SP can be removed, respectively, giving a total SP removal of 97%. Removal of SP greater than 95% has been achieved using a 0.1-μm pore size ceramic uniform transmembrane pressure (UTP) MF membrane after a 3-stage MF with diafiltration process. One stage of MF plus 2 stages of diafiltration of 50°C skim milk using a polyvinylidene fluoride polymeric SW 0.3-μm membrane yielded a total SP reduction of only 70.3% (stages 1, 2, and 3: 38.6, 20.8, and 10.9%, respectively). The SP removal rate for the polymeric SW MF membrane was lower in all 3 stages of processing (stages 1, 2, and 3: 0.05, 0.04, and 0.03 kg/m(2) per hour, respectively) than that of the comparable ceramic UTP MF membrane (stages 1, 2, and 3: 0.30, 0.11, and 0.06 kg/m(2) per hour, respectively), indicating that SW MF is less efficient at removing SP from 50°C skim milk than the ceramic UTP system. To estimate the number of steps required for the SW system to reach 95% SP removal, the third-stage SP removal rate (27.4% of the starting material SP content) was used to

  5. Linear, Star, and Comb Oxidation-Responsive Polymers: Effect of Branching Degree and Topology on Aggregation and Responsiveness.

    d'Arcy, Richard; Gennari, Arianna; Donno, Roberto; Tirelli, Nicola


    Families of amphiphilic oxidation-responsive polymers (poly(ethylene glycol)-polysulfides) with different architectures (linear, 4, 6, and 8-armed stars and 10, 15, and 20-armed combs) and compositions (variable ethylene sulfide/propylene sulfide ratio) are prepared. In water, all the polymers assemble in spherical micelles, with critical micellar concentrations <0.01 mg mL(-1) for all the branched polymers. Triple-detection gel permeation chromatography (GPC) and asymmetric field flow fractionation (AFFF) with dynamic and static light scattering detection, respectively, show an increasing compaction of the polymeric coil and a strong reduction of the aggregation number with increasing degree of branching. The key finding of this study is that the kinetics of the oxidative response sharply depend on the branching; in particular, it is highlighted that the degree of branching influences the lag time before a response can be observed rather than the speed of the response itself, a phenomenon that is attributed to a branching-dependent solubility of the oxidant in the polysulfide matrix.

  6. Distinguishing aggregate formation and aggregate clearance using cell based assays

    E. Eenjes, E.; J.M. Dragich; H. Kampinga (Harm); A. Yamamoto, A.


    textabstractThe accumulation of ubiquitinated proteinaceous inclusions represents a complex process, reflecting the disequilibrium between aggregate formation and aggregate clearance. Although decreasing aggregate formation or augmenting aggregate clearance will ultimately lead to diminished aggrega

  7. Characterization and classification of pseudo-stationary phases in micellar electrokinetic chromatography using chemometric methods.

    Fu, Cexiong; Khaledi, Morteza G


    Two types of chemometric methods, principal component analysis (PCA) and cluster analysis, are employed to characterize and classify a total of 70 pseudostationary phases (54 distinct systems and 16 decoy systems) in micellar electrokinetic chromatography (MEKC). PCA excels at removing redundant information for micellar phase characterization and retaining principal determinants for phase classification. While PCA is useful in the characterization of micelle selectivities, it is ineffective in defining the grouping of micellar phases. Hierarchical clustering yields a complete dendrogram of cluster structures but provides only limited cluster characterizations. The combination of these two chemometric methods leads to a comprehensive interpretation of the micellar phase classification. Moreover, the k-means analysis can further discern subtle differences among those closely located micellar phases. All three chemometric methods result in similar classifications with respect to the similarities and differences of the 70 micelle systems investigated. These systems are categorized into 3 major clusters: fluoro-surfactants represent cluster I, identified as strong hydrogen bond donors and dipolar but weak hydrogen bond acceptors. Cluster II includes sulfonated acrylamide/acrylate copolymers and surfactants with trimethylammonium head groups, characterized by strong hydrophobicity (v) and weak hydrogen bond acidity (b). The last cluster consists of two subclusters: clusters III and IV. Cluster III includes siloxane-based polymeric micelles, exhibiting weak hydrophobicity and medium hydrogen bond acidity and basicity (a), and the cluster IV micellar systems are characterized by their strong hydrophobicity and medium hydrogen bond acidity and basicity but rather weak dipolarity. Cluster III differs from cluster IV by its slightly weaker hydrophobicity and hydrogen bond donating capability. The classification by chemometric methods is in good agreement with the

  8. Fluid-Induced Propulsion of Rigid Particles in Wormlike Micellar Solutions

    Gagnon, David A; Shen, Xiaoning; Arratia, Paulo E


    In the absence of inertia, a reciprocal swimmer achieves no net motion in a viscous Newtonian fluid. Here, we investigate the ability of a reciprocally actuated particle to translate through a complex, "structured" fluid using tracking methods and birefringence imaging. A geometrically polar particle, a rod with a bead on one end, is reciprocally rotated using magnetic fields. The particle is immersed in a wormlike micellar solution that is known to be susceptible to shear banding and the formation of local anisotropic structures. Results show that the nonlinearities present in this structured fluid break time-reversal symmetry under certain conditions, and enable propulsion of an artificial "swimmer." We find three regimes dependent on the Deborah number (De): net motion towards the bead at low De, net motion towards the rod at intermediate De, and no propulsion at high De. At low De, we believe propulsion is caused by an imbalance in the first normal stress differences between the two ends of the particle (...

  9. Estimation of tea catechin levels using micellar electrokinetic chromatography: a quantitative approach.

    Liu, Chao-Ming; Chen, Chung-Yu; Lin, Yang-Wei


    A simple, inexpensive micellar electrokinetic chromatography (MEKC) method with UV detection was used to determine seven catechins and one xanthine (caffeine) in tea. All the compounds were successfully separated (15kV) within a 15-min migration period with a high number of theoretical plates (>8.0×10(4)) in a running buffer (pH 7) containing 10mmoll(-1) sodium tetraborate, 4mmoll(-1) sodium phosphate, and 25mmoll(-1) SDS. The regression lines of all standard catechins were linear within the range of 0.03-4μgml(-1). Green tea infused at 95°C for 10min showed higher levels of catechins (especially epigallocatechin galate, epicatechin gallate, and epicatechin) than tea infused at 80°C. In addition, major differences were observed in the levels of catechins in the first and second infusions (both brewed at 95°C for 10min). Finally, green tea leaves were infused separately with tap water, deionised water, spring water, reverse osmosis water, and distilled water at 95°C, and the catechin content of the infusions was investigated by the proposed method. In the infusion brewed with tap water, catechins appeared to be epimerisation from the epistructure to the nonepistructure. This epimerisation may take place more readily in tap water than in distilled water owing to the complexity of the ions present in tap water.

  10. Effect of calcium chelators on heat coagulation and heat-induced changes of concentrated micellar casein solutions: The role of calcium-ion activity and micellar integrity

    Kort, de E.J.P.; Minor, M.; Snoeren, T.A.L.; Hooijdonk, van A.C.M.; Linden, van der E.


    There is general consensus that calcium chelators enhance heat stability in milk. However, they increase the heat stability to considerably different extents. For this reason, the effect of various calcium chelators on heat coagulation and heat-induced changes of concentrated micellar casein

  11. Effect of calcium chelators on heat coagulation and heat-induced changes of concentrated micellar casein solutions: The role of calcium-ion activity and micellar integrity

    Kort, de E.J.P.; Minor, M.; Snoeren, T.A.L.; Hooijdonk, van A.C.M.; Linden, van der E.


    There is general consensus that calcium chelators enhance heat stability in milk. However, they increase the heat stability to considerably different extents. For this reason, the effect of various calcium chelators on heat coagulation and heat-induced changes of concentrated micellar casein solutio

  12. Ageing and hypoxia cause protein aggregation in mitochondria.

    Kaufman, Daniel M; Wu, Xia; Scott, Barbara A; Itani, Omar A; Van Gilst, Marc R; Bruce, James E; Michael Crowder, C


    Aggregation of cytosolic proteins is a pathological finding in disease states, including ageing and neurodegenerative diseases. We have previously reported that hypoxia induces protein misfolding in Caenorhabditis elegans mitochondria, and electron micrographs suggested protein aggregates. Here, we seek to determine whether mitochondrial proteins actually aggregate after hypoxia and other cellular stresses. To enrich for mitochondrial proteins that might aggregate, we performed a proteomics analysis on purified C. elegans mitochondria to identify relatively insoluble proteins under normal conditions (110 proteins identified) or after sublethal hypoxia (65 proteins). A GFP-tagged mitochondrial protein (UCR-11 - a complex III electron transport chain protein) in the normally insoluble set was found to form widespread aggregates in mitochondria after hypoxia. Five other GFP-tagged mitochondrial proteins in the normally insoluble set similarly form hypoxia-induced aggregates. Two GFP-tagged mitochondrial proteins from the soluble set as well as a mitochondrial-targeted GFP did not form aggregates. Ageing also resulted in aggregates. The number of hypoxia-induced aggregates was regulated by the mitochondrial unfolded protein response (UPRmt) master transcriptional regulator ATFS-1, which has been shown to be hypoxia protective. An atfs-1(loss-of-function) mutant and RNAi construct reduced the number of aggregates while an atfs-1(gain-of-function) mutant increased aggregates. Our work demonstrates that mitochondrial protein aggregation occurs with hypoxic injury and ageing in C. elegans. The UPRmt regulates aggregation and may protect from hypoxia by promoting aggregation of misfolded proteins.

  13. Modification of the murakami retention model in reversed-phase high-performance liquid chromatography for micellar chromatographic separations

    Loginova, L. P.; Boichenko, A. P.; Kulikov, A. Yu.


    A retention model for micellar liquid chromatography was tested based on the data of separation of three benzodiazepins and six β-blockers. The model was obtained by analyzing changes in the microenvironment of a sorbate in transferring from the mobile to stationary phase. It can be used to describe the retention of benzodiazepins, which are neutral under the separation conditions, and the positively charged β-blockers. The calculated model coefficients are indicative of an increase in the number of 1-pentanol molecules and sodium dodecyl sulfate monomers in the microenvironment of the sorbates in transferring from the mobile to stationary phase. The solvation of the positive β-blockers by anionic surfactant monomers was higher than that of neutral benzodiazepins.

  14. Population balance modeling of antibodies aggregation kinetics.

    Arosio, Paolo; Rima, Simonetta; Lattuada, Marco; Morbidelli, Massimo


    The aggregates morphology and the aggregation kinetics of a model monoclonal antibody under acidic conditions have been investigated. Growth occurs via irreversible cluster-cluster coagulation forming compact, fractal aggregates with fractal dimension of 2.6. We measured the time evolution of the average radius of gyration, , and the average hydrodynamic radius, , by in situ light scattering, and simulated the aggregation kinetics by a modified Smoluchowski's population balance equations. The analysis indicates that aggregation does not occur under diffusive control, and allows quantification of effective intermolecular interactions, expressed in terms of the Fuchs stability ratio (W). In particular, by introducing a dimensionless time weighed on W, the time evolutions of measured under various operating conditions (temperature, pH, type and concentration of salt) collapse on a single master curve. The analysis applies also to data reported in the literature when growth by cluster-cluster coagulation dominates, showing a certain level of generality in the antibodies aggregation behavior. The quantification of the stability ratio gives important physical insights into the process, including the Arrhenius dependence of the aggregation rate constant and the relationship between monomer-monomer and cluster-cluster interactions. Particularly, it is found that the reactivity of non-native monomers is larger than that of non-native aggregates, likely due to the reduction of the number of available hydrophobic patches during aggregation.

  15. Micelles and aggregates of oxyethylated isononylphenols and their extraction properties near cloud point.

    Arkhipov, Victor P; Idiyatullin, Zhamil Sh; Potapova, Elisaveta F; Antzutkin, Oleg N; Filippov, Andrey V


    We used nuclear magnetic resonance (NMR) spectroscopy and dynamic light scattering (DLS) techniques to study the structural and dynamic properties of micellar solutions of nonionic surfactants of a homologous series of oxyethylated isononylphenols--C9H19C6H4O(C2H4O)(n)H, where n = 6, 8, 9, 10, or 12--in a wide range of temperatures, including cloud points. The radii of the micelles and aggregates, as well as their compositions at different concentrations of surfactant, were determined. Using aqueous phenol solutions as a model, we studied the process of cloud point extraction with oxyethylated isononylphenols.

  16. Quantification of Lipophilicity of 1,2,4-Triazoles Using Micellar Chromatography.

    Janicka, Małgorzata; Stępnik, Katarzyna; Pachuta-Stec, Anna


    High-performance liquid chromatography (HPLC), over-pressured-layer chromatography (OPLC) and thin-layer chromatography (TLC) techniques with micellar mobile phases were proposed to evaluate the lipophilicity of 21 newly synthesized 1,2,4-triazoles, compounds of potential importance in medicine or agriculture as fungicides. Micellar parameters log k(m) were compared with extrapolated R(M0) values determined from reversed-phase (RP) TLC experimental data obtained on RP-8 stationary phases as well as with log P values (Alog Ps, AClog P, Alog P, Mlog P, KowWin, xlog P2 and xlog P3) calculated from molecular structures of solutes tested. The results obtained by applying principal component analysis (PCA) and linear regression showed considerable similarity between partition and retention parameters as alternative lipophilicity descriptors, and indicated micellar chromatography as a suitable technique to study lipophilic properties of organic substances. In micellar HPLC, RP-8e column (Purospher) was applied, whereas in OPLC and TLC, RP-CN plates were applied, which was the novelty of this study and allowed the use of micellar effluents in planar chromatography measurements.

  17. Effect of mixed micellar lipid on the absorption of cholesterol and vitamin D3 into lymph

    Thompson, Gilbert R.; Ockner, Robert K.; Isselbacher, Kurt J.


    The absorption of endogenous cholesterol, labeled with tracer doses of cholesterol 14C or cholesterol-3H and of near physiological doses of vitamin D3-3H was studied in rats with cannulated intestinal lymphatics. The effects of administering mixed micellar solutions of fatty acid, monoglyceride, and bile salt on the absorption of these labeled sterols was determined. It was observed that the specific activity of free cholesterol and the amounts of vitamin D3 appearing in lymph were significantly increased during the intraduodenal administration of mixed micellar solutions of either linoleic or palmitic acid, in contrast to control rats receiving a micellar solution of taurocholate. These increases were related linearly to the lymph triglyceride level. In addition it was observed that when the linoleic acid solution was administered there was a more marked increase in the ratio of the specific activities of free and esterified cholesterol in lymph than with either the palmitic acid or taurocholate solutions. Additional studies in rats with intact lymphatics showed that the uptake of labeled cholesterol and vitamin D3 from the intestinal lumen into the wall was similar whether the sterols were administered in taurocholate or in mixed micellar solution. These findings suggest that mixed micellar lipid increased the rate of appearance of labeled free cholesterol and vitamin D3 in lymph by enhancing their transport out of the intestinal mucosa, rather than by an effect on uptake. PMID:4303790

  18. Selection of reservoirs amenable to micellar flooding. First annual report, October 1978-December 1979

    Goldburg, A.; Price, H.


    The overall project objective is to build a solid engineering base upon which the Department of Energy (DOE) can improve and accelerate the application of micellar-polymer recovery technology to Mid-Continent and California sandstone reservoirs. The purpose of the work carried out under these two contracts is to significantly aid, both DOE and the private sector, in gaining the following Project Objectives: to select the better micellar-polymer prospects in the Mid-Continent and California regions; to assess all of the available field and laboratory data which has a bearing on recovering oil by micellar-polymer projects in order to help identify and resolve both the technical and economic constraints relating thereto; and to design and analyze improved field pilots and tests and to develop a micellar-polymer applications matrix for use by the potential technology users; i.e., owner/operators. The report includes the following: executive summary and project objectives; development of a predictive model for economic evaluation of reservoirs; reservoir data bank for micellar-polymer recovery evaluation; PECON program for preliminary economic evaluation; ordering of candidate reservoirs for additional data acquisition; validation of predictive model by numerical simulation; and work forecast. Tables, figures and references are included.

  19. Chemometric Deconvolution of Continuous Electrokinetic Injection Micellar Electrokinetic Chromatography Data for the Quantitation of Trinitrotoluene in Mixtures of Other Nitroaromatic Compounds


    ABSTRACT Chemometric Deconvolution of Continuous Electrokinetic Injection Micellar Electrokinetic Chromatography Data for the Quantitation of...Unclassified Unlimited Unclassified Unlimited 13 Braden C. Giordano (202) 404-6320 Micellar electrokinetic chromatography Nitroaromatic explosives...Capillary electrophoresis DNT – Dinitrotoluene EOF – Electroosmotic flow MEKC – Micellar electrokinetic chromatography PLS – Partial least squares regression TNT – Trinitrotoluene 11

  20. Glass and percolation transitions in dense attractive micellar system

    Mallamace, F.; Beneduci, R.; Gambadauro, P.; Lombardo, D.; Chen, S. H.


    In this work, we study a copolymer-micellar system characterized by clustering processes due to a short-range attractive interaction. This originates a percolation process and a new type of kinetic glass transition. We have studied these intriguing dynamical situations by means of an extensive set of light scattering and viscoelasticity experiments. Obtained data, in both the phenomena, are accounted for by considering in a proper way fractal clustering processes and the related scaling concepts. Near the percolation line the main role in the system structure and dynamics is played by the cluster's partial screening of hydrodynamic interaction, that behaves, on approaching the percolation threshold, dramatic effects on the rheological properties and on the density decay relaxations. The ergodic-nonergodic transition line (glass transition) is studied in terms of the intermediate scattering functions (ISF) in the frame of the mode coupling theory. The measured ISF gives evidence of a logarithmic decay on the density fluctuation followed by a power law behavior. This latter phenomenon is the signature of a high-order glass transition of the A3 type (cusp-like singularity).

  1. Micellar electrokinetic chromatography of organic and peroxide-based explosives.

    Johns, Cameron; Hutchinson, Joseph P; Guijt, Rosanne M; Hilder, Emily F; Haddad, Paul R; Macka, Mirek; Nesterenko, Pavel N; Gaudry, Adam J; Dicinoski, Greg W; Breadmore, Michael C


    CE methods have been developed for the analysis of organic and peroxide-based explosives. These methods have been developed for deployment on portable, in-field instrumentation for rapid screening. Both classes of compounds are neutral and were separated using micellar electrokinetic chromatography (MEKC). The effects of sample composition, separation temperature, and background electrolyte composition were investigated. The optimised separation conditions (25 mM sodium tetraborate, 75 mM sodium dodecyl sulfate at 25°C, detection at 200 nm) were applied to the separation of 25 organic explosives in 17 min, with very high efficiency (typically greater than 300,000 plates m(-1)) and high sensitivity (LOD typically less than 0.5 mg L(-1); around 1-1.5 μM). A MEKC method was also developed for peroxide-based explosives (10 mM sodium tetraborate, 100 mM sodium dodecyl sulfate at 25°C, detection at 200 nm). UV detection provided LODs between 5.5 and 45.0 mg L(-1) (or 31.2-304 μM), which is comparable to results achieved using liquid chromatography. Importantly, no sample pre-treatment or post-column reaction was necessary and the peroxide-based explosives were not decomposed to hydrogen peroxide. Both MEKC methods have been applied to pre-blast analysis and for the detection of post-blast residues recovered from controlled, small scale detonations of organic and peroxide-based explosive devices.

  2. Crystallization in Micellar Cores: confinement effects and dynamics

    Lund, Reidar; Zinn, Thomas; Willner, Lutz; Department of Chemistry, University of Oslo Team; Forschungszentrum Jülich Collaboration

    It is well known that liquids confined to small nanoscopic pores and droplets exhibit thermal behavior very different from bulk samples. Here we demonstrate that n-alkanes forming 2-3 nm small micellar cores are considerably affected by confinement in analogue with hard confined systems. We study micelles form by self-assembly of a series of well-defined n-Alkyl-PEO polymers in aqueous solutions. By using small-angle X-ray scattering (SAXS), densiometry and differential scanning calorimetry (DSC), we show that n-alkane exhibit a first-order phase transition i.e. melting. Correlating the structural and thermodynamic data, we find that a melting depression can be accurately described by the Gibbs-Thomson equation. ∖f1 The effect of core crystallinity on the molecular exchange kinetics is investigated using time-resolved small-angle neutron scattering (TR-SANS). We show that there are considerable entropic and enthalpic contributions from the chain packing that affect the kinetic stability of micelles. ∖pard

  3. Simultaneous micellar LC determination of lidocaine and tolperisone.

    Youngvises, Napaporn; Liawruangrath, Boonsom; Liawruangrath, Saisunee


    A micellar liquid chromatography (MLC) procedure was developed for the simultaneous separation and determination of lidocaine hydrochloride (LD HCl) and tolperisone hydrochloride (TP HCl) using a short-column C18 (12.5 mm x 4.6 mm, 5 microm), sodium dodecyl sulfate (SDS) with a small amount of isopropanol, and diode array detector. The optimum conditions for the simultaneous determination of both drugs were 0.075 mol l(-1) SDS-7.5% (v/v) isopropanol with a flow rate of 0.7 ml min(-1) and detection at 210 nm. The LOD (2S/N) of LD HCl was 0.73 ng 20 microl(-1), whereas that of TP HCl was 1.43 ng 20 microl(-1). The calibration curves for LD HCl and TP HCl were linear over the ranges 0.125-500 microg ml(-1) (r(2)=0.9999) and 1.00-500 microg ml(-1) (r(2)=0.9997), respectively. The %recoveries of both drugs were in the range 98-103% and the %RSD values were less than 2. The proposed method has been successfully applied to the simultaneous determination of TP HCl and LD HCl in various pharmaceutical preparations.

  4. PH-triggered micellar membrane for controlled release microchips

    Yang, Xiaoqiang


    A pH-responsive membrane based on polystyrene-b-poly(4-vinylpyridine) (PS-b-P4VP) block copolymer was developed on a model glass microchip as a promising controlled polymer delivery system. The PS-b-P4VP copolymer assembles into spherical and/or worm-like micelles with styrene block cores and pyridine coronas in selective solvents. The self-assembled worm-like morphology exhibited pH-responsive behaviour due to the protonation of the P4VP block at low pH and it\\'s deprotonation at high pH and thus constituting a switchable "off/on" system. Doxorubicin (Dox) was used as cargo to test the PS-b-P4VP membrane. Luminescence experiments indicated that the membrane was able to store Dox molecules within its micellar structure at neutral pH and then release them as soon as the pH was raised to 8.0. The performance of the cast membrane was predictable and most importantly reproducible. The physiochemical and biological properties were also investigated carefully in terms of morphology, cell viability and cell uptake. This journal is © The Royal Society of Chemistry.

  5. Use of ligand-modified micellar-enhanced ultrafiltration to selectively separate copper ions from wastewater streams

    Shadizadeh, S.B.


    The selective removal of target ions from an aqueous solution containing ions of like charge by ligand-modified micellar-enhanced ultrafiltration (LM-MEUF), is presented. In LM-MEUF, surfactant and specially tailored ligand are added to the contaminated stream. The surfactant forms aggregates called micelles, the hydrocarbon core of which the ligand complexed with the target species will solubilize. The surfactant is chosen to have the same charge type as the target ion; therefore, other ions (with similar charge) will not associate with the micelle, which makes the separation of the target ion selective. The solution is then processed by ultrafiltration, using a membrane with pore size small enough to block the passage of the micelles. In this study the divalent copper is the target ion in the solution containing divalent calcium. The surfactant is cetylpyridinium chloride (CPC) and the ligand is 4-hexadecyloxybenzyliminodiacetic acid (C{sub 16}BIDA). Experiments were conducted with batch stirred cells and the results have been compared to separation that take place under a variety of conditions in the LM-MEUF process. Rejections of copper of up to 99.8% are observed, with almost no rejection of calcium, showing that LM-MEUF has excellent selectivity and separation efficiency.

  6. Small angle neutron scattering study of sodium dodecyl sulfate micellar growth driven by addition of a hydrotropic salt.

    Hassan, P A; Fritz, Gerhard; Kaler, Eric W


    The structures of aggregates formed in aqueous solutions of an anionic surfactant, sodium dodecyl sulfate (SDS), with the addition of a cationic hydrotropic salt, p-toluidine hydrochloride (PTHC), have been investigated by small angle neutron scattering (SANS). The SANS spectra exhibit a pronounced peak at low salt concentration, indicating the presence of repulsive intermicellar interactions. Model-independent real space information about the structure is obtained from a generalized indirect Fourier transformation (GIFT) technique in combination with a suitable model for the interparticle structure factor. The interparticle interaction is captured using the rescaled mean spherical approximation (RMSA) closure relation and a Yukawa form of the interaction potential. Further quantification of the geometrical parameters of the micelles was achieved by a complete fit of the SANS data using a prolate ellipsoidal form factor and the RMSA structure factor. The present study shows that PTHC induces a decrease in the fractional charge of the micelles due to adsorption at the micellar surface and consequent growth of the SDS micelles from nearly globular to rodlike as the concentration of PTHC increases.

  7. Colloidal chirality in wormlike micellar systems exclusively originated from achiral species: Role of secondary assembly and stimulus responsivity.

    Zhao, Wenrong; Hao, Jingcheng


    Colloidal chirality in wormlike micellar systems exclusively originated from achiral species and discussion of the role of secondary assembly of fiber-like aggregates in chirality generation were presented in this paper. Herein, formation of colloidal wormlike micelles for the first time incorporated chirality and redox-responsiveness into one design via noncovalent interaction. A dual-stimuli-responsive gel of wormlike micelles which were designed by employing a dual-responsive cationic surfactant (FTMA) and a strong gelator (AzoNa4) and regulated by redox reaction and host-guest inclusion is presented. Both the redox and host-guest interaction play an important role in regulating the viscosity and supramolecular chirality of gels of the wormlike micelles. The supramolecular chirality and viscosity of the wormlike micelle gels were switched reversibly by exerting chemical redox onto the ferrocenyl groups. For the amphiphile FTMA containing redox-active ferrocenyl group, reversible control of the oxidation state of ferrocenyl groups leads to the charge and hydrophobicity changes of FTMA, therefore change its self-assembly behavior. Of equal interest, β-CD successfully detached the wormlike micelles via the recognition-inclusion behavior with FTMA and invalidate the H-bond and hydrophobic interaction between FTMA and AzoH4. This designed system provides a new strategy to tune the supramolecular chirality of colloidal aggregates and explore the specific packing mode detail within the micelles or the secondary assembly of the inter-micelles. We anticipate this dual-responsive H-bond-directed chiral gel switch could propose a new strategy when researchers designing new, multi-responsive functional gel materials.

  8. The magnetoviscous effect of micellar solutions doped with water based ferrofluids

    Arantes, Fabiana R., E-mail: [Institute of Physics, University of Sao Paulo (Brazil); Institute of Fluid Mechanics, Technische Universität Dresden (Germany); Odenbach, Stefan, E-mail: [Institute of Fluid Mechanics, Technische Universität Dresden (Germany)


    This work presents a magnetorheological study of micellar solutions of potassium laurate and water doped with magnetite nanoparticles, accompanied by auxiliary dynamic light scattering measurements. An increase in the viscosity of the samples under applied field was observed and, furthermore, a considerable magnetoviscous effect was revealed even at magnetic particles' concentrations as low as 0.005–0.01 vol%. This indicates that the rheological behavior of the micelles is changed by the interaction of the magnetic particles with the applied field, leading to different microscopic arrangements in the micellar solutions. - Highlights: • We study the magnetorheological behavior of micellar solutions doped with ferrofluids. • We observe an increase in the viscosity of the samples under an applied field. • We find a large magnetoviscous effect even at low magnetic particles' concentration. • Interaction of particles with the field changes the micelles' rheological behavior.

  9. Use of micellar liquid chromatography to analyze darunavir, ritonavir, emtricitabine, and tenofovir in plasma.

    Peris-Vicente, Juan; Villarreal-Traver, Mónica; Casas-Breva, Inmaculada; Carda-Broch, Samuel; Esteve-Romero, Josep


    Danuravir, ritonavir, emtricitabine, and tenofovir are together prescribed against AIDS as a highly active antiretroviral therapy regimen. Micellar liquid chromatography has been applied to determine these four antiretroviral drugs in plasma. The sample preparation is shortened to the dilution of the sample in a micellar solution, filtration, and injection. Clean-up steps are avoided, due to the solubilization of plasma matrix in micellar media. The drugs were analyzed in 0.995), accuracy (89.3-103.2%), precision (<8.2%) and robustness (<7.5%). Real plasma sample from patients taking this therapy were analyzed. This is the first paper showing the simultaneous detection of this four drugs. Therefore, the methodology was proven useful for the routine analysis of these samples in a hospital laboratory for clinical purposes.

  10. Demonstrating Chemical and Analytical Concepts in the Undergraduate Laboratory Using Capillary Electrophoresis and Micellar Electrokinetic Chromatography

    Palmer, Christopher P.


    This paper describes instrumental analysis laboratory exercises that utilize capillary electrophoresis and micellar electrokinetic chromatography to demonstrate several analytical and chemical principles. Alkyl parabens (4-hydroxy alkyl benzoates), which are common ingredients in cosmetic formulations, are separated by capillary electrophoresis. The electrophoretic mobilities of the parabens can be explained on the basis of their relative size. 3-Hydroxy ethylbenzoate is also separated to demonstrate the effect of substituent position on the acid dissociation constant and the effect this has on electrophoretic mobility. Homologous series of alkyl benzoates and alkyl phthalates (common plasticizers) are separated by micellar electrokinetic chromatography at four surfactant concentrations. This exercise demonstrates the separation mechanism of micellar electrokinetic chromatography, the concept of chromatographic phase ratio, and the concepts of micelle formation. A photodiode array detector is used in both exercises to demonstrate the advantages and limitations of the detector and to demonstrate the effect of pH and substituent position on the spectra of the analytes.

  11. Wheat alkylresorcinols reduce micellar solubility of cholesterol in vitro and increase cholesterol excretion in mice.

    Horikawa, Kazumasa; Hashimoto, Chiaki; Kikuchi, Yosuke; Makita, Miki; Fukudome, Shin-Ichi; Okita, Kimiko; Wada, Naoyuki; Oishi, Katsutaka


    Epidemiological studies have shown that the consumption of whole grains can reduce risk for metabolic disorders. We recently showed that chronic supplementation with wheat alkylresorcinols (ARs) prevents glucose intolerance and insulin resistance with hepatic lipid accumulation induced in mice by a high-fat high-sucrose diet (HFHSD). This study examines the effects of ARs on the micellar solubility of cholesterol in vitro, as well as the effects of transient AR supplementation on faecal lipid excretion and plasma lipid levels in mice. We found that ARs formed bile micelles with taurocholate independently of phospholipids, and dose-dependently decreased the micellar solubility of cholesterol in a biliary micelle model. Transient AR supplementation with HFHSD increased faecal cholesterol and triglyceride contents and decreased plasma cholesterol concentrations. These suggest that one underlying mechanism through which ARs suppress diet-induced obesity is by interfering with the micellar cholesterol solubilisation in the digestive tract, which subsequently decreases cholesterol absorption.

  12. Effective solubilization of chalcones in micellar phase: Conductivity and voltammetric study

    Ahmed, Safeer; Khan, Gul Tiaz; Shah, Syed Sakhawat


    The solubilization of four chalcones, between aqueous and micellar phases of ionic surfactants (SDS and CTAB), was investigated by conductivity and cyclic voltammetry (CV) techniques. From conductivity data, a decrease in the critical micellar concentration (CMC) of the surfactants, in presence of the chalcones was ascribed to the decreased charge density over the surfactants. The results were seconded by thermodynamic parameters including degree of ionization (α), counter ion binding (β), and standard Gibbs free energy of micellization (Δ G {m/○}). The added surfactant decreased the peak current of the oxidized chalcone and shifted the peak potential either positively (in presence of SDS) or negatively (in presence of CTAB). The effect is rationalized as chalcone-surfactant interaction and quantitated as binding constant ( K b) assorting values from 8.78 to 552.97 M-1. The preferred solubilization of the chalcones in the micellar phase has been inferred.

  13. Micellar lipid composition affects micelle interaction with class B scavenger receptor extracellular loops.

    Goncalves, Aurélie; Gontero, Brigitte; Nowicki, Marion; Margier, Marielle; Masset, Gabriel; Amiot, Marie-Josèphe; Reboul, Emmanuelle


    Scavenger receptors (SRs) like cluster determinant 36 (CD36) and SR class B type I (SR-BI) play a debated role in lipid transport across the intestinal brush border membrane. We used surface plasmon resonance to analyze real-time interactions between the extracellular protein loops and various ligands ranging from single lipid molecules to mixed micelles. Micelles mimicking physiological structures were necessary for optimal binding to both the extracellular loop of CD36 (lCD36) and the extracellular loop of SR-BI (lSR-BI). Cholesterol, phospholipid, and fatty acid micellar content significantly modulated micelle binding to and dissociation from the transporters. In particular, high phospholipid micellar concentrations inhibited micelle binding to both receptors (-53.8 and -74.4% binding at 0.32 mM compared with 0.04 mM for lCD36 and lSR-BI, respectively, P < 0.05). The presence of fatty acids was crucial for micelle interactions with both proteins (94.4 and 81.3% binding with oleic acid for lCD36 and lSR-BI, respectively, P < 0.05) and fatty acid type substitution within the micelles was the component that most impacted micelle binding to the transporters. These effects were partly due to subsequent modifications in micellar size and surface electric charge, and could be correlated to micellar vitamin D uptake by Caco-2 cells. Our findings show for the first time that micellar lipid composition and micellar properties are key factors governing micelle interactions with SRs.

  14. Co-delivery of doxorubicin and (131)I by thermosensitive micellar-hydrogel for enhanced in situ synergetic chemoradiotherapy.

    Huang, Pingsheng; Zhang, Yumin; Wang, Weiwei; Zhou, Junhui; Sun, Yu; Liu, Jinjian; Kong, Deling; Liu, Jianfeng; Dong, Anjie


    Combined chemoradiotherapy is potent to defeat malignant tumor. Concurrent delivery of radioisotope with chemotherapeutic drugs, which also act as the radiosensitizer, to tumor tissues by a single vehicle is essential to achieve this objective. To this end, a macroscale injectable and thermosensitive micellar-hydrogel (MHg) depot was constructed by thermo-induced self-aggregation of poly(ε-caprolactone-co-1,4,8-trioxa[4.6]spiro-9-undecanone)-poly(ethyleneglycol)-poly(ε-caprolactone-co-1,4,8-trioxa[4.6]spiro-9-undecanone) (PECT) triblock copolymer micelles (Ms), which could not only serve as a micellar drug reservoir to locally deliver concentrated nano chemotherapeutic drugs, but also immobilize radioisotopes at the internal irradiation hot focus. Doxorubicin (DOX) and iodine-131 labeled hyaluronic acid ((131)I-HA) were used as the model therapeutic agents. The aqueous mixture of drug-loaded PECT micelles and (131)I-HA exhibited sol-to-gel transition around body temperature. In vitro drug release study indicated that PECT/DOX Ms were sustainedly shed from the native PECT/DOX MHg formulation, which could be internalized by tumor cells with rapid intracellular DOX release. This hydrogel formulation demonstrated considerable in vitro antitumor effect as well as remarkable radiosensitization. In vivo subcutaneous injection of PECT MHg demonstrated that (131)I isotope was immobilized stably at the injection location and no obvious indication of damage to major organs were observed as indicated by the histopathological analysis. Furthermore, the peritumoral injection of chemo-radiation therapeutic agents-encapsulated MHg formulation on tumor-bearing nude mice resulted in the desired combined treatment effect, which significantly improved the tumor growth inhibition efficiency with minimized drug-associated side effects to major organs. Consequently, such a thermosensitive MHg formulation, which enabled the precise control over the dosage and ratio of combination

  15. Biopartitioning micellar chromatography as a predictive tool for skin and corneal permeability of newly synthesized 17β-carboxamide steroids.

    Dobričić, Vladimir; Nikolic, Katarina; Vladimirov, Sote; Čudina, Olivera


    In this paper, human skin and corneal permeability of twenty-two newly synthesized 17β-carboxamide steroids was predicted using biopartitioning micellar chromatography (BMC). These compounds are potential soft glucocorticoids with local anti-inflammatory activity when applied to the skin or eye. BMC systems are used to simulate physicochemical properties of human skin (BMC-skin) and cornea (BMC-cornea). Micellar mobile phase, consisted of 0.04 M solution of polyoxyethylene (23) lauryl ether (Brij 35), was prepared at different pH values - 5.50 (BMC-skin) and 7.50 (BMC-cornea). Retention factors (k), obtained by use of BMC, were calculated for all newly synthesized 17β-carboxamide steroids as well as for parent glucocorticoids (hydrocortisone, prednisolone, methylprednisolone, dexamethasone and betamethasone). Good correlation was obtained between BMC-skin retention factors and permeability coefficients calculated by use of the artificial membrane that simulates stratum corneum of the human skin. Quantitative structure-retention relationship (QSRR) study was performed in order to explain retention factors of these compounds in the tested BMC systems. ANN-QSRR(k), PLS-QSRR(k) and MLR-QSRR(k) models, created by use of BMC-skin retention data, were compared and optimal model (PLS-QSRR(k)) was selected. Molecular descriptors of the selected model indicate that lipophilicity and number of short C-C fragments of tested compounds have the strongest influence on the retention in the BMC-skin system and presumably on their in vivo permeability through human skin. The same model can be applied to the BMC-cornea system and the same conclusion can be drawn for corneal permeability. This model could be used as a predictive tool for the synthesis of novel 17β-carboxamide steroids with desirable permeability through human skin or cornea, depending on their potential pharmacological application.

  16. Radiation decomposition of alcohols and chloro phenols in micellar systems; Descomposicion por irradiacion de alcoholes y clorofenoles en sistemas micelares

    Moreno A, J


    The effect of surfactants on the radiation decomposition yield of alcohols and chloro phenols has been studied with gamma doses of 2, 3, and 5 KGy. These compounds were used as typical pollutants in waste water, and the effect of the water solubility, chemical structure, and the nature of the surfactant, anionic or cationic, was studied. The results show that anionic surfactant like sodium dodecylsulfate (SDS), improve the radiation decomposition yield of ortho-chloro phenol, while cationic surfactant like cetyl trimethylammonium chloride (CTAC), improve the radiation decomposition yield of butyl alcohol. A similar behavior is expected for those alcohols with water solubility close to the studied ones. Surfactant concentrations below critical micellar concentration (CMC), inhibited radiation decomposition for both types of alcohols. However radiation decomposition yield increased when surfactant concentrations were bigger than the CMC. Aromatic alcohols decomposition was more marked than for linear alcohols decomposition. On a mixture of alcohols and chloro phenols in aqueous solution the radiation decomposition yield decreased with increasing surfactant concentration. Nevertheless, there were competitive reactions between the alcohols, surfactants dimers, hydroxyl radical and other reactive species formed on water radiolysis, producing a catalytic positive effect in the decomposition of alcohols. Chemical structure and the number of carbons were not important factors in the radiation decomposition. When an alcohol like ortho-chloro phenol contained an additional chlorine atom, the decomposition of this compound was almost constant. In conclusion the micellar effect depend on both, the nature of the surfactant (anionic or cationic) and the chemical structure of the alcohols. The results of this study are useful for wastewater treatment plants based on the oxidant effect of the hydroxyl radical, like in advanced oxidation processes, or in combined treatment such as

  17. Mesoscopic simulation of a micellar poly(N-isopropyl acrylamide)-b-(polyethylene oxide) copolymer system

    Bautista-Reyes, Rubén; Soto-Figueroa, César; Vicente, Luis


    In this article we studied the micellar formation of poly(N-isopropyl acrylamide)-b-polyethylene oxide (PNIPAM-b-PEO) copolymers in an aqueous system. From molecular simulations the dependence on temperature of the Flory-Huggins interaction parameter χ for PNIPAM and PEO in water is obtained and compared with available experimental results and values from other theoretical calculations. By means of dissipative particle dynamics (DPD) we then simulated the coil-globule transition for PNIPAM chains in water with a transition temperature of around 305 K. The simulations for PNIPAM-b-PEO copolymers showed that at room temperature the chains are miscible in an aqueous phase but with a temperature increase the system turns into micelles at T  =  305 K. The change in micelle anisotropy due to a different ratio PNIPAM/PEO of chains is also analyzed. What is observed is that for large PEO the large number of dissolved PEO chains gives a large corona size and the micelle is not spherical but obloide and as the number of PNIPAM is increased the micelle acquires a spherical shape. As an important application we considered the system micelle-water/anionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate [BMIM]+[PF6]-). By increasing the temperature of the system from 306 K it is shown that at T  =  345 K there is a transfer of the micelle from water to the ionic liquid phase and this was due to the change in the relative affinity of PEO to water and ionic liquid expressed by the change in χ. All the simulation outcomes are qualitatively consistent with experimental results and thus to our knowledge we give the first set of χ values for the interaction between PNIPAM and water in a wide range of temperature values.

  18. Protonation of 5, 10, 15, 20-Tetra(4-hydroxyphenyl)-porphyrin in SDS Micellar Solution

    Xiao Hong ZHAO; Yun Hong ZHANG


    An amphiphilic porphyrin, 5, 10, 15, 20-tetra(4-hydroxyphenyl)-porphyrin (P) was solubilized in SDS micellar solutions. By taking advantage of protonation property of pyridine groups of amphiphilic porphyrin and the UV-Vis spectral sensitivity of Soret band and Q bands to the microenvironment of the porphyrin moiety, two-step protonation was studied in detail by means of UV-Vis spectroscopy. The free base, monocation and dication were described in detail in SDS micellar solution. The possibility of microphase transition was proposed to relate to the observation of two isosbestic points.

  19. Adsorption characteristics of zinc ions on sodium dodecyl sulfate in process of micellar-enhanced ultrafiltration


    To separate zinc ions from aqueous solution efficiently, micellar-enhanced ultrafiltration(MEUF) of hollow ultrafiltration membrane was used with sodium dodecyl sulfate(SDS) as surfactant. The formation of micellar and the adsorption mechanism were investigated, including the influence of the ratio of SDS to zinc ions on the micelle quantity, the micelle ratio, the gross adsorptive capacity, the rejection of zinc ions and the adsorption isotherm law. The results show that the rejection rate of zinc ions reaches 97% and the adsorption of zinc ions on SDS conforms to the Langmuir adsorption isotherm and the adsorption is a chemical adsorption process.

  20. Brownian Dynamics Simulation of Microstructures and Elongational Viscosities of Micellar Surfactant Solution

    WEI Jin-Jia; KAWAGUCHI Yasuo; YU Bo; LI Feng-Chen


    @@ Brownian dynamics simulation is conducted for a dilute surfactant solution under a steady uniaxial elongational flow.A new inter-cluster potential is used for the interaction among surfactant micelles to determine the micellar network structures in the surfactant solution.The micellar network is successfully simulated.It is formed at low elongation rates and destroyed by high elongation rates.The computed elongational viscosities show elongation-thinning characteristics.The relationship between the elongational viscosities and the microstructure of the surfactant solution is revealed.

  1. El Dorado Micellar-Polymer demonstration project. First annual report, January 1974-June 1975

    Coffman, C.L.; Rosenwald, G.W. (ed.); Miller, R.J. (ed.)


    Progress made in the implementation of a project designed to determine the economic feasibility of improved oil recovery using micellar-polymer processes and to determine the associated benefits and problems of each system tested is reported. The project allows a side-by-side comparison of two distinct micellar-polymer processes in the same abandoned field so that the reservoir conditions for the two floods are as nearly alike as possible. Results are reported for test wells drilled to obtain reservoir data, field injectivity and interference tests, and performance predictions. Engineering operations are summarized. (JSR)

  2. Marine particle aggregate breakup in turbulent flows

    Rau, Matthew; Ackleson, Steven; Smith, Geoffrey


    The dynamics of marine particle aggregate formation and breakup due to turbulence is studied experimentally. Aggregates of clay particles, initially in a quiescent aggregation tank, are subjected to fully developed turbulent pipe flow at Reynolds numbers of up to 25,000. This flow arrangement simulates the exposure of marine aggregates in coastal waters to a sudden turbulent event. Particle size distributions are measured by in-situ sampling of the small-angle forward volume scattering function and the volume concentration of the suspended particulate matter is quantified through light attenuation measurements. Results are compared to measurements conducted under laminar and turbulent flow conditions. At low shear rates, larger sized particles indicate that aggregation initially governs the particle dynamics. Breakup is observed when large aggregates are exposed to the highest levels of shear in the experiment. Models describing the aggregation and breakup rates of marine particles due to turbulence are evaluated with the population balance equation and results from the simulation and experiment are compared. Additional model development will more accurately describe aggregation dynamics for remote sensing applications in turbulent marine environments.

  3. Mobilization and micellar solubilization of NAPL contaminants in aquifer rocks

    Javanbakht, Gina; Goual, Lamia


    Surfactant-enhanced aquifer remediation is often performed to overcome the capillary forces that keep residual NAPL phases trapped within contaminated aquifers. The surfactant selection and displacement mechanism usually depend on the nature of NAPL constituents. For example, micellar solubilization is often used to cleanup DNAPLs from aquifers whereas mobilization is desirable in aquifers contaminated by LNAPLs. Although the majority of crude oils are LNAPLs, they often contain heavy organic macromolecules such as asphaltenes that are classified as DNAPLs. Asphaltenes contain surface-active components that tend to adsorb on rocks, altering their wettability. Previous studies revealed that surfactants that formed Winsor type III microemulsions could promote both mobilization and solubilization. However the extent by which these two mechanisms occur is still unclear, particularly in oil-contaminated aquifers. In this study we investigated the remediation of oil-contaminated aquifers using an environmentally friendly surfactant such as n-Dodecyl β-D-maltoside. Focus was given on asphaltenes to better understand the mechanisms of surfactant cleanup. Through phase behavior, spontaneous imbibition, dynamic interfacial tension and contact angle measurements, we showed that microemulsions formed by this surfactant are able to mobilize bulk NAPL (containing 9 wt.% asphaltenes) in the porous rock and solubilize DNAPL (i.e., 4-6 wt.% adsorbed asphaltenes) from the rock surface. Spontaneous imbibition tests, in particular, indicated that the ratio of mobilized to solubilized NAPL is about 6:1. Furthermore, aging the cores in NAPL beyond 3 days allowed for more NAPL to be trapped in the large pores of the rock but did not alter the amount of asphaltenes adsorbed on the mineral surface.

  4. Structure and kinetics of shear aggregation in turbulent flows. I. Early stage of aggregation.

    Bäbler, Matthäus U; Moussa, Amgad S; Soos, Miroslav; Morbidelli, Massimo


    Aggregation of rigid colloidal particles leads to fractal-like structures that are characterized by a fractal dimension d(f) which is a key parameter for describing aggregation processes. This is particularly true in shear aggregation where d(f) strongly influences aggregation kinetics. Direct measurement of d(f) in the early stages of shear aggregation is however difficult, as the aggregates are small and few in number. An alternative method for determining d(f) is to use an aggregation model that when fitted to the time evolution of the cluster mass distribution allows for estimating d(f). Here, we explore three such models, two of which are based on an effective collision sphere and one which directly incorporates the permeable structure of the aggregates, and we apply them for interpreting the initial aggregate growth measured experimentally in a turbulent stirred tank reactor. For the latter, three polystyrene latexes were used that differed only in the size of the primary particles (d(p) = 420, 600, and 810 nm). It was found that all three models describe initial aggregation kinetics reasonably well using, however, substantially different values for d(f). To discriminate among the models, we therefore also studied the regrowth of preformed aggregates where d(f) was experimentally accessible. It was found that only the model that directly incorporates the permeable structure of the aggregates is able to predict correctly this second type of experiments. Applying this model to the initial aggregation kinetics, we conclude that the actual initial fractal dimension is d(f) = 2.07 +/- 0.04 as found from this model.

  5. Aggregations in Flatworms.

    Liffen, C. L.; Hunter, M.


    Described is a school project to investigate aggregations in flatworms which may be influenced by light intensity, temperature, and some form of chemical stimulus released by already aggregating flatworms. Such investigations could be adopted to suit many educational levels of science laboratory activities. (DS)

  6. Platelet activation and aggregation

    Jensen, Maria Sander; Larsen, O H; Christiansen, Kirsten


    This study introduces a new laboratory model of whole blood platelet aggregation stimulated by endogenously generated thrombin, and explores this aspect in haemophilia A in which impaired thrombin generation is a major hallmark. The method was established to measure platelet aggregation initiated...

  7. Aggregates from mineral wastes

    Baic Ireneusz


    Full Text Available The problem concerning the growing demand for natural aggregates and the need to limit costs, including transportation from remote deposits, cause the increase in growth of interest in aggregates from mineral wastes as well as in technologies of their production and recovery. The paper presents the issue related to the group of aggregates other than natural. A common name is proposed for such material: “alternative aggregates”. The name seems to be fully justified due to adequacy of this term because of this raw materials origin and role, in comparison to the meaning of natural aggregates based on gravel and sand as well as crushed stones. The paper presents characteristics of the market and basic application of aggregates produced from mineral wastes, generated in the mining, power and metallurgical industries as well as material from demolished objects.

  8. Influence of Surfactant-polymer Complexes on Crystallization and Aggregation of CaCO3

    PAN Yan; GUO Yu-peng; ZHAO Xu; WANG Zi-chen


    Hollow calcium carbonate(CaCO3) microspheres with different morphologies were synthesized via the precipitation reaction of calcium chloride with sodium carbonate in the presence of different surfactant-polymer complexes.The selected anionic surfactants were sodium dodecyl sulfonate(SDS) and sodium dodecyl benzenesulfonate(SDBS),respectively.The selected water-soluble polymers were polyacrylic acid(PAA) and polyvinyl pyrrolidone(PVP).In this work,SDS-PVP "pearl-necklace model" micellar complex was formed via hydrophobic effectiveness between SDS and PVP and it served as the spherical template to generate spherical CaCO3 aggregates with hollow microspheres composed of about 500 nm irregular shaped particles.SDS-PAA complexes and SDBS-PAA complexes formed "core-shell model" aggregates with calcium ions serving as the medium to link the anionic surfactant and the polymer.SDS-PAA "core-shell model" aggregates would act as templates for hollow CaCO3 microspheres consisting of 30-50 nm irregular shaped crystallites.SDBS-PAA "core-shell model" aggregates served as the spherical aggregate templates to generate spherical CaCO3 aggregates consisted of many small spherical particles which had grown together.All the obtained CaCO3 hollow microspheres are calcite particles.This research may provide new insight into the control of morphologies of hollow CaCO3 microspheres in the presence of surfactantpolymer complexes.

  9. Determination of selected synthetic cannabinoids and their metabolites by micellar electrokinetic chromatography--mass spectrometry employing perfluoroheptanoic acid-based micellar phase.

    Švidrnoch, Martin; Přibylka, Adam; Maier, Vítězslav


    Perfluoroheptanoic acid was employed as a volatile micellar phase in background electrolyte for micellar electrokinetic chromatography-tandem mass spectrometry separation and determination of 15 selected naphthoyl- and phenylacetylindole- synthetic cannabinoids and main metabolites derived from JWH-018, JWH-019, JWH-073, JWH-200 and JWH-250. The influence of concentration of perfluoroheptanoic acid in background electrolytes on the separation was studied as well as the influence of perfluoroheptanoic acid on mass spectrometry detection. The background electrolyte consisted of 75 mM perfluoroheptanoic acid, 150 mM ammonium hydroxide pH 9.2 with 10% (v/v) propane-2-ol allowed micellar electrokinetic chromatography separation together with mass spectrometry identification of the studied parent synthetic cannabinoids and their metabolites. The limits of detection of studied synthetic cannabinoids and metabolites were in the range from 0.9 ng/mL for JWH-073 to 3.0 ng/mL for JWH-200 employing liquid-liquid extraction. The developed method was applied on the separation and identification of studied analytes after liquid-liquid extraction of spiked urine and serum samples to demonstrate the potential of the method applicability for forensic and toxicological purposes.

  10. Comparative study of multi walled carbon nanotubes-based electrodes in micellar media and their application to micellar electrokinetic capillary chromatography.

    Chicharro, Manuel; Arribas, Alberto Sánchez; Moreno, Mónica; Bermejo, Esperanza; Zapardiel, Antonio


    This work reports on a comparative study of the electrochemical performance of carbon nanotubes-based electrodes in micellar media and their application for amperometric detection in micellar electrokinetic capillary chromatography (MEKC) separations. These electrodes were prepared in two different ways: immobilization of a layer of carbon nanotubes dispersed in polyethylenimine (PEI), ethanol or Nafion onto glassy carbon electrodes or preparation of paste electrodes using mineral oil as binder. Scanning electron microscopy (SEM) was employed for surface morphology characterization while cyclic voltammetry of background electrolyte was used for capacitance estimation. The amperometric responses to hydrogen peroxide, amitrol, diuron and 2,3-dichlorophenol (2,3CP) in the presence and in the absence of sodium dodecylsulphate (SDS) were studied by flow injection analysis (FIA), demonstrating that the electrocatalytic activity, background current and electroanalytical performance were strongly dependent on the electrodes preparation procedure. Glassy carbon electrodes modified with carbon nanotubes dispersed in PEI (GC/(CNT/PEI)) displayed the most adequate performance in micellar media, maintaining good electrocatalytic properties combined with acceptable background currents and resistance to passivation. The advantages of using GC/(CNT/PEI) as detectors in capillary electrophoresis were illustrated for the MEKC separations of phenolic pollutants (phenol, 3-chlorophenol, 2,3-dichlorophenol and 4-nitrophenol) and herbicides (amitrol, asulam, diuron, fenuron, monuron and chlortoluron).

  11. Dynamics of proteins aggregation. I. Universal scaling in unbounded media

    Zheng, Size; Javidpour, Leili; Shing, Katherine S.; Sahimi, Muhammad


    It is well understood that in some cases proteins do not fold correctly and, depending on their environment, even properly-folded proteins change their conformation spontaneously, taking on a misfolded state that leads to protein aggregation and formation of large aggregates. An important factor that contributes to the aggregation is the interactions between the misfolded proteins. Depending on the aggregation environment, the aggregates may take on various shapes forming larger structures, such as protein plaques that are often toxic. Their deposition in tissues is a major contributing factor to many neuro-degenerative diseases, such as Alzheimer's, Parkinson's, amyotrophic lateral sclerosis, and prion. This paper represents the first part in a series devoted to molecular simulation of protein aggregation. We use the PRIME, a meso-scale model of proteins, together with extensive discontinuous molecular dynamics simulation to study the aggregation process in an unbounded fluid system, as the first step toward MD simulation of the same phenomenon in crowded cellular environments. Various properties of the aggregates have been computed, including dynamic evolution of aggregate-size distribution, mean aggregate size, number of peptides that contribute to the formation of β sheets, number of various types of hydrogen bonds formed in the system, radius of gyration of the aggregates, and the aggregates' diffusivity. We show that many of such quantities follow dynamic scaling, similar to those for aggregation of colloidal clusters. In particular, at long times the mean aggregate size S(t) grows with time as, S(t) ˜ tz, where z is the dynamic exponent. To our knowledge, this is the first time that the qualitative similarity between aggregation of proteins and colloidal aggregates has been pointed out.

  12. Determination of diuron, terbuthylazine, and terbutryn in wastewater and soil by micellar liquid chromatography.

    Pitarch-Andrés, Susana; Roca-Genovés, Pasqual; Peris-Vicente, Juan; Esteve-Romero, Josep


    An analytical method for the quantification of the herbicides and algaecides diuron, terbuthylazine, and terbutryn in wastewater and soil by micellar liquid chromatography was developed. The sample preparation was expedited to reduce the number of intermediate steps and the use of chemicals. The analytes in soils were recovered by ultrasonication in the mobile phase. The obtained supernatant and the water samples were directly injected, thus avoiding intermediate steps. The chromatographic behavior of the analytes, depending on the surfactant and alcohol was studied, in order to optimize the chromatographic run, by a chemometrical approach. The herbicides were resolved in <16 min using a C18 column and a mobile phase of 0.07 M sodium dodecyl sulfate/6% 1-pentanol phosphate buffered at pH 3, running under isocratic mode at 1 mL/min. The detection absorbance wavelength was set to 240 nm. The method was successfully validated in terms of selectivity, detection limit (0.06 mg/L in water and 0.3 mg/kg in soil), quantitation range (0.2-2 mg/L in water and 1-10 mg/kg in soil), trueness (-6.1 to +5.0%), precision (<9.4%), and ruggedness (<8.3%). The procedure was reliable, practical, easy-to-handle, available, short-time and ecofriendly and useful for routine analysis. Its applicability to real samples was evaluated by analyzing several wastewater, decorative reservoir, and soil samples from agricultural and urban sources.

  13. Micellar electrokinetic chromatography for the analysis of D-amygdalin and its epimer in apricot kernel.

    Kang, S H; Jung, H; Kim, N; Shin, D H; Chung, D S


    We have developed a simple, rapid and reproducible method for the determination of D-amygdalin and its epimer by using micellar electrokinetic chromatography (MEKC). Separation of D-amygdalin was performed in a 20 mM sodium borate buffer (pH 8.5) containing 300 mM sodium dodecyl sulfate using a bare fused-silica capillary. The eluates were monitored by the absorbance at 210 nm. The applied electric field was 278 V/cm, and the time needed for the separation of D-amygdalin did not exceed 6 min. The calibration curve for D-amygdalin showed excellent linearity in the concentration range of 5-500 microg/ml. The migration time and the corrected peak area show relative standard deviations (n=6) of 0.86% and 1.48%, respectively. The limit of detection (S/N=3) for D-amygdalin was 2 microg/ml. Under acidic and neutral conditions, amygdalin exists only as the D-form; however, under basic conditions, it shows both the D- and L-forms with a concentration ratio of 1:1.3 (D-amygdalin/L-amygdalin). Results of HPLC, UV-Vis spectrophotometry, and mass spectrometry reconfirmed the identification of D-amygdalin and its epimer. The number of theoretical plates of D-amygdalin is about 100,000 in MEKC, which is significantly higher than approximately 8,000 of HPLC. This method has been successfully applied to the determination of amygdalin epimers in various apricot kernel extracts and pharmaceutical products.

  14. Small-angle neutron scattering studies of sodium butyl benzene sulfonate aggregates in aqueous solution

    O R Pal; V G Gaikar; J V Joshi; P S Goyal; V K Aswal


    The aggregation behaviour of a hydrotrope, sodium -butyl benzene sulfonate (Na-NBBS), in aqueous solutions is investigated by small-angle neutron scattering (SANS). Nearly ellipsoidal aggregates of Na-NBBS at concentrations well above its minimum hydrotrope concentration were detected by SANS. The hydrotrope seems to form self-assemblies with aggregation number of 36–40 with a substantial charge on the aggregate. This aggregation number is weakly affected by the hydrotrope concentration.

  15. Protein aggregate myopathies

    Sharma M


    Full Text Available Protein aggregate myopathies (PAM are an emerging group of muscle diseases characterized by structural abnormalities. Protein aggregate myopathies are marked by the aggregation of intrinsic proteins within muscle fibers and fall into four major groups or conditions: (1 desmin-related myopathies (DRM that include desminopathies, a-B crystallinopathies, selenoproteinopathies caused by mutations in the, a-B crystallin and selenoprotein N1 genes, (2 hereditary inclusion body myopathies, several of which have been linked to different chromosomal gene loci, but with as yet unidentified protein product, (3 actinopathies marked by mutations in the sarcomeric ACTA1 gene, and (4 myosinopathy marked by a mutation in the MYH-7 gene. While PAM forms 1 and 2 are probably based on impaired extralysosomal protein degradation, resulting in the accumulation of numerous and diverse proteins (in familial types in addition to respective mutant proteins, PAM forms 3 and 4 may represent anabolic or developmental defects because of preservation of sarcomeres outside of the actin and myosin aggregates and dearth or absence of other proteins in these actin or myosin aggregates, respectively. The pathogenetic principles governing protein aggregation within muscle fibers and subsequent structural sarcomeres are still largely unknown in both the putative catabolic and anabolic forms of PAM. Presence of inclusions and their protein composition in other congenital myopathies such as reducing bodies, cylindrical spirals, tubular aggregates and others await clarification. The hitherto described PAMs were first identified by immunohistochemistry of proteins and subsequently by molecular analysis of their genes.

  16. Charged Dust Aggregate Interactions

    Matthews, Lorin; Hyde, Truell


    A proper understanding of the behavior of dust particle aggregates immersed in a complex plasma first requires a knowledge of the basic properties of the system. Among the most important of these are the net electrostatic charge and higher multipole moments on the dust aggregate as well as the manner in which the aggregate interacts with the local electrostatic fields. The formation of elongated, fractal-like aggregates levitating in the sheath electric field of a weakly ionized RF generated plasma discharge has recently been observed experimentally. The resulting data has shown that as aggregates approach one another, they can both accelerate and rotate. At equilibrium, aggregates are observed to levitate with regular spacing, rotating about their long axis aligned parallel to the sheath electric field. Since gas drag tends to slow any such rotation, energy must be constantly fed into the system in order to sustain it. A numerical model designed to analyze this motion provides both the electrostatic charge and higher multipole moments of the aggregate while including the forces due to thermophoresis, neutral gas drag, and the ion wakefield. This model will be used to investigate the ambient conditions leading to the observed interactions. This research is funded by NSF Grant 1414523.

  17. Effective short-range Coulomb correction to model the aggregation behavior of ionic surfactants

    Burgos-Mármol, J. Javier; Solans, Conxita; Patti, Alessandro


    We present a short-range correction to the Coulomb potential to investigate the aggregation of amphiphilic molecules in aqueous solutions. The proposed modification allows to quantitatively reproduce the distribution of counterions above the critical micelle concentration (CMC) or, equivalently, the degree of ionization, α, of the micellar clusters. In particular, our theoretical framework has been applied to unveil the behavior of the cationic surfactant C24H49N2O2+ CH3SO4-, which offers a wide range of applications in the thriving and growing personal care market. A reliable and unambiguous estimation of α is essential to correctly understand many crucial features of the micellar solutions, such as their viscoelastic behavior and transport properties, in order to provide sound formulations for the above mentioned personal care solutions. We have validated our theory by performing extensive lattice Monte Carlo simulations, which show an excellent agreement with experimental observations. More specifically, our coarse-grained model is able to reproduce and predict the complex morphology of the micelles observed at equilibrium. Additionally, our simulation results disclose the existence of a transition from a monodisperse to a bidisperse size distribution of aggregates, unveiling the intriguing existence of a second CMC.

  18. The Mobile Phase Motion in Ascending Micellar Thin-Layer Chromatography with Normal-Phase Plates

    Boichenko, Alexander P.; Makhno, Iryna V.; Renkevich, Anton Yu.; Loginova, Lidia P.


    The physical chemical characteristics (surface tension and viscosity) of micellar mobile phases based on the cationic surfactant cetylpiridinium chloride and additives of alcohols (ethanol, 1-propanol, 1-butanol, 1-pentanol) have been obtained in this work. The effect of mobile phase properties on t

  19. Phase Behavior and Micellar Packing of Impurity-Free Pluronic Block Copolymers in Water

    Ryu, Chang Yeol; Park, Hanjin

    We have investigated the impacts of the non-micellizable polymeric impurities on the micellar packing and solution phase behavior of Pluronic block copolymers in water. In particular, small angle x-ray scattering, rheology and dynamic light scattering techniques have been employed to elucidate how the low MW impurities affect the micellar packing and solution phase diagram in water, when ordered cubic structures of spherical micelles are formed. A silica slurry method has been developed using the competitive adsorption of the PEO-PPO-PEO triblock copolymers over the low MW polymeric impurities for a large scale purification of Pluronics and it purity of Pluronics has been assessed by interaction chromatography. Based on the comparative studies on micellar packing between As-Received (AR) and Purified (Pure) Pluronic F108 solutions, we found experimental evidence to support the hypothesis that the inter-micellar distance of Pluronic cubic structures in aqueous solution is governed by the effective polymer concentration in terms of PEO-PPO-PEO triblock copolymers. Removal of the impurities in AR F108 offers an important clue on window into the onset of BCC ordering via hydrodynamic contact between micelles in solution. NSF DMR Polymers.

  20. The Mobile Phase Motion in Ascending Micellar Thin-Layer Chromatography with Normal-Phase Plates

    Boichenko, Alexander P.; Makhno, Iryna V.; Renkevich, Anton Yu.; Loginova, Lidia P.


    The physical chemical characteristics (surface tension and viscosity) of micellar mobile phases based on the cationic surfactant cetylpiridinium chloride and additives of alcohols (ethanol, 1-propanol, 1-butanol, 1-pentanol) have been obtained in this work. The effect of mobile phase properties on

  1. [Solubilization of nitrobenzene in micellar solutions of Tween 80 and inorganic salts].

    Li, Sui; Zhao, Yong-sheng; Xu, Wei; Dai, Ning


    The solubilization of nitrobenzene by a nonionic surfactant Tween 80 was investigated at 10 degrees C. Experimental results indicated that the solubility of nitrobenzene in water was greatly enhanced by Tween 80 at surfactant concentration above CMC(critical micelle concentration) and a linear relationship was obtained between surfactant concentration and nitrobenzene concentration from the solubility curve. The molar solubilization ratio (MSR) value was 5.093 and IgKm was 3.499. The solubilization was attributed to the ethoxylation group in Tween 80 micellar. Effect of four inorganic salts such as NaCl, KCl, CaCl2 , MgCl2 on water solubilities of nitrobenzene in Tween 80 micellar solutions was also investigated by a matrix of batch experiments. Mix the Tween 80-inorganic salts at the total mass ratios of 2:1, 5:1 and 10:1. The results show that the inorganic salts at a high concentration( > or = 500 mg x L(-1)) can enhance the solubilization capacities of Tween 80 micellar solution and increase the value of MSR and IgKm . Because of the salting-out effect between the micellar of Tween 80 and inorganic salts, the volume of micelle turns bigger, which may provide larger solubility volume for nitrobenzene. The mixture of nonionic surfactant and inorganic salts can be used in subsurface remediation as a flushing solution.

  2. A kinetic study of 1,3-dipolar cycloadditions in micellar media

    Rispens, T; Engberts, JBFN


    The kinetics of the 1,3-dipolar cycloadditions (DC) of benzonitrile oxide with a series of N-substituted maleimides in micellar media have been investigated. Surfactants studied include anionic sodium dodecyl sulfate, cationic cetyltrimethylammonium bromide, and a series of nonionic alkyl poly(ethyl

  3. The Nature of the Micellar Stern Region As Studied by Reaction Kinetics. 2

    Buurma, Niklaas J.; Serena, Paola; Blandamer, Michael J.; Engberts, Jan B.F.N.


    The nature of rate-retarding effects of cationic micelles on the water-catalyzed hydrolyses of a series of para-substituted 1-benzoyl-1,2,4-triazoles (1a-f) and 1-benzoyl-3-phenyl-1,2,4-triazole (2) has been studied using kinetic methods. A comparison is drawn between medium effects in the micellar

  4. The Mobile Phase Motion in Ascending Micellar Thin-Layer Chromatography with Normal-Phase Plates

    Boichenko, Alexander P.; Makhno, Iryna V.; Renkevich, Anton Yu.; Loginova, Lidia P.


    The physical chemical characteristics (surface tension and viscosity) of micellar mobile phases based on the cationic surfactant cetylpiridinium chloride and additives of alcohols (ethanol, 1-propanol, 1-butanol, 1-pentanol) have been obtained in this work. The effect of mobile phase properties on t

  5. El Dorado Micellar-Polymer Demonstration Project third annual report, June 1976--August 1977

    Rosenwald, G.W.; Miller, R.J.; Vairogs, J. (eds.)


    The primary objectives of this project are to determine the economic feasibility of improved oil recovery using two micellar-polymer processes and to determine the associated benefits and problems of each process. The El Dorado Demonstration Project is designed to allow a side-by-side comparison of two distinct micellar-polymer processes in the same field so that the reservoir conditions for the two floods are as nearly alike as possible. Selection of sulfonates and polymers for both patterns was completed. Salinity changes in produced fluids and in observation well samples have shown that breakthrough of preflush (or preflood) has occurred at some wells in both patterns. Observation well sampling and logging data showed that preflush arrived earlier at the observation wells in the north pattern than the south pattern. Injectivities of the micellar system designed for the south pattern and components of that system were tested in three monitoring wells. Similarly, extensive injectivity testing of the surfactant and polymer slugs designed for the north pattern was conducted using two monitoring wells. Recommended preflush volumes for the south pattern were revised to reflect corrections in reservoir data (primarily due to the lack of the upper zone at well MP-213). Reservoir pressure forecasts of the superposition-of-line-sources simulator were compared with observed monitoring well pressures. Injection of the chemical preflush for the south pattern began on June 20, 1976. The micellar fluid injection began in the south pattern on March 22, 1977. (LK)

  6. Formation of DNA Adducts by Ellipticine and Its Micellar Form in Rats — A Comparative Study

    Marie Stiborova


    Full Text Available The requirements for early diagnostics as well as effective treatment of cancer diseases have increased the pressure on development of efficient methods for targeted drug delivery as well as imaging of the treatment success. One of the most recent approaches covering the drug delivery aspects is benefitting from the unique properties of nanomaterials. Ellipticine and its derivatives are efficient anticancer compounds that function through multiple mechanisms. Formation of covalent DNA adducts after ellipticine enzymatic activation is one of the most important mechanisms of its pharmacological action. In this study, we investigated whether ellipticine might be released from its micellar (encapsulated form to generate covalent adducts analogous to those formed by free ellipticine. The 32P-postlabeling technique was used as a useful imaging method to detect and quantify covalent ellipticine-derived DNA adducts. We compared the efficiencies of free ellipticine and its micellar form (the poly(ethylene oxide-block-poly(allyl glycidyl ether (PAGE-PEO block copolymer, P 119 nanoparticles to form ellipticine-DNA adducts in rats in vivo. Here, we demonstrate for the first time that treatment of rats with ellipticine in micelles resulted in formation of ellipticine-derived DNA adducts in vivo and suggest that a gradual release of ellipticine from its micellar form might produce the enhanced permeation and retention effect of this ellipticine-micellar delivery system.

  7. On the appearance of vorticity and gradient shear bands in wormlike micellar solutions of different CPCl/salt systems

    Mütze, Annekathrin, E-mail:; Heunemann, Peggy; Fischer, Peter [ETH Zürich, Institute of Food, Nutrition and Health, Schmelzbergstrasse 9, 8092 Zürich (Switzerland)


    Wormlike micellar salt/surfactant solutions (X-salicylate, cetylpyridinium chloride) are studied with respect to the applied shear stress, concentration, temperature, and composition of the counterions (X = lithium, sodium, potassium, magnesium, and calcium) of the salicylate salt solute to determine vorticity and gradient shear bands. A combination of rheological measurements, laser technique, video analysis, and rheo-small-angle neutron scattering allow for a detailed exploration of number and types of shear bands. Typical flow curves of the solutions show Newtonian, shear-thinning, and shear-thickening flow behavior. In the shear-thickening regime, the solutions show vorticity and gradient shear bands simultaneously, in which vorticity shear bands dominate the visual effect, while gradient shear bands always coexist and predominate the rheological response. It is shown that gradient shear bands change their phases (turbid, clear) with the same frequency as the shear rate oscillates, whereas vorticity shear bands change their phases with half the frequency of the shear rate. Furthermore, we show that with increasing molecular mass of the counterions the number of gradient shear bands increases, while the number of vorticity shear bands remains constant. The variation of temperature, shear stress, concentration, and counterions results in a predictable change in the rheological behavior and therefore allows adjustment of the number of vorticity shear bands in the shear band regime.

  8. Aggregated Computational Toxicology Online Resource

    U.S. Environmental Protection Agency — Aggregated Computational Toxicology Online Resource (AcTOR) is EPA's online aggregator of all the public sources of chemical toxicity data. ACToR aggregates data...

  9. First example of a lipophilic porphyrin-cardanol hybrid embedded in a cardanol-based micellar nanodispersion.

    Bloise, Ermelinda; Carbone, Luigi; Colafemmina, Giuseppe; D'Accolti, Lucia; Mazzetto, Selma Elaine; Vasapollo, Giuseppe; Mele, Giuseppe


    Cardanol is a natural and renewable organic raw material obtained as the major chemical component by vacuum distillation of cashew nut shell liquid. In this work a new sustainable procedure for producing cardanol-based micellar nanodispersions having an embedded lipophilic porphyrin itself peripherally functionalized with cardanol substituents (porphyrin-cardanol hybrid) has been described for the first time. In particular, cardanol acts as the solvent of the cardanol hybrid porphyrin and cholesterol as well as being the main component of the nanodispersions. In this way a "green" micellar nanodispersion, in which a high percentage of the micellar system is derived from renewable "functional" molecules, has been produced.

  10. Förster Resonance Energy Transfer Switchable Self-Assembled Micellar Nanoprobe: Ratiometric Fluorescent Trapping of Endogenous H2S Generation via Fluvastatin-Stimulated Upregulation.

    Zhao, Chunchang; Zhang, Xiuli; Li, Kaibin; Zhu, Shaojia; Guo, Zhiqian; Zhang, Lili; Wang, Feiyi; Fei, Qiang; Luo, Sihang; Shi, Ping; Tian, He; Zhu, Wei-Hong


    H2S produced in small amounts by mammalian cells has been identified in mediating biological signaling functions. However, the in situ trapping of endogenous H2S generation is still handicapped by a lack of straightforward methods with high selectivity and fast response. Here, we encapsulate a semi-cyanine-BODIPY hybrid dye (BODInD-Cl) and its complementary energy donor (BODIPY1) into the hydrophobic interior of an amphiphilic copolymer (mPEG-DSPE), especially for building up a ratiometric fluorescent H2S nanoprobe with extraordinarily fast response. A remarkable red-shift in the absorption band with a gap of 200 nm in the H2S response can efficiently switch off the Förster resonance energy transfer (FRET) from BODIPY1 to BODInD-Cl, subsequently recovering the donor fluorescence. Impressively, both the interior hydrophobicity of supramolecular micelles and electron-withdrawing nature of indolium unit in BODInD-Cl can sharply increase aromatic nucleophilic substitution with H2S. The ratiometric strategy based on the unique self-assembled micellar aggregate NanoBODIPY achieves an extremely fast response, enabling in situ imaging of endogenous H2S production and mapping its physiological and pathological consequences. Moreover, the amphiphilic copolymer renders the micellar assembly biocompatible and soluble in aqueous solution. The established FRET-switchable macromolecular envelope around BODInD-Cl and BODIPY1 enables cellular uptake, and makes a breakthrough in the trapping of endogenous H2S generation within raw264.7 macrophages upon stimulation with fluvastatin. This study manifests that cystathione γ-lyase (CSE) upregulation contributes to endogenous H2S generation in fluvastatin-stimulated macrophages, along with a correlation between CSE/H2S and activating Akt signaling pathway.

  11. Composition-insensitive highly viscous wormlike micellar solutions formed in anionic and cationic surfactant systems.

    Aramaki, Kenji; Iemoto, Suzuka; Ikeda, Naoaki; Saito, Keitaro


    We investigated phase behavior and rheological properties of aqueous micellar phase formed in water/cocoyl glutamate neutralized with triethanol amine (CGT-n)/hexadecyl trimethylammonium salt (CTAB or CTAC) systems, where n is a degree of neutralization. Micellar phase appears in wide composition range with respect to the surfactant mixing fraction in ternary phase diagrams at 25 degrees C. At high mixing fraction of cationic surfactant in the water/CGT-n/CTAB systems, one can observe a highly viscous micellar phase in which worm-like micelles are expected to form. Contrary to conventional systems in which worm-like micelles are formed, the zero-shear viscosity of the micellar solution in the water/CGT-n/CTAB system with n=1.2 increases with the addition of cationic cosurfactant and once decreases after a maximum, then increases again and decreases after the second maximum. At n=1.5 and 2, highly viscous solution is observed in the relatively wide range of surfactant mixing fraction instead of two maxima of the viscosity curve observed at n=1.2. In the case of CTAC instead of CTAB we can observe narrow composition range for the maximum viscosity. Frequency sweep measurements were performed on the highly viscous samples in the water/CGT-1.5/CTAB system. Typical viscoelastic behavior of worm-like micellar solutions is observed; i.e. the curves of storage (G') and loss (G") moduli make a crossover and the data points of G' and G" can be fitted to the Maxwell model. Relaxation time against the mixing fraction of two surfactants behaves similarly to the zero-shear viscosity change, whereas the plateau modulus continuously increases in the plateau region for the zero-shear viscosity curve.

  12. Recycled aggregates concrete: aggregate and mix properties

    González-Fonteboa, B.


    Full Text Available This study of structural concrete made with recycled concrete aggregate focuses on two issues: 1. The characterization of such aggregate on the Spanish market. This involved conducting standard tests to determine density, water absorption, grading, shape, flakiness and hardness. The results obtained show that, despite the considerable differences with respect to density and water absorption between these and natural aggregates, on the whole recycled aggregate is apt for use in concrete production. 2. Testing to determine the values of basic concrete properties: mix design parameters were established for structural concrete in non-aggressive environments. These parameters were used to produce conventional concrete, and then adjusted to manufacture recycled concrete aggregate (RCA concrete, in which 50% of the coarse aggregate was replaced by the recycled material. Tests were conducted to determine the physical (density of the fresh and hardened material, water absorption and mechanical (compressive strength, splitting tensile strength and modulus of elasticity properties. The results showed that, from the standpoint of its physical and mechanical properties, concrete in which RCA accounted for 50% of the coarse aggregate compared favourably to conventional concrete.

    Se aborda el estudio de hormigones estructurales fabricados con áridos reciclados procedentes de hormigón, incidiéndose en dos aspectos: 1. Caracterización de tales áridos, procedentes del mercado español. Para ello se llevan a cabo ensayos de densidad, absorción, granulometría, coeficiente de forma, índice de lajas y dureza. Los resultados obtenidos han puesto de manifiesto que, a pesar de que existen diferencias notables (sobre todo en cuanto a densidad y absorción con los áridos naturales, las características de los áridos hacen posible la fabricación de hormigones. 2. Ensayos sobre propiedades básicas de los hormigones: se establecen parámetros de dosificaci

  13. Protein Colloidal Aggregation Project

    Oliva-Buisson, Yvette J. (Compiler)


    To investigate the pathways and kinetics of protein aggregation to allow accurate predictive modeling of the process and evaluation of potential inhibitors to prevalent diseases including cataract formation, chronic traumatic encephalopathy, Alzheimer's Disease, Parkinson's Disease and others.

  14. Aggregation and Averaging.

    Siegel, Irving H.

    The arithmetic processes of aggregation and averaging are basic to quantitative investigations of employment, unemployment, and related concepts. In explaining these concepts, this report stresses need for accuracy and consistency in measurements, and describes tools for analyzing alternative measures. (BH)

  15. Cell aggregation and sedimentation.

    Davis, R H


    The aggregation of cells into clumps or flocs has been exploited for decades in such applications as biological wastewater treatment, beer brewing, antibiotic fermentation, and enhanced sedimentation to aid in cell recovery or retention. More recent research has included the use of cell aggregation and sedimentation to selectively separate subpopulations of cells. Potential biotechnological applications include overcoming contamination, maintaining plasmid-bearing cells in continuous fermentors, and selectively removing nonviable hybridoma cells from perfusion cultures.

  16. Familial aggregation and childhood blood pressure.

    Wang, Xiaoling; Xu, Xiaojing; Su, Shaoyong; Snieder, Harold


    There is growing concern about elevated blood pressure (BP) in children. The evidence for familial aggregation of childhood BP is substantial. Twin studies have shown that a large part of the familial aggregation of childhood BP is due to genes. The first part of this review provides the latest progress in gene finding for childhood BP, focusing on the combined effects of multiple loci identified from the genome-wide association studies on adult BP. We further review the evidence on the contribution of the genetic components of other family risk factors to the familial aggregation of childhood BP including obesity, birth weight, sleep quality, sodium intake, parental smoking, and socioeconomic status. At the end, we emphasize the promise of using genomic-relatedness-matrix restricted maximum likelihood (GREML) analysis, a method that uses genome-wide data from unrelated individuals, in answering a number of unsolved questions in the familial aggregation of childhood BP.

  17. Active matter model of Myxococcus xanthus aggregation

    Patch, Adam; Bahar, Fatmagul; Liu, Guannan; Thutupalli, Shashi; Welch, Roy; Yllanes, David; Shaevitz, Joshua; Marchetti, M. Cristina

    Myxococcus xanthus is a soil-dwelling bacterium that exhibits several fascinating collective behaviors including streaming, swarming, and generation of fruiting bodies. A striking feature of M. xanthus is that it periodically reverses its motility direction. The first stage of fruiting body formation is characterized by the aggregation of cells on a surface into round mesoscopic structures. Experiments have shown that this aggregation relies heavily on regulation of the reversal rate and local mechanical interactions, suggesting motility-induced phase separation may play an important role. We have adapted self-propelled particle models to include cell reversal and motility suppression resulting from sporulation observed in aggregates. Using 2D molecular dynamics simulations, we map the phase behavior in the space of Péclet number and local density and examine the kinetics of aggregation for comparison to experiments.

  18. A new application of micellar liquid chromatography in the determination of free ampicillin concentration in the drug-human serum albumin standard solution in comparison with the adsorption method.

    Stępnik, Katarzyna E; Malinowska, Irena; Maciejewska, Małgorzata


    The determination of free drug concentration is a very important issue in the field of pharmacology because only the unbound drug fraction can achieve a pharmacological effect. Due to the ability to solubilize many different compounds in micellar aggregates, micellar liquid chromatography (MLC) can be used for direct determination of free drug concentration. Proteins are not retained on the stationary phase probably due to the formation of protein - surfactant complexes which are excluded from the pores of stationary phase. The micellar method is simple and fast. It does not require any pre-preparation of the tested samples for analysis. The main aim of this paper is to demonstrate a completely new applicability of the analytical use of MLC concerning the determination of free drug concentration in the standard solution of human serum albumin. The well-known adsorption method using RP-HPLC and the spectrophotometric technique was applied as the reference method. The results show that the free drug concentration value obtained in the MLC system (based on the RP-8 stationary phase and CTAB) is similar to that obtained by the adsorption method: both RP-HPLC (95.83μgmL(-1), 79.86% of free form) and spectrophotometry (95.71μgmL(-1), 79.76%). In the MLC the free drug concentration was 93.98μgmL(-1) (78.3%). This indicates that the obtained results are within the analytical range of % of free ampicillin fraction and the MLC with direct sample injection can be treated like a promising method for the determination of free drug concentration.

  19. Micellar and sub-micellar ultra-high performance liquid chromatography of hydroxybenzoic acid and phthalic acid positional isomers.

    Fasciano, Jennifer M; Danielson, Neil D


    Micellar liquid chromatography (MLC) has been used primarily for the separation of neutral analytes of varying polarities, most commonly phenols and polyaromatic hydrocarbons, but does not seem to have been used to study aromatic hydroxy acids in detail. We have studied the separation of hydroxybenzoic acid mixtures, including monohydroxybenzoic and dihydroxybenzoic acid positional isomers by MLC. Sodium dodecylsulfate (SDS) is investigated as the modifying surfactant on a C18 ultra-high performance liquid chromatography (UHPLC) column (100 × 2.1mm, 1.8 μm). The addition of only SDS (no organic solvent) to the mobile phase reduced the influence of hydrophobic interactions while improving the retention times, resolution, and peak shapes, even at concentrations below the critical micellization concentration (CMC). The UHPLC separation of 7 hydroxybenzoic acids, including 6 dihydroxybenzoic acid positional isomers and one trihydroxybenzoic acid, is achieved with high efficiency using 0.1% SDS in 1.84 mM sulfuric acid (pH 2.43) mobile phase, in less than 6 min with a flow rate of 0.3 mL min(-1), and in less than four min with a flow rate of 0.7 mL min(-1). Six monohydroxybenzoic acid isomers are also effectively separated by MLC, using a 0.5% SDS mobile phase modifier, in less than 20 min with a flow rate of 0.3 mL min(-1), and in less than 14 min with a flow rate of 0.7 mL min(-1). The 3 phthalic acid isomers could be separated using a similar mobile phase and flow rates in less than 6 and 4 min. Solute-micelle equilibrium constants and partition coefficients are calculated for 6 monohydroxybenzoic acids based on a plot of MLC retention factor vs. mobile phase micelle concentration. All aromatic acid isomers studied can be classified as binding solutes in the MLC retention mechanism. Less effective separations are observed with shorter chain surfactants, leading to higher retention times and poor peak shapes. It is concluded that increasing chain length led to more


    Micellar electrokinetic chromatography (MEKC) with laser-induced fluorescence (LIF) detection was used for the trace analysis of phenoxy acid herbicides. Capillary electrophoresis (CE) with LIF detection, which has not previously been used for pesticide analysis, overcomes the po...

  1. Penn Grade Micellar Displacement Project. Third annual report, June 1977--June 1978. [Lawry project in Bradford field

    Danielson, H.H.; Paynter, W.T.; Ondrusek, P.S.; Finalle, L.L.


    During third year operations of the jointly funded Penn Grade Micellar Displacement Project, the plant facilities were completed for the 24-acre test designated Phase II. The transient testing program and the pre-flush brine and micellar slug injection stages were all completed. Biopolymer injection was initiated. This report details the development, testing, and operations of Phase II, as well as plans for continuing the test.

  2. Thermodynamic analysis of unimer-micelle and sphere-to-rod micellar transitions of aqueous solutions of sodium dodecylbenzenesulfonate


    Temperature dependence of specific conductivity of sodium dodecylbenzenesulfonate (NaDBS) aqueous solutions was analyzed. Two breaks on the plot appeared for all temperature, which suggest two micellar transitions. This has been corroborated by surface tension measurements. The first transition concentration occurs at the critical micelle concentration (CMC), whilst the second critical concentration (so-called transition micellar concentration, TMC) is due to a sphere-to-rod micelles transiti...

  3. Optical dynamics of molecular aggregates

    de Boer, Steven


    The subject of this thesis is the spectroscopy and dynamics of molecular aggregates in amorphous matrices. Aggregates of three different molecules were studied. The molecules are depicted in Fig. (1.1). Supersaturated solutions of these molecules show aggregate formation. Aggregation is a process si

  4. Observing Convective Aggregation

    Holloway, Christopher E.; Wing, Allison A.; Bony, Sandrine; Muller, Caroline; Masunaga, Hirohiko; L'Ecuyer, Tristan S.; Turner, David D.; Zuidema, Paquita


    Convective self-aggregation, the spontaneous organization of initially scattered convection into isolated convective clusters despite spatially homogeneous boundary conditions and forcing, was first recognized and studied in idealized numerical simulations. While there is a rich history of observational work on convective clustering and organization, there have been only a few studies that have analyzed observations to look specifically for processes related to self-aggregation in models. Here we review observational work in both of these categories and motivate the need for more of this work. We acknowledge that self-aggregation may appear to be far-removed from observed convective organization in terms of time scales, initial conditions, initiation processes, and mean state extremes, but we argue that these differences vary greatly across the diverse range of model simulations in the literature and that these comparisons are already offering important insights into real tropical phenomena. Some preliminary new findings are presented, including results showing that a self-aggregation simulation with square geometry has too broad distribution of humidity and is too dry in the driest regions when compared with radiosonde records from Nauru, while an elongated channel simulation has realistic representations of atmospheric humidity and its variability. We discuss recent work increasing our understanding of how organized convection and climate change may interact, and how model discrepancies related to this question are prompting interest in observational comparisons. We also propose possible future directions for observational work related to convective aggregation, including novel satellite approaches and a ground-based observational network.

  5. Conformational transition and mass transfer in extraction of proteins by AOT--alcohol--isooctane reverse micellar systems.

    Hong, D P; Lee, S S; Kuboi, R


    We examined quantitatively the effect of alcohols on protein and reverse micellar structure. We used circular dichroism (CD) to compare the effects of various alcohols on the protein structure, and percolation phenomena to evaluate the effects of various alcohols on reverse micellar structure. Upon the addition of alcohols to the bulk aqueous phase, proteins were denatured significantly, depending on the alcohol species and concentration, suggesting that use of alcohol directly to the stripping solution is not effective in back-extraction processes of proteins. In the present study, a new method, a small amount of alcohol is added to the surfactant-organic solution to improve the back-extraction behaviors of proteins. Practically, in the back-extraction process, the alcohols suppressing the cluster formation of reverse micelles (high value of beta1), remarkably improved the back-extraction behavior of proteins. In addition, the same alcohol molecules showed a positive effect on the rate and fraction of protein back-extraction. From a result of the CD measurement of the back-extracted proteins, it was known that the alcohols added to reverse micellar solution allowed the proteins to back-extract safely without causing structural changes. These results show that the values of beta(t), defined by the variation of percolation processes, and the back-extraction behaviors of proteins have a good relationship, suggesting that the back-extraction processes were controlled by the micellar-micellar and protein-micellar interactions.

  6. Simultaneous optimization of variables influencing selectivity and elution strength in micellar liquid chromatography. Effect of organic modifier and micelle concentration.

    Strasters, J K; Breyer, E D; Rodgers, A H; Khaledi, M G


    Previously, the simultaneous enhancement of separation selectivity with elution strength was reported in micellar liquid chromatography (MLC) using the hybrid eluents of water-organic solvent-micelles. The practical implication of this phenomenon is that better separations can be achieved in shorter analysis times by using the hybrid eluents. Since both micelle concentration and volume fraction of organic modifier influence selectivity and solvent strength, only an investigation of the effects of a simultaneous variation of these parameters will disclose the full separation capability of the method, i.e. the commonly used sequential solvent optimization approach of adjusting the solvent strength first and then improving selectivity in reversed-phase liquid chromatography is inefficient for the case of MLC with the hybrid eluents. This is illustrated in this paper with two examples: the optimization of the selectivity in the separation of a mixture of phenols and the optimization of a resolution-based criterion determined for the separation of a number of amino acids and small peptides. The large number of variables involved in the separation process in MLC necessitates a structured approach in the development of practical applications of this technique. A regular change in retention behavior is observed with the variation of the surfactant concentration and the concentration of organic modifier, which enables a successful prediction of retention times. Consequently interpretive optimization strategies such as the interative regression method are applicable.

  7. An Identity Based Aggregate Signature from Pairings

    Yike Yu


    Full Text Available An aggregate signature is a useful digital signature that supports aggregation: Given n signatures on n distinct messages from n distinct users, aggregate signature scheme is possible to aggregate all these signature into a single short signature. This single signature, along with the n original messages will convince any verifier that the n users did indeed sign the n original messages respectively (i.e., for i=1,...,n user i signed message  mi. In this paper, we propose an identity based aggregate signature scheme which requires constant pairing operations in the verification and the size of aggregate signature is independent of the number of signers. We prove that the proposed signature scheme is secure against existential forgery under adaptively chosen message and identity attack in the random oracle model assuming the intractability of the computational Diffie-Hellman problem.

  8. Modeling transport and aggregation of volcanic ash particles

    Costa, Antonio; Folch, Arnau; Macedonio, Giovanni; Durant, Adam


    A complete description of ash aggregation processes in volcanic clouds is an very arduous task and the full coupling of ash transport and ash aggregation models is still computationally prohibitive. A large fraction of fine ash injected in the atmosphere during explosive eruptions aggregate because of complex interactions of surface liquid layers, electrostatic forces, and differences in settling velocities. The formation of aggregates of size and density different from those of the primary particles dramatically changes the sedimentation dynamics and results in lower atmospheric residence times of ash particles and in the formation of secondary maxima of tephra deposit. Volcanic ash transport models should include a full aggregation model accounting for all particle class interaction. However this approach would require prohibitive computational times. Here we present a simplified model for wet aggregation that accounts for both atmospheric and volcanic water transport. The aggregation model assumes a fractal relationship for the number of primary particles in aggregates, average efficiencies factors, and collision frequency functions accounting for Brownian motion, laminar and turbulent fluid shear, and differential settling velocity. We implemented the aggregation model in the WRF+FALL3D coupled modelling system and applied it to different eruptions where aggregation has been recognized to play an important role, such as the August and September 1992 Crater Peak eruptions and the 1980 Mt St Helens eruption. Moreover, understanding aggregation processes in volcanic clouds will contribute to mitigate the risks related with volcanic ash transport and sedimentation.

  9. Fractal dimension and mechanism of aggregation of apple juice particles.

    Benítez, E I; Lozano, J E; Genovese, D B


    Turbidity of freshly squeezed apple juice is produced by a polydisperse suspension of particles coming from the cellular tissue. After precipitation of coarse particles by gravity, only fine-colloidal particles remain in suspension. Aggregation of colloidal particles leads to the formation of fractal structures. The fractal dimension is a measure of the internal density of these aggregates and depends on their mechanism of aggregation. Digitized images of primary particles and aggregates of depectinized, diafiltered cloudy apple juice were obtained by scanning electron microscopy (SEM). Average radius of the primary particles was found to be a = 40 ± 11 nm. Maximum radius of the aggregates, R(L), ranged between 250 and 7750 nm. Fractal dimension of the aggregates was determined by analyzing SEM images with the variogram method, obtaining an average value of D(f) = 2.3 ± 0.1. This value is typical of aggregates formed by rapid flocculation or diffusion limited aggregation. Diafiltration process was found to reduce the average size and polydispersity of the aggregates, determined by photon correlation spectroscopy. Average gyration radius of the aggregates before juice diafiltration was found to be R(g) = 629 ± 87 nm. Average number of primary particles per aggregate was calculated to be N = 1174.

  10. Fractals of Silica Aggregates

    ZhinhongLi; DongWu; Yuhansun; JunWang; YiLiu; BaozhongDong; Zhinhong


    Silica aggregates were prepared by base-catalyzed hydrolysis and condensation of alkoxides in alcohol.Polyethylene glycol(PEG) was used as organic modifier.The sols were characterized using Small Angle X-ray Scattering (SAXS) with synchrotron radiation as X-ray source.The structure evolution during the sol-gel process was determined and described in terms of the fractal geometry.As-produced silica aggregates were found to be mass fractals.The fractl dimensions spanned the regime 2.1-2.6 corresponding to more branched and compact structures.Both RLCA and Eden models dominated the kinetic growth under base-catalyzed condition.

  11. Investigating cold gelation properties of recombined highly concentrated micellar casein concentrate and cream for use in cheese making.

    Lu, Y; McMahon, D J; Vollmer, A H


    Highly concentrated micellar casein concentrate (HC-MCC), a potential ingredient for cheese making, contains ~20% casein with ~70% of serum proteins removed by microfiltration and diafiltration of skim milk, followed by vacuum evaporation. Our objective was to investigate cold gelation properties of recombined concentrated milk (RCM) by mixing thawed frozen HC-MCC and cream under different casein levels, pH, and protein-to-fat ratios, and with addition of sodium citrate or calcium. The HC-MCC was recombined with cream using low shear at 50°C for 30 min, and rheological measurements were conducted. Cold-gelling temperature [the temperature at which storage modulus (G')=loss modulus (G″)] was linearly correlated with casein levels from 8.6 to 11.5% (R(2)=0.71), pH from 6.6 to 7.0 (R(2)=0.96), and addition of sodium citrate from 0 to 0.36mmol/g of casein (R(2)=0.80). At pH 7.0, gelation occurred at 12, 26, and 38°C with 9, 10, and 11% casein, respectively. At pH 6.6, 6.8, and 7.0, RCM with 12% casein gelled at a mean temperature of 12, 26, and 37°C, respectively. Adding calcium chloride at 0.17mmol/g of casein significantly increased cold-gelling temperature from 18 to ≥50°C, whereas no significant change was observed at levels up to 0.12mmol/g of casein. Different protein to fat ratios ranging from 0.8 to 1.2 did not significantly influence gelling temperature. In transmission electron micrographs of RCM with 12% casein, casein micelles were nonspherical and partially dissociated into small protein strands. Upon addition of calcium chloride at 0.21mmol/g of casein, casein micelles were more spherical and retained colloidal structure with the presence of aggregated casein micelles. These gelation processes of RCM with or without addition of trisodium citrate were both reversible. We propose that cold gelation of RCM occurs when protein strands that have been partially released from the casein micelles entangle, restrict their mobility, and form a fine

  12. Pseudo Peak Phenomena in Micellar Electrokinetic Capillary Chromatography by Using Ionic Surfactant


    The origin of pseudo peak was studied by means of micellar electrokinetic capillary chromatography with cetyltrimethylaminium bromide as the pseudo stationary phase. It has been pointed that two peaks may appear for one component under certain conditions. Experiments showed that the relative areas of the two peaks of analyte depended on the time and the temperature of reaction between analyte and surfactant, and the concentration of surfactant in the sample solution. It means that the interaction between the analyte and the surfactant is a slow process, and a stable substance can be produced from the interaction. It is the substance and the analyte that may lead to the formation of two peaks. The fast interaction mechanism between the solute and the micellar should be queried from the experiment result.

  13. Study of Micellar-Enhanced Ultrafiltration. Progress report, March 1, 1985-February 28, 1986

    Scamehorn, J.F.; Christian, S.D.


    The feasibility of Micellar-Enhanced Ultrafiltration (MEUF) to remove dissolved organics from water has been established. One of the first tasks was to determine the best surfactant to use in MEUF for various situations. From a thorough analysis of the properties and characteristics of a variety of surfactants, combined with preliminary runs with several surfactants, cationic surfactants were determined to be the best surfactant for general use in MEUF. Further, cetylpyridinium chloride was identifid as a near-optimum surfactant in most applications. Therefore, all further studies reported used this surfactant. Elimination of surfactant type as a variable permits more detailed investigation of other important variables. A major effort has been made to develop techniques for measuring the extent of solubilization of organic solutes by aqueous micellar systems. An important accomplishment during the past year has been the development of the so-called semi-equilibrium dealysis (SED) technique for studying solubilization.

  14. Pseudo Peak Phenomena in Micellar Electrokinetic Capillary Chromatography by Using Ionic Surfactant

    CHENGuan-hua; YANGGeng-liang; TIANYi-ling; CHENYi


    The origin of pseudo peak was studied by means of micellar electrokinetic capillary chromatography with cetyltrimethylaminium bormide as the pseudo stationary phase.It has been pointed that two peaks may appear for one component under certain conditions.Experiments showed that the relative areas of the two peaks of analyte depended on the time and the temperature of reaction between analyte and surfactant,and the concentration of surfactant in the sample solution.It means that the interaction between the analyte and the surfactant is a slow process,and a stable substance can be produced from the interaction.It is the substance and the analyte that may lead to the formation of two peaks.The fast interaction mechanism between the solute and the micellar should be queried from the experiment result.

  15. A core cross-linked polymeric micellar platium(IV) prodrug with enhanced anticancer efficiency.

    Hou, Jie; Shang, Jincai; Jiao, Chengbin; Jiang, Peiyue; Xiao, Huijie; Luo, Lan; Liu, Tongjun


    A core cross-linked polymeric micellar cisplatin(IV) conjugate prodrug is prepared by attaching the cisplatin(IV) to mPEG-b-PLL biodegradable copolymers to form micellar nanoparticles that can disintegrate to release the active anticancer agent cisplatin(II) in a mild reducing environment. Moreover, in vitro studies show that this cisplatin(IV) conjugate prodrug displays enhanced cytotoxicity against HepG2 cancer cells compared with cisplatin(II). Further studies demonstrate that the high cellular uptake and platinum-DNA adduct of this cisplatin(IV) conjugate prodrug can induce more cancer-cell apoptosis than cisplatin(II), which is responsible for its enhanced anticancer activity.

  16. Nanoparticles of complex metal oxides synthesized using the reverse-micellar and polymeric precursor routes

    Ashok K Ganguli; Tokeer Ahmad; Padam R Arya; Pika Jha


    Current interest in the properties of materials having grains in the nanometer regime has led to the investigation of the size-dependent properties of various dielectric and magnetic materials. We discuss two chemical methods, namely the reverse-micellar route and the polymeric citrate precursor route used to obtain homogeneous and monophasic nanoparticles of several dielectric oxides like BaTiO3, Ba2TiO4, SrTiO3, PbTiO3, PbZrO3 etc. In addition we also discuss the synthesis of some transition metal (Mn and Cu) oxalate nanorods using the reverse-micellar route. These nanorods on decomposition provide a facile route to the synthesis of transition metal oxide nanoparticles. We discuss the size dependence of the dielectric and magnetic properties in some of the above oxides.

  17. Structural micellar transition for fluorinated and hydrogenated sodium carboxylates induced by solubilization of benzyl alcohol.

    González-Pérez, Alfredo; Ruso, Juan M; Prieto, Gerardo; Sarmiento, Félix


    The solubility of benzyl alcohol in micellar solutions of sodium octanoate and sodium perfluorooctanoate was studied. From the isotherms of specific conductivity versus molality at different alcohol concentrations, the critical micelle concentration and the degree of ionization of the micelles were determined. The cmc linearly decreases upon increasing the amount of benzyl alcohol present in aqueous solutions with two distinct slopes. This phenomenon was interpreted as a clustering of alcohol molecules above a critical point, around 0.1 mol kg(-1). Attending to the equivalent conductivity versus square root of molality, the presence of a second micellar structure for the fluorinated compound was assumed. The thermodynamic parameters associated with the process of micellization were estimated by applying Motomura's model for binary surfactant mixtures, modified by Pérez-Villar et al. (Colloid Polym. Sci 1990, 268, 965) for the case of alcohol-surfactant solutions. A comparison of the hydrogenated and fluorinated compounds was carried out and discussed.

  18. Mixed-micellar proliposomal systems for enhanced oral delivery of progesterone.

    Potluri, Praveen; Betageri, Guru V


    The objective of our study was to develop a mixed-micellar proliposomal formulation of poorly water-soluble drug progesterone and evaluate the dissolution profile and membrane transport. Several formulations of proliposomes were prepared by mixing different concentrations of lipid, progesterone, polysorbate 80, and microcrystalline cellulose. The mixed-micellar formulation of drug:dimyristoyl-phosphatidycholine:polysorbate 80 (1:20:3.3) exhibited the maximum dissolution (75.27%), while pure progesterone resulted in low dissolution. The above formulation showed a 4-fold increase in transport in Caco-2 cells and a 6-fold increase in transport across the everted rat intestinal sac experiments compared with control. Proliposomal formulations enhance the extent of dissolution and membrane transport of progesterone and serve as ideal carriers for oral delivery of drugs with low water solubility.

  19. Penn Grade Micellar Displacement project. First annual report, June 1975--June 1976

    Danielson, H.H.; Paynter, W.T.; Midkiff, F.R.; Finalle, L.L.


    The main objective of the Penn Grade-ERDA Micellar Displacement Project is to assess and hopefully, demonstrate the feasibility of commercial application of the micellar-polymer process for tertiary oil recovery from a rather large, but relatively ''tight'' section of the Bradford Third Sand. The initial phase of this project involves pertinent core and field injectivity measurements from a freshly drilled well, as a basis for assessing the feasibility of a small demonstration test flood to be performed under Phase II. This report details the work done and results obtained under Phase I (Injectivity Test) completed during the first year of the project. These results, having indicated that the pattern test envisaged under Phase II is indeed feasible, work is now in progress to carry the project to the pattern test phase, in pursuit of project goals.

  20. Interfacial properties of nonionic micellar agregates as a function of temperatures and concentrations

    Falconi, L; Briganti, G; D'Arrigo, G; Falconi, Luca; Maccarini, Marco; Briganti, Giuseppe; Arrigo, Giovanni D'


    By means of density, dielectric spectroscopy and sound velocity measurements we perform a systematic study on the polyoxyethylene $C_{12}E_{6}$ nonionic surfactant solutions as a function of temperature and concentration. Both density and sound velocity data, at about $34^{\\circ}C$, coincide with the value obtained for pure water. Above this temperature the density is lower than the water density whereas below it is greater, the opposite happens for the compressibility. Combining results from these different techniques we tempt a very detailed description of the evolution of the micellar interfacial properties with temperature. It is well known that nonionic surfactant solutions dehydrate, growing temperature. Our results indicate that this process is associated with a continuous change in the polymer conformation and in the local density of the micellar interface.

  1. Interaction of antihypertensive drug amiloride with metal ions in micellar medium using fluorescence spectroscopy

    Gujar, Varsha; Pundge, Vijaykumar; Ottoor, Divya, E-mail:


    Steady state and life time fluorescence spectroscopy have been employed to study the interaction of antihypertensive drug amiloride with biologically important metal ions i.e. Cu{sup 2+}, Fe{sup 2+}, Ni{sup 2+} and Zn{sup 2+} in various micellar media (anionic SDS (sodium dodecyl sulfate), nonionic TX-100 (triton X-100) and cationic CTAB (cetyl trimethyl ammonium bromide)). It was observed that fluorescence properties of drug remain unaltered in the absence of micellar media with increasing concentration of metal ions. However, addition of Cu{sup 2+}, Fe{sup 2+} and Ni{sup 2+} caused fluorescence quenching of amiloride in the presence of anionic micelle, SDS. Binding of drug with metal ions at the charged micellar interface could be the possible reason for this pH-dependent metal-mediated fluorescence quenching. There were no remarkable changes observed due to metal ions addition when drug was present in cationic and nonionic micellar medium. The binding constant and bimolecular quenching constant were evaluated and compared for the drug–metal complexes using Stern–Volmer equation and fluorescence lifetime values. - Highlights: • Interaction of amiloride with biologically important metal ions, Fe{sup 2+}, Cu{sup 2+}, Ni{sup 2+} and Zn{sup 2+}. • Monitoring the interaction in various micelle at different pH by fluorescence spectroscopy. • Micelles acts as receptor, amiloride as transducer and metal ions as analyte in the present system. • Interaction study provides pH dependent quenching and binding mechanism of drug with metal ions.

  2. Micellar properties and surface activity of some bolaform drugs in aqueous solution.

    Attwood, D; Natarajan, R


    The micellar properties of a series of dicationic drugs with structures resembling those of the bolaform electrolytes have been examined using light scattering, surface tension and conductivity techniques. The compounds investigated included, demecarium bromide, ambenonium chloride, dequalinium acetate, distigmine bromide and chlorhexidine acetate. Demecarium and dequalinium formed micelles at critical concentrations of 9 x 10(-3) and 4 x 10(-3) mol kg-1 respectively. No significant association of chlorhexidine acetate could be detected, contrary to previous reports.

  3. Applying Theoretical Approach for Predicting the Selective Calcium Channel Blockers Pharmacological Parameter by Biopartitioning Micellar Chromatography

    WANG Su-Min; YANG Geng-Liang; LI Zhi-Wei; LIU Hai-Yan; GUO Hui-Juan


    The usefulness of biopartitioning micellar chromatography (BMC) for predicting oral drug acute toxicity and apparent bioavailability was demonstrated. A logarithmic model (an LD50 model) and the second order polynomial models (apparent bioavailability model) have been obtained using the retention data of the selective calcium channel blockers to predict pharmacological properties of compounds. The use of BMC is simple, reproducible and can provide key information about the acute toxicity and transport properties of new compounds during the drug discovery process.

  4. Studies of Micellar Electrokinetic Chromatography as an Analytical Technique in Pharmaceutical Analysis - an Industrial Perspective

    Stubberud, Karin


    Studies have been performed to evaluate the use of micellar electrokinetic chromatography (MEKC), one mode of capillary electrophoresis (CE), as an analytical technique in industrial pharmaceutical analysis. The potential for using chemometrics for the optimisation of MEKC methods has also been studied as well as the possibilities of coupling MEKC with mass spectrometry (MS). Two methods were developed, one for the determination of ibuprofen and codeine and another for pilocarpine, together ...

  5. Conditions for and characteristics of nonaqueous micellar solutions and microemulsions with ionic liquids

    Zech, Oliver; Kunz, Werner


    Research on nonaqueous microemulsions containing ionic liquids as polar and/or apolar phase, respectively, is growing at a fast rate. One key property of ionic liquids that highlights their potential and their diversification compared to water is their wide liquid temperature range. In this emerging-area review article we survey recent developments in the field of nonaqueous micellar solutions and microemulsions containing ionic liquids in general with a strong emphasis on the effect of tempe...

  6. Geoinformation Generalization by Aggregation

    Tomislav Jogun


    Full Text Available Geoinformation generalization can be divided into model generalization and cartographic generalization. Model generalization is the supervised reduction of data in a model, while cartographic generalization is the reduction of the complexity of map content adapted to the map scale, and/or use by various generalization operators (procedures. The topic of this paper is the aggregation of geoinformation. Generally, aggregation is the joining of nearby, congenial objects, when the distance between them is smaller than the minimum sizes. Most researchers in geoinformation generalization have focused on line features. However, the appearance of web-maps with point features and choropleth maps has led to the development of concepts and algorithms for the generalization of point and polygonal features. This paper considers some previous theoretical premises and actual examples of aggregation for point, line and polygonal features. The algorithms for aggregation implemented in commercial and free GIS software were tested. In the conclusion, unresolved challenges that occur in dynamic cartographic visualizations and cases of unusual geometrical features are highlighted.

  7. Erosion of dust aggregates

    Seizinger, Alexander; Kley, Wilhelm


    Aims: The aim of this work is to gain a deeper insight into how much different aggregate types are affected by erosion. Especially, it is important to study the influence of the velocity of the impacting projectiles. We also want to provide models for dust growth in protoplanetary disks with simple recipes to account for erosion effects. Methods: To study the erosion of dust aggregates we employed a molecular dynamics approach that features a detailed micro-physical model of the interaction of spherical grains. For the first time, the model has been extended by introducing a new visco-elastic damping force which requires a proper calibration. Afterwards, different sample generation methods were used to cover a wide range of aggregate types. Results: The visco-elastic damping force introduced in this work turns out to be crucial to reproduce results obtained from laboratory experiments. After proper calibration, we find that erosion occurs for impact velocities of 5 m/s and above. Though fractal aggregates as ...

  8. Diffusion in aggregated soil.

    Rappoldt, C.


    The structure of an aggregated soil is characterized by the distribution of the distance from an arbitrary point in the soil to the nearest macropore or crack. From this distribution an equivalent model system is derived to which a diffusion model can be more easily applied. The model system consist

  9. Dye-sensitized photo-oxidation of amino acids in reversed micellar membrane mimetic system

    刘剑波; 张复实; 赵瑜; 赵福群; 唐应武; 宋心琦


    The photochemistry of a novel photosensitizer H[TBC(O’Pr)4P(OH)],and the photo-oxidation of amino acids sensitized by H[TBC(OiPr)4P(OH)] have been investigated in the AOT/H2O/toluene reversed micellar system.Absorption and fluorescence measurements indicate that H[TBC(O’Pr)4P(OH)] can interact with the re versed micelles by adsorption to the micellar surface,resulting in the disaggregation of the sensitizer and the enhance ment of its photoactivity.In micellar solutions,H[TBC(O’Pr)4P(OH)] can efficiently photo-generate O2(Type Ⅱ mechanism) and O2(Type Ⅰ mechanism) as shown by stationary photolysis and ESR spin-trapping techniques Amino acids dissolved in water pools of reversed micelles can be photo-oxidized via Type Ⅱ mechanism as sensitized by H[TBC(O’Pr)4P(OH)].The photo-oxidation of tryptophan follows the first-order kinetics,while that of tyrosine is much slower.Kinetic studies of the photodynamic behavior in this microheterogeneous system shows that the micro-heterogeneity can alter the mechani

  10. Isocratic and gradient elution in micellar liquid chromatography with Brij-35.

    Peris-García, Ester; Ortiz-Bolsico, Casandra; Baeza-Baeza, Juan José; García-Alvarez-Coque, María Celia


    Polyoxyethylene(23)lauryl ether (known as Brij-35) is a nonionic surfactant, which has been considered as an alternative to the extensively used in micellar liquid chromatography anionic surfactant sodium lauryl (dodecyl) sulfate, for the analysis of drugs and other types of compounds. Brij-35 is the most suitable nonionic surfactant for micellar liquid chromatography, owing to its commercial availability, low cost, low toxicity, high cloud temperature, and low background absorbance. However, it has had minor use. In this work, we gather and discuss some results obtained in our laboratory with several β-blockers, sulfonamides, and flavonoids, concerning the use of Brij-35 as mobile phase modifier in the isocratic and gradient modes. The chromatographic performance for purely micellar eluents (with only surfactant) and hybrid eluents (with surfactant and acetonitrile) is compared. Brij-35 increases the polarity of the alkyl-bonded stationary phase and its polyoxyethylene chain with the hydroxyl end group allows hydrogen-bond interactions, especially for phenolic compounds. This offers the possibility of using aqueous solutions of Brij-35 as mobile phases with sufficiently short retention times. The use of gradients of acetonitrile to keep the concentration of Brij-35 constant is another interesting strategy that yields a significant reduction in the peak widths, which guarantee high resolution.

  11. Simultaneous isocratic separation of phenolic acids and flavonoids using micellar liquid chromatography.

    Hadjmohammadi, Mohammad Reza; Nazari, S Saman S J


    The simultaneous isocratic separation of a mixture of five phenolic acids and four flavonoids (two important groups of natural polyphenolic compounds with very different polarities) was investigated in three different RPLC modes using a hydro-organic mobile phase, and mobile phases containing SDS at concentrations below and above the critical micellar concentration (submicellar LC and micellar LC (MLC), respectively). In the hydro-organic mode, methanol and acetonitrile; in the submicellar mode methanol; and in the micellar mode, methanol and 1-propanol were examined individually as organic modifiers. Regarding the other modes, MLC provided more appropriate resolutions and analysis time and was preferred for the separation of the selected compounds. Optimization of separation in MLC was performed using an interpretative approach for each alcohol. In this way, the retention of phenolic acids and flavonoids were modeled using the retention factors obtained from five different mobile phases, then the Pareto optimality method was applied to find the best compatibility between analysis time and quality of separation. The results of this study showed some promising advantages of MLC for the simultaneous separation of phenolic acids and flavonoids, including low consumption of organic solvent, good resolution, short analysis time, and no requirement of gradient elution.

  12. Can neutral analytes be concentrated by transient isotachophoresis in micellar electrokinetic chromatography and how much?

    Matczuk, Magdalena; Foteeva, Lidia S; Jarosz, Maciej; Galanski, Markus; Keppler, Bernhard K; Hirokawa, Takeshi; Timerbaev, Andrei R


    Transient isotachophoresis (tITP) is a versatile sample preconcentration technique that uses ITP to focus electrically charged analytes at the initial stage of CE analysis. However, according to the ruling principle of tITP, uncharged analytes are beyond its capacity while being separated and detected by micellar electrokinetic chromatography (MEKC). On the other hand, when these are charged micelles that undergo the tITP focusing, one can anticipate the concentration effect, resulting from the formation of transient micellar stack at moving sample/background electrolyte (BGE) boundary, which increasingly accumulates the analytes. This work expands the enrichment potential of tITP for MEKC by demonstrating the quantitative analysis of uncharged metal-based drugs from highly saline samples and introducing to the BGE solution anionic surfactants and buffer (terminating) co-ions of different mobility and concentration to optimize performance. Metallodrugs of assorted lipophilicity were chosen so as to explore whether their varying affinity toward micelles plays the role. In addition to altering the sample and BGE composition, optimization of the detection capability was achieved due to fine-tuning operational variables such as sample volume, separation voltage and pressure, etc. The results of optimization trials shed light on the mechanism of micellar tITP and render effective determination of selected drugs in human urine, with practical limits of detection using conventional UV detector.

  13. Micellar Packing in Aqueous Solutions of As-Received and Pure Pluronic Block Copolymers

    Ryu, Chang; Park, Han Jin


    Pluronic block copolymers (Pluronics) are produced on a commercial scale to enable wide range of novel applications from emulsification and colloidal stabilization as nonionic surfactants. While the Pluronic block copolymers offer the advantages of being readily available for such applications, it contains non-micellizable low molecular weight (MW) impurities that would interfere with the self-assembly and micellar packing of PEO-PPO-PEO triblock copolymers in aqueous solutions. The impacts of the low MW impurities will be discussed on the micellar packing of Pluronics F108 and F127 solutions, which form BCC and FCC. While as-received Pluronic samples typically contain about 20 wt.% low MW impurities, we were able to reduce the impurity level to less than 2 wt.% using our large scale purification technique. Comparative studies on small angle x-ray scattering (SAXS) experiments on as-received and purified Pluronics solutions revealed that the contents of triblock copolymers in solutions essentially governs the inter-micellar distance of Pluronic cubic structures. A universal relationship between triblock copolymer concentration and SAXS-based domain spacing has been finally discussed. Funding from Agency for Defense Development, Korea.

  14. Structural investigation of viscoelastic micellar water/CTAB/NaNO3 solutions

    K Kuperkar; L Abezgauz; D Danino; G Verma; P A Hassan; V K Aswal; D Varade; P Bahadur


    A highly viscoelastic worm-like micellar solution is formed in hexa-decyltrimethylammonium bromide (CTAB) in the presence of sodium nitrate (NaNO3). A gradual increase in micellar length with increasing NaNO3 was assumed from the rheological measurements where the zero-shear viscosity (0) versus NaNO3 concentration curve exhibits a maximum. However, upon increase in temperature, the viscosity decreases. Changes in the structural parameters of the micelles with addition of NaNO3 were inferred from small angle neutron scattering measurements (SANS). The intensity of scattered neutrons in the low region was found to increase with increasing NaNO3 concentration. This suggests an increase in the size of the micelles and/or decrease of intermicellar interaction with increasing salt concentration. Analysis of the SANS data using prolate ellipsoidal structure and Yukawa form of interaction potential between mi-celles indicate that addition of NaNO3 leads to a decrease in the surface charge of the ellipsoidal micelles which induces micellar growth. Cryo-TEM measurements support the presence of thread-like micelles in CTAB and NaNO3.

  15. Polymeric micellar nanocarriers of benzoyl peroxide as potential follicular targeting approach for acne treatment.

    Kahraman, Emine; Özhan, Gül; Özsoy, Yıldız; Güngör, Sevgi


    The aim of this work was to optimize polymeric nano-sized micellar carriers of the anti-acne compound benzoyl peroxide (BPO) and to examine the ability of these carriers to deposit into hair follicles with the objective of improving skin delivery of BPO. BPO loaded polymeric micelles composed of Pluronic(®) F127 were prepared by the thin film hydration method and characterized in terms of size, loading capacity, morphology and physical stability. The optimized micelle formulation was then selected for skin delivery studies. The penetration of BPO loaded micellar carriers into skin and skin appendages across full thickness porcine skin was examined in vitro. Confocal microscopy images confirmed the penetration of Nile Red into hair follicles, which was loaded into micellar carriers as a model fluorescent compound. The relative safety of the polymeric micelles was evaluated with the MTT viability test using mouse embryonic fibroblasts. The results indicated that nano-sized polymeric micelles of BPO composed of Pluronic(®) F127 offer a potential approach to enhance skin delivery of BPO and that targeting of micelles into hair follicles may be an effective and safe acne treatment.

  16. Bell Creek Field micellar-polymer pilot demonstration. Fourth annual report, October 1979-September 1980

    Goldburg, A.


    The pilot is a contained 40-acre 5-spot located in a representative watered-out portion of the Unit A Reservoir. The pay is sandstone with an average net pay of 6.4 feet, air permeability of 1050 md, and water TDS of 2500 ppM. The average remaining oil saturation in the 40-acre pilot area was estimated to be 28% at the start of chemical injection. The Pilot has four injectors (Wells MPP-1, MPP-2, MPP-3, and MPP-4) and one producer (Well 12-1). The overall micellar-polymer oil recovery is estimated at 47% of the remaining oil at the initiation of the micellar-polymer flood. In the fourth contract year, micellar slug injection was completed and injection of the graded mobility buffer began. A second radioactive/chemical tracer test was begun at the start of the polymer phase. A delay of approximately one year was experienced during the reservoir description phase. Otherwise, the project has remained on schedule.

  17. Bell Creek Fiel micellar-polymer pilot demonstration first annual report, July 1976--September 1977


    A Pilot Demonstration is being conducted to determine whether micellar-polymer flooding is an economically feasible technique for enhanced oil recovery from the Muddy Sand Unit ''A'' Reservoir of the Bell Creek Field, Powder River and Carter Counties, Montana. During the first year of this project extensive reservoir studies, site and pattern selection, design and selection of an optimal micellar-polymer system, water flood history matching and preliminary process simulations by numerical models, and development of pilot injection and production wells were completed. The major effort during the first contract year was the design for the Bell Creek pilot of two optimal micellar-polymer processes--one oil-external and one water-external; and the concomitant development of a Selection Methodology by which to decide upon the more suitable process by means of a standard set of laboratory experiments and numerical simulations. This effort was completed. The oil-external design was selected for Bell Creek application based upon its superior performance in the standard test series and simulations. The advantages of the Bell Creek oil-external design appear to be better recovery performance, mobility control, and protection against divalent ions. 30 tables, 41 figs.

  18. Microwave enhanced electroanalysis of formulations: processes in micellar media at glassy carbon and at platinum electrodes.

    Ghanem, Mohamed A; Compton, Richard G; Coles, Barry A; Canals, Antonio; Marken, Frank


    The direct electroanalysis of complex formulations containing alpha-tocopherol (vitamin E) is possible in micellar solution and employing microwave-enhanced voltammetry. In the presence of microwave radiation substantial heating and current enhancement effects have been observed at 330 microm diameter glassy carbon electrodes placed into a micellar aqueous solution and both hydrophilic and highly hydrophobic redox systems are detected. For the water soluble Fe(CN)(6)(3-/4-) redox system in micellar aqueous solutions of 0.1 M NaCl and 0.1 M sodium dodecylsulfate (SDS) at low to intermediate microwave power, thermal effects and convection effects are observed. At higher microwave power, thermal cavitation is induced and dominates the mass transport at the electrode surface. For the micelle-soluble redox systems tert-butylferrocene and 2,5-di-tert-butyl-1,4-benzoquinone, strong and concentration dependent current responses are observed only in the presence of microwave radiation. For the oxidation of micelle-soluble alpha-tocopherol current responses at glassy carbon electrodes are affected by adsorption and desorption processes whereas at platinum electrodes, analytical limiting currents are obtained over a wide range of alpha-tocopherol concentrations. However, for the determination of alpha-tocopherol in a commercial formulation interference from proteins is observed at platinum electrodes and direct measurements are possible only over a limited concentration range and at glassy carbon electrodes.

  19. Mixtures of lecithin and bile salt can form highly viscous wormlike micellar solutions in water.

    Cheng, Chih-Yang; Oh, Hyuntaek; Wang, Ting-Yu; Raghavan, Srinivasa R; Tung, Shih-Huang


    The self-assembly of biological surfactants in water is an important topic for study because of its relevance to physiological processes. Two common types of biosurfactants are lecithin (phosphatidylcholine) and bile salts, which are both present in bile and involved in digestion. Previous studies on lecithin-bile salt mixtures have reported the formation of short, rodlike micelles. Here, we show that lecithin-bile salt micelles can be further induced to grow into long, flexible wormlike structures. The formation of long worms and their resultant entanglement into transient networks is reflected in the rheology: the fluids become viscoelastic and exhibit Maxwellian behavior, and their zero-shear viscosity can be up to a 1000-fold higher than that of water. The presence of worms is further confirmed by data from small-angle neutron and X-ray scattering and from cryo-transmission electron microscopy (cryo-TEM). We find that micellar growth peaks at a specific molar ratio (near equimolar) of bile salt:lecithin, which suggests a strong binding interaction between the two species. In addition, micellar growth also requires a sufficient concentration of background electrolyte such as NaCl or sodium citrate that serves to screen the electrostatic repulsion of the amphiphiles and to "salt out" the amphiphiles. We postulate a mechanism based on changes in the molecular geometry caused by bile salts and electrolytes to explain the micellar growth.

  20. Hydrophobically modified inulin as an amphiphilic carbohydrate polymer for micellar delivery of paclitaxel for intravenous route.

    Muley, Pratik; Kumar, Sunny; El Kourati, Fadoua; Kesharwani, Siddharth S; Tummala, Hemachand


    Micellization offers several advantages for the delivery of water insoluble drugs including a nanoparticulate 'core-shell' delivery system for drug targeting. Recently, hydrophobically modified polysaccharides (HMPs) are gaining recognition as micelle forming polymers to encapsulate hydrophobic drugs. In this manuscript, for the first time, we have evaluated the self-assembling properties of a lauryl carbamate derivative of the poly-fructose natural polymer inulin (Inutec SP1(®) (INT)) to form paclitaxel (PTX) loaded micelles. INT self-assembled into well-defined micellar structures in aqueous environment with a low critical micellar concentration of 27.8 μg/ml. INT micelles exhibited excellent hemocompatibility and low toxicity to cultured cells. PTX loaded INT micelles exhibited a mean size of 256.37 ± 10.45 nm with excellent drug encapsulation efficiency (95.66 ± 2.25%) and loading (8.69 ± 0.22%). PTX loaded micelles also displayed sustained release of PTX and enhanced anti-cancer efficacy in-vitro in mouse melanoma cells (B16F10) compared to Taxol formulation with Cremophor EL as solvent. In addition, PTX loaded INT micelles exhibited comparable in-vivo antitumor activity in B16F10 allograft mouse model at half the dose of Taxol. In conclusion, INT offers safe, inexpensive and natural alternative to widely used PEG-modified polymers for the formulation of micellar delivery systems for paclitaxel.

  1. Micellar Electrokinetic Chromatography with Laser-Induced Fluorescence Detection for Separation of Red and Yellow Historical Dyes

    Shokoufeh Ahmadi


    Full Text Available In this study, the separation parameters in micellar electrokinetic chromatography (MEKC-laser-induced fluorescence (LIF were optimized for the separation of red and yellow historical dyes in 20 mM borate buffer with 20 mM sodium dodecyl sulfate (SDS. Separation conditions were optimized by changing pH, organic modifier (methanol and acetonitrile concentrations and applied voltage. The mixtures of dyes used in this study included four anthraquinone dyes (alizarin, purpurin, emodin and carmine and six flavonoid dyes (luteolin, apigenin, kaempferol, quercetin, morin and myricetin. For this work, dyes were introduced electro-kinetically (10 kV for 5 s into a 50 cm capillary (10 µm id and separated using a running potential of 18, 20, 22 and 25 kV. Absolute limits of detection for most of these dyes was less than 1 pg. For dyes such as alizarin, improved detection limits were achieved at pH = 9.24; however dyes such as purpurin had significantly improved detection limits at pH = 8.0. The successful extraction and identification of a number of dyes in plants and textiles samples is also described.

  2. Fault tolerant aggregation for power system services

    Kosek, Anna Magdalena; Gehrke, Oliver; Kullmann, Daniel


    Exploiting the flexibility in distributed energy resources (DER) is seen as an important contribution to allow high penetrations of renewable generation in electrical power systems. However, the present control infrastructure in power systems is not well suited for the integration of a very large...... number of small units. A common approach is to aggregate a portfolio of such units together and expose them to the power system as a single large virtual unit. In order to realize the vision of a Smart Grid, concepts for flexible, resilient and reliable aggregation infrastructures are required...

  3. Sequence dependent aggregation of peptides and fibril formation

    Hung, Nguyen Ba; Le, Duy-Manh; Hoang, Trinh X.


    Deciphering the links between amino acid sequence and amyloid fibril formation is key for understanding protein misfolding diseases. Here we use Monte Carlo simulations to study the aggregation of short peptides in a coarse-grained model with hydrophobic-polar (HP) amino acid sequences and correlated side chain orientations for hydrophobic contacts. A significant heterogeneity is observed in the aggregate structures and in the thermodynamics of aggregation for systems of different HP sequences and different numbers of peptides. Fibril-like ordered aggregates are found for several sequences that contain the common HPH pattern, while other sequences may form helix bundles or disordered aggregates. A wide variation of the aggregation transition temperatures among sequences, even among those of the same hydrophobic fraction, indicates that not all sequences undergo aggregation at a presumable physiological temperature. The transition is found to be the most cooperative for sequences forming fibril-like structures. For a fibril-prone sequence, it is shown that fibril formation follows the nucleation and growth mechanism. Interestingly, a binary mixture of peptides of an aggregation-prone and a non-aggregation-prone sequence shows the association and conversion of the latter to the fibrillar structure. Our study highlights the role of a sequence in selecting fibril-like aggregates and also the impact of a structural template on fibril formation by peptides of unrelated sequences.

  4. Aggregation in Organic Solutions of Malonamides: Consequences for Water Extraction

    Meridiano, Y.; Berthon, L.; Crozes, X.; Sorel, C. [CEA ValRho, DEN DRCP SCPS LCSE, F-30207 Bagnols Sur Ceze, (France); Dannus, P. [CEA Saclay, INSTN UEIN, F-91191 Gif Sur Yvette, (France); Antonio, M.R.; Chiarizia, R. [Argonne Natl Lab, CSE Div, Argonne, IL 60439 (United States); Zemb, T. [CEA CNRS UM2 ENSCM, Inst Chin Separat Marcoule, Bagnols Sur Ceze, (France)


    The molecular organization of N, N'-dimethyl-N, N'-dioctyl-hexyl-ethoxy-malonamide (DMDOHEMA), the current reference extractant for the DIAMEX (Diamide Extraction) process, is correlated with its water extraction properties from neutral media. The aggregation of DMDOHEMA in n-heptane was investigated by vapor pressure osmometry (VPO) and the aggregate speciation characterized by combined small-angle neutron and X-ray scattering (SANS and SAXS, respectively). Two approaches were taken to model the aggregation of the diamide and the water extraction as a function of the diamide concentration by taking into account a single aggregation equilibrium with an average aggregation number N equal to 4.28 {+-} 0.05; and a competition between two types of aggregates in the organic phase, namely, aggregates of the reverse micelle type with 4 diamides per aggregate, and an oligomeric structure composed of about 10 diamide molecules which appears at high extractant concentration ({>=} 1 mol/L). In both cases, the supramolecular speciation representing the monomers/aggregates distribution was determined, and for each supramolecular organization, a solubilization parameter was calculated using the Sergievskii-Dannus relationship. Thus, the correlation between the two types of micellization of the diamide and the extraction of water into the organic phase was demonstrated. The larger aggregates can extract about five times more water than monomers. (authors)

  5. Solvation dynamics of DCM in a polypeptide-surfactant aggregate: gelatin-sodium dodecyl sulfate.

    Halder, Arnab; Sen, Pratik; Burman, Anupam Das; Bhattacharyya, Kankan


    Solvation dynamics of 4-(dicyanomethylidene)-2-[p-(dimethylamino)styryl]-6-methyl-4H-pyran (DCM) is studied in a polypeptide-surfactant aggregate consisting of gelatin and sodium dodecyl sulfate (SDS) in potassium dihydrogen phosphate (KP) buffer. The average solvation time (tauS) in gelatin-SDS aggregate at 45 degrees C is found to be 1780 ps, which is about 13 times slower than that in 15 mM SDS in KP buffer at the same temperature. The fluorescence anisotropy decay in gelatin-SDS aggregate is also different from that in SDS micelles in KP buffer. DCM displays negligible emission in the presence of gelatin in aqueous solution. Thus the solvation dynamics in the presence of gelatin and SDS is exclusively due to the probe (DCM) molecules at the gelatin-micelle interface. The slow solvation dynamics is ascribed to the restrictions imposed on the water molecules trapped between the polypeptide chain and micellar aggregates. The critical association concentration (cac) of SDS for gelatin is determined to be 0.5 +/- 0.1 mM.

  6. Pyridine Aggregation in Helium Nanodroplets

    Nieto, Pablo; Poerschke, Torsten; Habig, Daniel; Schwaab, Gerhard; Havenith, Martina


    Pyridine crystals show the unusual property of isotopic polymorphism. Experimentally it has been observed that deuterated pyridine crystals exist in two phases while non-deuterated pyridine does not show a phase transition. Therefore, although isotopic substitution is the smallest possible modification of a molecule it greatly affects the stability of pyridine crystals. A possible experimental approach in order to understand this striking effect might be the study of pyridine aggregation for small clusters. By embedding the clusters in helium nanodroplets the aggregates can be stabilized and studied by means of Infrared Depletion Spectroscopy. Pyridine oligomers were investigated in the C-H asymmetric vibration region (2980-3100 cm-1) using this experimental technique. The number of molecules for the clusters responsibles for each band were determined by means of pick-up curves as well as mass sensitive depletion spectra. Furthermore, the intensity dependence of the different bands on applying a dc electric field was studied. The assignment of the different structures for pyridine clusters on the basis of these measurements were also carried out. S. Crawford et al., Angew. Chem. Int. Ed., 48, 755 (2009).

  7. Simulation of red blood cell aggregation in shear flow.

    Lim, B; Bascom, P A; Cobbold, R S


    A simulation model has been developed for red blood cell (RBC) aggregation in shear flow. It is based on a description of the collision rates of RBC, the probability of particles sticking together, and the breakage of aggregates by shear forces. The influence of shear rate, hematocrit, aggregate fractal dimension, and binding strength on aggregation kinetics were investigated and compared to other theoretical and experimental results. The model was used to simulate blood flow in a long large diameter tube under steady flow conditions at low Reynolds numbers. The time and spatial distribution of the state of aggregation are shown to be in qualitative agreement with previous B-mode ultrasound studies in which a central region of low echogenicity was noted. It is suggested that the model can provide a basis for interpreting prior measurements of ultrasound echogenicity and may help relate them to the local state of aggregation.

  8. Aggregation of organic matter by pelagic tunicates

    Pomeroy, L.R. (Univ. of Georgia, Athens); Deibel, D.


    Three genera of pelagic tunicates were fed concentrates of natural seston and an axenic diatom culture. Fresh and up to 4-day-old feces resemble flocculent organic aggregates containing populations of microorganisms, as described from highly productive parts of the ocean, and older feces resemble the nearly sterile flocculent aggregates which are ubiquitous in surface waters. Fresh feces consist of partially digested phytoplankton and other inclusions in an amorphous gelatinous matrix. After 18 to 36 h, a population of large bacteria develops in the matrix and in some of the remains of phytoplankton contained in the feces. From 48 to 96 h, protozoan populations arise which consume the bacteria and sometimes the remains of the phytoplankton in the feces. Thereafter only a sparse population of microorganisms remains, and the particles begin to fragment. Water samples taken in or below dense populations of salps and doliolids contained greater numbers of flocculent aggregates than did samples from adjacent stations.

  9. Proteins aggregation and human diseases

    Hu, Chin-Kun


    Many human diseases and the death of most supercentenarians are related to protein aggregation. Neurodegenerative diseases include Alzheimer's disease (AD), Huntington's disease (HD), Parkinson's disease (PD), frontotemporallobar degeneration, etc. Such diseases are due to progressive loss of structure or function of neurons caused by protein aggregation. For example, AD is considered to be related to aggregation of Aβ40 (peptide with 40 amino acids) and Aβ42 (peptide with 42 amino acids) and HD is considered to be related to aggregation of polyQ (polyglutamine) peptides. In this paper, we briefly review our recent discovery of key factors for protein aggregation. We used a lattice model to study the aggregation rates of proteins and found that the probability for a protein sequence to appear in the conformation of the aggregated state can be used to determine the temperature at which proteins can aggregate most quickly. We used molecular dynamics and simple models of polymer chains to study relaxation and aggregation of proteins under various conditions and found that when the bending-angle dependent and torsion-angle dependent interactions are zero or very small, then protein chains tend to aggregate at lower temperatures. All atom models were used to identify a key peptide chain for the aggregation of insulin chains and to find that two polyQ chains prefer anti-parallel conformation. It is pointed out that in many cases, protein aggregation does not result from protein mis-folding. A potential drug from Chinese medicine was found for Alzheimer's disease.

  10. Analysis of Aggregation Delay for Multisource Sensor Data with On-Off Traffic Pattern in Wireless Body Area Networks

    Kim, Un-Ha; Kong, Eutteum; Choi, Hyun-Ho; Lee, Jung-Ryun


    Data aggregation plays an important role to improve the transmission efficiency in wireless body area networks (WBANs); however, it inherently induces additional aggregation delay. Therefore, the effect of packet aggregation on WBAN applications, which are vulnerable to delay, must be analyzed rigorously. In this paper, we analyze the packet aggregation delay for multisource sensor data with an on-off traffic pattern in WBANs. Considering two operational parameters of the aggregation threshold and aggregation timer, we calculate the probability that a packet aggregation occurs during a unit time and then derive the average aggregation delay in closed-form. The analysis results show that the aggregation delay increases as the aggregation timer or aggregation threshold increases, but is bounded below a certain level according to the number of active sensors and their on-off traffic attribute. This implies that the data aggregation technique can maximize the transmission efficiency while satisfying a given delay requirement in the WBAN system. PMID:27706029

  11. Topological data analysis of biological aggregation models.

    Topaz, Chad M; Ziegelmeier, Lori; Halverson, Tom


    We apply tools from topological data analysis to two mathematical models inspired by biological aggregations such as bird flocks, fish schools, and insect swarms. Our data consists of numerical simulation output from the models of Vicsek and D'Orsogna. These models are dynamical systems describing the movement of agents who interact via alignment, attraction, and/or repulsion. Each simulation time frame is a point cloud in position-velocity space. We analyze the topological structure of these point clouds, interpreting the persistent homology by calculating the first few Betti numbers. These Betti numbers count connected components, topological circles, and trapped volumes present in the data. To interpret our results, we introduce a visualization that displays Betti numbers over simulation time and topological persistence scale. We compare our topological results to order parameters typically used to quantify the global behavior of aggregations, such as polarization and angular momentum. The topological calculations reveal events and structure not captured by the order parameters.

  12. Hydrophobic aggregation of ultrafine kaolinite

    ZHANG Xiao-ping; HU Yue-hua; LIU Run-Qing


    The hydrophobic aggregation of ultrafine kaolinite in cationic surfactant suspension was investigated by sedimentation test, zeta potential measurement and SEM observation. SEM images reveal that kaolinite particles show the self-aggregation of edge-face in acidic media, the aggregation of edge-face and edge-edge in neutral media, and the dispersion in alkaline media due to electrostatic repulsion. In the presence of the dodecylammonium acetate cationic surfactant and in neutral and alkaline suspension, the hydrophobic aggregation of face-face is demonstrated. The zeta potential of kaolinite increases with increasing the concentration of cationic surfactant. The small and loose aggregation at a low concentration but big and tight aggregation at a high concentration is presented At pH=7 alkyl quarterly amine salt CTAB has the best hydrophobic aggregation among three cationic surfactants, namely, dodecylammonium acetate, alkyl quarterly amine salts 1227 and CTAB.

  13. Absorption Spectra of Astaxanthin Aggregates

    Olsina, Jan; Minofar, Babak; Polivka, Tomas; Mancal, Tomas


    Carotenoids in hydrated polar solvents form aggregates characterized by dramatic changes in their absorption spectra with respect to monomers. Here we analyze absorption spectra of aggregates of the carotenoid astaxanthin in hydrated dimethylsulfoxide. Depending on water content, two types of aggregates were produced: H-aggregates with absorption maximum around 390 nm, and J-aggregates with red-shifted absorption band peaking at wavelengths >550 nm. The large shifts with respect to absorption maximum of monomeric astaxanthin (470-495 nm depending on solvent) are caused by excitonic interaction between aggregated molecules. We applied molecular dynamics simulations to elucidate structure of astaxanthin dimer in water, and the resulting structure was used as a basis for calculations of absorption spectra. Absorption spectra of astaxanthin aggregates in hydrated dimethylsulfoxide were calculated using molecular exciton model with the resonance interaction energy between astaxanthin monomers constrained by semi-e...

  14. Non-Arrhenius protein aggregation.

    Wang, Wei; Roberts, Christopher J


    Protein aggregation presents one of the key challenges in the development of protein biotherapeutics. It affects not only product quality but also potentially impacts safety, as protein aggregates have been shown to be linked with cytotoxicity and patient immunogenicity. Therefore, investigations of protein aggregation remain a major focus in pharmaceutical companies and academic institutions. Due to the complexity of the aggregation process and temperature-dependent conformational stability, temperature-induced protein aggregation is often non-Arrhenius over even relatively small temperature windows relevant for product development, and this makes low-temperature extrapolation difficult based simply on accelerated stability studies at high temperatures. This review discusses the non-Arrhenius nature of the temperature dependence of protein aggregation, explores possible causes, and considers inherent hurdles for accurately extrapolating aggregation rates from conventional industrial approaches for selecting accelerated conditions and from conventional or more advanced methods of analyzing the resulting rate data.

  15. First Example of a Lipophilic Porphyrin-Cardanol Hybrid Embedded in a Cardanol-Based Micellar Nanodispersion

    Giuseppe Vasapollo


    Full Text Available Cardanol is a natural and renewable organic raw material obtained as the major chemical component by vacuum distillation of cashew nut shell liquid. In this work a new sustainable procedure for producing cardanol-based micellar nanodispersions having an embedded lipophilic porphyrin itself peripherally functionalized with cardanol substituents (porphyrin-cardanol hybrid has been described for the first time. In particular, cardanol acts as the solvent of the cardanol hybrid porphyrin and cholesterol as well as being the main component of the nanodispersions. In this way a “green” micellar nanodispersion, in which a high percentage of the micellar system is derived from renewable “functional” molecules, has been produced.

  16. Quantitation of antihistamines in pharmaceutical preparations by liquid chromatography with a micellar mobile phase of sodium dodecyl sulfate and pentanol.

    Gil-Agustí, M; Monferrer-Pons, L; Esteve-Romero, J; García-Alvarez-Coque, M C


    A reversed-phase liquid chromatographic procedure with a micellar mobile phase of sodium dodecyl sulfate (SDS), containing a small amount of pentanol, was developed for the control of 7 antihistamines of diverse action in pharmaceutical preparations (tablets, capsules, powders, solutions, and syrups): azatadine, carbinoxamine, cyclizine, cyproheptadine, diphenhydramine, doxylamine, and tripelennamine. The retention times of the drugs were <9 min with a mobile phase of 0.15M SDS-6% (v/v) pentanol. The recoveries with respect to the declared compositions were in the range of 93-110%, and the intra- and interday repeatabilities and interday reproducibility were <1.2%. The results were similar to those obtained with a conventional 60 + 40 (v/v) methanol-water mixture, with the advantage of reduced toxicity, flammability, environmental impact, and cost of the micellar-pentanol solutions. The lower risk of evaporation of the organic solvent dissolved in the micellar solutions also increased the stability of the mobile phase.

  17. Single step purification of lactoperoxidase from whey involving reverse micelles-assisted extraction and its comparison with reverse micellar extraction.

    Nandini, K E; Rastogi, Navin K


    The extraction of lactoperoxidase (EC from whey was studied using single step reverse micelles-assisted extraction and compared with reverse micellar extraction. The reverse micelles-assisted extraction resulted in extraction of contaminating proteins and recovery of lactoperoxidase in the aqueous phase leading to its purification. Reverse micellar extraction at the optimized condition after forward and backward steps resulted in activity recovery of lactoperoxidase and purification factor of the order of 86.60% and 3.25-fold, respectively. Whereas reverse micelles-assisted extraction resulted in higher activity recovery of lactoperoxidase (127.35%) and purification factor (3.39-fold). The sodium dodecyl sulfate polyacrylamide gel electrophoresis (SDS-PAGE) profiles also evidenced that higher purification was obtained in reverse micelles-assisted extraction as compared of reverse micellar extracted lactoperoxidase.

  18. Optical properties and inclusion of an organic fluorophore in organized media of micellar solutions and beta-cyclodextrin

    El-Sayed, Yusif S.


    In this study, we prepared a new chalcone compound (3-(4'-diethylaminophenyl)-1-(2-pyridinyl) prop-2-en-1-one abbreviated as DEAPPP) and examined its characterization and photophysical properties such as singlet absorption, molar absorptivity, fluorescence spectra, and fluorescence quantum yield (ϕf). DEAPPP dye exhibited a large red shift in both absorption and emission spectra as solvent polarity increases, indicating a large change in dipole moment of molecule upon excitation. Also, the fluorescence quantum yield was solvent dependent. The absorption and fluorescence emission spectral properties of DEAPPP have been investigated in organized media of aqueous micellar and β-cyclodextrin (CD) solutions. While the absorption spectra were less sensitive to the nature of the added surfactant or CD, the characteristics of the intramolecular charge transfer (ICT) fluorescence were highly sensitive to the properties of the medium. The ICT maximum was strongly blue-shifted with a great enhancement in the fluorescence quantum yield on adding micellar or CD. This indicated that the solubilization of DEAPPP increased in the micellar core and an inclusion complex with β-CD was formed. The critical micelle concentration (CMC) as well as the polarity of the micellar core of sodium dodecyl sulfate (SDS), Cetyltrimethylammonium bromide (CTAB) and Triton X-100 (TX-100) have been determined. The CMC values were in good agreement with the reported values while the polarity was lower indicating that DEAPPP molecules were incorporated in the micellar core not at the micellar interface. The binding constants of DEAPPP: micelles or DEAPPP: CD complexes have been also determined.

  19. Research on Judgment Aggregation Based on Logic

    Li Dai


    Full Text Available Preference aggregation and judgment aggregation are two basic research models of group decision making. And preference aggregation has been deeply studied in social choice theory. However, researches of social choice theory gradually focus on judgment aggregation which appears recently. Judgment aggregation focuses on how to aggregate many consistent logical formulas into one, from the perspective of logic. We try to start with judgment aggregation model based on logic and then explore different solutions to problem of judgment aggregation.

  20. Analysis of catechins in Theobroma cacao beans by cyclodextrin-modified micellar electrokinetic chromatography.

    Gotti, Roberto; Furlanetto, Sandra; Pinzauti, Sergio; Cavrini, Vanni


    A micellar electrokinetic chromatography (MEKC) method was developed for the quantitation of polyphenols (+)-catechin and (-)-epicatechin (catechin monomers) and the methylxanthine theobromine in Theobroma cacao beans. Owing to the poor stability of catechin monomers in alkaline conditions, a 50 mM Britton-Robinson buffer at a pH 2.50 was preferred as the background electrolyte. Under these conditions, the addition of hydroxypropyl-beta-cyclodextrin (HP-beta-CD) at a concentration of 12 mM to the SDS micellar solution (90 mM), resulted in a cyclodextrin-modified micellar electrokinetic chromatography (CD-MEKC) endowed with two peculiar advantages compare to the conventional MEKC: (i) strong improvement of separation of the most important phytomarkers of T. cacao and (ii) enantioselectivity toward (+/-)-catechin. In particular, separation of methylxanthines (theobromine and caffeine), procyanidin dimers B1 and B2, and catechins (epicatechin and catechin) was obtained simultaneously to the enantioseparation of racemic catechin within 10min. The enantioselectivity of the method makes it suitable in evaluation of possible epimerisation at the C-2 position of epicatechin monomer potentially occurring during heat processing and storage of T. cacao beans. The extraction procedure of the phytomarkers from the beans was approached using ultrasonic bath under mild conditions optimized by a multivariate strategy. The method was validated for robustness, selectivity, sensitivity, linearity, range, accuracy and precision and it was applied to T. cacao beans from different countries; interestingly, the native enantiomer (+)-catechin was found in the beans whereas, for the first time we reported that in chocolate, predominantly (-)-catechin is present, probably yielded by epimerisation of (-)-epicatechin occurred during the manufacture of chocolate.

  1. Micellar control of the photooxidation pathways of 10-methyl phenothiazine: electron versus energy transfer mechanisms.

    Manju, Thankamoniamma; Manoj, Narayanapillai; López Gejo, Juan; Braun, André M; Oliveros, Esther


    10-Methyl phenothiazine (MPS) was chosen as a model compound to investigate the effects of compartmentalisation and of charged interfaces on the primary mechanisms involved in the phototoxic reactions related to phenothiazine drugs. Two most important pathways resulting from the interaction of the triplet excited state of MPS ((3)MPS*) with molecular oxygen ((3)O2) have to be considered: (i) energy transfer producing singlet oxygen ((1)O2) and (ii) electron transfer generating the superoxide anion (O2˙(-)) and the radical cation (MPS˙(+)). The quantum yields of (1)O2 production by MPS solubilized in the dispersed pseudo-phase of aqueous micellar systems were found to be similar to those determined in solvents of various polarities, regardless of the anionic or cationic nature of the surfactant (SDS or CTAC). However, micellar compartmentalisation and surfactant charge affect considerably both the sensitized and the self-sensitized photooxidation of MPS. The formation of 10-methyl phenothiazine sulfoxide (MPSO), produced by the reaction of MPS with (1)O2, proceeds at a higher rate in SDS micelles than in neat polar solvents. This result may be explained by the protonation of the zwitterionic intermediate Z (MPS(+)OO(-)) at the micellar interface to yield the corresponding cation C (MPS(+)OOH) that is stabilized in the negatively charged micelles and reacts much faster with MPS than Z to yield MPSO. The electron transfer reaction from (3)MPS* to O2 yielding MPS˙(+) and O2˙(-) is also enhanced in SDS micelles, as back electron transfer (BET) is prevented by ejection of O2˙(-) to the aqueous bulk phase and stabilization of MPS˙(+) in the anionic micelles. The size of the SDS micelles modulates the relative contribution of each pathway (formation of MPSO or MPS˙(+)) to the overall conversion of MPS to its oxidation products. Photooxidation of MPS in cationic micelles is a very slow process, as the formation of neither C nor MPS˙(+) is favoured in positively

  2. Efficiency enhancements in micellar liquid chromatography through selection of stationary phase and alcohol modifier.

    Thomas, David P; Foley, Joe P


    Micellar liquid chromatography (MLC) remains hindered by reduced chromatographic efficiency compared to reversed phase liquid chromatography (RPLC) using hydro-organic mobile phases. The reduced efficiency has been partially explained by the adsorption of surfactant monomers onto the stationary phase, resulting in a slow mass transfer of the analyte within the interfacial region of the mobile phase and stationary phase. Using an array of 12 columns, the effects of various bonded stationary phases and silica pore sizes, including large-pore short alkyl chain, non-porous, superficially porous and perfluorinated, were evaluated to determine their impact on efficiency in MLC. Additionally, each stationary phase was evaluated using 1-propanol and 1-butanol as separate micellar mobile phase alcohol additives, with several columns also evaluated using 1-pentanol. A simplified equation for calculation of A' and C' terms from reduced plate height (h) versus reduced velocity (nu) plots was used to compare the efficiency data obtained with the different columns and mobile phases. Analyte diffusion coefficients needed for the h versus nu plots were determined by the Taylor-Aris dispersion technique. The use of a short alkyl chain, wide-pore silica column, specifically, Nucleosil C4, 1000A, was shown to have the most improved efficiency when using a micellar mobile phase compared to a hydro-organic mobile phase for all columns evaluated. The use of 1-propanol was also shown to provide improved efficiency over 1-butanol or 1-pentanol in most cases. In a second series of experiments, column temperatures were varied from 40 to 70 degrees C to determine the effect of temperature on efficiency for a subset of the stationary phases. Efficiency improvements ranging from 9% for a Chromegabond C8 column to 58% for a Zorbax ODS column were observed over the temperature range. Based on these observed improvements, higher column temperatures may often yield significant gains in column

  3. Removal of phenol from synthetic waste water using Gemini micellar-enhanced ultrafiltration (GMEUF)

    Zhang, Wenxiang [MOE Key Laboratory of Regional Energy and Environmental Systems Optimization, Resources and Environmental Research Academy, North China Electric Power University, Beijing 102206 (China); Huang, Guohe, E-mail: [MOE Key Laboratory of Regional Energy and Environmental Systems Optimization, Resources and Environmental Research Academy, North China Electric Power University, Beijing 102206 (China); Wei, Jia [Faculty of Engineering and Applied Science, University of Regina, Regina, Saskatchewan, Canada S4S 0A2 (Canada); Li, Huiqin; Zheng, Rubing; Zhou, Ya [MOE Key Laboratory of Regional Energy and Environmental Systems Optimization, Resources and Environmental Research Academy, North China Electric Power University, Beijing 102206 (China)


    Highlights: Black-Right-Pointing-Pointer Gemini surfactant micellar enhanced ultrafiltration was used to remove phenol. Black-Right-Pointing-Pointer The effect of different hydrophilic head groups of surfactant was analyzed. Black-Right-Pointing-Pointer SEM, ATR-FTIR and mercury porosimeter were applied to elucidate membrane fouling. Black-Right-Pointing-Pointer Gemini surfactant had superior performance in comparing with conventional surfactant. - Abstract: Comprehensive studies were conducted on the phenol wastewater ultrafiltration (UF) with the help of various concentrations of cationic Gemini surfactant (N1-dodecyl-N1,N1,N2,N2-tetramethyl-N2-octylethane-1,2-diaminium bromide, CG), conventional cationic surfactant (dodecyl trimethyl ammonium bromide, DTAB), anionic surfactant (sodium dodecyl sulfate, SDS) and nonionic surfactant ((dodecyloxy)polyethoxyethanol, Brij35). A flat sheet module with polyethersulfone (PES) membrane was employed in this investigation. The effects of feed concentration (phenol and surfactant) on the retention of phenol and surfactant, permeate flux and membrane fouling by micelles were evaluated. The distribution coefficient (D), the loading of the micelles (L{sub m}) and the equilibrium distribution constant (K) were also utilized to estimate the micellar-enhanced ultrafiltration ability for phenol. Scanning electron microscope (SEM), Fourier transform infrared spectrometer with attenuated total reflectance accessory (ATR-FTIR) and mercury porosimeter were applied to analyze membrane surface morphology, membrane material characteristics and membrane fouling for the original and fouled membranes. Based on the above analysis, the performance of the selected Gemini surfactant was proved superior in the following aspects: retention of phenol/surfactant (peak value is 95.8% for phenol retention), permeate flux and membrane fouling with respect to other conventional surfactants possessing equal alkyl chain length. These results demonstrated

  4. Micellar bolaform and omega-carboxylate phosphatidylcholines as substrates for phospholipases.

    Lewis, K A; Soltys, C E; Yu, K; Roberts, M F


    A series of mixed-chain diacyl-PCs which contain an omega-COOH on the sn-2 chain [1-Cx-2-Cy-(COOH)-PC] and bolaform (1-Cx-2,2'-Cy-1'-Cx-PC) phosphatidylcholines were synthesized and examined as substrates for phospholipase A2 (Naja naja naja) and C (Bacillus cereus). There is very little detectable phospholipase A2 activity toward pure micellar 1-acyl-2-acyl-(omega-COOH) species. In addition, when these same omega-COOH species are present at concentrations above their CMCs, they are potent inhibitors of phospholipase A2 hydrolysis of other micellar lipids. In contrast, phospholipase C hydrolysis of the same 1-acyl-2-acyl-omega-COOH)-PC species proceeds with rates comparable to that of diheptanoyl-PC. The bolaform lipids, which are tethered through a common sn-2 acyl chain, (e.g., 1-C8-2,2'-C12-1'-C8-PC) display quite different kinetic results. Under limiting Ca2+ conditions (100 microM) all the available sn-2 acyl bonds of the dimer are hydrolyzed. However, at high Ca2+ concentrations (1-10 mM) the reaction curves have a biphasic nature, characterized by an initial burst of activity followed by much slower rate. This is consistent with only the micellar 1-acyl-2-acyl-(omega-COOH)-PC produced in situ from phospholipase A2 hydrolysis of the dimer acting as an inhibitor of subsequent phospholipase A2 activity. Phospholipase C hydrolysis of the PC dimer and the sn-2 omega-COOH PC is rapid, with both available glycerophosphate groups cleaved at presumably the same rate. These results are discussed in terms of the unique physical properties (as measured by NMR and fluorescence experiments) of these phospholipids.

  5. Optimal aggregation of noisy observations: A large deviations approach

    Murayama, Tatsuto; Davis, Peter, E-mail:, E-mail: [NTT Communication Science Laboratories, NTT Corporation, 2-4, Hikaridai, Seika-cho, Keihanna, Kyoto 619-0237 (Japan)


    Sensing and data aggregation tasks in distributed systems should not be considered as separate issues. The quality of collective estimation involves a fundamental tradeoff between sensing quality, which can be increased by increasing the number of sensors, and aggregation quality under a given capacity of the network, which decreases if the number of sensors is too large. In this paper, we examine a system level strategy for optimal aggregation of data from an ensemble of independent sensors. In particular, we consider large scale aggregation from very many sensors, in which case the network capacity diverges to infinity. Then, by applying the large deviations techniques, we conclude the following significant result: larger scale aggregation always outperforms smaller scale aggregation at higher noise levels, while below a critical value of noise, there exist moderate scale aggregation levels at which optimal estimation is realized. At a critical value of noise, there is an abrupt change in the behavior of a parameter characterizing the aggregation strategy, similar to a phase transition in statistical physics.

  6. Determination of oxolinic acid, danofloxacin, ciprofloxacin, and enrofloxacin in porcine and bovine meat by micellar liquid chromatography with fluorescence detection.

    Terrado-Campos, David; Tayeb-Cherif, Khaled; Peris-Vicente, Juan; Carda-Broch, Samuel; Esteve-Romero, Josep


    A method was developed for the determination of oxolinic acid, danofloxacin, ciprofloxacin and enrofloxacin by micellar liquid chromatography - fluorescence detection in commercial porcine and bovine meat. The samples were ultrasonicated in a micellar solution, free of organic solvent, to extract the analytes, and the supernatant was directly injected. The quinolones were resolved in 0.9998), trueness (89.3-105.1%), precision (<8.3%), decision limit (<12% over the maximum residue limit), detection capability (<21% over the maximum residue limit), ruggedness (<5.6%) and stability. The procedure was rapid, eco-friendly, safe and easy-to-handle.

  7. A mode coupling theory analysis of viscoelasticity near the kinetic glass transition of a copolymer micellar system

    Mallamace, Francesco [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Tartaglia, Piero [Dipartimento di Fisica, INFM and Statistical Mechanics and Complexity Center, Universita di Roma La Sapienza, I-00185 Rome (Italy); Chen W R [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Faraone, Antonio [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States); Chen, S H [Department of Nuclear Engineering, Massachusetts Institute of Technology, Cambridge, MA 02139 (United States)


    We report a set of viscoelastic measurements in concentrated aqueous solutions of a copolymer micellar system with short-range inter-micellar attractive interactions, a colloidal system characterized, in different regions of the composition-temperature phase diagram, by the existence of a percolation line (PT) and a kinetic glass transition (KGT). Both these transitions cause dramatic changes in the system viscoelasticity. Whereas the observed variations of the shear moduli at the PT are described in terms of percolation models, for the structural arrest at the KGT we investigate the frequency-dependent shear modulus behaviours by using a mode coupling theory (MCT) approach.

  8. Viscoelastic processes in non-ergodic states (percolation and glass transitions) of attractive micellar systems

    Mallamace, F.; Broccio, M.; Tartaglia, P.; Chen, W. R.; Faraone, A.; Chen, S. H.


    We report a set of viscoelastic measurements in aqueous solutions of a copolymer micellar system with attractive interactions, a system characterized by a percolation line (PT), and a structural arrest (SA) in the particle diffusion motions of a kinetic glass transition (KGT). We observe, in both transitions, dramatic variations in both the elastic (or storage G‧( ω)) and loss components ( G″( ω)) of the shear moduli. At the PT, rheological data are characterized by a scaling behavior, whereas at the SA G‧ and G″ develop a plateau and a marked minimum, respectively. These behaviors are described in the frame of percolation models and mode coupling theory (MCT).

  9. Micellar-polymer joint demonstration project, Wilmington Field, California. Third annual report, June 1978-July 1979

    Staub, H.L.


    The micellar-polymer demonstration project to be conducted - through the design phase - in the HXa sand of Wilmington Field is proceeding satisfactorily but has fallen behind schedule. Results of some core floods were unsatisfactory. The recovery efficiencies were much lower than those achieved using the laboratory sample cosurfactant final design slug. Nearly six months of reformulating and additional core testing were required to finally achieve satisfactory laboratory results. Other laboratory tests were performed to optimize the polymer buffer for size and concentration. Other reservoir and reservoir fluid problems have been encountered in production and injection operations during the pre-flush period.

  10. Impact of Micellar Surfactant on Supersaturation and Insight into Solubilization Mechanisms in Supersaturated Solutions of Atazanavir.

    Indulkar, Anura S; Mo, Huaping; Gao, Yi; Raina, Shweta A; Zhang, Geoff G Z; Taylor, Lynne S


    The goals of this study were to determine: 1) the impact of surfactants on the "amorphous solubility"; 2) the thermodynamic supersaturation in the presence of surfactant micelles; 3) the mechanism of solute solubilization by surfactant micelles in supersaturated solutions. The crystalline and amorphous solubility of atazanavir was determined in the presence of varying concentrations of micellar sodium dodecyl sulfate (SDS). Flux measurements, using a side-by-side diffusion cell, were employed to determine the free and micellar-bound drug concentrations. The solubilization mechanism as a function of atazanavir concentration was probed using fluorescence spectroscopy. Pulsed gradient spin-echo proton nuclear magnetic resonance (PGSE-NMR) spectroscopy was used to determine the change in micelle size with a change in drug concentration. Changes in the micelle/water partition coefficient, K m/w , as a function of atazanavir concentration led to erroneous estimates of the supersaturation when using concentration ratios. In contrast, determining the free drug concentration using flux measurements enabled improved determination of the thermodynamic supersaturation in the presence of micelles. Fluorescence spectroscopic studies suggested that K m/w changed based on the location of atazanavir solubilization which in turn changed with concentration. Thus, at a concentration equivalent to the crystalline solubility, atazanavir is solubilized by adsorption at the micelle corona, whereas in highly supersaturated solutions it is also solubilized in the micellar core. This difference in solubilization mechanism can lead to a breakdown in the prediction of amorphous solubility in the presence of SDS as well as challenges with determining supersaturation. PGSE-NMR suggested that the size of the SDS micelle is not impacted at the crystalline solubility of the drug but increases when the drug concentration reaches the amorphous solubility, in agreement with the proposed changes in

  11. Application of micellar electrokinetic capillary chromatography for routine analysis of different materials

    Injac Rade


    Full Text Available Micellar electrokinetic capillary chromatography (MEKC has become a popular mode among the several capillary electro-migration techniques. Most drug analysis can be performed by using MEKC because of its wide applicability. Separation of very complex mixtures, determination of drugs in the biological materials, etc., can be successfully achieved by MEKC. This review surveys typical applications of MEKC analysis. Recent advances in MEKC, especially with solid-phase extraction and large-volume sample stacking, are described. Modes of electrokinetic chromatography including MEKC, a separation theory of MEKC, environmental friendly analysis, and selectivity manipulation in MEKC are also briefly mentioned.

  12. Features of the micellar solubility of metal-containing surfactants in hydrocarbons

    Fedorov, A.B.; Zdobnova, O.L.; Zaichenko, L.P.; Proskuryakov, V.A.


    Metal-containing surfactants (SF) are now widely used as different additives to oils and fuels. The micellar solubility of a series of individual metal-containing SF and widely used additives was investigated as a function of the structure and polarity of the additive, type of hydrocarbon solvent, and presence of water in this study. Individual decyl benzenesulfonates (DBS) of different metals and samples of surfactant additives for oils of the alkylphenolate (VNII NP-370), sulfonate (PMSA, PMSya, S-150, S-300, Lubrizol 58, SB-3, PMSya (bariated), alkylsalicylate (ASK, MASK), and dialkyldithiophosphate (DF-11, VNII NP-354) types were investigated.

  13. Monte Carlo simulation for the micellar behavior of amphiphilic comb-like copolymers

    冯莺; 隋家贤; 赵季若; 陈欣方


    Micellar behaviors in 2D and 3D lattice models for amphiphilic comb-like copolymers in water phase and in water/oil mixtures were simulated. A dynamical algorithm together with chain reptation movements was used in the simulation. Three-dimension displaying program was pro-grammed and free energy was estimated by Monte Carlo technigue. The results demonstrate that reduced interaction energy influences morphological structures of micelle and emulsion ??stems greatly; 3D simulation showing can display more direct images of morphological structures; the amphiphilic comb-like polymers with a hydrophobic main chain and hydrophilic side chains have lower energy in water than in oil.

  14. Effect of acidity of drugs on the prediction of human oral absorption by biopartitioning micellar chromatography


    Biopartitioning micellar chromatography(BMC)is a potentially high throughput and low cost alternative for in vitro prediction of drug absorption,which can mimic the drug partitioning process in biological systems.In this paper,a data set of 56 compounds representing acidic,basic,neutral and amphoteric drugs from various structure classes with human oral absorption(HOA)data available were employed to show the effect of acidity of drugs in oral absorption prediction.HOA was reciprocally correlated to the nega...

  15. Quantitative determination of amygdalin epimers by cyclodextrin-modified micellar electrokinetic chromatography.

    Isoza, T; Matano, Y; Yamamoto, K; Kosaka, N; Tani, T


    A new capillary electrophoresis method was developed for the quantitative determination of the amygdalin epimers, amygdalin and neoamygdalin, which are biologically significant constituents in the crude drugs, namely Persicae Semen and Armeniacae Semen. The effects of surfactants, additives and other analytical parameters were studied. As a result, the resolution of two epimers was performed by cyclodextrin-modified micellar electrokinetic chromatography with a buffer containing alpha-cyclodextrin and sodium deoxycholate. By the application of this method, a simple, fast and simultaneous quantitative determinations of amygdalin epimers in the crude drugs (Persicae Semen and Armeniacae Semen) and the Chinese herbal prescriptions (Keishi-bukuryo-gan and Mao-to) were achieved.

  16. Photoactive bile salts with critical micellar concentration in the micromolar range.

    Gomez-Mendoza, Miguel; Marin, M Luisa; Miranda, Miguel A


    The aggregation behavior of bile salts is strongly dependent on the number of hydroxyl groups. Thus, cholic acid (CA), with three hydroxyls, starts forming aggregates at 15 mM, while deoxycholic, chenodeoxycholic or ursodeoxycholic acids, with two hydroxyls, start aggregating at 5-10 mM; for lithocholic acid, with only one hydroxyl group, aggregation is observed at lower concentration (2-3 mM). Here, the singular self-assembling properties of dansyl and naproxen derivatives of CA (3β-Dns-CA and 3β-NPX-CA, respectively) have been demonstrated on the basis of their photoactive properties. Thus, the emission spectra of 3β-Dns-CA registered at increasing concentrations (25-140 μM) showed a remarkable non-linear enhancement in the emission intensity accompanied by a hypsochromic shift of the maximum and up to a three-fold increase in the singlet lifetime. The inflection point at around 50-70 μM pointed to the formation of unprecedented assemblies at such low concentrations. In the case of 3β-NPX-CA, when the NPX relative triplet lifetime was plotted against concentration, a marked increase (up to two-fold) was observed at 40-70 μM, indicating the formation of new 3β-NPX-CA assemblies at ca. 50 μM. Additional evidence supporting the formation of new 3β-Dns-CA or 3β-NPX-CA assemblies at 40-70 μM was obtained from singlet excited state quenching experiments using iodide. Moreover, to address the potential formation of hybrid assemblies, 1 : 1 mixtures of 3β-Dns-CA and 3β-NPX-CA (2-60 μM, total concentration) were subjected to steady-state fluorescence experiments, and their behavior was compared to that of the pure photoactive derivatives. A lower increase in the emission was observed for 3β-NPX-CA in the mixture, while a huge increase was experienced by 3β-Dns-CA in the same concentration range (up to 60 μM total). A partial intermolecular energy transfer from NPX to Dns, consistent with their reported singlet energies, was revealed, pointing to the

  17. Neutral Aggregation in Finite Length Genotype space

    Houchmandzadeh, Bahram


    The advent of modern genome sequencing techniques allows for a more stringent test of the neutrality hypothesis of Evolution, where all individuals have the same fitness. Using the individual based model of Wright and Fisher, we compute the amplitude of neutral aggregation in the genome space, i.e., the probability PL,$\\Theta$,M (k) of finding two individuals at genetic distance k for a genome of size L and mutation and migration number $\\Theta$ and M. In well mixed populations, we show that for $\\Theta$ $\\ll$ L, neutral aggregation is the dominant force and most individuals are found at short genetic distances from each other. For $\\Theta$ $\\sim$ L/2 on the contrary, individuals are randomly dispersed in genome space. For a geographically dispersed population, the controlling parameter is a combination of mutation and migration numbers. The theory we develop can be used to test the neutrality hypothesis in various ecological and evolutionary systems.

  18. Fluorosurfactants at structural extremes: adsorption and aggregation.

    Eastoe, Julian; Rogers, Sarah E; Martin, Laura J; Paul, Alison; Guittard, Frédéric; Guittard, Elisabeth; Heenan, Richard K; Webster, John R P


    Fluorosurfactants with several structural modifications have been synthesized, and the air/water interface and bulk aggregation properties investigated. The compounds were fluorinated ethylene oxide (EO) nonionics where the number and position of the hydrophilic group(s) has been radically altered to generate linear, bolaform, and Y-shaped analogues. A noticeable structure-interfacial packing relationship was observed via both tensiometric measurements and neutron reflection studies: the limiting molecular areas, a(cmc), and surface excesses, gamma(cmc), are strongly dependent on the number and position of the EO headgroups. Differing bulk aqueous properties were also observed. Small-angle neutron scattering shows an evolution of micelle structure from cylindrical to disk-like aggregates on changing from Y-shaped to bolaform molecular structure.

  19. Combined research effort on aggregate road materials

    Kuznetsova, Elena; Hoff, Inge; Willy Danielsen, Svein; Wigum, Børge Johannes; Fladvad, Marit; Rieksts, Karlis; Loranger, Benoit; Barbieri, Diego


    In European countries, the average aggregate consumption per capita is 5 tons per year (European Aggregates Association 2016), while the corresponding number in Norway is 11 tons (Neeb 2015). Due to the increased demand for sand and gravel for construction purposes, e.g. in road construction, the last decade has seen a significant trend towards the use of crushed rock aggregates. Neeb (2015) reports that half of the Norwegian aggregate production (sand, gravel and crushed rock) is used for road construction, and 33 % of the overall sold tonnage of crushed rock is exported. This resource has been more and more preferred over sand and gravel due to the significant technological development of its process and utilization phase. In Norway, the development and implementation of crushed aggregate technology has been the main approach to solve natural resource scarcity (Danielsen and Kuznetsova 2015). In order to reduce aggregates transportation, it is aimed to use local aggregates and aggregates processed from rock excavations, tunneling, road cuts, etc. One issue focused in this research is the influence from blasting and processing on the final quality of the crushed aggregates, specifically relating to the properties for road construction purposes. It is therefor crucial to plan utilization of available materials for use in different road layers following the same production line. New developments and improved availability of mobile crushing and screening equipment could produce more sustainable and profitable sources of good quality aggregate materials from small volume deposits in proximity to construction sites. One of the biggest challenges today to use these materials is that the pavement design manual sets rigid requirements for pavement layers. Four research projects are being conducted in Norway to improve the use of local materials for road construction. Four aspects are to be covered by the research: a) geological characteristics of the materials, their b

  20. Urea decreases specific ion effects on the LCST of PMMA-block-PDMAEMA aggregates

    João Carlos Perbone de Souza


    Full Text Available Urea is a well-known additive used as a mild protein denaturant. The effect of urea on proteins, micellar systems and other colloids is still under debate. In particular, urea has shown interesting effects on the ion binding in systems like charged micelles, vesicles or Langmuir-Blodgett films. The urea effect on polymeric aggregates in water is still an open field. For instance, the additive may affect properties such as cmc, LCST, UCST and others. In particular, LCST is a property that can be very convenient for designing smart systems that respond to temperature. Previous studies have indicated that the LCST of positive charged copolymers aggregates based on poly[N-dimethyl(ethylamine methacrylate], PDMAEMA, can be nicely modulated by anions in aqueous solution and such phenomenon depends on the nature of the anion present. In this work, it has been demonstrated that urea also affects the LCST of PMMA-block-PDMAEMA aggregates in aqueous solution. In addition, in the presence of high concentrations of the additive, the specific behavior of the anions is lost, supporting the general mechanism of urea reducing the differences on ion binding to surfaces in aqueous solutions. To the best of our knowledge, this is the first time those phenomena are shown in polymer micelles.

  1. Novel aspects of platelet aggregation

    Roka-Moya Y. M.


    Full Text Available The platelet aggregation is an important process, which is critical for the hemostatic plug formation and thrombosis. Recent studies have shown that the platelet aggregation is more complex and dynamic than it was previously thought. There are several mechanisms that can initiate the platelet aggregation and each of them operates under specific conditions in vivo. At the same time, the influence of certain plasma proteins on this process should be considered. This review intends to summarize the recent data concerning the adhesive molecules and their receptors, which provide the platelet aggregation under different conditions.

  2. Fractal Aggregation Under Rotation

    WU Feng-Min; WU Li-Li; LU Hang-Jun; LI Qiao-Wen; YE Gao-Xiang


    By means of the Monte Carlo simulation, a fractal growth model is introduced to describe diffusion-limited aggregation (DLA) under rotation. Patterns which are different from the classical DLA model are observed and the fractal dimension of such clusters is calculated. It is found that the pattern of the clusters and their fractal dimension depend strongly on the rotation velocity of the diffusing particle. Our results indicate the transition from fractal to non-fractal behavior of growing cluster with increasing rotation velocity, i.e. for small enough angular velocity ω the fractal dimension decreases with increasing ω, but then, with increasing rotation velocity, the fractal dimension increases and the cluster becomes compact and tends to non-fractal.

  3. Fractal Aggregation Under Rotation

    WUFeng-Min; WULi-Li; LUHang-Jun; LIQiao-Wen; YEGao-Xiang


    By means of the Monte Carlo simulation, a fractal growth model is introduced to describe diffusion-limited aggregation (DLA) under rotation. Patterns which are different from the classical DLA model are observed and the fractal dimension of such clusters is calculated. It is found that the pattern of the clusters and their fractal dimension depend strongly on the rotation velocity of the diffusing particle. Our results indicate the transition from fractal to non-fractal behavior of growing cluster with increasing rotation velocity, i.e. for small enough angular velocity ω; thefractal dimension decreases with increasing ω;, but then, with increasing rotation velocity, the fractal dimension increases and the cluster becomes compact and tends to non-fractal.

  4. Platelet aggregation following trauma

    Windeløv, Nis A; Sørensen, Anne M; Perner, Anders


    We aimed to elucidate platelet function in trauma patients, as it is pivotal for hemostasis yet remains scarcely investigated in this population. We conducted a prospective observational study of platelet aggregation capacity in 213 adult trauma patients on admission to an emergency department (ED......). Inclusion criteria were trauma team activation and arterial cannula insertion on arrival. Blood samples were analyzed by multiple electrode aggregometry initiated by thrombin receptor agonist peptide 6 (TRAP) or collagen using a Multiplate device. Blood was sampled median 65 min after injury; median injury...... severity score (ISS) was 17; 14 (7%) patients received 10 or more units of red blood cells in the ED (massive transfusion); 24 (11%) patients died within 28 days of trauma: 17 due to cerebral injuries, four due to exsanguination, and three from other causes. No significant association was found between...

  5. Propagation of Tau Aggregates and Neurodegeneration.

    Goedert, Michel; Eisenberg, David S; Crowther, R Anthony


    A pathway from the natively unfolded microtubule-associated protein Tau to a highly structured amyloid fibril underlies human Tauopathies. This ordered assembly causes disease and represents the gain of toxic function. In recent years, evidence has accumulated to suggest that Tau inclusions form first in a small number of brain cells, from where they propagate to other regions, resulting in neurodegeneration and disease. Propagation of pathology is often called prion-like, which refers to the capacity of an assembled protein to induce the same abnormal conformation in a protein of the same kind, initiating a self-amplifying cascade. In addition, prion-like encompasses the release of protein aggregates from brain cells and their uptake by neighboring cells. In mice, the intracerebral injection of Tau inclusions induces the ordered assembly of monomeric Tau, followed by its spreading to distant brain regions. Conformational differences between Tau aggregates from transgenic mouse brain and in vitro assembled recombinant protein account for the greater seeding potency of brain aggregates. Short fibrils constitute the major species of seed-competent Tau in the brains of transgenic mice. The existence of multiple human Tauopathies with distinct fibril morphologies has led to the suggestion that different molecular conformers (or strains) of aggregated Tau exist.

  6. A universal concept for stacking neutral analytes in micellar capillary electrophoresis.

    Palmer, J; Munro, N J; Landers, J P


    Unlike recent studies that have depended on manipulation of separation buffer parameters to facilitate stacking of neutral analytes in micellar capillary electrophoresis (MCE) mode, we have developed a method of stacking based simply on manipulation of the sample matrix. Many solutions for sample stacking in MCE are based on strict control of pH, micelle type, electroosmotic flow (EOF) rate, and separation-mode polarity. However, a universal solution to sample stacking in MCE should allow for free manipulation of separation buffer parameters without substantially affecting separation of analytes. Analogous to sample stacking in capillary zone electrophoresis by invoking field amplification of charged analytes in a low-conductivity sample matrix, the proposed method utilizes a high-conductivity sample matrix to transfer field amplification from the sample zone to the separation buffer. This causes the micellar carrier in the separation buffer to stack before it enters the sample zone. Neutral analytes moving out of the sample zone with EOF are efficiently concentrated at the micelle front. Micelle stacking is induced by simply adding salt to the sample matrix to increase the conductivity 2-3-fold higher than the separation buffer. This solution allows free optimization of separation buffer parameters such as micelle concentration, organic modifiers, and pH, providing a method that may complement virtually any existing MCE protocol without restricting the separation method.

  7. Micellarization and intestinal cell uptake of beta-carotene and lutein from drumstick (Moringa oleifera) leaves.

    Pullakhandam, Raghu; Failla, Mark L


    The leaves and pods of the drumstick tree are used as food and medicine in some Asian and African countries. Although relatively high concentrations of beta-carotene and lutein have been reported in the leaves, the bioavailability of these carotenoids from this source is unknown. We have analyzed the digestive stability and bioaccessibility of carotenoids in fresh and lyophilized drumstick leaves using the coupled in vitro digestion/Caco-2 cell model. Beta-carotene and lutein were stable during simulated gastric and small intestinal digestion. The efficiency of micellarization of lutein during the small intestinal phase of digestion exceeded that of beta-carotene. Addition of peanut oil (5% vol/wt) to the test food increased micellarization of both carotenoids, and particularly beta-carotene. Caco-2 cells accumulated beta-carotene and lutein from micelles generated during digestion of drumstick leaves in a time- and concentration-dependent manner. The relatively high bioaccessibility of beta-carotene and lutein from drumstick leaves ingested with oil supports the potential use of this plant food for improving vitamin A nutrition and perhaps delaying the onset of some degenerative diseases such as cataracts.

  8. Indirect detection by semiconductor laser-induced fluorometry in micellar electrokinetic chromatography

    Kaneta, Takashi; Imasaka, Totaro


    Indirect fluorescence detection of electrically neutral compounds separated by micellar electrokinetic chromatography is performed using a semiconductor laser as an exciting light source. Oxazine 750 is used as a visualizing agent of which absorption maximum is near 680 nm. A surfactant, tetradecyltrimethylammonium chloride, is used to form micelles and to prevent adsorption of oxazine 750 with a positive charge on the capillary wall negatively charged. This surfactant coats on the capillary wall so that oxazine 750 is repulsed electrically on the capillary wall. In this technique, some aromatic compounds with relatively polar functional groups, such as aniline and nitrobenzene, could be separated and detected, while nonpolar compounds such as benzene and toluene can not be detected. The range of the detection limit is from 4.2 X 10-4 to 1.6 X 10-3 M (S/N equals 3) for the aromatic compounds. The detection mechanism is based on enhancement of the fluorescence intensity in the micellar solution and on exclusion of the fluorophore attached at the hydrophilic moiety of the micelle by a hydrophilic sample.

  9. A micellar liquid chromatography method for the quantification of abacavir, lamivudine and raltegravir in plasma.

    Peris-Vicente, Juan; Villareal-Traver, Mónica; Casas-Breva, Inmaculada; Carda-Broch, Samuel; Esteve-Romero, Josep


    An analytical methodology based on micellar liquid chromatography has been developed to quantify abacavir, lamivudine and raltegravir in plasma. These three antiretroviral drugs are prescribed as a set in highly active antiretroviral therapy to acquired immunodeficiency syndrome patients. The experimental procedure consists in the dilution of the sample in micellar media, followed by filtration and, without cleanup step. The analytes were resolved in less than 30min using a mobile phase of 0.05M sodium dodecyl sulphate at pH 7, running at 1mLmin(-1) under isocratic mode at room temperature through a C18 column (125×4.6mm, 5μm particle size). The UV detection wavelength was set at 260nm. The method was successfully validated following the requirements of ICH guidelines in terms of: linear range (0.25-2.5μgmL(-1)), linearity (r(2)>0.990), intra- and interday precision (<6.8%) and accuracy (92.3-104.2%) and robustness (<7.1%). To the extent of our knowledge, this is the first published method to quantify these three drugs in plasma. Several blood samples from AIDS patients taking this HAART set provided by a local hospital were analyzed with satisfactory results.

  10. A concise review of applications of micellar liquid chromatography to study biologically active compounds.

    Stępnik, Katarzyna E


    The features of micellar systems are outstanding compared with conventional RP-LC ones. Therefore, the unique properties of micellar chromatography (MLC) are widely recognized. In this short review the applicability of MLC as an in vitro method for the determination of biological activity is discussed. For this purpose many specific examples of MLC applications supported by the theoretical backgrounds of the cited biological activity areas as well as the factors affecting them are presented. This study collects and organizes the most important references of bioactivity determination which were created both recently and in the past, using the MLC method. Although there are many papers on the MLC there is no literature review focused particularly on its applicability in the study of biological activity of various compounds. This work can be treated as a significant review of so far published papers which particularly emphasizes the importance of MLC as in vitro method for determination of bioactivity of different compounds. Copyright © 2016 John Wiley & Sons, Ltd.

  11. Micellar LC Separation of Sesquiterpenic Acids and Their Determination in Valeriana officinalis L. Root and Extracts

    Artem U. Kulikov


    Full Text Available A simple micellar liquid chromatography (MLC method was developed and validated according to ICH Guidelines for the determination of sesquiterpenic acids (valerenic, hydroxyvalerenic, and acetoxyvalerenic acids in root and rhizome extract from Valeriana officinalis L. and valerian dry hydroalcoholic extract. Samples were analyzed on Nucleosil C18 column (150mm×4.6mm, 5 μm using an isocratic mobile phase which consisted of Brij 35 (5% (w/v aqueous solution; pH 2.3±0.1 by phosphoric acid and 1-butanol (6% (v/v; UV detection was at 220 nm. Micellar mobile phase using allows to fully separate valerenic acids within 25 minutes. Linearity for hydroxyvalerenic, acetoxyvalerenic, and valerenic acids was 1.9–27.9, 4.2–63.0, and 6.1–91·3 μg.mL−1, and limit of detection was 0.14, 0.037, and 0.09 μg·mL−1, respectively. Intraday and interday precisions were not less than 2% for all investigated compounds. The proposed method was found to be reproducible and convenient for quantitative analysis of sesquiterpenic acids in valerian root and related preparations.

  12. Removal of phenol from synthetic waste water using Gemini micellar-enhanced ultrafiltration (GMEUF).

    Zhang, Wenxiang; Huang, Guohe; Wei, Jia; Li, Huiqin; Zheng, Rubing; Zhou, Ya


    Comprehensive studies were conducted on the phenol wastewater ultrafiltration (UF) with the help of various concentrations of cationic Gemini surfactant (N1-dodecyl-N1,N1,N2,N2-tetramethyl-N2-octylethane-1,2-diaminium bromide, CG), conventional cationic surfactant (dodecyl trimethyl ammonium bromide, DTAB), anionic surfactant (sodium dodecyl sulfate, SDS) and nonionic surfactant ((dodecyloxy)polyethoxyethanol, Brij35). A flat sheet module with polyethersulfone (PES) membrane was employed in this investigation. The effects of feed concentration (phenol and surfactant) on the retention of phenol and surfactant, permeate flux and membrane fouling by micelles were evaluated. The distribution coefficient (D), the loading of the micelles (L(m)) and the equilibrium distribution constant (K) were also utilized to estimate the micellar-enhanced ultrafiltration ability for phenol. Scanning electron microscope (SEM), Fourier transform infrared spectrometer with attenuated total reflectance accessory (ATR-FTIR) and mercury porosimeter were applied to analyze membrane surface morphology, membrane material characteristics and membrane fouling for the original and fouled membranes. Based on the above analysis, the performance of the selected Gemini surfactant was proved superior in the following aspects: retention of phenol/surfactant (peak value is 95.8% for phenol retention), permeate flux and membrane fouling with respect to other conventional surfactants possessing equal alkyl chain length. These results demonstrated that CG surfactant with exceptional structure has favorable prospects in the treatment of phenol wastewater by the micellar-enhanced ultrafiltration. Copyright © 2012 Elsevier B.V. All rights reserved.

  13. Chromatographic performance of large-pore versus small-pore columns in micellar liquid chromatography.

    McCormick, Timothy J; Foley, Joe P; Lloyd, David K


    Micellar liquid chromatography (MLC) is useful in bioanalysis because proteinaceous biofluids can be directly injected onto the column. The technique has been limited in part because of the apparently weak eluting power of micellar mobile phases. It has recently been shown [Anal. Chem. 72 (2000) 294] that this may be overcome by the use of large pore size stationary phases. In this work, large-pore (1000 A) C(18) stationary phases were evaluated relative to conventional small-pore (100 A) C(18) stationary phases for the direct sample injection of drugs in plasma. Furthermore, the difference between the large and small pore phases in gradient elution separations of mixtures of widely varying hydrophobicities was investigated. Large-pore stationary phases were found to be very effective for eluting moderately to highly hydrophobic compounds such as ibuprofen, crotamiton, propranolol, and dodecanophenone, which were highly retained on the small-pore stationary phases typically used in MLC. The advantages of direct introduction of biological samples (drugs in plasma) and rapid column re-equilibration after gradient elution in MLC were maintained with large-pore phases. Finally, recoveries, precision, linearity, and detection limits for the determination of quinidine and DPC 961 in spiked bovine plasma were somewhat better using MLC with wide pore phases.

  14. Aliphatic carboxylic acids and alcohols as efficiency and elution strength enhancers in micellar liquid chromatography.

    Boichenko, Alexander P; Berthod, Alain


    Micellar liquid chromatography (MLC) uses surfactant solutions as mobile phases with added organic additives to enhance both the elution strength and the chromatographic efficiency. Two aliphatic carboxylic acids (1-butanoic and 1-pentanoic) were used as MLC additives and compared with the two corresponding alcohols (1-butanol, 1-pentanol) in terms of elution strength, efficiency and selectivity. A set of 11 phenol derivatives was used as probe compounds. All micellar mobile phases were prepared with sodium dodecylsulfate (SDS) with concentration ranging from 0.05 to 0.15M and the modifier content within 1.0 and 5.0% (v/v). The elution strength of different mobile phases containing a constant amount of SDS and different amounts of modifiers; and mobile phases containing a constant amount of modifier and different SDS concentration were determined and discussed. The effect of the acid modifiers on efficiency was studied constructing van Deemter plots that showed no minimum within the 0.01-0.7mL/min flow rate range studied. Temperature effects were also studied constructing the classical van't Hoff plots. The slight curvature of the plots in the 25-70 degrees C range may indicate some modification of the surfactant-bonded moiety layer on the stationary phase surface. Since no definitive advantage of the use of aliphatic acids were established compared to their alcohol counterpart, their terrible smell will probably preclude their use as MLC organic modifiers.

  15. Use of micellar mobile phases for the chromatographic determination of clorazepate, diazepam, and diltiazem in pharmaceuticals.

    Gil-Agustí, M; Carda-Broch, S; García-Alvarez-Coque, M C; Esteve-Romero, J


    An ODS-2 column, a micellar mobile phase of high elution strength containing 0.1M sodium dodecyl sulfate and 3% (v/v) butanol, and ultraviolet detection at 230 nm are used for the determination of either of two benzodiazepines (clorazepate and diazepam) and a benzothiazepine (diltiazem) in pharmaceuticals. The procedure is shown to be competitive against conventional chromatography with methanol-water mobile phases, especially for diltiazem. The composition of the micellar mobile phase is selected using a predictive strategy based on an accurate retention model and assisted by computer simulation. Calibration graphs are linear at least in the 2.5 to 20 microg/mL, 4 to 20 microg/mL, and 5 to 40 microg/mL ranges for clorazepate, diazepam, and diltiazem, respectively. The intra- and interday repeatabilities (%) are clorazepate (1.7, 5.2), diazepam (0.43, 3.7), and diltiazem (0.36, 3.1). Limits of detection are well below the concentrations of the drugs found in the commercial pharmaceutical preparations analyzed. The drug contents evaluated with the proposed procedure are compared with the declared contents given by the manufacturers. The achieved percentages of label claim are usually between 95 and 104%.

  16. Magnetic Properties of FePt Nanoparticles Prepared by a Micellar Method

    Gao Y


    Full Text Available Abstract FePt nanoparticles with average size of 9 nm were synthesized using a diblock polymer micellar method combined with plasma treatment. To prevent from oxidation under ambient conditions, immediately after plasma treatment, the FePt nanoparticle arrays were in situ transferred into the film-growth chamber where they were covered by an SiO2 overlayer. A nearly complete transformation of L10 FePt was achieved for samples annealed at temperatures above 700 °C. The well control on the FePt stoichiometry and avoidance from surface oxidation largely enhanced the coercivity, and a value as high as 10 kOe was obtained in this study. An evaluation of magnetic interactions was made using the so-called isothermal remanence (IRM and dc-demagnetization (DCD remanence curves and Kelly–Henkel plots (ΔM measurement. The ΔM measurement reveals that the resultant FePt nanoparticles exhibit a rather weak interparticle dipolar coupling, and the absence of interparticle exchange interaction suggests no significant particle agglomeration occurred during the post-annealing. Additionally, a slight parallel magnetic anisotropy was also observed. The results indicate the micellar method has a high potential in preparing FePt nanoparticle arrays used for ultrahigh density recording media.

  17. Micellar cathodes from self-assembled nitroxide-containing block copolymers in battery electrolytes.

    Hauffman, Guillaume; Maguin, Quentin; Bourgeois, Jean-Pierre; Vlad, Alexandru; Gohy, Jean-François


    This contribution describes the synthesis of block copolymers containing electrochemically active blocks, their micellization, and finally their use as micellar cathodes in a lithium battery. The self-assembly of the synthesized poly(styrene)-block-poly(2,2,6,6-tetramethylpiperidinyloxy-4-yl methacrylate) (PS-b-PTMA) diblock copolymers is realized in a typical battery electrolyte made of 1 m lithium trifluoromethanesulfonate dissolved in a mixture of ethylene carbonate/diethyl carbonate/dimethyl carbonate(1:1:1, in volume). Dynamic light scattering and atomic force micro-scopy indicate the formation of well-defined spherical micelles with a PS core and a PTMA corona. The electrochemical properties of those micelles are further investigated. Cyclic voltammograms show a reversible redox reaction at 3.6 V (vs Li(+) /Li). The charge/discharge profiles indicate a flat and reversible plateau around 3.6 V (vs Li(+) /Li). Finally, the cycling performances of the micellar cathodes are demonstrated. Such self-assembled block copolymers open new opportunities for nanostructured organic radical batteries. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

  18. Capillaries modified by noncovalent anionic polymer adsorption for capillary zone electrophoresis, micellar electrokinetic capillary chromatography and capillary electrophoresis mass spectrometry

    Bendahl, L; Hansen, S H; Gammelgaard, Bente


    A simple coating procedure for generation of a high and pH-independent electroosmotic flow in capillary zone electrophoresis (CZE) and micellar electrokinetic capillary chromatography (MEKC) is described. The bilayer coating was formed by noncovalent adsorption of the ionic polymers Polybrene...

  19. Equipment for the Characterization of Synthetic Bio-hybrid Polymers and Micellar Nanoparticles for Stimuli Responsive Materials


    reactions. These materials couple together synthetic polymers with biopolymers including DNA, peptides and proteins. The project therefore requires a... Synthetic Bio-hybrid Polymers and Micellar Nanoparticles for Stimuli Responsive Materials. The views, opinions and/or findings contained in this...this instrument in terms of fully characterizing biomolecule interactions occurring at the interface of semi- synthetic biopolymer -based nano materials

  20. Exciton dynamics in molecular aggregates

    Augulis, R.; Pugžlys, A.; Loosdrecht, P.H.M. van; Pugzlys, A


    The fundamental aspects of exciton dynamics in double-wall cylindrical aggregates of cyanine dyes are studied by means of frequency resolved femtosecond pump-probe spectroscopy. The collective excitations of the aggregates, resulting from intermolecular dipole-dipole interactions have the characteri

  1. Aggregate resources in the Netherlands

    Meulen, M.J. van der; Gessel, S.F. van; Veldkamp, J.G.


    We have built a 3D lithological model of the Netherlands, for the purpose of mapping on-land aggregate resources down to 50 m below the surface. The model consists of voxel cells (1000 · 1000 · 1 m), with lithological composition and aggregate content estimates as primary attributes. These attribute

  2. Exciton dynamics in molecular aggregates

    Augulis, R.; Pugžlys, A.; Loosdrecht, P.H.M. van; Pugzlys, A


    The fundamental aspects of exciton dynamics in double-wall cylindrical aggregates of cyanine dyes are studied by means of frequency resolved femtosecond pump-probe spectroscopy. The collective excitations of the aggregates, resulting from intermolecular dipole-dipole interactions have the

  3. Microbial properties of soil aggregates created by earthworms and other factors: spherical and prismatic soil aggregates from unreclaimed post-mining sites.

    Frouz, J; Krištůfek, V; Livečková, M; van Loo, D; Jacobs, P; Van Hoorebeke, L


    Soil aggregates between 2 and 5 mm from 35- and 45-year-old unreclaimed post-mining sites near Sokolov (Czech Republic) were divided into two groups: spherical and prismatic. X-ray tomography indicated that prismatic aggregates consisted of fragments of claystone bonded together by amorphous clay and roots while spherical aggregates consisted of a clay matrix and organic fragments of various sizes. Prismatic aggregates were presumed to be formed by plant roots and physical processes during weathering of Tertiary mudstone, while earthworms were presumed to contribute to the formation of spherical aggregates. The effects of drying and rewetting and glucose addition on microbial respiration, microbial biomass, and counts of bacteria in these aggregates were determined. Spherical aggregates contained a greater percentage of C and N and a higher C-to-N ratio than prismatic ones. The C content of the particulate organic matter was also higher in the spherical than in the prismatic aggregates. Although spherical aggregates had a higher microbial respiration and biomass, the growth of microbial biomass in spherical aggregates was negatively correlated with initial microbial biomass, indicating competition between bacteria. Specific respiration was negatively correlated with microbial biomass. Direct counts of bacteria were higher in spherical than in prismatic aggregates. Bacterial numbers were more stable in the center than in the surface layers of the aggregates. Transmission electron microscopy indicated that bacteria often occurred as individual cells in prismatic aggregates but as small clusters of cells in spherical aggregates. Ratios of colony forming units (cultivatable bacteria) to direct counts were higher in spherical than in prismatic aggregates. Spherical aggregates also contained faster growing bacteria.

  4. Microbial properties of soil aggregates created by earthworms and other factors: spherical and prismatic soil aggregates from unreclaimed post-mining sites

    Frouz, J.; Kristufek, V.; Liveckova, M.; van Loo, D.; Jacobs, P.; Van Hoorebeke, L. [Charles University of Prague, Prague (Czech Republic). Inst. of Environmental Studies


    Soil aggregates between 2 and 5 mm from 35- and 45-year-old unreclaimed post-mining sites near Sokolov (Czech Republic) were divided into two groups: spherical and prismatic. X-ray tomography indicated that prismatic aggregates consisted of fragments of claystone bonded together by amorphous clay and roots while spherical aggregates consisted of a clay matrix and organic fragments of various sizes. Prismatic aggregates were presumed to be formed by plant roots and physical processes during weathering of Tertiary mudstone, while earthworms were presumed to contribute to the formation of spherical aggregates. The effects of drying and rewetting and glucose addition on microbial respiration, microbial biomass, and counts of bacteria in these aggregates were determined. Spherical aggregates contained a greater percentage of C and N and a higher C-to-N ratio than prismatic ones. The C content of the particulate organic matter was also higher in the spherical than in the prismatic aggregates. Although spherical aggregates had a higher microbial respiration and biomass, the growth of microbial biomass in spherical aggregates was negatively correlated with initial microbial biomass, indicating competition between bacteria. Specific respiration was negatively correlated with microbial biomass. Direct counts of bacteria were higher in spherical than in prismatic aggregates. Bacterial numbers were more stable in the center than in the surface layers of the aggregates. Transmission electron microscopy indicated that bacteria often occurred as individual cells in prismatic aggregates but as small clusters of cells in spherical aggregates. Ratios of colony forming units (cultivatable bacteria) to direct counts were higher in spherical than in prismatic aggregates. Spherical aggregates also contained faster growing bacteria.

  5. A Computationally Efficient Aggregation Optimization Strategy of Model Predictive Control


    Model Predictive Control (MPC) is a popular technique and has been successfully used in various industrial applications. However, the big drawback of MPC involved in the formidable on-line computational effort limits its applicability to relatively slow and/or small processes with a moderate number of inputs. This paper develops an aggregation optimization strategy for MPC that can improve the computational efficiency of MPC. For the regulation problem, an input decaying aggregation optimization algorithm is presented by aggregating all the original optimized variables on control horizon with the decaying sequence in respect of the current control action.

  6. Commercial Building Tenant Energy Usage Aggregation and Privacy

    Livingston, Olga V.; Pulsipher, Trenton C.; Anderson, David M.; Wang, Na


    A growing number of building owners are benchmarking their building energy use. This requires the building owner to acquire monthly whole-building energy usage information, which can be challenging for buildings in which individual tenants have their own utility meters and accounts with the utility. Some utilities and utility regulators have turned to aggregation of customer energy use data (CEUD) as a way to give building owners whole-building energy usage data while protecting customer privacy. Meter profile aggregation adds a layer of protection that decreases the risk of revealing CEUD as the number of meters aggregated increases. The report statistically characterizes the similarity between individual energy usage patterns and whole-building totals at various levels of meter aggregation.

  7. Molecular aggregation of humic substances

    Wershaw, R. L.


    Humic substances (HS) form molecular aggregates in solution and on mineral surfaces. Elucidation of the mechanism of formation of these aggregates is important for an understanding of the interactions of HS in soils arid natural waters. The HS are formed mainly by enzymatic depolymerization and oxidation of plant biopolymers. These reactions transform the aromatic and lipid plant components into amphiphilic molecules, that is, molecules that consist of separate hydrophobic (nonpolar) and hydrophilic (polar) parts. The nonpolar parts of the molecules are composed of relatively unaltered segments of plant polymers and the polar parts of carboxylic acid groups. These amphiphiles form membrane-like aggregates on mineral surfaces and micelle-like aggregates in solution. The exterior surfaces of these aggregates are hydrophilic, and the interiors constitute separate hydrophobic liquid-like phases.

  8. Optical monitoring of particle aggregates

    John Gregory


    Methods for monitoring particle aggregation are briefly reviewed. Most of these techniques are based on some form of light scattering and may be greatly dependent on the optical properties of aggregates, which are not generally known. As fractal aggregates grow larger their density can become very low and this has important practical consequences for light scattering. For instance, the scattering coefficient may be much less than for solid objects, which means that the aggregates can appear much smaller than their actual size by a light transmission method. Also, for low-density objects, a high proportion of the scattered light energy is within a small angle of the incident beam, which may also be relevant for measurements with aggregates.Using the 'turbidity fluctuation' technique as an example, it is shown how the apparent size of hydroxide flocs depends mainly on the included impurity particles, rather than the hydroxide precipitate itself. Results using clay suspensions with hydrolyzing coagulants and under are discussed.

  9. Dye Aggregation in Ink Jet

    Thomas Paul; Sarfraz Hussain


    Dye aggregation has long been recognised as a key factor in performance, and this is no less so in ink jet applications. The aggregation state was shown to be important in many different areas ranging from the use of dyes in photodynamic therapies all the way to colorants for dying of fabrics. Therefore different methods to investigate dye association qualitatively and quantitatively were developed. A simple procedure to study aggregation could be a useful tool to characterise dyes for ink jet printing. It is critically reviewed the methods used to study dye aggregation, and discussed some of the main conclusions. This will be illustrated by examples of ink jet dye aggregation and its study in aqueous and ink systems. The results are used to correlate the solution behaviour of dyes with their print performance.


    F.; Einar; Kruis


    A new procedure was developed for estimating the effective collision diameter of an aggregate composed of primary particles of any size. The coagulation coefficient of two oppositely charged particles was measured experimentally and compared with classic Fuchs theory, including a new method to account for particle non-sphericity. A second set of experiments were performed on well-defined nanoparticle aggregates at different stages of sintering, i.e. from the aggregate to the fully sintered stage. Here, electrical mobility was used to characterize the particle drag. The aggregates are being built from two different size-fractionated nanoparticle aerosols, the non-aggregated particles are discarded by an electrofilter and then they are passed through a furnace at concentrations low enough not to induce coagulation.

  11. Perspectives on Preference Aggregation.

    Regenwetter, Michel


    For centuries, the mathematical aggregation of preferences by groups, organizations, or society itself has received keen interdisciplinary attention. Extensive theoretical work in economics and political science throughout the second half of the 20th century has highlighted the idea that competing notions of rational social choice intrinsically contradict each other. This has led some researchers to consider coherent democratic decision making to be a mathematical impossibility. Recent empirical work in psychology qualifies that view. This nontechnical review sketches a quantitative research paradigm for the behavioral investigation of mathematical social choice rules on real ballots, experimental choices, or attitudinal survey data. The article poses a series of open questions. Some classical work sometimes makes assumptions about voter preferences that are descriptively invalid. Do such technical assumptions lead the theory astray? How can empirical work inform the formulation of meaningful theoretical primitives? Classical "impossibility results" leverage the fact that certain desirable mathematical properties logically cannot hold in all conceivable electorates. Do these properties nonetheless hold true in empirical distributions of preferences? Will future behavioral analyses continue to contradict the expectations of established theory? Under what conditions do competing consensus methods yield identical outcomes and why do they do so?

  12. Orthogonal flexible Rydberg aggregates

    Leonhardt, K.; Wüster, S.; Rost, J. M.


    We study the link between atomic motion and exciton transport in flexible Rydberg aggregates, assemblies of highly excited light alkali-metal atoms, for which motion due to dipole-dipole interaction becomes relevant. In two one-dimensional atom chains crossing at a right angle adiabatic exciton transport is affected by a conical intersection of excitonic energy surfaces, which induces controllable nonadiabatic effects. A joint exciton-motion pulse that is initially governed by a single energy surface is coherently split into two modes after crossing the intersection. The modes induce strongly different atomic motion, leading to clear signatures of nonadiabatic effects in atomic density profiles. We have shown how this scenario can be exploited as an exciton switch, controlling direction and coherence properties of the joint pulse on the second of the chains [K. Leonhardt et al., Phys. Rev. Lett. 113, 223001 (2014), 10.1103/PhysRevLett.113.223001]. In this article we discuss the underlying complex dynamics in detail, characterize the switch, and derive our isotropic interaction model from a realistic anisotropic one with the addition of a magnetic bias field.

  13. Orthogonal flexible Rydberg aggregates

    Leonhardt, K; Rost, J M


    We study the link between atomic motion and exciton transport in flexible Rydberg aggregates, assemblies of highly excited light alkali atoms, for which motion due to dipole-dipole interaction becomes relevant. In two one-dimensional atom chains crossing at a right angle adiabatic exciton transport is affected by a conical intersection of excitonic energy surfaces, which induces controllable non-adiabatic effects. A joint exciton/motion pulse that is initially governed by a single energy surface is coherently split into two modes after crossing the intersection. The modes induce strongly different atomic motion, leading to clear signatures of non-adiabatic effects in atomic density profiles. We have shown how this scenario can be exploited as an exciton switch, controlling direction and coherence properties of the joint pulse on the second of the chains [K.~Leonhardt {\\it et al.}, Phys.~Rev.~Lett. {\\bf 113} 223001 (2014)]. In this article we discuss the underlying complex dynamics in detail, characterise the ...

  14. Structural Transitions and Aggregation in Amyloidogenic Proteins

    Steckmann, Timothy; Chapagain, Prem; Gerstman, Bernard; Computational and Theoretical Biophysics Group at Florida International University Team


    Amyloid fibrils are a common component in many debilitating human neurological diseases such as Alzheimer's and Parkinson's. A detailed molecular-level understanding of the formation process of amyloid fibrils is crucial for developing methods to slow down or prevent these horrific diseases. Alpha-helix to beta-sheet structural transformation is commonly observed in the process of fibril formation. We performed replica-exchange molecular dynamics simulations of structural transformations in an engineered model peptide cc-beta. Several sets of simulations with different number of cc-beta monomers were considered. Conversion of alpha-helix monomers to beta strands and the aggregation of beta strand monomers into sheets were analyzed as a function of the system size. Hydrogen bond analysis was performed and the beta-aggregate structures were characterized by a nematic order parameter.

  15. Diffusion-Limited Aggregation with Polygon Particles

    邓礼; 王延颋; 欧阳钟灿


    Diffusion-limited aggregation (DLA) assumes that particles perform pure random walk at a finite tem- perature and aggregate when they come close enough and stick together. Although it is well known that DLA in two dimensions results in a ramified fractal structure, how the particle shape influences the formed morphology is still un- clear. In this work, we perform the off-lattice two-dimensional DLA simulations with different particle shapes of triangle, quadrangle, pentagon, hexagon, and octagon, respectively, and compare with the results for circular particles. Our results indicate that different particle shapes only change the local structure, but have no effects on the global structure of the formed fractal duster. The local compactness decreases as the number of polygon edges increases.

  16. DBAS: A Deployable Bandwidth Aggregation System

    Habak, Karim; Harras, Khaled A


    The explosive increase in data demand coupled with the rapid deployment of various wireless access technologies have led to the increase of number of multi-homed or multi-interface enabled devices. Fully exploiting these interfaces has motivated researchers to propose numerous solutions that aggregate their available bandwidths to increase overall throughput and satisfy the end-user's growing data demand. These solutions, however, have faced a steep deployment barrier that we attempt to overcome in this paper. We propose a Deployable Bandwidth Aggregation System (DBAS) for multi-interface enabled devices. Our system does not introduce any intermediate hardware, modify current operating systems, modify socket implementations, nor require changes to current applications or legacy servers. The DBAS architecture is designed to automatically estimate the characteristics of applications and dynamically schedule various connections or packets to different interfaces. Since our main focus is deployability, we fully i...

  17. Role of Standard Demand Response Signals for Advanced Automated Aggregation

    Lawrence Berkeley National Laboratory; Kiliccote, Sila


    Emerging standards such as OpenADR enable Demand Response (DR) Resources to interact directly with Utilities and Independent System Operators to allow their facility automation equipment to respond to a variety of DR signals ranging from day ahead to real time ancillary services. In addition, there are Aggregators in today’s markets who are capable of bringing together collections of aggregated DR assets and selling them to the grid as a single resource. However, in most cases these aggregated resources are not automated and when they are, they typically use proprietary technologies. There is a need for a framework for dealing with aggregated resources that supports the following requirements: • Allows demand-side resources to participate in multiple DR markets ranging from wholesale ancillary services to retail tariffs without being completely committed to a single entity like an Aggregator; • Allow aggregated groups of demand-side resources to be formed in an ad hoc fashion to address specific grid-side issues and support the optimization of the collective response of an aggregated group along a number of different dimensions. This is important in order to taylor the aggregated performance envelope to the needs to of the grid; • Allow aggregated groups to be formed in a hierarchical fashion so that each group can participate in variety of markets from wholesale ancillary services to distribution level retail tariffs. This paper explores the issues of aggregated groups of DR resources as described above especially within the context of emerging smart grid standards and the role they will play in both the management and interaction of various grid-side entities with those resources.

  18. Probabilistic prediction models for aggregate quarry siting

    Robinson, G.R.; Larkins, P.M.


    Weights-of-evidence (WofE) and logistic regression techniques were used in a GIS framework to predict the spatial likelihood (prospectivity) of crushed-stone aggregate quarry development. The joint conditional probability models, based on geology, transportation network, and population density variables, were defined using quarry location and time of development data for the New England States, North Carolina, and South Carolina, USA. The Quarry Operation models describe the distribution of active aggregate quarries, independent of the date of opening. The New Quarry models describe the distribution of aggregate quarries when they open. Because of the small number of new quarries developed in the study areas during the last decade, independent New Quarry models have low parameter estimate reliability. The performance of parameter estimates derived for Quarry Operation models, defined by a larger number of active quarries in the study areas, were tested and evaluated to predict the spatial likelihood of new quarry development. Population density conditions at the time of new quarry development were used to modify the population density variable in the Quarry Operation models to apply to new quarry development sites. The Quarry Operation parameters derived for the New England study area, Carolina study area, and the combined New England and Carolina study areas were all similar in magnitude and relative strength. The Quarry Operation model parameters, using the modified population density variables, were found to be a good predictor of new quarry locations. Both the aggregate industry and the land management community can use the model approach to target areas for more detailed site evaluation for quarry location. The models can be revised easily to reflect actual or anticipated changes in transportation and population features. ?? International Association for Mathematical Geology 2007.

  19. Differentiation between naproxen, naproxen-protein conjugates, and naproxen-lysine in plasma via micellar electrokinetic capillary chromatography : a new approach in the bioanalysis of drug targeting preparations

    Albrecht, C.; Reichen, J; Visser, Jan; Meijer, D.K F; Thormann, W


    Pharmacotherapy through the targeting of drugs is a promising new approach that requires adequate analytical methods capable of differentiating between the free drug the drug carrier, and metabolites. Using micellar electrokinetic capillary chromatography (MECC), we report the separation of naproxen

  20. Effect of tartarate and citrate based food additives on the micellar properties of sodium dodecylsulfate for prospective use as food emulsifier.

    Banipal, Tarlok S; Kaur, Harjinder; Kaur, Amanpreet; Banipal, Parampaul K


    Citrate and tartarate based food preservatives can be used to enhance the emulsifying properties of sodium dodecylsulfate (SDS) based micellar system and thus making it appropriate for food applications. Exploration of interactions between the two species is the key constraint for execution of such ideas. In this work various micellar and thermodynamic parameters of SDS like critical micellar concentration (CMC), standard Gibbs free energy of micellization (ΔG(0)mic.) etc. have been calculated in different concentrations of disodium tartarate (DST) and trisodium citrate (TSC) in the temperature range (288.15-318.15)K from the conductivity and surface tension measurements. The parameters obtained from these studies reveal the competitive nature of both the additives with SDS for available positions at the air/water interface. TSC is found to be more effective additive in order to make SDS micellar system better for its potential applications as food emulsifier.

  1. Importance of critical micellar concentration for the prediction of solubility enhancement in biorelevant media.

    Ottaviani, G; Wendelspiess, S; Alvarez-Sánchez, R


    This study evaluated if the intrinsic surface properties of compounds are related to the solubility enhancement (SE) typically observed in biorelevant media like fasted state simulated intestinal fluids (FaSSIF). The solubility of 51 chemically diverse compounds was measured in FaSSIF and in phosphate buffer and the surface activity parameters were determined. This study showed that the compound critical micellar concentration parameter (CMC) correlates strongly with the solubility enhancement (SE) observed in FaSSIF compared to phosphate buffer. Thus, the intrinsic capacity of molecules to form micelles is also a determinant for each compound's affinity to the micelles of biorelevant surfactants. CMC correlated better with SE than lipophilicity (logD), especially over the logD range typically covered by drugs (2 media, thereby enhancing oral bioavailability of drug candidates.

  2. Biomedical Evaluation of Cortisol, Cortisone, and Corticosterone along with Testosterone and Epitestosterone Applying Micellar Electrokinetic Chromatography

    Bączek, Tomasz; Olędzka, Ilona; Konieczna, Lucyna; Kowalski, Piotr; Plenis, Alina


    The validated micellar electrokinetic chromatography (MEKC) was proposed for the determination of five steroid hormones in human urine samples. That technique allowed for the separation and quantification of cortisol, cortisone, corticosterone, testosterone, and epitestosterone and was sensitive enough to detect low concentrations of these searched steroids in urine samples at the range of 2–300 ng/mL. The proposed MEKC technique with solid-phase extraction (SPE) procedure was simple, rapid, and has been successfully applied as a routine procedure to analyze steroids in human urine samples. The MEKC method offered a potential in clinical routine practice because of the short analysis time (8 min), low costs, and simultaneous analysis of five endogenous hormones. Due to its simplicity, speed, accuracy, and high recovery, the proposed method could offer a tool to determine steroid hormones as potential biomarkers in biomedical investigations, what was additionally revealed with healthy volunteers. PMID:22536129

  3. Determination of adrenal steroids by microfluidic chip using micellar electrokinetic chromatography.

    Shen, Shuanglong; Li, Yan; Wakida, Shin-ichi; Takeda, Sahori


    This paper describes a sensitive and convenient method to separate progesterone, 17alpha-hydroxy progesterone, cortexolone, hydrocortisone and cortisone, all of which are steroids and have similar structures, using microfluidic chip-based technology with UV detection at 252 nm. We successfully obtained high-speed separation of the five steroids within 70 s in optimized microfluidic controls and micellar electrokinetic chromatography (MEKC) separation conditions. Fairly good linearity with correlation coefficient of over 0.98 from 10 or 20 to 100 mg/l steroid chemicals was obtained. The limits of detection obtained at a signal to noise ratio of 3 were from 3.89 to 7.80 mg/l. The values of the relative standard deviation (RSD) were 0.98-1.34% for repetitive injection (n = 12) and the intraday and interday RSDs were below 6%. The highly stable response reflected the feasibility of this method.


    WANG Erjian; FANG Peiji; FENG Xinde


    A kind of cationic compounds, having benzophenone end group and various length chain (PKT) (BP-CH2N + R2R'·X-, R&R' different chain length alkyl group)were used as photosensitizers. Various BP/TEA systems have been used for study, The efficiency of MMA photopolymerization initiated by them shows PKT > BP in homogeneous water solution and PKT> BP/CTAB in micellar water solution. The results obtained indicate that catalytic effects of PKT type functional micelles are far greater than that of common micelle with the enhancement of polymerization rate over 10 times compared with BP in water solution. The catalytic role,reaction character of PKT, effect of counter ions and retarding effect of oxygen have also been discussed.

  5. Two-peak phenomena and formation origin in micellar electrokinetic capillary chromatography

    陈冠华; 杨更亮; 田益玲; 陈义


    The formation origin of two peaks in micellar electrokinetic capillary chromatography by using cetyltrimethylaminium bromide (or sodium dodecyl sulfate) as pseudo stationary phase is studied. It is pointed out that two peaks may appear for one component in certain conditions. Experiments show that the relative areas of the two peaks of the corresponding component depend on the time and temperature of reaction between the analyte and the surfactant, and the concentration of surfactant in the sample solution. One of the two peaks increase with the increase of surfactant concentration in the sample solution while reverse for another peak. Temperature can accelerate the reaction process. This means that the interaction between analyte and surfactant is a slow process, and a stable substance can be produced from the interaction and leads to the formation of two peaks. The standpoint is confirmed by the infrared and nuclear magnetic resonance spectra of the product from the reaction between cetyltrimethylaminium bromide and m-hydroxyl benzoic acid.

  6. Analysis of pharmaceutical preparations containing antihistamine drugs by micellar liquid chromatography.

    Martínez-Algaba, C; Bermúdez-Saldaña, J M; Villanueva-Camañas, R M; Sagrado, S; Medina-Hernández, M J


    Rapid chromatographic procedures for analytical quality control of pharmaceutical preparations containing antihistamine drugs, alone or together with other kind of compounds are proposed. The method uses C18 stationary phases and micellar mobile phases of cetyltrimethylammonium bromide (CTAB) with either 1-propanol or 1-butanol as organic modifier. The proposed procedures allow the determination of the antihistamines: brompheniramine, chlorcyclizine, chlorpheniramine, diphenhydramine, doxylamine, flunarizine, hydroxyzine, promethazine, terfenadine, tripelennamine and triprolidine, in addition to caffeine, dextromethorphan, guaifenesin, paracetamol and pyridoxine in different pharmaceutical presentations (tablets, capsules, suppositories, syrups and ointments). The methods require minimum handling sample and are rapid (between 3 and 12 min at 1 mLmin(-1) flow rate) and reproducible (R.S.D. values<5%). Limits of detection are lower than 1 microgmL(-1) and the recoveries of the analytes in the pharmaceutical preparations are in the range 100+/-10%.

  7. Separation of human, bovine, and porcine insulins, three very closely related proteins, by micellar electrokinetic chromatography.

    Lamalle, Caroline; Roland, Diane; Crommen, Jacques; Servais, Anne-Catherine; Fillet, Marianne


    Human, bovine, and porcine insulins are small proteins with very closely related amino acid sequences, which makes their separation challenging. In this study, we took advantage of the high-resolution power of CE, and more particularly of micellar electrokinetic chromatography, to separate those biomolecules. Among several surfactants, perfluorooctanoic acid ammonium salt was selected. Then, using a design of experiments approach, the optimal BGE composition was found to consist of 50 mM ammonium acetate pH 9.0, 65 mM perfluorooctanoic acid ammonium salt, and 4% MeOH. The three insulins could be separated within 12 min with a satisfactory resolution. This method could be useful to detect possible counterfeit pharmaceutical formulations. Indeed, it would be easy to determine if human insulin was replaced by bovine or porcine insulin.

  8. Predicting human intestinal absorption in the presence of bile salt with micellar liquid chromatography.

    Waters, Laura J; Shokry, Dina S; Parkes, Gareth M B


    Understanding intestinal absorption for pharmaceutical compounds is vital to estimate the bioavailability and therefore the in vivo potential of a drug. This study considers the application of micellar liquid chromatography (MLC) to predict passive intestinal absorption with a selection of model compounds. MLC is already known to aid prediction of absorption using simple surfactant systems; however, with this study the focus was on the presence of a more complex, bile salt surfactant, as would be encountered in the in vivo environment. As a result, MLC using a specific bile salt has been confirmed as an ideal in vitro system to predict the intestinal permeability for a wide range of drugs, through the development of a quantitative partition-absorption relationship. MLC offers many benefits including environmental, economic, time-saving and ethical advantages compared with the traditional techniques employed to obtain passive intestinal absorption values. Copyright © 2016 John Wiley & Sons, Ltd.

  9. Biomedical Evaluation of Cortisol, Cortisone, and Corticosterone along with Testosterone and Epitestosterone Applying Micellar Electrokinetic Chromatography

    Tomasz Bączek


    Full Text Available The validated micellar electrokinetic chromatography (MEKC was proposed for the determination of five steroid hormones in human urine samples. That technique allowed for the separation and quantification of cortisol, cortisone, corticosterone, testosterone, and epitestosterone and was sensitive enough to detect low concentrations of these searched steroids in urine samples at the range of 2–300 ng/mL. The proposed MEKC technique with solid-phase extraction (SPE procedure was simple, rapid, and has been successfully applied as a routine procedure to analyze steroids in human urine samples. The MEKC method offered a potential in clinical routine practice because of the short analysis time (8 min, low costs, and simultaneous analysis of five endogenous hormones. Due to its simplicity, speed, accuracy, and high recovery, the proposed method could offer a tool to determine steroid hormones as potential biomarkers in biomedical investigations, what was additionally revealed with healthy volunteers.

  10. Chiral cyclodextrin-modified micellar electrokinetic chromatography and chemometric techniques for green tea samples origin discrimination.

    Pasquini, Benedetta; Orlandini, Serena; Goodarzi, Mohammad; Caprini, Claudia; Gotti, Roberto; Furlanetto, Sandra


    Catechins and methylxanthines were determined in 92 green tea (GT) samples originating from Japan and China by using micellar electrokinetic chromatography with the addition of (2-hydroxypropyl)-β-cyclodextrin. GT samples showed high concentrations of (-)-epigallocatechin gallate and caffeine, with (-)-epigallocatechin, (-)-epicatechin gallate and (-)-epicatechin in relevant content and (+)-catechin, (-)-catechin and theobromine in much lower amounts. The amount of all the considered compounds was higher for Chinese GTs, with the exception of (-)-epicatechin gallate. Pattern recognition methods were applied to discriminate GTs according to geographical origin, which is an important factor to determine quality and reputation of a commercial tea product. Data analysis was performed by principal component analysis and hierarchical cluster analysis as exploratory techniques. Linear discriminant analysis and quadratic discriminant analysis were utilized as discrimination techniques, obtaining a very good rate of correct classification and prediction.

  11. Silver and gold nanocluster catalyzed reduction of methylene blue by arsine in micellar medium

    Subrata Kundu; Sujit Kumar Ghosh; Madhuri Mandal; Tarasankar Pal


    Arsenic can be determined in parts-per-million (ppm) level by absorbance measurement. This method is based on the quantitative colour bleaching of the dye, methylene blue by arsine catalyzed by nanoparticles in micellar medium. The arsine has been generated in situ from sodium arsenate by NaBH4 reduction. The absorbance measurement was carried out at the max of the dye at 660 nm. The calibration graph set-up for three linear dynamic ranges (LDR) are 0–8.63 ppm, 0–1.11 ppm and 0–0.11 ppm and limit of detections (LODs) are 1.3, 0.53 and 0.03 ppm, respectively. This method is simple, sensitive and easy to carry out. It is free from phosphate and silicate interference and applicable to real sample analysis.

  12. Absorption, fluorescence, and acid-base equilibria of rhodamines in micellar media of sodium dodecyl sulfate

    Obukhova, Elena N.; Mchedlov-Petrossyan, Nikolay O.; Vodolazkaya, Natalya A.; Patsenker, Leonid D.; Doroshenko, Andrey O.; Marynin, Andriy I.; Krasovitskii, Boris M.


    Rhodamine dyes are widely used as molecular probes in different fields of science. The aim of this paper was to ascertain to what extent the structural peculiarities of the compounds influence their absorption, emission, and acid-base properties under unified conditions. The acid-base dissociation (HR+ ⇄ R + H+) of a series of rhodamine dyes was studied in sodium n-dodecylsulfate micellar solutions. In this media, the form R exists as a zwitterion R±. The indices of apparent ionization constants of fifteen rhodamine cations HR+ with different substituents in the xanthene moiety vary within the range of pKaapp = 5.04 to 5.53. The distinct dependence of emission of rhodamines bound to micelles on pH of bulk water opens the possibility of using them as fluorescent interfacial acid-base indicators.

  13. Determination of catechins in matcha green tea by micellar electrokinetic chromatography.

    Weiss, David J; Anderton, Christopher R


    Catechins in green tea are known to have many beneficial health properties. Recently, it has been suggested that matcha has greater potential health benefits than other green teas. Matcha is a special powdered green tea used in the Japanese tea ceremony. However, there has been no investigation to quantitate the catechin intake from matcha compared to common green teas. We have developed a rapid method of analysis of five catechins and caffeine in matcha using micellar electrokinetic chromatography. Results are presented for water and methanol extractions of matcha compared with water extraction of a popular green tea. Using a mg catechin/g of dry leaf comparison, results indicate that the concentration of epigallocatechin gallate (EGCG) available from drinking matcha is 137 times greater than the amount of EGCG available from China Green Tips green tea, and at least three times higher than the largest literature value for other green teas.

  14. Study of Tea Digitized Chromatographic Fingerprint Spectra Using Micellar Electrokinetic Chromatography

    SONG, Guan-Qun; LIN, Jin-Ming; QU, Feng; DONG, Wen-Ju


    This paper described the principle of digitized chromatographic fingerprint spectrum and established digitized chromatographic fingerprint spectra of ten brands of Chinese famous tea by the micellar electrokinetic chromatography. This work was done using a 25 mmol. L- 1 sodium dodecylsulfate in a 20 mmol· L-1borate (pH 7.0) solution as running buffer, 20 kV applied potential and detection at 280 nm. The chromatographic fingerprint spectra were digitized by the relative retention value (α)and the relative area (Sr), and were analyzed to identify the tea samples. In the absence of the standard samples, the present method was easy setup and inexpensive, and provided the applicable information for the quality assessment of teas.

  15. Influence of boundary conditions and confinement on nonlocal effects in flows of wormlike micellar systems.

    Masselon, Chloé; Colin, Annie; Olmsted, Peter D


    In this paper we report on the influence of different geometric and boundary constraints on nonlocal (spatially inhomogeneous) effects in wormlike micellar systems. In a previous paper, nonlocal effects were observable by measuring the local rheological flow curves of micelles flowing in a microchannel under different pressure drops, which appeared to differ from the flow curve measured using conventional rheometry. Here we show that both the confinement and the boundary conditions can influence those nonlocal effects. The role of the nature of the surface is analyzed in detail using a simple scalar model that incorporates inhomogeneities, which captures the flow behavior in both wide and confined geometries. This leads to an estimate for the nonlocal "diffusion" coefficient (i.e., the shear curvature viscosity) which corresponds to a characteristic length from 1 to 10 microm.

  16. Simultaneous determination of four bioactive constituents in Liuwei Dihuang Pills by micellar electrokinetic chromatography.

    Zhao, Xinfeng; Wang, Yue; Sun, Yuqing


    A micellar electrokinetic chromatography (MEKC) method for the simultaneous determination of four bioactive constituents (morroniside, loganin, paeoniflorin and paeonal) in the Chinese patent medicine Liuwei Dihuang Pills is established. A carrier composed of 0.2M boric acid, 0.02 M sodium dodecyl sulfate (SDS) and 5% acetonitrile (pH was adjusted to 10.5 with 0.1 M NaOH) is found to be the most suitable electrolyte for this separation. The four constituents in Liuwei Dihuang Pills can be easily determined within 16 min. Optimization of separation is realized with the univariate approach by studying the effects of four factors relevant to run buffer on migration times.

  17. Fluoride binding in water with the use of micellar nanodevices based on salophen complexes.

    Keymeulen, Flore; De Bernardin, Paolo; Giannicchi, Ilaria; Galantini, Luciano; Bartik, Kristin; Dalla Cort, Antonella


    The use of micelles to transpose lipophilic receptors, such as uranyl-salophen complexes, into an aqueous environment is a valuable and versatile tool. Receptor 1 incorporated into CTABr micelles forms a supramolecular system that exhibits excellent binding properties towards fluoride in water, despite the competition of the aqueous medium. To fully evaluate the potential of micellar nanodevices, we extended our previous study to other types of surfactants and to a uranyl-salophen receptor with a more extended aromatic surface. Paramagnetic relaxation enhancement experiments were used to obtain information on the location of the two receptors within the micelles and complementary information was obtained from dynamic light scattering experiments. With these data it is possible to account for the key factors necessary to obtain an efficient supramolecular device for anion binding in water.

  18. Optimization of the Separation of Quinolines in Micellar Liquid Chromatography by Experimental Design and Regression Models



    The chemometrics approach was applied to the optimization of separation of quinolines in micellar liquid tigated by means of multivariate analysis. The factors considered were the concentration of sodium dodecyl sulfate (SDS), the organic modifier concentration and the length of its alkyl chain, and pH of the mobile phase. The ex-periments were performed according to a face centered cube response surface experimental design. In order to op-timize the separation a Pareto-optimality method was employed. The models were verified, because a good agree-ment was observed between the predicted and experimental values of the chromatographic response function in the optimal condition. The obtained regression models were characterized by both descriptive and predictive ability (R2≥0.97 and R2cv≥0.92) and allowed the chromatographic separation of the quinolines with a good resolution and a total analysis time of 50 min.

  19. Nonequilibrium Fluctuation Relation for Sheared Micellar Gel in a Jammed State

    Majumdar, Sayantan; Sood, A. K.


    We show that the shear rate at a fixed shear stress in a micellar gel in a jammed state exhibits large fluctuations, showing positive and negative values, with the mean shear rate being positive. The resulting probability distribution functions of the global power flux to the system vary from Gaussian to non-Gaussian, depending on the driving stress, and in all cases show similar symmetry properties as predicted by the Gallavotti-Cohen steady state fluctuation relation. The fluctuation relation allows us to determine an effective temperature related to the structural constraints of the jammed state. We have measured the stress dependence of the effective temperature. Further, experiments reveal that the effective temperature and the standard deviation of the shear-rate fluctuations increase with the decrease of the system size.

  20. Sagan numbers

    Mendonça, J. Ricardo G.


    We define a new class of numbers based on the first occurrence of certain patterns of zeros and ones in the expansion of irracional numbers in a given basis and call them Sagan numbers, since they were first mentioned, in a special case, by the North-american astronomer Carl E. Sagan in his science-fiction novel "Contact." Sagan numbers hold connections with a wealth of mathematical ideas. We describe some properties of the newly defined numbers and indicate directions for further amusement.

  1. Fibonacci numbers

    Vorob'ev, Nikolai Nikolaevich


    Fibonacci numbers date back to an 800-year-old problem concerning the number of offspring born in a single year to a pair of rabbits. This book offers the solution and explores the occurrence of Fibonacci numbers in number theory, continued fractions, and geometry. A discussion of the ""golden section"" rectangle, in which the lengths of the sides can be expressed as a ration of two successive Fibonacci numbers, draws upon attempts by ancient and medieval thinkers to base aesthetic and philosophical principles on the beauty of these figures. Recreational readers as well as students and teacher

  2. Analysis of epinephrine, norepinephrine, and dopamine in urine samples of hospital patients by micellar liquid chromatography.

    García Ferrer, Daniel; García García, Aurelio; Peris-Vicente, Juan; Gimeno-Adelantado, José Vicente; Esteve-Romero, Josep


    An analytical method based on micellar liquid chromatography was developed to determine the concentration of three catecholamines (epinephrine, norepinephrine, and dopamine) in urine. The detection of these compounds in urine can be useful to diagnose several diseases, related to stress and sympathoadrenal system dysfunction, using a non-invasive collection procedure. The sample pretreatment was a simple dilution in a micellar solution, filtration, and direct injection, thus avoiding time-consuming and tedious extraction steps. Therefore, there is no need to use an internal standard. The three catecholamines were eluted using a C18 column and a mobile phase of 0.055 M sodium dodecyl sulfate-1.5% methanol buffered at pH 3.8 running at 1.5 mL/min under isocratic mode in less than 25 min. The detection was performed by amperometry applying a constant potential of +0.5 V. The procedure was validated following the guidelines of the European Medicines Agency in terms of the following: calibration range (0.09-5 μg/mL), linearity (r(2) > 0.9995), limit of detection (0.02 μg/mL), within- and between-run accuracy (-6.5 to +8.4%) and precision (<10.2%), dilution integrity, matrix effect, robustness (<8.4), and stability. The obtained values were below those required by the guide. The method was rapid, easy-to-handle, eco-friendly, and safe and provides reliable quantitative data, and is thus useful for routine analysis. The procedure was applied to the analysis of epinephrine, norepinephrine, and dopamine in urine samples from patients of a local hospital.

  3. Electrophoretic concentration and sweeping-micellar electrokinetic chromatography analysis of cationic drugs in water samples.

    Wuethrich, Alain; Haddad, Paul R; Quirino, Joselito P


    Sample preparation by electrophoretic concentration, followed by analysis using sweeping-micellar electrokinetic chromatography, was studied as a green and simple analytical strategy for the trace analysis of cationic drugs in water samples. Electrophoretic concentration was conducted using 50 mmol/L ammonium acetate at pH 5 as acceptor electrolyte. Electrophoretic concentration was performed at 1.0 kV for 50 min and 0.5 kV and 15 min for purified and 10-fold diluted waste water samples, respectively. Sweeping-micellar electrokinetic chromatography was with 100 mmol/L sodium phosphate at pH 2, 100 mmol/L sodium dodecyl sulfate and 27.5%-v/v acetonitrile as separation electrolyte. The separation voltage was -20 kV, UV-detection was at 200 nm, and the acidified concentrate was injected for 36 s at 1 bar (or 72% of the total capillary length, 60 cm). Both purified water and 10-fold diluted waste water exhibited a linear range of two orders of concentration magnitude. The coefficient of determination, and intra- and interday repeatability were 0.991-0.997, 2.5-6.2, and 4.4-9.7%RSD (n=6), respectively, for purified water. The values were 0.991-0.997, 3.4-7.1, and 8.7-9.8%RSD (n=6), correspondingly, for 10-fold diluted waste water. The method detection limit was in the range from 0.04-0.09 to 1.20-6.97 ng/mL for purified and undiluted waste water, respectively.

  4. Formation and properties of reverse micellar cubic liquid crystals and derived emulsions.

    Rodríguez-Abreu, Carlos; Shrestha, Lok Kumar; Varade, Dharmesh; Aramaki, Kenji; Maestro, Alicia; Quintela, Arturo López; Solans, Conxita


    The structure of the reverse micellar cubic (I2) liquid crystal and the adjacent micellar phase in amphiphilic block copolymer/water/oil systems has been studied by small-angle X-ray scattering (SAXS), rheometry, and differential scanning calorimetry (DSC). Upon addition of water to the copolymer/oil mixture, spherical micelles are formed and grow in size until a disorder-order transition takes place, which is related to a sudden increase in the viscosity and shear modulus. The transition is driven by the packing of the spherical micelles into a Fd3m cubic lattice. The single-phase I2 liquid crystals show gel-like behavior and elastic moduli higher than 104 Pa, as determined by oscillatory measurements. Further addition of water induces phase separation, and it is found that reverse water-in-oil emulsions with high internal phase ratio and stabilized by I2 liquid crystals can be prepared in the two-phase region. Contrary to liquid-liquid emulsions, both the elastic modulus and the viscosity decrease with the fraction of dispersed water, due to a decrease in the crystalline fraction in the sample, although the reverse emulsions remain gel-like even at high volume fractions of the dispersed phase. A temperature induced order-disorder transition can be detected by calorimetry and rheometry. Upon heating the I2 liquid crystals, two thermal events associated with small enthalpy values were detected: one endothermic, related to the "melting" of the liquid crystal, and the other exothermic, attributed to phase separation. The melting of the liquid crystal is associated with a sudden drop in viscosity and shear moduli. Results are relevant for understanding the formation of cubic-phase-based reverse emulsions and for their application as templates for the synthesis of structured materials.

  5. Micellar-polymer joint demonstration project, Wilmington Field, California. Annual report, 1976--1977

    Wade, J.E.


    Work accomplished under the contract during the first year of operation consisted of Micellar-Polymer laboratory systems design; Test Pattern Model Studies; Drilling and coring injection well FT-1; Pressure Transient Tests of Wells Z-81, Z1-16and FT-1; as well as design and construction of a portion of the surface facilities. Radial core floods conducted by Marathon Research Center using reservoir rock and fluid samples from the Wilmington Field demonstrated that Micellar-Polymer systems showing good recovery efficiency could be made from several different commercially available sulfonates. Residual oil saturations obtained were as low as 7 to 10% pore volume. Sulfonates made from Wilmington crude oil also proved to be effective. Polyacrylamides, both liquid and dry, as well as polysaccharides proved equally effective as a mobility buffer. Test pattern model studies were conducted on seven different arrays of wells. These studies showed that the pattern originally proposed exhibited poor areal sweep efficiency and was seriously affected by waterflood operations in the North Flank of the fault block. An E-W staggered line drive backed-up against the Pier A Fault appeared to be the best pattern studied, assuming the Pier A Fault to be a pressure barrier. Injection well FT-1 was drilled, cored and completed in the Hx/sub a/ sand. Cores were taken using low-solids, polymer drilling fluid and were frozen on site. The frozen cores from the project area will be used in the Phase B laboratory work. Pressure Transient Tests run in Z-81 and Z1-16 indicated the Pier A Fault to be pressure competent. The plant site was located adjacent to a railroad siding near the injection wells. The site was graded and seven 2000 barrel tanks were erected. The tanks were internally plastic coated on site. Mixing, filtering and injection facilities are being installed.

  6. Invertible micellar polymer assemblies for delivery of poorly water-soluble drugs.

    Hevus, Ivan; Modgil, Amit; Daniels, Justin; Kohut, Ananiy; Sun, Chengwen; Stafslien, Shane; Voronov, Andriy


    Strategically designed amphiphilic invertible polymers (AIPs) are capable of (i) self-assembling into invertible micellar assemblies (IMAs) in response to changes in polarity of environment, polymer concentration, and structure, (ii) accommodating (solubilizing) substances that are otherwise insoluble in water, and (iii) inverting their molecular conformation in response to changes in the polarity of the local environment. The unique ability of AIPs to invert the molecular conformation depending on the polarity of the environment can be a decisive factor in establishing the novel stimuli-responsive mechanism of solubilized drug release that is induced just in response to a change in the polarity of the environment. The IMA capability to solubilize lipophilic drugs and deliver and release the cargo molecules by conformational inversion of polymer macromolecules in response to a change of the polarity of the environment was demonstrated by loading IMA with a phytochemical drug, curcumin. It was demonstrated that four sets of micellar vehicles based on different AIPs were capable of delivering the curcumin from water to an organic medium (1-octanol) by means of unique mechanism: AIP conformational inversion in response to changing polarity from polar to nonpolar. The IMAs are shown to be nontoxic against human cells up to a concentration of 10 mg/L. On the other hand, the curcumin-loaded IMAs are cytotoxic to breast carcinoma cells at this concentration, which confirms the potential of IMA-based vehicles in controlled delivery of poorly water-soluble drug candidates and release by means of this novel stimuli-responsive mechanism.

  7. Binding of chloroquine to ionic micelles: Effect of pH and micellar surface charge

    Souza Santos, Marcela de, E-mail: [Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Avenida do Café, s/n, Ribeirão Preto, São Paulo 14040-903 (Brazil); Perpétua Freire de Morais Del Lama, Maria, E-mail: [Departamento de Física e Química, Faculdade de Ciências Farmacêuticas de Ribeirão Preto, Universidade de São Paulo, Avenida do Café, s/n, Ribeirão Preto, São Paulo 14040-903 (Brazil); Instituto Nacional de Ciência e Tecnologia de Bioanalítica, Departamento de Química Analítica, Universidade Estadual de Campinas, Cidade Universitária Zeferino Vaz, s/n, Campinas, São Paulo 13083-970 (Brazil); Siuiti Ito, Amando, E-mail: [Departamento de Física, Faculdade de Filosofia, Ciências e Letras de Ribeirão Preto, Universidade de São Paulo, Avenida Bandeirantes, 3900, Ribeirão Preto, São Paulo 14040-901 (Brazil); and others


    The pharmacological action of chloroquine relies on its ability to cross biological membranes in order to accumulate inside lysosomes. The present work aimed at understanding the basis for the interaction between different chloroquine species and ionic micelles of opposite charges, the latter used as a simple membrane model. The sensitivity of absorbance and fluorescence of chloroquine to changes in its local environment was used to probe its interaction with cetyltrimethylammonium micelles presenting bromide (CTAB) and sulfate (CTAS) as counterions, in addition to dodecyl sulfate micelles bearing sodium (SDS) and tetramethylammonium (TMADS) counterions. Counterion exchange was shown to have little effect on drug–micelle interaction. Chloroquine first dissociation constant (pKa{sub 1}) shifted to opposite directions when anionic and cationic micelles were compared. Chloroquine binding constants (K{sub b}) revealed that electrostatic forces mediate charged drug–micelle association, whereas hydrophobic interactions allowed neutral chloroquine to associate with anionic and cationic micelles. Fluorescence quenching studies indicated that monoprotonated chloroquine is inserted deeper into the micelle surface of anionic micelles than its neutral form, the latter being less exposed to the aqueous phase when associated with cationic over anionic assemblies. The findings provide further evidence that chloroquine–micelle interaction is driven by a tight interplay between the drug form and the micellar surface charge, which can have a major effect on the drug biological activity. -- Highlights: • Chloroquine (CQ) pKa{sub 1} increased for SDS micelles and decreased for CTAB micelles. • CQ is solubilized to the surface of both CTAB and SDS micelles. • Monoprotonated CQ is buried deeper into SDS micelles than neutral CQ. • Neutral CQ is less exposed to aqueous phase in CTAB over SDS micelles. • Local pH and micellar surface charge mediate interaction of CQ with

  8. Self-aggregation of vapor-liquid phase transition


    The concept of the molecular free path is introduced to derive a criterion distinguishing active molecules from inactive molecules in liquid phase. Based on molecular self-aggregation theory a concept of the critical aggregation concentration (CAC) of active molecules is proposed to describe the physical configuration before the formation of the nuclei in the process of vapor-liquid phase transition. All active molecules exist in the form of the monomer when the concentration of active molecules is lower than CAC, while the active molecules will generate aggregation once the concentration of the active molecules reaches CAC. However, these aggregates with the aggregation number N smaller than 5 can steadily exist in bulk phase. The other excess active molecules can only produce infinite aggregation and form a critical nucleus of vapor-liquid phase transition. Without outer perturbation the state point of CAC corresponds to the critical superheated or supercooled state in the process of vapor-liquid phase transition. With the aggregate property, the interfacial tension between the bulk phase and the tiny new phase is predicted and a correction is made for the classical nucleation rate in a quite good agreement with experimental results.

  9. Number names and number understanding

    Ejersbo, Lisser Rye; Misfeldt, Morten


    through using mathematical names for the numbers such as one-ten-one for 11 and five-ten-six for 56. The project combines the renaming of numbers with supporting the teaching with the new number names. Our hypothesis is that Danish children have more difficulties learning and working with numbers, because...... the Danish number names are more complicated than in other languages. Keywords: A research project in grade 0 and 1th in a Danish school, Base-10 system, two-digit number names, semiotic, cognitive perspectives....

  10. Aggregating and Disaggregating Flexibility Objects

    Siksnys, Laurynas; Valsomatzis, Emmanouil; Hose, Katja


    In many scientific and commercial domains we encounter flexibility objects, i.e., objects with explicit flexibilities in a time and an amount dimension (e.g., energy or product amount). Applications of flexibility objects require novel and efficient techniques capable of handling large amounts...... energy data management and discuss strategies for aggregation and disaggregation of flex-objects while retaining flexibility. This paper further extends these approaches beyond flex-objects originating from energy consumption by additionally considering flex-objects originating from energy production...... and aiming at energy balancing during aggregation. In more detail, this paper considers the complete life cycle of flex-objects: aggregation, disaggregation, associated requirements, efficient incremental computation, and balance aggregation techniques. Extensive experiments based on real-world data from...

  11. Dependability in Aggregation by Averaging

    Jesus, Paulo; Almeida, Paulo Sérgio


    Aggregation is an important building block of modern distributed applications, allowing the determination of meaningful properties (e.g. network size, total storage capacity, average load, majorities, etc.) that are used to direct the execution of the system. However, the majority of the existing aggregation algorithms exhibit relevant dependability issues, when prospecting their use in real application environments. In this paper, we reveal some dependability issues of aggregation algorithms based on iterative averaging techniques, giving some directions to solve them. This class of algorithms is considered robust (when compared to common tree-based approaches), being independent from the used routing topology and providing an aggregation result at all nodes. However, their robustness is strongly challenged and their correctness often compromised, when changing the assumptions of their working environment to more realistic ones. The correctness of this class of algorithms relies on the maintenance of a funda...

  12. The heat-chill method for preparation of self-assembled amphiphilic poly(ε-caprolactone)-poly(ethylene glycol) block copolymer based micellar nanoparticles for drug delivery.

    Payyappilly, Sanal Sebastian; Dhara, Santanu; Chattopadhyay, Santanu


    A new method is developed for preparation of amphiphilic block copolymer micellar nanoparticles and investigated as a delivery system for celecoxib, a hydrophobic model drug. Biodegradable block copolymers of poly(ethylene glycol) (PEG) and poly(ε-caprolactone) (PCL) were synthesized by ring opening copolymerization and characterized thoroughly using FTIR, (1)H NMR and GPC. The block copolymer was dispersed in distilled water at 60 °C and then it was chilled in an ice bath for the preparation of the micellar nanoparticles. Polymers self-assembled to form micellar nanoparticles (HR-TEM, DLS and DSC. The cytotoxicity of the polymer micellar nanoparticles was investigated against HaCaT cell lines. The study of celecoxib release from the micellar nanoparticles was carried out to assess their suitability as a drug delivery vehicle. Addition of the drug to the system at low temperature is an added advantage of this method compared to the other temperature assisted nanoparticle preparation techniques. In a nutshell, polymer micellar nanoparticles prepared using the heat-chill method are believed to be promising for the controlled drug release system of labile drugs, which degrade in toxic organic solvents and at higher temperatures.

  13. Model for amorphous aggregation processes

    Stranks, Samuel D.; Ecroyd, Heath; van Sluyter, Steven; Waters, Elizabeth J.; Carver, John A.; von Smekal, Lorenz


    The amorphous aggregation of proteins is associated with many phenomena, ranging from the formation of protein wine haze to the development of cataract in the eye lens and the precipitation of recombinant proteins during their expression and purification. While much literature exists describing models for linear protein aggregation, such as amyloid fibril formation, there are few reports of models which address amorphous aggregation. Here, we propose a model to describe the amorphous aggregation of proteins which is also more widely applicable to other situations where a similar process occurs, such as in the formation of colloids and nanoclusters. As first applications of the model, we have tested it against experimental turbidimetry data of three proteins relevant to the wine industry and biochemistry, namely, thaumatin, a thaumatinlike protein, and α -lactalbumin. The model is very robust and describes amorphous experimental data to a high degree of accuracy. Details about the aggregation process, such as shape parameters of the aggregates and rate constants, can also be extracted.

  14. Asbestos Tailings as Aggregates for Asphalt Mixture

    LIU Xinoming; XU Linrong


    To use many asbestos tailings collected in Ya-Lu highway, and to explore the feasibility of using asbestos tailings as aggregates in common asphalt mixtures, and properties of some asphalt mixtures were evaluated as well. X-ray diffraction (XRD), X-ray fluorescent (XRF), and atomic absorption spectrophotometry (AAS) were employed to determine the solid waste content of copper, zinc, lead, and cadmium. Volume properties and pavement performances of AC-25 asphalt mixture with asbestos tailings were also evaluated compared with those with basalt as aggregates.XRD and XRF measurement results infer that asbestos tailing is an excellent road material. Volume properties of AC-25 asphalt mixture with asbestos tailings satisfied the related specifications. No heavy metals and toxic pollution were detected in AAS test and the value of pH test is 8.23, which is help to the adhesion with asphalt in the asphalt concrete. When compared with basalt, high temperature property and the resistance to low temperature cracking of AC-25 asphalt mixture was improved by using asbestos tailings as aggregates. In-service AC-25 asphalt pavement with asbestos tailings also presented excellent performance and British Pendulum Number (BPN) coefficient of surface.

  15. Eulerian numbers

    Petersen, T Kyle


    This text presents the Eulerian numbers in the context of modern enumerative, algebraic, and geometric combinatorics. The book first studies Eulerian numbers from a purely combinatorial point of view, then embarks on a tour of how these numbers arise in the study of hyperplane arrangements, polytopes, and simplicial complexes. Some topics include a thorough discussion of gamma-nonnegativity and real-rootedness for Eulerian polynomials, as well as the weak order and the shard intersection order of the symmetric group. The book also includes a parallel story of Catalan combinatorics, wherein the Eulerian numbers are replaced with Narayana numbers. Again there is a progression from combinatorics to geometry, including discussion of the associahedron and the lattice of noncrossing partitions. The final chapters discuss how both the Eulerian and Narayana numbers have analogues in any finite Coxeter group, with many of the same enumerative and geometric properties. There are four supplemental chapters throughout, ...

  16. Aggregation and non aggregation techniques for large facility location problems: A survey

    Irawan Chandra Ade


    Full Text Available A facility location problem is concerned with determining the location of some useful facilities in such a way so to fulfil one or a few objective functions and constraints. We survey those problems where, in the presence of a large number of customers, some form of aggregation may be required. In addition, a review on conditional location problems where some (say q facilities already exist in the study area is presented.

  17. A specialist’s audit of aggregated occurrence records

    Robert Mesibov


    Full Text Available Occurrence records for named, native Australian millipedes from the Global Biodiversity Information Facility (GBIF and the Atlas of Living Australia (ALA were compared with the same records from the Millipedes of Australia (MoA website, compiled independently by the author. The comparison revealed some previously unnoticed errors in MoA, and a much larger number of errors and other problems in the aggregated datasets. Errors have been corrected in MoA and in some data providers’ databases, but will remain in GBIF and ALA until data providers have supplied updates to these aggregators. An audit by a specialist volunteer, as reported here, is not a common occurrence. It is suggested that aggregators should do more, or more effective, data checking and should query data providers when possible errors are detected, rather than simply disclaim responsibility for aggregated content.

  18. Developmental competence of porcine chimeric embryos produced by aggregation

    Li, Juan; Jakobsen, Jannik E.; Xiong, Qiang


    The purpose of our study was to compare the developmental competence and blastomere allocation of porcine chimeric embryos formed by micro-well aggregation. Chimeras were created by aggregating either two blastomeres originating from 2-cell embryos or two whole embryos, where embryos were produced...... either by parthenogenetic activation (PA) or handmade cloning (HMC). Results showed that the developmental competence of chimeric embryos, evaluated based on their blastocyst rate and total cell number per blastocyst, was increased when two whole 2-cell stage embryos (PA or HMC) were aggregated....... In comparison, when two blastomeres were aggregated, the developmental competence of the chimeric embryos decreased if the blastomeres were either from PA or from HMC embryos, but not if they were from different sources, i.e. one PA and one HMC blastomere. To evaluate the cell contribution in embryo formation...

  19. Scaling Behavior of an Aggregation-Migration Model

    KE Jian-Hong; LIN Zhen-Quan; ZHUANG You-Yi


    We study the kinetic behavior of a two-species aggregation-migration model in which an irreversible aggregation occurs between any two clusters of the same species and a reversible migration occurs simultaneously between two different species. For a simple model with constant aggregation rates and with the migration rates KA(i;j) =K'A (i;j) ∝ijv1 and KB(i; j) = K'B (i; j) ∝ ijv2, we find that the evolution behavior of the system depends crucially on the values of the indexes v1 and v2. The aggregate size distribution of either species obeys a conventional scaling law for most cases. Moreover, we also generalize the two-species system to the multi-species case and analyze its kinetic behavior under the symmetrical conditions.PACS numbers: 82.20.-w, 05.40.-a, 68.43.Jk, 89.75.Da

  20. Developmental competence of porcine chimeric embryos produced by aggregation

    Li, Juan; Jakobsen, Jannik E.; Xiong, Qiang


    The purpose of our study was to compare the developmental competence and blastomere allocation of porcine chimeric embryos formed by micro-well aggregation. Chimeras were created by aggregating either two blastomeres originating from 2-cell embryos or two whole embryos, where embryos were produced...... either by parthenogenetic activation (PA) or handmade cloning (HMC). Results showed that the developmental competence of chimeric embryos, evaluated based on their blastocyst rate and total cell number per blastocyst, was increased when two whole 2-cell stage embryos (PA or HMC) were aggregated....... In comparison, when two blastomeres were aggregated, the developmental competence of the chimeric embryos decreased if the blastomeres were either from PA or from HMC embryos, but not if they were from different sources, i.e. one PA and one HMC blastomere. To evaluate the cell contribution in embryo formation...

  1. Control of Large-Scale Boolean Networks via Network Aggregation.

    Zhao, Yin; Ghosh, Bijoy K; Cheng, Daizhan


    A major challenge to solve problems in control of Boolean networks is that the computational cost increases exponentially when the number of nodes in the network increases. We consider the problem of controllability and stabilizability of Boolean control networks, address the increasing cost problem by partitioning the network graph into several subnetworks, and analyze the subnetworks separately. Easily verifiable necessary conditions for controllability and stabilizability are proposed for a general aggregation structure. For acyclic aggregation, we develop a sufficient condition for stabilizability. It dramatically reduces the computational complexity if the number of nodes in each block of the acyclic aggregation is small enough compared with the number of nodes in the entire Boolean network.

  2. An aggregation model for ash particles in volcanic clouds

    Costa, A.; Folch, A.; Macedonio, G.; Durant, A.


    A large fraction of fine ash particles injected into the atmosphere during explosive eruptions aggregate through complex interactions of surface liquid layers, electrostatic forces, and differences in particle settling velocities. The aggregates formed have a different size and density compared to primary particles formed during eruption which dramatically changes the dynamics of sedimentation from the volcanic cloud. Consequently, the lifetime of ash particles in the atmosphere is reduced and a distal mass deposition maximum is often generated in resulting tephra deposits. A complete and rigorous description of volcanic ash fallout requires the full coupling of models of volcanic cloud dynamics and dispersion, and ash particle transport, aggregation and sedimentation. Furthermore, volcanic ash transport models should include an aggregation model that accounts for the interaction of all particle size classes. The problem with this approach is that simulations would require excessively long computational times thereby prohibiting its application in an operational setting during an explosive volcanic eruption. Here we present a simplified model for ash particle transport and aggregation that includes the effects of water in the volcanic cloud and surrounding atmosphere. The aggregation model assumes a fractal relationship for the number of primary particles in aggregates, average sticking efficiency factors, and collision frequency functions that account for Brownian motion, laminar and turbulent fluid shear, and differential settling velocity. A parametric study on the key parameters of the model was performed. We implemented the aggregation model in the WRF+FALL3D coupled modelling system and applied it to different eruptions where aggregation has been recognized to play an important role, including the August and September 1992 Crater Peak eruptions and the 1980 Mt St Helens eruption. In these cases, mass deposited as a function of deposit area and the particle

  3. The Role of Content Aggregators In GEOValue

    Wright, D. J.; Breyer, S.; Hogeweg, M.; Foust, J.; Jordan, L.; Plunkett, G.


    Data (aka content) in the form of numbers or layers, and transformed into information by way of maps, images, graphs, charts, tables, even stories, are foundational for a myriad of decision-makers. Recent advances in information technology, as well as civil remote sensing of the Earth, are rapidly allowing us to advance beyond mere static data collection and archiving, further enabling information awareness and understanding, and leading us towards knowledge and better decision making. However, such volumes, velocities, and varieties of data streams also bring with them serious dilemmas with regard to effective organization, cataloging, and easy access. This is where the role of aggregator comes in, with their provision of the necessary sustainability and reliability of information via proven, well-engineered platforms, all with the necessary interoperability and openness as guaranteed through the adoption of established standards. Information technology (IT) giants such as Google, Facebook, IBM and Apple are well known for aggregating just about every aspect of life in modern society, from our music to our mood swings. A use case of the Environmental Systems Research Institute (aka Esri) is presented as a geospatial aggregator. It has over the years, compiled, assembled and produced a carefully curated library of public content into a global "Living Atlas of the World," organized into different themes such as Earth observation, transportation, demographics, natural hazards, ecological land units, elevation, and more. Among a myriad of decision scenarios with this content to be presented is the tracking of sea ice in the Arctic, estimating potential impact to shipping lanes or coastal infrastructure, and forecasting future conditions. Esri as the main aggregator of Living Atlas content continues to welcome not only contributors who will publish new content to be included in this global Atlas, but fellow curators who will assist in reviewing, organizing, and even

  4. Aggregate driver model to enable predictable behaviour

    Chowdhury, A.; Chakravarty, T.; Banerjee, T.; Balamuralidhar, P.


    The categorization of driving styles, particularly in terms of aggressiveness and skill is an emerging area of interest under the broader theme of intelligent transportation. There are two possible discriminatory techniques that can be applied for such categorization; a microscale (event based) model and a macro-scale (aggregate) model. It is believed that an aggregate model will reveal many interesting aspects of human-machine interaction; for example, we may be able to understand the propensities of individuals to carry out a given task over longer periods of time. A useful driver model may include the adaptive capability of the human driver, aggregated as the individual propensity to control speed/acceleration. Towards that objective, we carried out experiments by deploying smartphone based application to be used for data collection by a group of drivers. Data is primarily being collected from GPS measurements including position & speed on a second-by-second basis, for a number of trips over a two months period. Analysing the data set, aggregate models for individual drivers were created and their natural aggressiveness were deduced. In this paper, we present the initial results for 12 drivers. It is shown that the higher order moments of the acceleration profile is an important parameter and identifier of journey quality. It is also observed that the Kurtosis of the acceleration profiles stores major information about the driving styles. Such an observation leads to two different ranking systems based on acceleration data. Such driving behaviour models can be integrated with vehicle and road model and used to generate behavioural model for real traffic scenario.

  5. A Glimpse of Our Journey into the Design of Optical Probes in Self-assembled Surfactant Aggregates.

    Dey, Nilanjan; Bhattacharya, Santanu


    Dynamic self-assembling amphiphilic surfactant molecules, popularly known as "micelles", have received widespread attention, due to their ability to modulate the photophysical properties of various organic dyes upon encapsulation. Along with their well-known use as cleaning agents, catalysts in organic reactions, and even for drug delivery purposes, these surfactant assemblies also show promising pertinence in the recognition of both ionic and nonionic targeted analytes. Low micropolarity and relatively hydrophobic environments promote their interaction with ionic analytes, whereas neutral species mostly affect the aggregation pattern of the probe molecules upon partitioning inside the micellar hydrophobic milieu. The environment-sensitive nature of micelle-based self-assembled probes also prompts us to devise new sensor arrays for the recognition of multiple analytes. While this account will largely focus on our own work in developing surfactant-triggered self-assembled sensors, our findings have been placed in the context of the relevant contributions from others during their strategic evolution.

  6. Solvent blends can control cationic reversed micellar interdroplet interactions. The effect of n-heptane:benzene mixture on BHDC reversed micellar interfacial properties: droplet sizes and micropolarity.

    Agazzi, Federico M; Falcone, R Dario; Silber, Juana J; Correa, N Mariano


    We have investigated, for the first time, the effect of the composition of the nonpolar organic media on the benzyl-n-hexadecyl-dimethylammonium chloride (BHDC) reversed micelles (RMs) properties at fixed temperature. To achieve this goal we have used the solvatochromic behavior of 1-methyl-8-oxyquinolinium betaine (QB) as absorption probe and dynamic light scattering (DLS), to monitor droplet sizes, interfacial micropolarity, and sequestrated water structure of water/BHDC/n-heptane:benzene RMs. DLS results confirm the formation of the water/BHDC/n-heptane:benzene RMs at every n-heptane mole fraction (X(Hp)) investigated, that is, X(Hp) = 0.00, 0.13, 0.21, 0.30, and 0.38. Also, DLS was used to measure the RMs diffusion coefficient and to calculate the apparent droplet hydrodynamic diameter (d(App)) at different compositions of the nonpolar organic medium. The data suggest that as the n-heptane content increases, the interdroplet attractive interactions also increase with the consequent increment in the droplet size. Moreover, the interdroplet attractive interactions can be "switched on (increased)" or "switched off (decreased)" by formulation of appropriate n-heptane:benzene mixtures. Additionally, QB spectroscopy was used to obtain the "operational" critical micellar concentration (cmc) and to investigate both the RMs interfacial micropolarity and the sequestrated water structure in every RMs studied. The results show that BHDC RMs are formed at lower surfactant concentration when n-heptane or water content increases. When the interdroplet interaction "switches on", the RMs droplet sizes growth expelling benzene molecules from the RMs interface, favoring the water-BHDC interaction at the interface with the consequent increases in the interfacial micropolarity. Therefore, changing the solvent blend is possible to affect dramatically the interfacial micropolarity, the droplet sizes and the structure of the entrapped water.

  7. Ash Aggregates in Proximal Settings

    Porritt, L. A.; Russell, K.


    Ash aggregates are thought to have formed within and been deposited by the eruption column and plume and dilute density currents and their associated ash clouds. Moist, turbulent ash clouds are considered critical to ash aggregate formation by facilitating both collision and adhesion of particles. Consequently, they are most commonly found in distal deposits. Proximal deposits containing ash aggregates are less commonly observed but do occur. Here we describe two occurrences of vent proximal ash aggregate-rich deposits; the first within a kimberlite pipe where coated ash pellets and accretionary lapilli are found within the intra-vent sequence; and the second in a glaciovolcanic setting where cored pellets (armoured lapilli) occur within Diamond Mine, Canada, are the residual deposits within the conduit and vent of the volcano and are characterised by an abundance of ash aggregates. Coated ash pellets are dominant but are followed in abundance by ash pellets, accretionary lapilli and rare cored pellets. The coated ash pellets typically range from 1 - 5 mm in diameter and have core to rim ratios of approximately 10:1. The formation and preservation of these aggregates elucidates the style and nature of the explosive phase of kimberlite eruption at A418 (and other pipes?). First, these pyroclasts dictate the intensity of the kimberlite eruption; it must be energetic enough to cause intense fragmentation of the kimberlite to produce a substantial volume of very fine ash (sustained plume attended by concomitant production of pyroclastic density currents. The size and internal structure of the armoured lapilli provide constraints on the nature of the initial explosive phase of eruption at Kima'Kho. Their proximity to the vent also indicates rapid aggregation within the eruption plume. Within both sequences rapid aggregation of ash particles occurred in proximity to the vent. However, the conditions were substantially different leading to the production of armoured

  8. Subassembly aggregates of papaya mosaic virus protein.

    Erickson, J W; Hallett, F R; Bancroft, J B


    An examination of the number of subunits in small aggregates of papaya mosaic virus (PMV) coat protein is presented based on a model system which gives results consistent with the experimental observation that the 14 S subassembly species is a double disc, composed of two rows of nine subunits each. The estimated hydration of the disc, about 0.85 g 1H20/9 protein, is unusually large and indicates a cavitated structure for the disc. Comparison with other rod-shaped viruses suggests that the flexuous nature of PMV is a consequence of sparse axial inter-subunit contacts at high radius.

  9. Supramolecular micellar nanoaggregates based on a novel chitosan/vitamin E succinate copolymer for paclitaxel selective delivery

    Lian H


    experiments, conducted by confocal laser scanning microscopy, showed an enhanced cellular uptake efficiency of the CS-VES micelles in MCF-7 cells compared with Taxol. The PTX-micelles exhibited a comparable but delayed cytotoxic effect compared with Taxol against MCF-7 cells, due to the sustained-release characteristics of the nanomicelles. More interestingly, blank nanomicelles based on CS-VES copolymer demonstrated significant cytotoxicity against MCF-7 cells.Conclusion: The supramolecular micellar aggregates based on CS-VES copolymer is a promising nanocarrier and efficacy enhancer when used as an anticancer drug-delivery system.Keywords: nanomicelles, cellular uptake, cytotoxicity

  10. Effects of chemical mechanical planarization slurry additives on the agglomeration of alumina nanoparticles II: aggregation rate analysis.

    Brahma, Neil; Talbot, Jan B


    The aggregation rate and mechanism of 150 nm alumina particles in 1mM KNO3 with various additives used in chemical mechanical planarization of copper were investigated. The pH of each suspension was ∼8 such that the aggregation rate was slow enough to be measured and analyzed over ∼120 min. In general, an initial exponential growth was observed for most suspensions indicating reaction-limited aggregation. After aggregate sizes increase to >500 nm, the rate followed a power law suggesting diffusion-limited aggregation. Stability ratios and fractal dimension numbers were also calculated to further elucidate the aggregation mechanism. Copyright © 2013 Elsevier Inc. All rights reserved.

  11. Spectroscopic Behavior of Some A3B Type Tetrapyrrolic Complexes in Several Organic Solvents and Micellar Media

    Radu Socoteanu


    Full Text Available The paper presents spectral studies of some unsymmetrical A3B tetrapyrrolic, porphyrin-type complexes with Cu(II and Zn(II in different solvents and micellar media aimed at estimating their properties in connection with the living cell. The results indicate that the position of the absorption and emission peaks is mostly influenced by the central metal ion and less by the environmental polarity or the peripheric substituents of the porphyrinic core. The comparison between the overall absorption and emission spectra of the compounds in methanol or cyclohexane vs. direct and reverse Triton X micellar systems, respectively, suggests for all compounds the localization at the interface between the polyethylene oxide chains and the tert-octyl-phenyl etheric residue of the Triton X-100 molecules. These findings could be important when testing the compounds embedded in liposomes or other delivery systems to the targeted cell.

  12. Preparation of TiO2 nanometer thin films with high photocatalytic activity by reverse micellar method


    Two kinds of TiO2 nanometer thin films were prepared on stainless steel by the reverse micellar and sol-gelmethods, respectively. The calcined TiO2 thin films were characterized by X-ray diffraction (XRD), atomic force micros-copy (AFM), BET surface area and X-ray photoelectron spectroscopy (XPS). Photocatalytic activity was evaluated byphotocatalytic decoloration of methyl orange aqueous solution. The results showed that the TiO2 thin films prepared by re-verse micellar method (designated as RM-TiO2 films) showed higher photocatalytic activity than those by sol-gel method(designated as SG-TiO2 films). This is attributed to the fact that the former is composed of smaller monodispersed sphericalparticles with a size of about 15 nm and possesses higher surface areas.

  13. Enantiomeric Separation of Epinephrine and Salbutamol by Micellar Electrokinetic Chromatography Using β-Cyclodextrin as Chiral Additive

    ZHENG,Yan-Peng(郑妍鹏); MO,Jin-Yuan(莫金垣)


    Enantiomeric separations of epinephrine and salbutamol, by means of micellar electrokinetic chromatography (MEKC) employing β-cyclodextrin as chiral additive in ammonium chloride-ammonia solution were investigated.In this system, the analytes migrated with the micellar phase towards the anode and were detected by electrochemistry using gold microelectrode at +0.65 V vs. SCE. The success of the chiral separations is strongly dependent on the concentration of β-CD and SDS, and the optimal concentration is 8 mmol·L-1 and 15 mmol·L-1 respectively.The effects of detection potential, pH value of electrolyte and applied voltage were discussed also. Using the proposed method, baseline separation of the enantiomers could be accomplished in 6 min. Further, an attempt was made to elucidate the plausible mechanism of the chiral recognition.

  14. Can affinity interactions influence the partitioning of glucose-6-phosphate dehydrogenase in two-phase aqueous micellar systems?

    André M. Lopes


    Full Text Available In this work, we provide an investigation of the role and strength of affinity interactions on the partitioning of the glucose-6-phosphate dehydrogenase in aqueous two-phase micellar systems. These systems are constituted of micellar surfactant solutions and offer both hydrophobic and hydrophilic environments, providing selectivity to biomolecules. We studied G6PD partitioning in systems composed of the nonionic surfactants, separately, in the presence and absence of affinity ligands. We observed that G6PD partitions to the micelle-poor phase, owing to the strength of excluded-volume interactions in these systems that drive the protein to the micelle-poor phase, where there is more free volume available.

  15. Enantiomeric Separation of Epinephrine and Salbutamol by Micellar Electrokinetic Chromatography Using β-Cyclodextrin as Chiral Additive

    Yan Peng ZHENG; Jin Yuan MO


    Enantiomeric separation of epinephrine and salbutamol was investigated by micellar electrokinetic chromatography employing β-cyclodextrin as chiral additive in ammonium chloride-ammonia solution. The analytes were detected by electrochemistry using gold microelectrode at +0.65 V versus SCE reference electrode. The effects of detection potential,concentration of β-cyclodextrin, concentration of sodium dodecyl sulfate, pH value of electrolyte and applied voltage were discussed.

  16. Magic Numbers


    THE last digit of my home phone number in Beijing is 4. “So what?” European readers might ask.This was my attitude when I first lived in China; I couldn't understand why Chinese friends were so shocked at my indifference to the number 4. But China brings new discoveries every day, and I have since seen the light. I know now that Chinese people have their own ways of preserving their well being, and that they see avoiding the number 4 as a good way to stay safe.

  17. Number theory

    Andrews, George E


    Although mathematics majors are usually conversant with number theory by the time they have completed a course in abstract algebra, other undergraduates, especially those in education and the liberal arts, often need a more basic introduction to the topic.In this book the author solves the problem of maintaining the interest of students at both levels by offering a combinatorial approach to elementary number theory. In studying number theory from such a perspective, mathematics majors are spared repetition and provided with new insights, while other students benefit from the consequent simpl

  18. Hierarchical organization in aggregates of protein molecules

    Bohr, Henrik; Kyhle, Anders; Sørensen, Alexis Hammer


    The aggregation of proteins into small clusters is studied by atomic force and electron microscopy. Scaling laws and fractal behaviour in the growth of the aggregates and in the correlation between aggregates is seen. A phase diagram of the aggregation process where the protonic concentration...

  19. A Functional Reference Architecture for Aggregators

    Bondy, Daniel Esteban Morales; Heussen, Kai; Gehrke, Oliver;


    Aggregators are considered to be a key enabling technology for harvesting power system services from distributed energy resources (DER). As a precondition for more widespread use of aggregators in power systems, methods for comparing and validating aggregator designs must be established. This paper...... proposes a functional reference architecture for aggregators to address this requirement....

  20. Fractal Aggregates in Tennis Ball Systems

    Sabin, J.; Bandin, M.; Prieto, G.; Sarmiento, F.


    We present a new practical exercise to explain the mechanisms of aggregation of some colloids which are otherwise not easy to understand. We have used tennis balls to simulate, in a visual way, the aggregation of colloids under reaction-limited colloid aggregation (RLCA) and diffusion-limited colloid aggregation (DLCA) regimes. We have used the…

  1. Aggregate stability in citrus plantations. The impact of drip irrigation

    Cerdà, A.; Mataix-Solera, J.; Arcenegui, V.


    Soil aggregate stability is a key property for soil and water conservation, and a synthetic parameter to quantify the soil degradation. Aggregation is relevant in soils where vegetation cover is scarce (Cerdà, 1996). Most of the research carried out to determine the soil aggregate stability was done in forest soils (Mataix-Solera et al., 2011) and little is done on farms (Cerdà, 2000). The research have show the effect of vegetation cover on soil aggregate stability (Cerdà, 1998) but little is known when vegetation is scarce, rare or not found such it can be seeing in agriculture soils. Then, aggregation is the main factor to control the soil losses and to improve the water availability. Moreover, agriculture management can improve the soil aggregate characteristics and the first step in this direction should be to quantify the aggregate stability. There is no information about the aggregate stability of soils under citrus production, although the research did show that the soil losses in the farms with citrus plantations is very high (Cerdà et al., 2009), and that aggregation should play a key role as the soils are bare due to the widespread use of herbicides. From 2009 to 2011, samples were collected in summer and winter in a chemically managed farm in Montesa, Eastern Iberian Peninsula. Ten irrigated patches and ten non-irrigated patches were selected to compare the effect of the drip irrigation on the soil aggregate stability. The Ten Drop Impacts (TDI) and the Counting the number of drops (CND) tests were applied at 200 aggregates (10 samples x 10 aggregates x 2 sites) in winter and summer in 2009, 2010 and 2011. The results show that the irrigated patches had TDI values that ranged from 43 to 56 % and that the non-irrigated reached values of 41 to 54 %. The CND samples ranged from 29 to 38 drops in the non-irrigated patches to 32 to 42 drop-impacts in the irrigated soil patches. No trends were found from winter to summer during the three years time period

  2. Thermodynamics of sodium dodecyl sulphate-salicylic acid based micellar systems and their potential use in fruits postharvest.

    Cid, A; Morales, J; Mejuto, J C; Briz-Cid, N; Rial-Otero, R; Simal-Gándara, J


    Micellar systems have excellent food applications due to their capability to solubilise a large range of hydrophilic and hydrophobic substances. In this work, the mixed micelle formation between the ionic surfactant sodium dodecyl sulphate (SDS) and the phenolic acid salicylic acid have been studied at several temperatures in aqueous solution. The critical micelle concentration and the micellization degree were determined by conductometric techniques and the experimental data used to calculate several useful thermodynamic parameters, like standard free energy, enthalpy and entropy of micelle formation. Salicylic acid helps the micellization of SDS, both by increasing the additive concentration at a constant temperature and by increasing temperature at a constant concentration of additive. The formation of micelles of SDS in the presence of salicylic acid was a thermodynamically spontaneous process, and is also entropically controlled. Salicylic acid plays the role of a stabilizer, and gives a pathway to control the three-dimensional water matrix structure. The driving force of the micellization process is provided by the hydrophobic interactions. The isostructural temperature was found to be 307.5 K for the mixed micellar system. This article explores the use of SDS-salicylic acid based micellar systems for their potential use in fruits postharvest.

  3. Impact of selected wastewater constituents on the removal of sulfonamide antibiotics via ultrafiltration and micellar enhanced ultrafiltration.

    Exall, Kirsten; Balakrishnan, Vimal K; Toito, John; McFadyen, Renée


    To better understand the environmental mobility of sulfonamide antibiotics and develop improved processes for their removal during wastewater treatment, stirred cell ultrafiltration (UF) experiments were conducted using both synthetic and real wastewater effluent. The interactions between selected sulfonamides (sulfaguanidine, sulfathiazole and sulfamerazine), solids and dissolved organic matter were systematically explored. The further impact of micellar enhanced ultrafiltration (MEUF), a process in which surfactants are added at micellar concentrations to enhance removal of various trace contaminants from aqueous streams, was then explored by using a cationic surfactant, cetyltrimethylammonium bromide (CTAB). Ultrafiltration of sulfonamides in the absence of other materials generally removed only 15-20% of the antibiotics. The presence of micellar solutions of CTAB generally improved removal of sulfonamides over UF alone, with rejections ranging from 20 to 74%. Environmental solids (sediment) further increased retention of sulfonamides using both UF and MEUF, but the presence of DOM did not influence rejection. Similar trends were observed on UF and MEUF of real effluent samples that had been spiked with the sulfonamides, confirming the environmental relevance of the observed interactions between sulfonamides, surfactant, and wastewater constituents. The results demonstrate that MEUF processes can be designed for the selective removal of such trace contaminants as sulfonamide antibiotics.

  4. Separation and analysis of cis-diol-containing compounds by boronate affinity-assisted micellar electrokinetic chromatography.

    Wang, Heye; Lü, Chenchen; Li, Hengye; Chen, Yang; Zhou, Min; Ouyang, Jian; Liu, Zhen


    Cis-diol-containing compounds (CDCCs) are usually highly hydrophilic compounds and are therefore difficult to separate by conventional reversed-phase-based micellar electrokinetic chromatography (MEKC) due to poor selectivity. Here, we report a new method, called boronate affinity-assisted micellar electrokinetic chromatography (BAA-MEKC), to solve this issue. A boronic acid with a hydrophobic alkyl chain was added to the background electrolyte, which acted as a modifier to adjust the selectivity. CDCCs can covalently react with the boronic acid to form negatively charged surfactant-like complexes, which can partition into micelles formed with a cationic surfactant. Thus, CDCCs can be separated according to the differential partition constants of their boronic acid complexes between the micellar phase and the surrounding aqueous phase. To verify this method, eight nucleosides were employed as the test compounds and their separation confirmed that the combination of boronate affinity interaction with MEKC can effectively enhance the separation of CDCCs. The effects of experimental conditions on the separation were investigated. Finally, the BAA-MEKC method was applied to the separation and analysis of nucleosides extracted from human urine. BAA-MEKC exhibited better selectivity and improved separation as compared with conventional MEKC and CZE. Successful quantitative analysis of urinary nucleosides by BAA-MEKC was demonstrated.

  5. Rapid ultrasonic and microwave-assisted micellar extraction of zingiberone, shogaol and gingerols from gingers using biosurfactants.

    Peng, Li-Qing; Cao, Jun; Du, Li-Jing; Zhang, Qi-Dong; Xu, Jing-Jing; Chen, Yu-Bo; Shi, Yu-Ting; Li, Rong-Rong


    Two kinds of extraction methods ultrasonic-assisted micellar extraction (UAME) and microwave-assisted micellar extraction (MAME) coupled with ultra-high performance liquid chromatography with ultraviolet detector (UHPLC-UV) were developed and evaluated for extraction and determination of zingerone, 6-gingerol, 8-gingerol, 6-shogaol and 10-gingerol in Rhizoma Zingiberis and Rhizoma Zingiberis Preparata. A biosurfactant, hyodeoxycholic acid sodium salt, was used in micellar extraction. Several experimental parameters were studied separately by a univariate method. The result indicated that the MAME was more efficient than UAME. The optimal conditions of MAME were as follows: 100mM of hyodeoxycholic acid sodium salt was used as surfactant, the irradiation time was set at 10s and the extraction temperature was set at 60°C. The validation results indicated that the limits of detection were in the range of 3.80-8.11ng/mL. The average recoveries were in the range of 87.32-103.12% for the two samples at two spiking levels. Compared with other reported methods, the proposed MAME-UHPLC-UV method was more effective, quicker (10s) and more eco-friendly. Copyright © 2017 Elsevier B.V. All rights reserved.

  6. An exact approach for aggregated formulations

    Gamst, Mette; Spoorendonk, Simon; Røpke, Stefan

    optimality cannot be guaranteed by branching on aggregated variables. We present a generic exact solution method to remedy the drawbacks of aggregation. It combines the original and aggregated formulations and applies Benders' decomposition. We apply the method to the Split Delivery Vehicle Routing Problem.......Aggregating formulations is a powerful approach for problems to take on tractable forms. Aggregation may lead to loss of information, i.e. the aggregated formulation may be an approximation of the original problem. In branch-and-bound context, aggregation can also complicate branching, e.g. when...

  7. Nice numbers

    Barnes, John


    In this intriguing book, John Barnes takes us on a journey through aspects of numbers much as he took us on a geometrical journey in Gems of Geometry. Similarly originating from a series of lectures for adult students at Reading and Oxford University, this book touches a variety of amusing and fascinating topics regarding numbers and their uses both ancient and modern. The author intrigues and challenges his audience with both fundamental number topics such as prime numbers and cryptography, and themes of daily needs and pleasures such as counting one's assets, keeping track of time, and enjoying music. Puzzles and exercises at the end of each lecture offer additional inspiration, and numerous illustrations accompany the reader. Furthermore, a number of appendices provides in-depth insights into diverse topics such as Pascal’s triangle, the Rubik cube, Mersenne’s curious keyboards, and many others. A theme running through is the thought of what is our favourite number. Written in an engaging and witty sty...

  8. Analysis of Various Deterioration Factors of Data Aggregation in Wireless Sensor Networks



    Full Text Available In embedded systems, wireless sensor network is the interesting field which provides various applications such as battlefield surveillance, disaster management, habitat monitoring, home automation, health caresystems etc. Wireless sensor network (WSN handles a huge number of tiny, cost effective, low powered, autonomous devices called sensor nodes which can perform sensing, processing and communicating operations. WSN has many constraints like energy utilization, limited memory and power consumption. Data aggregation is an intelligent technique which accumulates data from disparate sources by usingvarious aggregation techniques. One of the crucial techniques in WSN is data aggregation which greatly increases the energy efficiency and network lifetime by reducing the number of data transmissions. Toperform data aggregation in an efficient manner, there are lot of issues are to be considered. In this paper several issues related with data aggregation are discussed and comparisons of various design issues of various data aggregation protocols are also addressed.

  9. Erythrocyte aggregation: Basic aspects and clinical importance

    Oğuz K. Başkurt; Meiselman, Herbert J.


    Red blood cells (RBC) aggregate to form two- and three-dimensional structures when suspended in aqueous solutions containing large plasma proteins or polymers; this aggregation is reversible and shear dependent (i.e., dispersed at high shear and reformed at low or stasis). The extent of aggregation is the main determinant of low shear blood viscosity, thus predicting an inverse relationship between aggregation and in vivo blood flow. However, the effects of aggregation on hemodynamic mechanis...

  10. Molecular Aggregation in Disodium Cromoglycate

    Singh, Gautam; Agra-Kooijman, D.; Collings, P. J.; Kumar, Satyendra


    Details of molecular aggregation in the mesophases of the anti-asthmatic drug disodium cromoglycate (DSCG) have been studied using x-ray synchrotron scattering. The results show two reflections, one at wide angles corresponding to π-π stacking (3.32 å) of molecules, and the other at small angles which is perpendicular to the direction of molecular stacking and corresponds to the distance between the molecular aggregates. The latter varies from 35 - 41 å in the nematic (N) phase and 27 -- 32 å in the columnar (M) phase. The temperature evolution of the stack height, positional order correlations in the lateral direction, and orientation order parameter were determined in the N, M, and biphasic regions. The structure of the N and M phases and the nature of the molecular aggregation, together with their dependence on temperature and concentration, will be presented.


    Jing Hu


    Full Text Available As a composite material, the performance of concrete materials can be expected to depend on the properties of the interfaces between its two major components, aggregate and cement paste. The microstructure at the interfacial transition zone (ITZ is assumed to be different from the bulk material. In general, properties of conventional concrete have been found favoured by optimum packing density of the aggregate. Particle size is a common denominator in such studies. Size segregation in the ITZ among the binder particles in the fresh state, observed in simulation studies by concurrent algorithm-based SPACE system, additionally governs density as well as physical bonding capacity inside these shell-like zones around aggregate particles. These characteristics have been demonstrated qualitatively pertaining also after maturation of the concrete. Such properties of the ITZs have direct impact on composite properties. Despite experimental approaches revealed effects of aggregate grain shape on different features of material structure (among which density, and as a consequence on mechanical properties, it is still an underrated factor in laboratory studies, probably due to the general feeling that a suitable methodology for shape characterization is not available. A scientific argument hindering progress is the interconnected nature of size and shape. Presently, a practical problem preventing shape effects to be emphasized is the limitation of most computer simulation systems in concrete technology to spherical particles. New developments at Delft University of Technology will make it possible in the near future to generate jammed states, or other high-density fresh particle mixtures of non-spherical particles, which thereupon can be subjected to hydration algorithms. This paper will sketch the outlines of a methodological approach for shape assessment of loose (non-embedded aggregate grains, and demonstrate its use for two types of aggregate, allowing

  12. Dithiol-mediated incorporation of CdS nanoparticles from reverse micellar system into Zn-doped SBA-15 mesoporous silica and their photocatalytic properties.

    Hirai, Takayuki; Nanba, Masanori; Komasawa, Isao


    CdS nanoparticles, as prepared in reverse micellar systems, were incorporated into alkanedithiol-modified Zn-doped SBA-15 mesoporous silica (dtz.sbnd;ZnSBA-15; pore diameter, ca. 4 nm), which were themselves prepared via hydrolysis of tetraethylorthosilicate (TEOS) in the presence of Zn(NO(3))(2) and triblock copolymer, as a nonsurfactant template and pore-forming agent, followed by contact with dithiol molecules. A particle-sieving effect for the dtz.sbnd;ZnSBA-15 was observed, in that the incorporation of the nanoparticles was remarkably decreased with increasing the nanoparticle size. The resulting CdSz.sbnd;ZnSBA-15 composite was then used as photocatalysts for the generation of H(2) from 2-propanol aqueous solution. Under UV irradiation (lambda>300 nm), a high photocatalytic activity was observed for this composite material. This is effected by electron transfer from the photoexcited ZnS (dithiol-bonded Zn on SBA-15) to CdS nanoparticles. The photocatalytic activity is increased with a decrease in the number of methylene groups in the dithiol molecules, according to the rank order 1,10-decanedithiol < 1,6-hexanedithiol < 1,2-ethanedithiol.

  13. Signature of an aggregation-prone conformation of tau

    Eschmann, Neil A.; Georgieva, Elka R.; Ganguly, Pritam; Borbat, Peter P.; Rappaport, Maxime D.; Akdogan, Yasar; Freed, Jack H.; Shea, Joan-Emma; Han, Songi


    The self-assembly of the microtubule associated tau protein into fibrillar cell inclusions is linked to a number of devastating neurodegenerative disorders collectively known as tauopathies. The mechanism by which tau self-assembles into pathological entities is a matter of much debate, largely due to the lack of direct experimental insights into the earliest stages of aggregation. We present pulsed double electron-electron resonance measurements of two key fibril-forming regions of tau, PHF6 and PHF6*, in transient as aggregation happens. By monitoring the end-to-end distance distribution of these segments as a function of aggregation time, we show that the PHF6(*) regions dramatically extend to distances commensurate with extended β-strand structures within the earliest stages of aggregation, well before fibril formation. Combined with simulations, our experiments show that the extended β-strand conformational state of PHF6(*) is readily populated under aggregating conditions, constituting a defining signature of aggregation-prone tau, and as such, a possible target for therapeutic interventions.

  14. On individual preferences and aggregation in economic evaluation in healthcare.

    Liljas, B; Lindgren, B


    For practical reasons, in order to carry out economic evaluations of collective decisions, total costs will generally be compared with total benefits; hence, individuals' willingness to pay (WTP) or quality-adjusted life-years (QALYs) have to be estimated at an aggregate level. So far, aggregation has usually been done by taking the individuals' mean WTP or the unweighted number of QALYs. Since the aggregation process is closely related to the way that income, health and/or utility of different individuals are compared and weighted, it also has significant equity implications. Thus. the explicit (or, more often, implicit) assumptions behind the aggregation process will largely affect how health and welfare are distributed is society. The aggregation problem in economic evaluation is certainly not trivial, but is seldom addressed in current practice. This paper shows the underlying assumptions of aggregate cost-benefit analysis (CBA) and cost-effectiveness analysis/cost-utility analysis (CEA/CUA), and it emphasises the particularly strong assumptions which have to be made when QALYs are interpreted as utilities in the welfare economics sense. Naturally, the appropriate method to choose depends on what is to be maximised: welfare or health. If decisions of resource allocation are to be based on economic welfare theory, then CBA should be preferred. However, if QALYs are interpreted as measures of health, rather than as utilities, then CEA/CUA would be appropriate.

  15. Evaluation of Nanoparticle Tracking for Characterization of Fibrillar Protein Aggregates.

    Yang, Dennis T; Lu, Xiaomeng; Fan, Yamin; Murphy, Regina M


    Amyloidogenesis is the process of formation of protein aggregates with fibrillar morphology. Because amyloidogenesis is linked to neurodegenerative disease, there is interest in understanding the mechanism of fibril growth. Kinetic models of amyloidogenesis require data on the number concentration and size distribution of aggregates, but this information is difficult to obtain using conventional methods. Nanoparticle tracking analysis (NTA) is a relatively new technique that may be uniquely suited for obtaining these data. In NTA, the two-dimensional (2-D) trajectory of individual particles is tracked, from which the diffusion coefficient, and, hence, hydrodynamic radius is obtained. Here we examine the validity of NTA in tracking number concentration and size of DNA, as a model of a fibrillar macromolecule. We use NTA to examine three amyloidogenic materials: beta-amyloid, transthyretin, and polyglutamine-containing peptides. Our results are instructive in demonstrating the advantages and some limitations of single-particle diffusion measurements for investigating aggregation in protein systems.

  16. Environmentalism and natural aggregate mining

    Drew, L.J.; Langer, W.H.; Sachs, J.S.


    Sustaining a developed economy and expanding a developing one require the use of large volumes of natural aggregate. Almost all human activity (commercial, recreational, or leisure) is transacted in or on facilities constructed from natural aggregate. In our urban and suburban worlds, we are almost totally dependent on supplies of water collected behind dams and transported through aqueducts made from concrete. Natural aggregate is essential to the facilities that produce energy-hydroelectric dams and coal-fired powerplants. Ironically, the utility created for mankind by the use of natural aggregate is rarely compared favorably with the environmental impacts of mining it. Instead, the empty quarries and pits are seen as large negative environmental consequences. At the root of this disassociation is the philosophy of environmentalism, which flavors our perceptions of the excavation, processing, and distribution of natural aggregate. The two end-member ideas in this philosophy are ecocentrism and anthropocentrism. Ecocentrism takes the position that the natural world is a organism whose arteries are the rivers-their flow must not be altered. The soil is another vital organ and must not be covered with concrete and asphalt. The motto of the ecocentrist is "man must live more lightly on the land." The anthropocentrist wants clean water and air and an uncluttered landscape for human use. Mining is allowed and even encouraged, but dust and noise from quarry and pit operations must be minimized. The large volume of truck traffic is viewed as a real menace to human life and should be regulated and isolated. The environmental problems that the producers of natural aggregate (crushed stone and sand and gravel) face today are mostly difficult social and political concerns associated with the large holes dug in the ground and the large volume of heavy truck traffic associated with quarry and pit operations. These concerns have increased in recent years as society's demand for

  17. Aggregating energy flexibilities under constraints

    Valsomatzis, Emmanouil; Pedersen, Torben Bach; Abello, Alberto


    The flexibility of individual energy prosumers (producers and/or consumers) has drawn a lot of attention in recent years. Aggregation of such flexibilities provides prosumers with the opportunity to directly participate in the energy market and at the same time reduces the complexity of scheduling...... the energy units. However, aggregated flexibility should support normal grid operation. In this paper, we build on the flex-offer (FO) concept to model the inherent flexibility of a prosumer (e.g., a single flexible consumption device such as a clothes washer). An FO captures flexibility in both time...

  18. Transcendental numbers

    Murty, M Ram


    This book provides an introduction to the topic of transcendental numbers for upper-level undergraduate and graduate students. The text is constructed to support a full course on the subject, including descriptions of both relevant theorems and their applications. While the first part of the book focuses on introducing key concepts, the second part presents more complex material, including applications of Baker’s theorem, Schanuel’s conjecture, and Schneider’s theorem. These later chapters may be of interest to researchers interested in examining the relationship between transcendence and L-functions. Readers of this text should possess basic knowledge of complex analysis and elementary algebraic number theory.

  19. Numbers, Please!

    Thelin, John R.


    What topic would you choose if you had the luxury of writing forever? In this article, John Thelin provides his response: He would opt to write about the history of higher education in a way that relies on quantitative data. "Numbers, please!" is his research request in taking on a longitudinal study of colleges and universities over…

  20. Numbers, Please!

    Thelin, John R.


    What topic would you choose if you had the luxury of writing forever? In this article, John Thelin provides his response: He would opt to write about the history of higher education in a way that relies on quantitative data. "Numbers, please!" is his research request in taking on a longitudinal study of colleges and universities over…

  1. Negative Numbers

    Galbraith, Mary J.


    Examination of models for representing integers demonstrates that formal operational thought is required for establishing the operations on integers. Advocated is the use of many models for introducing negative numbers but, apart from addition, it is recommended that operations on integers be delayed until the formal operations stage. (JP)

  2. Positron studies on reverse micellar systems of AOT/isooctane/water

    Ferreira Marques, M.; Lopes Gil, C.; Lima, A.; Burrows, H.; Da GraÇa Miguel, M.


    AOT/Isooctane and water/AOT/Isooctane systems have been studied by positron annihilation techniques. Studies of the binary system show that AOT is a strong positron scavenger and support the idea of polydisperse aggregates. Results, for the ternary system, indicate the presence of monomers, even when aggregates are present, and show that Ps is in a water-free region. The effects of the addition of nitrobenzene, sodium nitrobenzoate and 4-phenylbutyric acid to the ternary system are studied. P...

  3. Diversity, intent, and aggregated search

    de Rijke, M.


    Diversity, intent and aggregated search are three core retrieval concepts that receive significant attention. In search result diversification one typically considers the relevance of a document in light of other retrieved documents. The goal is to identify the probable "aspects" of an ambiguous

  4. Diversity, intent, and aggregated search

    M. de Rijke


    Diversity, intent and aggregated search are three core retrieval concepts that receive significant attention. In search result diversification one typically considers the relevance of a document in light of other retrieved documents. The goal is to identify the probable "aspects" of an ambiguous que

  5. Quantitative investigations of aggregate systems.

    Rai, D K; Beaucage, G; Jonah, E O; Britton, D T; Sukumaran, S; Chopra, S; Gonfa, G Goro; Härting, M


    Nanomaterials with disordered, ramified structure are increasingly being used for applications where low cost and enhanced performance are desired. A particular example is the use in printed electronics of inorganic conducting and semiconducting nanoparticles. The electrical, as well as other physical properties depend on the arrangement and connectivity of the particles in such aggregate systems. Quantification of aggregate structure and development of structure/property relationships is difficult and progress in the application of these materials in electronics has mainly been empirical. In this paper, a scaling model is used to parameterize the structure of printed electronic layers. This model has chiefly been applied to polymers but surprisingly it shows applicability to these nanolayers. Disordered structures of silicon nanoparticles forming aggregates are investigated using small angle x-ray scattering coupled with the scaling model. It is expected that predictions using these structural parameters can be made for electrical properties. The approach may have wide use in understanding and designing nano-aggregates for electronic devices.

  6. Cyclosporine A enhances platelet aggregation.

    Grace, A A; Barradas, M A; Mikhailidis, D P; Jeremy, J Y; Moorhead, J F; Sweny, P; Dandona, P


    In view of the reported increase in thromboembolic episodes following cyclosporine A (CyA) therapy, the effect of this drug on platelet aggregation and thromboxane A2 release was investigated. The addition of CyA, at therapeutic concentrations to platelet rich plasma from normal subjects in vitro was found to increase aggregation in response to adrenaline, collagen and ADP. Ingestion of CyA by healthy volunteers was also associated with enhanced platelet aggregation. The CyA-mediated enhancement of aggregation was further enhanced by the addition in vitro of therapeutic concentrations of heparin. Platelets from renal allograft recipients treated with CyA also showed hyperaggregability and increased thromboxane A2 release, which were most marked at "peak" plasma CyA concentration and less so at "trough" concentrations. Platelet hyperaggregability in renal allograft patients on long-term CyA therapy tended to revert towards normal following the replacement of CyA with azathioprine. Hypertensive patients with renal allografts on nifedipine therapy had normal platelet function and thromboxane release in spite of CyA therapy. These observations suggest that CyA-mediated platelet activation may contribute to the pathogenesis of the thromboembolic phenomena associated with the use of this drug. The increased release of thromboxane A2 (a vasoconstrictor) may also play a role in mediating CyA-related nephrotoxicity.

  7. Structural and phase transition changes of sodium dodecyl sulfate micellar solution in alcohols probed by small-angle neutron scattering (SANS)

    Putra, Edy Giri Rachman [Neutron Scattering Laboratory, National Nuclear Energy Agency of Indonesia (BATAN), Gedung 40 BATAN, Kawasan Puspiptek Serpong, Tangerang 15314 (Indonesia); Patriati, Arum [Neutron Scattering Laboratory, National Nuclear Energy Agency of Indonesia (BATAN), Gedung 40 BATAN, Kawasan Puspiptek Serpong, Tangerang 15314 (Indonesia); Department of Chemistry, Faculty of Mathematics and Natural Sciences, University of Gadjah Mada, Bulaksumur, Yogyakarta 55281, Indonesia (Indonesia)


    Small-angle neutron scattering (SANS) measurements on 0.3M sodium dodecyl sulfate (SDS) micellar solutions have been performed in the presence of n-alcohols, from ethanol to decanol at different alcohol concentrations, 2–10 wt%. The ellipsoid micellar structure which occurred in the 0.3M SDS in aqueous solution with the size range of 30–50 Å has different behavior at various hydrocarbon chain length and concentration of alcohols. At low concentration and short chain-length of alcohols, such as ethanol, propanol, and butanol, the size of micelles reduced and had a spherical-like structure. The opposite effect occurred as medium to long chain alcohols, such as hexanol, octanol and decanol was added into the 0.3M SDS micellar solutions. The micelles structure changed to be more elongated in major axis and then crossed the critical phase transition from micellar solution into liquid crystal phase as lamellar structure emerged by further addition of alcohols. The inter-lamellar distances were also depending on the hydrocarbon chain length and concentration of alcohols. In the meantime, the persistent micellar structures occurred in addition of medium chain of n-alcohol, pentanol at all concentrations.

  8. Separation and determination of nimesulide related substances for quality control purposes by micellar electrokinetic chromatography.

    Zacharis, Constantinos K; Tzanavaras, Paraskevas D; Notou, Maria; Zotou, Anastasia; Themelis, Demetrius G


    A micellar electrokinetic chromatography (MEKC) method has been developed and validated for the determination of nimesulide related compounds in pharmaceutical formulations. Electrophoretic separation of six European Pharmacopoeia (EP) impurities (A-F) was performed using a fused silica capillary (L(eff.)=50 cm, L(tot.)=57 cm, 50 microm i.d.) with a background electrolyte (BGE) containing 25 mM borate buffer (pH 9.5), 30 mM sodium dodecyl sulphate and phi=3% (v/v) acetonitrile. The influence of several factors (surfactant and buffer concentration, pH, organic modifier, applied voltage, capillary temperature and injection time) was studied. The method was suitably validated with respect to linearity, limit of detection and quantification, accuracy, precision and selectivity. The calibration curves obtained for the six compounds were linear over the range 5-12 microgml(-1) (0.05-0.12%). The relative standard deviations (s(r)) of intra- and inter-day experiments were less than 5.0%. The detection limits ranged between 0.7 and 1.6 microgml(-1) depending on the impurity. The proposed method was applied successfully to the quantification of nimesulide impurities in its pharmaceutical formulation.

  9. Environmental monitoring of phenolic pollutants in water by cloud point extraction prior to micellar electrokinetic chromatography

    Stege, Patricia W.; Sombra, Lorena L.; Messina, German A.; Martinez, Luis D. [National University of San Luis, CONICET, INQUISAL, Department of Chemistry, San Luis (Argentina); Silva, Maria F. [Universidad Nacional de Cuyo, Departamento de Biomatematica y Fisicoquimica, Facultad de Ciencias Agrarias, Mendoza (Argentina); Consejo Nacional de Investigaciones Cientificas y Tecnologicas (CONICET), Buenos Aires (Argentina)


    Many aromatic compounds can be found in the environment as a result of anthropogenic activities and some of them are highly toxic. The need to determine low concentrations of pollutants requires analytical methods with high sensitivity, selectivity, and resolution for application to soil, sediment, water, and other environmental samples. Complex sample preparation involving analyte isolation and enrichment is generally necessary before the final analysis. The present paper outlines a novel, simple, low-cost, and environmentally friendly method for the simultaneous determination of p-nitrophenol (PNP), p-aminophenol (PAP), and hydroquinone (HQ) by micellar electrokinetic capillary chromatography after preconcentration by cloud point extraction. Enrichment factors of 180 to 200 were achieved. The limits of detection of the analytes for the preconcentration of 50-ml sample volume were 0.10{mu}g L{sup -1} for PNP, 0.20 {mu}g L{sup -1} for PAP, and 0.16{mu}g L{sup -1} for HQ. The optimized procedure was applied to the determination of phenolic pollutants in natural waters from San Luis, Argentina. (orig.)

  10. Application of Sigmoidal Transformation Functions in Optimization of Micellar Liquid Chromatographic Separation of Six Quinolone Antibiotics.

    Hadjmohammadi, Mohammadreza; Salary, Mina


    A chemometrics approach has been used to optimize the separation of six quinolone compounds by micellar liquid chromatography (MLC). A Derringer's desirability function, a multicriteria decision-making (MCDM) method, was tested for evaluation of two different measures of chromatographic performance (resolution and analysis time). The effect of three experimental parameters on a chromatographic response function (CRF) expressed as a product of two sigmoidal desirability functions was investigated. The sigmoidal functions were used to transform the optimization criteria, resolution and analysis time into the desirability values. The factors studied were the concentration of sodium dodecyl sulfate, butanol content and pH of the mobile phase. The experiments were done according to the face-centered cube central composite design, and the calculated CRF values were fitted to a polynomial model to correlate the CRF values with the variables and their interactions. The developed regression model showed good descriptive and predictive ability (R(2) = 0.815, F = 6.919, SE = 0.038, [Formula: see text]) and used, by a grid search algorithm, to optimize the chromatographic conditions for the separation of the mixture. The efficiency of prediction of polynomial model was confirmed by performing the experiment under the optimal conditions.

  11. Determination of polymer log D distributions by micellar and microemulsion electrokinetic chromatography.

    Jin, Xiaoyun; Leclercq, Laurent; Cottet, Hervé


    The characterization of the hydrophobicity of polymer compounds in solution remains a challenging issue of importance, especially for biomedical or pharmaceutical applications. To our knowledge, there is no data of polymer hydrophobicity (log D) in the literature. In this work, for the first time, the log D distributions of cationic polymers were characterized using micellar or microemulsion electrokinetic chromatography at physiological pH. The log D distributions of the polymer samples were obtained from the electrophoretic/chromatographic retardation of the polymer derivatives in presence of neutral micelles (or neutral microemulsion), using small cationic molecules for calibration. Separating electrolytes were based on a TRIS–chloride buffer containing a neutral surfactant (polyoxyethyleneglycoldodecyl ether) for the formation of micelles (in water) or microemulsion (in water/n-pentanol mixture).The log D distributions obtained at pH 7.4 using this method were in good agreement with the chemical structures of cationic polypeptides: poly(lys, phe) 1:1 > poly(lys, tyr) 1:1 > poly(lys, trp) 4:1 > poly(lys, ser)3:1 > poly(l-lysine), where x:y represents the molar ratio of each amino acid in the copolymer. Weight average octanol–water log D values and the dispersion of the log D distribution were also defined and determined for each polymer sample.

  12. Micellar nanotubes dispersed electrokinetic chromatography for the simultaneous determination of antibiotics in bovine milk.

    Springer, Valeria H; Lista, Adriana G


    A method to determine four antibiotics for veterinary use (ciprofloxacin, enrofloxacin, florfenicol, and chloramphenicol) of different families (fluoroquinolones and amphenicols) in bovine milk was developed. The determination of the analytes was carried out using micellar electrokinetic capillary chromatography (MEKC) with a common sodium borate-SDS buffer solution containing single-walled carbon nanotubes (SWCNTs). In this way, a great improvement in the electrophoretic resolution and the separation efficiency was achieved compared to MEKC. An online reverse electrode polarity-stacking mode (REPSM) was carried out to enhance sensitivity. This step was performed in only 2 min and it allowed a stacked percentage of 103. That means that all the amount of injected analytes is effectively stacked. When this stacking procedure was combined with an off-line preconcentration step, based on SPE, analytes could be detected in lower concentration than the established maximum residue limits (MRLs). The LODs for the four compounds were between 6.8 and 13.8 μg L(-1) and the RSD values were between 1.1% and 6.6%. The whole method was applied to spiked real samples with acceptable precision and satisfactory recoveries.

  13. On the role of a coumarin derivative for sensing applications: Nucleotide identification using a micellar system.

    Bettoschi, Alexandre; Ceglie, Andrea; Lopez, Francesco; Meli, Valeria; Murgia, Sergio; Tamburro, Manuela; Caltagirone, Claudia; Cuomo, Francesca


    The recognition of nucleotides is of crucial importance because they are the basic constituents of nucleic acids. The present study is focused on the selective interaction between a novel amphiphilic fluorophore containing coumarin and imidazole, CI (1-methyl-3-(12-((2-oxo-2H-chromen-7-yl)oxy)dodecyl)-1H-imidazol-3-ium bromide), and different nucleotide-monophosphates (NMPs). It was supposed that the solubilization of the low water soluble CI in a micelle system of hexadecyltrimethylammonium chloride (CTAC) would make the coumarin moiety of CI available to the interaction with the water-soluble NMPs. Changes in CTAC critical micelle concentration suggested that CI strongly interacted with the host cationic surfactant, thus forming a positively charged interface enriched with coumarin able to interact with the anionic NMPs. Steady-state fluorescence quenching revealed that CI/CTAC system was capable of distinguish between purine- and pyrimidine-based nucleotides. A modified Stern-Volmer equation permitted the use of a quenching model that accounted for the possible interactions between the micelles and the nucleotides. The data analysis allowed calculating selective parameters that differentiated according to the type of nucleotide either at 25 or 50°C. Our results established the utility of the novel coumarin derivative fluorophore, supported by the simple and suitable micellar systems, as a tool for DNA sensing applications.

  14. Iron(Ⅱ) tetrasulfophthalocyanine mimetic enzymatic synthesis of conducting polyaniline in micellar system

    HU Xing; LIU Hui; ZOU Guo-lin


    Iron(Ⅱ) tetrasulfophthalocyanine (FeTSPc), as a novel mimetic enzyme of peroxidase, was used in the synthesis of a conducting polyaniline (PANI)/sodium dodecylsulfate (SDS) complex in SDS aqueous micellar solutions. The effects of pH, concentrations of aniline, SDS and H_2O_2, and reaction time on polymerization of aniline were studied in this case as shown by UV-Vis absorption spectroscopy. The results show that a wide range of pH (0.5-4.0) is required to produce the conducting PANI, and the optimal pH is 1.0 in SDS micelle. The optimal concentrations of aniline, SDS and H_2O_2 in feed, and reaction time in this case for the production of conducting PANI are respectively 10 mmol/L, 10 mmol/L, 25 mmol/L, and 15 h. FT-IR spectrum, elemental analysis, conductivity, cyclic voltammetry and thermogravimetric analysis confirm the thermal stability and electroactive form of PANI.

  15. Micellar enhanced ultrafiltration process for the treatment of olive mill wastewater.

    El-Abbassi, Abdelilah; Khayet, Mohamed; Hafidi, Abdellatif


    Olive mill wastewater (OMW) is an important environmental pollution problem, especially in the Mediterranean, which is the main olive oil production region worldwide. Environmental impact of OMW is related to its high organic load and particularly to the phytotoxic and antibacterial action of its phenolic content. In fact, polyphenols are known as powerful antioxidants with interesting nutritional and pharmaceutical properties. In the present work, the efficiency of OMW Micellar Enhanced Ultrafiltration (MEUF) treatment for removal and concentration of polyphenols was investigated, using an anionic surfactant (Sodium Dodecyl Sulfate salt, SDS) and a hydrophobic poly(vinyldene fluoride) (PVDF) membrane. The effects of the process experimental conditions on the permeate flux were investigated, and the secondary membrane resistance created by SDS molecules was evaluated. The initial fluxes of OMW processing by MEUF using SDS were 25.7 and 44.5 l/m2 h under transmembrane pressures of 3.5 and 4.5 bar, respectively. The rejection rate of polyphenols without using any surfactant ranged from 5 to 28%, whereas, it reached 74% when SDS was used under optimum pH (pH 2). The MEUF provides a slightly colored permeate (about 88% less dark), which requires clearly less chemical oxygen demand (COD) for its oxidation (4.33% of the initial COD). These results showed that MEUF process can efficiently be applied to the treatment of OMW and for the concentration and recovery of polyphenols.

  16. The usage of micellar extraction for analysis of fluvastatin in water and wastewater samples.

    Hryniewicka, Marta; Starczewska, Barbara


    This work illustrates the development of new procedures for the isolation and preconcentration of fluvastatin (FLU) from aqueous solutions. Micellar extraction (ME) combined with high performance liquid chromatography (HPLC-UV) has been successfully applied for this purpose. It was found that the analyte created micelle with anionic sodium dodecylsulfate (SDS) and/or with the binary mixture of surfactants nonionic triton X114 (TX114) and cationic tetra-n-butyloammonium bromide (TBAB). The optimal analytical conditions for the proposed extraction procedures (solution pH, concentration of surfactants, centrifugation time and electrolyte type) were ascertained. The calibration curves were recorded. The linearity ranges for FLU, isolated by SDS and the mixture of TX114/TBAB, were 0.21-28.79 μg mL(-1) and 0.21-16.45 μg mL(-1) with limit of detection (LOD) 0.19 μg mL(-1) and 0.14 μg mL(-1), respectively. The recoveries afforded by the proposed methods were high, approximately 97%. These preconcentration procedures were applied for the isolation of the statin from water and wastewater samples taken from the local rivers and wastewater treatment plants.

  17. Micellar Liquid Chromatographic Determination of Carbaryl and 1-Naphthol in Water, Soil, and Vegetables

    Mei-Liang Chin-Chen


    Full Text Available A liquid chromatographic procedure has been developed for the determination of carbaryl, a phenyl-N-methylcarbamate, and its main metabolite 1-naphthol, using a C18 column (250’mm’ × ’4.6’mm with a micellar mobile phase and fluorescence detection at maximum excitation/emission wavelengths of 225/333’nm, respectively. In the optimization step, surfactants sodium dodecyl sulphate (SDS, Brij-35 and N-cetylpyridinium chloride monohydrate, and organic solvents propanol, butanol, and pentanol were considered. The selected mobile phase was 0.15’M SDS-6% (v/v-pentanol-0.01’M NaH2PO4 buffered at pH 3. Validation studies, according to the ICH Tripartite Guideline, included linearity (r>0.999, limit of detection (5 and 18’ng mL-1, for carbaryl and 1-naphthol, resp., and limit of quantification (15 and 50’ng mL-1, for carbaryl and 1-naphthol, resp., with intra- and interday precisions below 1%, and robustness parameters below 3%. The results show that the procedure was adequate for the routine analysis of these two compounds in water, soil, and vegetables samples.

  18. Influence of ultrasound on chemically induced gelation of micellar casein systems.

    Chandrapala, Jayani; Zisu, Bogdan; Kentish, Sandra; Ashokkumar, Muthupandian


    Gelation is a significant operation in dairy processing. Protein gelation can be affected by several factors such as temperature, pH, or enzyme addition. Recently, the use of ultrasonication has been shown to have a significant impact on the formation of whey protein gels. In this work, the effect of ultrasonication on the gelation of casein systems was investigated. Gels were formed by the addition of 7.6 mm Tetra Sodium Pyro Phosphate (TSPP) to 5 wt% micellar casein (MC) solutions. Sonication at 20 KHz and 31 W for up to 30 min changed the surface hydrophobicity of the proteins, whereas surface charge was unaltered. Sonication before the addition of TSPP formed a firm gel with a fine protein network and low syneresis. Conversely, sonication after TSPP addition led to an inconsistent weak-gel-like structure with high syneresis. Gel strength in both cases increased significantly after short sonication times, while the viscoelastic properties were less affected. Overall, the results showed that ultrasonication can have a significant effect on the final gel properties of casein systems.

  19. Modeling transport effects of perfluorinated and hydrocarbon surfactants in groundwater by using micellar liquid chromatography

    Simmons, Rashad N. [Department of Chemistry and Center for Integrative Toxicology, Michigan State University, East Lansing, MI 48824-1322 (United States); McGuffin, Victoria L. [Department of Chemistry and Center for Integrative Toxicology, Michigan State University, East Lansing, MI 48824-1322 (United States)], E-mail:


    The effects of hydrocarbon and perfluorinated surfactants, above their critical micelle concentration (CMC), on the transport of neutral environmental pollutants are compared. Reversed-phase micellar liquid chromatography is used to model the groundwater system. The octadecylsilica stationary phase serves to simulate soil particles containing organic matter, whereas the aqueous surfactant mobile phases serve to simulate groundwater containing a surfactant at varying concentrations. Sodium dodecyl sulfate and lithium perfluorooctane sulfonate are used as representatives of the hydrocarbon and perfluorinated surfactants, respectively. Benzene, mono- and perhalogenated benzenes, and polycyclic aromatic hydrocarbons are used as models for environmental pollutants. Transport effects were elucidated from the retention factor, k, and the equilibrium constant per micelle, K{sub eq}, of the model pollutants in the individual surfactants. Based on k values, the transport of the model pollutants increased in both surfactant solutions in comparison to pure water. As the concentration of the surfactants increased, the transport of the pollutants increased as well. Notably, the K{sub eq} values of the pollutants in the perfluorinated surfactant were at least an order of magnitude less than those in the hydrocarbon surfactant. Overall, these results suggest that the presence of a perfluorinated surfactant, above its CMC, increases the transport of pollutants in a groundwater system. However, the perfluorinated surfactant exhibits a lesser transport effect than the hydrocarbon surfactant.

  20. Micellar electrokinetic chromatography method development for simultaneous determination of thiabendazole, carbendazim, and fuberidazole.

    Soliman, Laiel C; Donkor, Kingsley K


    Thiabendazole (TBz), carbendazim (CBz), and fuberidazole (FBz) are systemic benzimidazole-type fungicides used for pre- and post-harvest treatment to control various types of fungal diseases on a variety of crops. Significant levels of these fungicides could alter the composition or flavour of crops, and being possible carcinogens, they could also pose risks for humans and the environment. A mode of capillary electrophoresis called micellar electrokinetic chromatography (MEKC) was investigated for the determination of these three benzimidazole fungicides. The study involved two kinds of surfactants in which several experimental conditions were optimized, i.e., buffer concentration, pH, micelle concentration, and percent organic modifier (methanol). Using the optimum experimental conditions, the fungicides were successfully separated by MEKC. The limits of detection and quantification were in the range of 0.6-0.7 and 2.1-2.5 mg L(-1), respectively, and the calibration curves were linear over the range of 5-60 mg L(-1) for the three fungicides. The potential of the proposed MEKC method was demonstrated by analyzing water samples which were fortified with the fungicides. The proposed method enabled simultaneous determination of the three benzimidazole fungicides and method validation with spiked water samples yielded satisfactory quantitative recoveries for all the three fungicides.

  1. Determination of seven preservatives in cosmetic products by micellar electrokinetic chromatography.

    Huang, Jun-Qiang; Hu, Cho-Chun; Chiu, Tai-Chia


    A micellar electrokinetic chromatography method using cetyltrimethylammonium bromide (CTAB) as a cationic surfactant, coupled with UV-Vis detection, was developed for the simultaneous determination of seven preservatives, including methyl-, ethyl-, propyl- and butyl-paraben and phenol, phenoxyethanol and resorcinol. The method involved optimizing the pH of the phosphate buffer and concentrations of CTAB, ethanol and 2-hydroxypropyl-β-cyclodextrin (HP-β-CD). The preservatives were well separated using optimum conditions and separated within 10 min at a separation voltage of -12.5 kV with the 1.0 mM phosphate buffer (pH 7.0) containing 90 mM CTAB, 25 mM HP-β-CD and 10% (v/v) ethanol. Satisfactory recoveries (84.1-103.0%), migration time (RSD < 3.1%) and peak area (RSD < 4.5%) repeatabilities were achieved. Detection limits of the preservatives were between 0.31 and 1.52 μg mL(-1) (S/N = 3, n = 5). The optimized method was successfully applied to the simultaneous determination of these preservatives in 10 commercial cosmetic products.

  2. Use of micellar liquid chromatography for rapid monitoring of fungicides post harvest applied to citrus wastewater.

    Peris-Vicente, Juan; Marzo-Mas, Ana; Roca-Genovés, Pasqual; Carda-Broch, Samuel; Esteve-Romero, Josep


    A method based on micellar liquid chromatography has been developed to simultaneously monitor four pesticides largely post-harvest applied to citrus: thiabendazole, pyrimethanil, o-phenylphenol and imazalil. Water samples were filtered and directly injected without other treatment, thus avoiding extraction steps. The composition of the mobile phase was optimized using a chemometrical approach to achieve and excellent resolution to 0.07 mol/L SDS/5%, V/V 1-pentanol buffered at pH3. Mobile phase run through a C18 column at 1 mL/min at room temperature. The detection was performing by UV-Visible absorbance using a wavelength program: 0-10 min, 305 nm (for thiabendazole); 10-12; 265 nm (for pyrimethanil) and 12-18, 220 nm (o-phenylphenol and imazalil). The developed method was validated following the guidelines of the US Environmental Protection Agency in terms of: quantitation range, (0.5-4 to 15 μg/mL), linearity (r(2)>0.9995), sensitivity (LOD, 0.18-1.4 μg/mL), precision (<9.2%), trueness (93.9%-103.7%), and ruggedness (<9.9%). It was found that the fungicides remain up to eight days in surface water at outdoor conditions. The method was used to screen the presence of the analytes in several waste water samples, and was proved to be useful in routine analysis.

  3. Sequential micellar electrokinetic chromatography analysis of racemization reaction of alanine enantiomers.

    Fu, Rao; Liu, Lina; Guo, Yingna; Guo, Liping; Yang, Li


    A novel method for online monitoring racemization reaction of alanine (Ala) enantiomers was developed, by combining sequential sample injection and micellar electrokinetic chromatography (MEKC) technique. Various conditions were investigated to optimize the sequential injection, Ala derivatization and MEKC chiral separation of d-/l-Ala. High reproducibility of the sequential MEKC analysis was demonstrated by analyzing the standard Ala samples, with relative standard deviation values (n=20) of 1.35%, 1.98%, and 1.09% for peak height, peak area and migration time, respectively. Ala racemization was automatically monitored every 40s from the beginning to the end of the reaction, by simultaneous detection of the consumption of the substrate enantiomer and the formation of the product enantiomer. The Michaelis constants of the racemization reaction were obtained by the sequential MEKC method, and were in good agreement with those obtained by traditional off-line enzyme assay. Our study indicated that the present sequential MEKC method can perform fast, efficient, accurate and reproducible analysis of racemization reaction of amino acids, which is of great importance for the determination of the activity of racemase and thus understanding its metabolic functions.

  4. Comparison of monolithic capillary electrochromatography and micellar electrokinetic chromatography for the separation of polycyclic aromatic hydrocarbons.

    Salwiński, Aleksander; Delépée, Raphaël


    Atmospheric pollution of anthropic origin is recognized as a major risk factor for health, in particular for respiratory and cardio-vascular systems. Among these pollutants, polycyclic aromatic hydrocarbons (PAHs) are placed on the list of US Environmental Protection Agency (EPA) as 'priority' pollutants and four of them are assigned as potential carcinogens by The International Agency for Research on Cancer (IARC). In the present work two capillary techniques-micellar electrokinetic chromatography (MEKC) and monolithic capillary electrochromatography (CEC)-were compared for the separation of eleven PAHs. Both techniques compared in the present work are fully compatible with every standard apparatus of capillary electrophoresis. For MEKC, enhancement of selectivity and decrease of the separation window of eleven PAHs were obtained with methanol:borate 25 mM (20/80, v/v) running buffer containing 10 mM of hydroxypropylated γ-cyclodextrins with low SDS content (25 mM). In case of CEC, two acrylate-based monolithic stationary phases (MSPs) were evaluated for their application in the separation of eleven PAHs. The best MSP based on butyl acrylate was compared with MEKC in terms of sample capacity, PAHs elution order, LOQ, efficiency and effect of pH. Influence of the hydrophobicity of mobile phase on the PAHs elution order was also studied.

  5. Headspace in-tube microextraction coupled with micellar electrokinetic chromatography of neutral aromatic compounds.

    Cho, Sung Min; Park, Bum Su; Jung, Woo Sung; Lee, Sang Won; Jung, Yunhwan; Chung, Doo Soo


    Headspace (HS) extraction can be carried out easily and aptly via single drop microextraction coupled with capillary electrophoresis (CE). However, one drawback is the difficulty of keeping the single drop stably at the capillary tip. To solve this problem, we have recently demonstrated HS in-tube microextraction (ITME) of acidic compounds such as chlrophenols in an acidic sample using a basic run buffer plug in the separation capillary for CE as an acceptor phase. In this report, an organic acceptor plug in a capillary was used to extract neutral organic volatile pollutants such as BTEX (benzene, toluene, ethylbenzene, and m-xylene). After extraction, the analytes enriched in the organic acceptor plug were analyzed with micellar electrokinetic chromatography (MEKC). The enrichment factors for BTEX in a standard solution were up to 350 under an optimal condition of 25°C for 20 min. As an application, BTEX spiked into bottled water were analyzed with HS-ITME-MEKC, and the enrichment factors for BTEX were up to 320. The limits of detections were 1-4 ppb, which are at least 200 times lower than the US Environmental Protection Agency guidelines for drinking water, except benzene. The entire procedure of HS-ITME-MEKC was carried out automatically using a commercial CE instrument.

  6. A Novel Micellar Electrokinetic Chromatographic Method for Separation of Metal-DDTC Complexes

    Arfana Mallah


    Full Text Available Micellar electrokinetic chromatography (MEKC was examined for the separation and determination of Mo(VI, Cr(VI, Ni(II, Pd(II, and Co(III as diethyl dithiocarbamate (DDTC chelates. The separation was achieved from fused silica capillary (52 cm × 75 m id with effective length 40 cm, background electrolyte (BGE borate buffer pH 9.1 (25 mM, CTAB 30% (100 mM, and 1% butanol in methanol (70 : 30 : 5 v/v/v with applied voltage of −10 kV using reverse polarity. The photodiode array detection was achieved at 225 nm. The linear calibration for each of the element was obtained within 0.16–10 g/mL with a limit of detection (LOD 0.005–0.0167 g/mL. The separation and determination was repeatable with relative standard deviation (RSD within 2.4–3.3% (=4 in terms of migration time and peak height/peak area. The method was applied for the determination of Mo(VI from potatoes and almond, Ni(II from hydrogenated vegetable oil, and Co(III from pharmaceutical preparations with RSD within 3.9%. The results obtained were checked by standard addition and rechecked by atomic absorption spectrometry.

  7. Simple micellar electrokinetic chromatography method for the determination of hydrogen sulfide in hen tissues.

    Kubalczyk, Paweł; Borowczyk, Kamila; Chwatko, Grażyna; Głowacki, Rafał


    A new method for the determination of hydrogen sulfide in hen tissues has been developed and validated. For estimation of hydrogen sulfide content, a sample (0.1 g) of hen tissue was treated according to the procedure consisted of some essential steps: simultaneous homogenization of a tissue and derivatization of hydrogen sulfide to its S-quinolinium derivative with 2-chloro-1-methylquinolinium tetrafluoroborate, separation of so-formed derivative by micellar electrokinetic chromatography with sweeping, and detection and quantitation with the use of UV detector set to measure analytical signals at 375 nm. Effective electrophoretic separation was achieved using fused silica capillary (effective length 41.5 cm, 75 μm id) and 0.05 mol/L, pH 8 phosphate buffer with the addition of 0.04 mol/L SDS and 26% ACN. The lower limit of quantification was 0.12 μmol hydrogen sulfide in 1 g of tissue. The calibration curve prepared in tissue homogenate for hydrogen sulfide showed linearity in the range from 0.15 to 2.0 μmol/g, with the coefficient of correlation 0.9978. The relative standard deviation of the points of the calibration curve varied from 8.3 to 3.2% RSD.

  8. Stereospecific micellar electrokinetic chromatography assay of methionine sulfoxide reductase activity employing a multiple layer coated capillary.

    Zhu, Qingfu; El-Mergawy, Rabab G; Heinemann, Stefan H; Schönherr, Roland; Jáč, Pavel; Scriba, Gerhard K E


    A micellar electrokinetic chromatography method for the analysis of the l-methionine sulfoxide diastereomers employing a successive multiple ionic-polymer layer coated fused-silica capillary was developed and validated in order to investigate the stereospecificity of methionine sulfoxide reductases. The capillary coating consisted of a first layer of hexadimethrine and a second layer of dextran sulfate providing a stable strong cathodic EOF and consequently highly repeatable analyte migration times. The methionine sulfoxide diastereomers, methionine as product as well as β-alanine as internal standard were derivatized by dabsyl chloride and separated using a 35 mM sodium phosphate buffer, pH 8.0, containing 25 mM SDS as BGE and a separation voltage of 25 kV. The method was validated in the range of 0.15-2.0 mM with respect to linearity and precision. The LODs of the analytes ranged between 0.04 and 0.10 mM. The assay was subsequently applied to determine the stereospecificity of methionine sulfoxide reductases as well as the enzyme kinetics of human methionine sulfoxide reductase A. Monitoring the decrease of the l-methionine-(S)-sulfoxide Km = 411.8 ± 33.8 μM and Vmax = 307.5 ± 10.8 μM/min were determined.

  9. Simultaneous determination of ten preservatives in ten kinds of foods by micellar electrokinetic chromatography.

    Ding, Xiao-Jing; Xie, Na; Zhao, Shan; Wu, Yu-Chen; Li, Jiang; Wang, Zhi


    An improved micellar electrokinetic capillary chromatography method (MEKC) for the simultaneous determination of ten preservatives in ten different kinds of food samples was reported. An uncoated fused-silica capillary with 50 μm i.d. and 70 cm total length was used. Under the optimized conditions, the linear response was observed in the range of 1.2-200mg/L for the analytes. The limits of detection (LOD, S/N=3) and limits of quantitation (LOQ, S/N=10) ranging from 0.4 to 0.5mg/L and 1.2 to 1.5mg/L, respectively were obtained. The method was used for the determination of sorbic and benzoic acids in two FAPAS® (Food Analysis Performance Assessment Scheme) proficiency test samples (jam and chocolate cake). The results showed that the current method with simple sample pretreatment and small reagent consumption could meet the needs for routine analysis of the ten preservatives in ten types of food products.

  10. Micellar electrokinetic chromatography: a review of methodological and instrumental innovations focusing on practical aspects.

    Silva, Manuel


    This review article addresses recent methodological and instrumental innovations in MEKC with emphasis on practical aspects. Like its predecessors, this review is intended to provide an updated overview covering work on the most salient methodological contributions to enhancing sensitivity and resolution in MEKC-based determinations published over the past two years. The most widespread approaches to enhancing sensitivity, which include improving "classical" online sample concentration techniques, combinations of on- and off-line sample concentration protocols and recent developments are discussed, and so are modifications of existing MEKC systems with various micellar phases, the use of BGE additives (organic modifiers, chiral selectors, gold nanoparticles) and coated capillaries, and the implementation of 2D separations and chemometric methods to enhance resolution. Instrumental approaches such as MS and LIF are also discussed, and proposals for overcoming the problems typically encountered in directly coupling MEKC with MS, and the recent inception of quantum dots with a great potential for LIF detection in MEKC, are also dealt with. Finally, foreseeable developments on potential future directions are also expressed.

  11. Modulating Pluronics micellar rupture with cyclodextrins and drugs: effect of pH and temperature

    Valero, M.; Dreiss, C. A.


    Micelles of the triblock copolymer Pluronic F127 can encapsulate drugs with various chemical structures and their architecture has been studied by small-angle neutron scattering (SANS). Interaction with a derivative of β-cyclodextrin, namely, heptakis(2,6-di-O- methyl)-β-cyclodextrin (DIMEB), induces a complete break-up of the micelles, providing a mechanism for drug release. In the presence of drugs partitioned within the micelles, competitive interactions between polymer, drug and cyclodextrin lead to a modulation of the micellar rupture, depending on the nature of the drug and the exact composition of the ternary system. These interactions can be further adjusted by temperature and pH. While the most widely accepted mechanism for the interaction between Pluronics and cyclodextrins is through polypseudorotaxane (PR) formation, involving the threading of β-CD on the polymer backbone, time-resolved SANS experiments show that de-micellisation takes place in less than 100 ms, thus unambiguously ruling out an inclusion complex between the cyclodextrin and the polymer chains.

  12. Micellar and structural stability of nanoscale amphiphilic polymers: Implications for anti-atherosclerotic bioactivity.

    Zhang, Yingyue; Li, Qi; Welsh, William J; Moghe, Prabhas V; Uhrich, Kathryn E


    Atherosclerosis, a leading cause of mortality in developed countries, is characterized by the buildup of oxidized low-density lipoprotein (oxLDL) within the vascular intima, unregulated oxLDL uptake by macrophages, and ensuing formation of arterial plaque. Amphiphilic polymers (AMPs) comprised of a branched hydrophobic domain and a hydrophilic poly(ethylene glycol) (PEG) tail have shown promising anti-atherogenic effects through direct inhibition of oxLDL uptake by macrophages. In this study, five AMPs with controlled variations were evaluated for their micellar and structural stability in the presence of serum and lipase, respectively, to develop underlying structure-atheroprotective activity relations. In parallel, molecular dynamics simulations were performed to explore the AMP conformational preferences within an aqueous environment. Notably, AMPs with ether linkages between the hydrophobic arms and sugar backbones demonstrated enhanced degradation stability and storage stability, and also elicited enhanced anti-atherogenic bioactivity. Additionally, AMPs with increased hydrophobicity elicited increased atheroprotective bioactivity in the presence of serum. These studies provide key insights for designing more serum-stable polymeric micelles as prospective cardiovascular nanotherapies.

  13. Development and validation of micellar liquid chromatographic methods for the determination of antibiotics in different matrixes.

    Rambla-Alegre, Maria; Esteve-Romero, Josep; Carda-Broch, Samuel


    Antibiotics are the most important bioactive and chemotherapeutic compounds to be produced by microbiological synthesis, and they have proved their worth in a variety of fields, such as medicinal chemistry, agriculture, and the food industry. Interest in antibiotics has grown in parallel with an increasingly high degree of productivity in the field of analytical applications. Therefore, it is necessary to develop chromatographic procedures capable of determining various drugs simultaneously in the shortest possible time. Micellar liquid chromatography (MLC) is an RP-HPLC technique that offers advantages over conventional HPLC as far as sample preparation, selectivity, and versatility are concerned. Its main advantage is that samples can be injected directly into the chromatographic system with no previous preparation step. This paper mainly focuses on the results of the authors' own recent research and reports the chromatographic conditions for determination of various antibiotics (penicillins, quinolones, and sulfonamides) in different matrixes (pharmaceuticals, biological fluids, and food). The work of other authors on MLC-based antibiotic determination has been included.

  14. LPS removal from an E. coli fermentation broth using aqueous two-phase micellar system.

    Lopes, André M; Magalhães, Pérola O; Mazzola, Priscila G; Rangel-Yagui, Carlota O; de Carvalho, João C M; Penna, Thereza C V; Pessoa, Adalberto


    In biotechnology, endotoxin (LPS) removal from recombinant proteins is a critical and challenging step in the preparation of injectable therapeutics, as endotoxin is a natural component of bacterial expression systems widely used to manufacture therapeutic proteins. The viability of large-scale industrial production of recombinant biomolecules of pharmaceutical interest significantly depends on the separation and purification techniques used. The aim of this work was to evaluate the use of aqueous two-phase micellar system (ATPMS) for endotoxin removal from preparations containing recombinant proteins of pharmaceutical interest, such as green fluorescent protein (GFPuv). Partition assays were carried out initially using pure LPS, and afterwards in the presence of E. coli cell lysate. The ATPMS technology proved to be effective in GFPuv recovery, preferentially into the micelle-poor phase (K(GFPuv) 98.00%). Therefore, this system can be exploited as the first step for purification in biotechnology processes for removal of higher LPS concentrations. Copyright © 2010 American Institute of Chemical Engineers (AIChE).

  15. Analysis of carbofuran, carbosulfan, isoprocarb, 3-hydroxycarbofuran, and 3-ketocarbofuran by micellar electrokinetic chromatography.

    Hsu, Chien-Hua; Hu, Cho-Chun; Chiu, Tai-Chia


    We developed an analytical method for the detection and quantitation of five pesticides and some of their metabolites - 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, carbosulfan, and isoprocarb - using micellar electrokinetic chromatography coupled with a UV-Vis detector. The optimum separation conditions were 20 mM phosphate buffer (pH 8.0) containing 15 mM sodium dodecyl sulfate. The detection wavelength was set at 200 nm and the applied voltage was 12.5 kV. Under these conditions, baseline separation of five pesticides was achieved in 15 min, and the detection limits (S/N = 3) of 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, carbosulfan, and isoprocarb were 0.3, 0.3, 0.3, 4.0, and 0.3 μM, respectively. The linear ranges for 3-hydroxycarbofuran, 3-ketocarbofuran, carbofuran, and isoprocarb were between 1.0 and 50.0 μM and that for carbosulfan was between 10.0 and 100.0 μM, with R(2) larger than 0.995. When applied to the analysis of a carbofuran-spiked rice sample, this approach yielded results with excellent repeatability (3.3%, n = 5), reproducibility (4.5%, n = 5), separation efficiency (>2.1 × 10(4) theoretical plates), and recovery (95.5 ± 1.4%, n = 5).

  16. Analysis of reducing carbohydrates by reductive tryptamine derivatization prior to micellar electrokinetic capillary chromatography.

    Andersen, Keld E; Bjergegaard, Charlotte; Sørensen, Hilmer


    A micellar electrokinetic capillary chromatography method for determination of low molecular weight carbohydrates (dp 1-2) with an unbound carbonyl group as in aldoses or other reducing carbohydrates has been developed. Reductive amination of aldoses on the carbonyl group using tryptamine introduced a chromophor system to the carbohydrates enabling their sensitive UV detection at 220 nm and identification based on the indole group using diode array detection. Twelve carbohydrates including pentoses (d-ribose, l-arabinose, and d-xylose), hexoses (d-glucose, d-mannose, and d-galactose), deoxy sugars (l-rhamnose and l-fucose), uronic acids (d-glucuronic acid and d-galacturonic acid), and disaccharides (cellobiose and melibiose) are included in the study, using d-thyminose (2-deoxy-d-ribose) as the internal standard. Detection of all 12 carbohydrates is performed within 30 min. Linearity with correlation coefficients from 0.9864 to 0.9992 was found in the concentration range of 25-2500 micromol/L for all carbohydrates; the relative standard deviation on the migration times was between 0.27 and 0.80 min, and limits of quantification and limits of determination were in the picomole range.

  17. Quantitative analysis of synthetic dyes in lipstick by micellar electrokinetic capillary chromatography.

    Desiderio, C; Marra, C; Fanali, S


    The separation of synthetic dyes, used as color additives in cosmetics, by micellar electrokinetic capillary chromatography (MEKC) is described in this study. The separation of seven dyes, namely eosine, erythrosine, cyanosine, rhodamine B, orange II, chromotrope FB and tartrazine has been achieved in about 3 min in an untreated fused silica capillary containing as background electrolyte a 25 mM tetraborate/phosphate buffer, pH 8.0, and 30 mM sodium dodecyl sulfate. The electrophoretic method exhibits precision and relatively high sensitivity. A detection limit (LOD, signal/noise = 3) in the range of 5-7.5 X 10(-7) M of standard compounds was recorded. Intra-day repeatability of all the studied dye determinations (8 runs) gave the following results (limit values), % standard deviation: 0.24-1.54% for migration time, 0.99-1.24% for corrected peak areas, 0.99-1.24% for corrected peak area ratio (analyte/internal standard) and 1.56-2.74% for peak areas. The optimized method was successfully applied to the analysis of a lipstick sample where eosine and cyanosine were present.

  18. Micellar-enhanced ultrafiltration process (MEUF) for removing copper from synthetic wastewater containing ligands.

    Liu, Chuan-Kun; Li, Chi-Wang; Lin, Ching-Yu


    The effects of the type and concentration of ligands on the removal of Cu by micellar-enhanced ultrafiltration (MEUF) with the help of either anionic or cationic surfactants were investigated. The removal efficiency of copper by anionic surfactant-(SDS-) MEUF depends on the ligand-to-Cu ratio and the ligand-to-Cu complexation constant. At fixed ligand-to-Cu ratio, the Cu removal efficiency decreases in the order of citric acid>NTA>EDTA, which is the reverse order of Cu-ligand complexation constants for these ligands. Increasing SDS-ligand ratios from 12 to 60 at fixed ligand concentration did not improve copper removal efficiency. The cationic surfactant, CPC, enhances Cu removal efficiency in systems with condition of ligand-copper ratios higher than 1.0, where Cu removal is not very efficient using SDS-MEUF process. The Cu removal efficiency with CPC-MEUF depends on both the ligand-to-Cu ratio and the type of ligands.

  19. Extraction of catechins and caffeine from different tealeaves and comparison with micellar electrokinetic chromatography

    SONG Guanqun; LIN Jinming; Qu Feng; C.W.Huie


    This work describes the simultaneous deter- mination of catechins and caffeine in green, black tealeaves and canned tea-drink using micellar electrokinetic chromatography. The catechins analyzed include (+)-catechin, (-)- epicatechin, (-)-epigallocatechin, (-)-epicatechin gallate and (-)-epigallocatechin gallate. Using UV absorption method at 280 nm, the limits of detections of catechins and caffeine are 10-6 mol/L, which is suitable for the real sample determination. Using this analytical method, the extraction of these compounds from the tealeaves with hot water is compared under different temperatures. The effects of temperature on the amount of catechins and caffeine extracted are evident, showing that (-)-epigallocatechin gallate is the most easiest to be extracted at 100℃. The stability of catechins and caffeine in stocking solution of tea-drink at 4℃ is also compared on five consecutive days. The contents of catechins and caffeine in green and black teas are discussed and the difference of the content between different tealeaves can provide a reference for the assessment of tea quality.

  20. Kinetics and mechanism of the cutinase-catalyzed transesterification of oils in AOT reversed micellar system.

    Badenes, Sara M; Lemos, Francisco; Cabral, Joaquim M S


    The kinetics of the enzymatic transesterification between a mixture of triglycerides (oils) and methanol for biodiesel production in a bis(2-ethylhexyl) sodium sulfosuccinate (AOT)/isooctane reversed micellar system, using recombinant cutinase from Fusarium solani pisi as a catalyst, was investigated. In order to describe the results that were obtained, a mechanistic scheme was proposed, based on the literature and on the experimental data. This scheme includes the following reaction steps: the formation of the active enzyme-substrate complex, the addition of an alcohol molecule to the complex followed by the separation of a molecule of the fatty acid alkyl ester and a glycerol moiety, and release of the active enzyme. Enzyme inhibition and deactivation effects due to methanol and glycerol were incorporated in the model. This kinetic model was fitted to the concentration profiles of the fatty acid methyl esters (the components of biodiesel), tri-, di- and monoglycerides, obtained for a 24 h transesterification reaction performed in a stirred batch reactor under different reaction conditions of enzyme and initial substrates concentration.

  1. Quantitative analysis of flavonoids and phenolic acids in Arnica montana L. by micellar electrokinetic capillary chromatography.

    Ganzera, Markus; Egger, Christoph; Zidorn, Christian; Stuppner, Hermann


    Arnica montana preparations have been used in Europe for centuries to treat skin disorders. Among the biologically active ingredients in the flower heads of the plant are sequiterpenes, flavonoids and phenolic acids. For the simultaneous determination of compounds belonging to the latter two groups a micellar electrokinetic capillary chromatography (MEKC) method was developed and validated. By using an electrolyte solution containing 50 mM borax, 25 mM sodium dodecyl sulfate and 30% of acetonitrile the separation of seven flavonoids and four caffeic acid derivatives was feasible in less than 20 min. The optimized system was validated for repeatability (sigma(rel) or = 0.9996), and then successfully applied to assay several plant samples. In all of them the most dominant flavonoid was found to be quercetin 3-O-glucuronic acid, whereas 3,5-dicaffeoylquinic acid was the major phenolic acid; the total content of flavonoids and phenolic acids varied in the samples from 0.60 to 1.70%, and 1.03 to 2.24%, respectively.

  2. Holistic analysis of seven active ingredients by micellar electrokinetic chromatography from three medicinal herbs composing Shuanghuanglian.

    Zhou, Xian-Jing; Chen, Juan; Li, Ying-Dong; Jin, Ling; Shi, Yan-Ping


    A simple and reliable method has been developed with a new strategy named holistic analysis of multiple constituents to evaluate the quality of the well-known traditional Chinese medicine (TCM) Shuanghuanglian (SHL) oral liquid and soft capsule. Seven main constituents of the medicine, i.e., baicalein, baicalin, chlorogenic acid, wogonin, scutellarin, forsythin and hyperin, were selected as the evaluation markers and analyzed by micellar electrokinetic chromatography. The effects of buffer pH, concentration of electrolyte, organic modifier and applied voltage on migration behavior were studied systematically. The optimum conditions for the separation were achieved in a 12.5 mM borate-10 mM sodium dihydrogen phosphate-10 mM sodium dodecyl sulfate buffer at pH 9.1 containing 10% (v/v) acetonitrile under 15 kV. The analytes were identified by their relative time with regard to para-hydroxybenzoic acid migration time used as an internal standard. The method was validated in terms of linearity, limit of detection and quantification, precision, accuracy and recoveries. The correlation coefficient ranged from 0.9962 to 0.9992. The limits of detection (S/N = 3) were from 0.15 to 3.95 μg mL(-1). Recoveries of seven analytes in the SHL samples ranged from 89.00 to 103.04%. The proposed method was successfully applied for the quality control of complicated TCM SHL.

  3. Micellar-polymer for enhanced oil recovery for Upper Assam Basin

    B.M. Das


    Full Text Available One of the major enhanced oil recovery (EOR processes is chemical flooding especially for the depleted reservoirs. Chemical flooding involves injection of various chemicals like surfactant, alkali, polymer etc. to the aqueous media. Bhogpara and Nahorkatiya are two depleted reservoirs of upper Assam basin where chemical flooding can be done to recover the trapped oil that cannot be recovered by conventional flooding process. Micellar-polymer (MP flooding involves injection of micelle and polymer to the aqueous phase to reduce interfacial tension and polymer is added to control the mobility of the solution, which helps in increasing both displacement and volumetric sweep efficiency and thereby leads to enhanced oil recovery. This work represents the use of black liquor as micelle or surfactant that is a waste product of Nowgong Paper Mills, Jagiroad, Assam, which is more efficient than the synthetic surfactants. The present study examines the effect of MP flooding through the porous media of two depleted oil fields of upper Assam basin i.e. Bhogpara and Nahorkatiya for MP EOR. This work also compares the present MP flood with the earlier work done on surfactant (S flooding. It was experimentally determined that the MP flood is more efficient EOR process for Bhogpara and Nahorkatiya reservoirs. The study will pertain to the comprehensive interfacial tension (IFT study and the displacement mechanism in conventional core samples.

  4. Role of spacer lengths of gemini surfactants in the synthesis of silver nanorods in micellar media.

    Bhattacharya, Santanu; Biswas, Joydeep


    In this work, we have prepared Ag-nanorods using biscationic gemini surfactant micelles as the media by a seed-mediated wet synthesis method. Towards this end, we first synthesized Ag-nanoseeds of diameter ~7 nm stabilized by trisodium citrate (as the capping agent). Then these Ag-nanoseeds were used to synthesize Ag-nanorods of different aspect ratios. With decreasing Ag-nanoseed concentration, the aspect ratios of the Ag-nanorods stabilized by these gemini surfactants increased gradually. Various Ag-nanoseeds and Ag-nanospecies were characterized using UV-Vis spectroscopy (to know the surface plasmon bands), transmission electron microscopy (to find out their particle sizes and distribution), energy-dispersive X-ray spectroscopy and X-ray diffraction. When we used micelles derived from gemini surfactants of shorter spacer -(CH(2))(n)- (n = 2 or 4) to stabilize the Ag-nanorods, the λ(max) of the longitudinal band shifted more towards the blue region compared to that of the gemini surfactant micelles with a longer spacer -(CH(2))(n)- (n = 5, 12) at a given amount of the Ag-nanoseed solution. So, the growth of Ag-nanorods in the gemini micellar solutions depends on the spacer-chain length of gemini surfactants employed.

  5. Prostaglandin H synthase kinetics in the two-phase aqueous-micellar system.

    Ponomareva, Olga A; Trushkin, Nikita A; Filimonov, Ivan S; Krivoshey, Alexandr V; Barkhatov, Vladimir I; Mitrofanov, Sergey I; Vrzheshch, Petr V


    Reaction mixture for PGHS (prostaglandin-H-synthase) is a two-phase system including micellar hydrophobic phase and hydrophilic aqueous phase. Reagents added to the mixture are distributed between phases, thus concentrations of reagents dissolved in phases can differ significantly from their overall contents. Using dynamic light scattering we found that the hydrophobic phase produced by tween-20 consists of micelles, which radius (4-5nm) does not depend on either tween-20 overall content (0.1%-1% v/v) or arachidonic acid (AA) addition (10-1000μM) or PGHS addition (1μM). Tween-20 overall content changing from 0.1% to 2% v/v dramatically affected COX kinetic, but accounting AA distribution between phases allowed us to estimate "true" parameters, independent of the tween-20 overall content and the concentration of another substrate: KM(Ox) equals 9.8μM O2 in the aqueous phase or 0.0074bar in the gaseous phase, KM(AA) equals 5400μM AA in the phase of tween-20 micelles and 5400/PμM AA in the aqueous phase (P is the distribution ratio for the AA between the aqueous phase and the hydrophobic phase (P≫1000)). This approach allowed to evaluate PS, the distribution ratio for the AA between the hydrophobic phase and the PGHS active center (PS ~310). This coefficient indicates the AA selectivity toward the cyclooxygenase active center.

  6. Origin of shear thickening in semidilute wormlike micellar solutions and evidence of elastic turbulence

    Marín-Santibáñez, Benjamín M. [Escuela Superior de Ingeniería Química e Industrias Extractivas, Instituto Politécnico Nacional, U.P.A.L.M. C.P. 07738, Col. S. P. Zacatenco, Del. Gustavo A. Madero, Mexico D.F. (Mexico); Pérez-González, José, E-mail: [Laboratorio de Reología y Física de la Matería Blanda, Escuela Superior de Física y Matemáticas, Instituto Politécnico Nacional, U.P.A.L.M. C.P. 07730, Col. S. P. Zacatenco, Del. Gustavo A. Madero, Mexico D.F. (Mexico); Rodríguez-González, Francisco [Departamento de Biotecnología, Centro de Desarrollo de Productos Bióticos, Instituto Politécnico Nacional, C.P. 62731, Col. San Isidro, Yautepec, Morelos (Mexico)


    The origin of shear thickening in an equimolar semidilute wormlike micellar solution of cetylpyridinium chloride and sodium salicylate was investigated in this work by using Couette rheometry, flow visualization, and capillary Rheo-particle image velocimetry. The use of the combined methods allowed the discovery of gradient shear banding flow occurring from a critical shear stress and consisting of two main bands, one isotropic (transparent) of high viscosity and one structured (turbid) of low viscosity. Mechanical rheometry indicated macroscopic shear thinning behavior in the shear banding regime. However, local velocimetry showed that the turbid band increased its viscosity along with the shear stress, even though barely reached the value of the viscosity of the isotropic phase. This shear band is the precursor of shear induced structures that subsequently give rise to the average increase in viscosity or apparent shear thickening of the solution. Further increase in the shear stress promoted the growing of the turbid band across the flow region and led to destabilization of the shear banding flow independently of the type of rheometer used, as well as to vorticity banding in Couette flow. At last, vorticity banding disappeared and the flow developed elastic turbulence with chaotic dynamics.

  7. Simultaneous determination of eleven preservatives in cosmetics by micellar electrokinetic chromatography.

    Wang, Ping; Ding, Xiaojing; Li, Yun; Yang, Yuanyuan


    A new method for the simultaneous quantitation of 11 preservatives-imidazolidinyl urea, benzyl alcohol, dehydroacetic acid, sorbic acid, phenoxyethanol, benzoic acid, salicylic acid, and four parabens (methyl, ethyl, propyl, and butyl)-in cosmetics by micellar electrokinetic capillary chromatography was established and validated. The separation was performed using an uncoated fused-silica capillary (50 pm id x 60.2 cm, effective length 50 cm) with a running buffer consisting of 15 mmol/L sodium tetraborate, 60 mmol/L boric acid, and 100 mmol/L sodium dodecyl sulfate. A 1:10 dilution of the running buffer was used as the sample buffer to extract the cosmetic samples. The key factors, such as the concentration and pH of the running and sample buffers, which influence quantitative analysis of the above 11 preservatives in cosmetic samples, were investigated in detail. The linear ranges of the calibration curves for imidazolidinyl urea and the other 10 preservatives were 50-1000 and 10-200 mg/L, respectively. The correlation coefficients of the standard curves were all higher than 0.999. The recoveries at the concentrations studied ranged from 93.0 to 102.7%. RSDs were all less than 5%. The new method with simple sample pretreatment met the needs for routine analysis of the 11 preservatives in cosmetics.

  8. A Benchmarking Algorithm to Determine Minimum Aggregation Delay for Data Gathering Trees and an Analysis of the Diameter-Aggregation Delay Tradeoff

    Natarajan Meghanathan


    Full Text Available Aggregation delay is the minimum number of time slots required to aggregate data along the edges of a data gathering tree (DG tree spanning all the nodes in a wireless sensor network (WSN. We propose a benchmarking algorithm to determine the minimum possible aggregation delay for DG trees in a WSN. We assume the availability of a sufficient number of unique CDMA (Code Division Multiple Access codes for the intermediate nodes to simultaneously aggregate data from their child nodes if the latter are ready with the data. An intermediate node has to still schedule non-overlapping time slots to sequentially aggregate data from its own child nodes (one time slot per child node. We show that the minimum aggregation delay for a DG tree depends on the underlying design choices (bottleneck node-weight based or bottleneck link-weight based behind its construction. We observe the bottleneck node-weight based DG trees incur a smaller diameter and a larger number of child nodes per intermediate node; whereas, the bottleneck link-weight based DG trees incur a larger diameter and a much lower number of child nodes per intermediate node. As a result, we observe a complex diameter-aggregation delay tradeoff for data gathering trees in WSNs.

  9. Number names and number understanding

    Ejersbo, Lisser Rye; Misfeldt, Morten


    This paper concerns the results from the first year of a three-year research project involving the relationship between Danish number names and their corresponding digits in the canonical base 10 system. The project aims to develop a system to help the students’ understanding of the base 10 syste...

  10. The Data Aggregation Project: Free Software that Transforms the Student Laboratory Experience.

    Brewer, Steven D.; Hoogendky, Tom; Hoagland, Donald B.


    Found that in an introductory biology course at the University of Massachusetts Amherst, adoption of the Data Aggregation Project (free software that allows students in a course to aggregate a large body of data for some particular problem) resulted in an increase in the number of data points students analyzed per semester by a factor of almost…

  11. Solubilization isotherms of aromatic solutes in surfactant aggregates

    Gadelle, F.; Koros, W.J.; Schechter, R.S. (Univ. of Texas, Austin, TX (United States). Dept. of Chemical Engineering)


    Several factors affecting solubilization of aromatic solutes in surfactant micelles have been investigated. Solubilization isotherms of benzene, toluene, and chlorobenzene in various aqueous micellar solutions were determined using head space gas chromatography. Cationic surfactants such as cetylpyridinium chloride or cetyltrimethylammonium bromide present high solubilization capacities. Comparable anionic surfactants exhibit lower solubilization and a greater tendency to precipitate. It was observed that nonionic surfactants show high solubilization on a molar basis. Solubilization in mixed cationic-anionic micelles was also investigated. It also appears that the molecular size of the solute determines the extent of the solubilization. Finally, the shape of the different isotherms indicates that knowing the amount solubilized at saturation of the micellar solution is not sufficient to estimate solubilization at solute concentrations lower than the solute aqueous solubility. Solubilization of organics in surfactant micelles is of major importance in many applications. One new application is micellar-enhanced ultrafiltration. Another application of interest is the surfactant-enhanced aquifer remediation, a process in which a micellar aqueous solution is flushed into contaminated groundwaters to enhance recovery of pollutants by micellar solubilization.

  12. Role of streams in myxobacteria aggregate formation

    Kiskowski, Maria A.; Jiang, Yi; Alber, Mark S.


    Cell contact, movement and directionality are important factors in biological development (morphogenesis), and myxobacteria are a model system for studying cell-cell interaction and cell organization preceding differentiation. When starved, thousands of myxobacteria cells align, stream and form aggregates which later develop into round, non-motile spores. Canonically, cell aggregation has been attributed to attractive chemotaxis, a long range interaction, but there is growing evidence that myxobacteria organization depends on contact-mediated cell-cell communication. We present a discrete stochastic model based on contact-mediated signaling that suggests an explanation for the initialization of early aggregates, aggregation dynamics and final aggregate distribution. Our model qualitatively reproduces the unique structures of myxobacteria aggregates and detailed stages which occur during myxobacteria aggregation: first, aggregates initialize in random positions and cells join aggregates by random walk; second, cells redistribute by moving within transient streams connecting aggregates. Streams play a critical role in final aggregate size distribution by redistributing cells among fewer, larger aggregates. The mechanism by which streams redistribute cells depends on aggregate sizes and is enhanced by noise. Our model predicts that with increased internal noise, more streams would form and streams would last longer. Simulation results suggest a series of new experiments.

  13. High-Throughput Screening Methodology to Identify Alpha-Synuclein Aggregation Inhibitors.

    Pujols, Jordi; Peña-Díaz, Samuel; Conde-Giménez, María; Pinheiro, Francisca; Navarro, Susanna; Sancho, Javier; Ventura, Salvador


    An increasing number of neurodegenerative diseases are being found to be associated with the abnormal accumulation of aggregated proteins in the brain. In Parkinson's disease, this process involves the aggregation of alpha-synuclein (α-syn) into intraneuronal inclusions. Thus, compounds that inhibit α-syn aggregation represent a promising therapeutic strategy as disease-modifying agents for neurodegeneration. The formation of α-syn amyloid aggregates can be reproduced in vitro by incubation of the recombinant protein. However, the in vitro aggregation of α-syn is exceedingly slow and highly irreproducible, therefore precluding fast high throughput anti-aggregation drug screening. Here, we present a simple and easy-to-implement in-plate method for screening large chemical libraries in the search for α-syn aggregation modulators. It allows us to monitor aggregation kinetics with high reproducibility, while being faster and requiring lower protein amounts than conventional aggregation assays. We illustrate how the approach enables the identification of strong aggregation inhibitors in a library of more than 14,000 compounds.

  14. Protein aggregates in Huntington’s disease

    Arrasate, Montserrat; Finkbeiner, Steven


    Huntington’s disease (HD) is an incurable neurodegenerative disease characterized by abnormal motor movements, personality changes, and early death. HD is caused by a mutation in the IT-15 gene that expands abnormally the number of CAG nucleotide repeats. As a result, the translated protein huntingtin contains disease-causing expansions of glutamines (polyQ) that make it prone to misfold and aggregate. While the gene and mutations that cause HD are known, the mechanisms underlying HD pathogenesis are not. Here we will review the state of knowledge of HD, focusing especially on a hallmark pathological feature—intracellular aggregates of mutant Htt called inclusion bodies (IBs). We will describe the role of IBs in the disease. We speculate that IB formation could be just one component of a broader coping response triggered by misfolded Htt whose efficacy may depend on the extent to which it clears toxic forms of mutant Htt. We will describe how IB formation might be regulated and which factors could determine different coping responses in different subsets of neurons. A differential regulation of IB formation as a function of the cellular context could, eventually, explain part of the neuronal vulnerability observed in HD. PMID:22200539

  15. Application of Surfactant Micellar Solutions as Extractants and Mobile Phases for TLC-Determination of Purine Bases and Doping Agents in Biological Liquids

    Daria Victorovna Yedamenko


    Full Text Available Separation of caffeine and its metabolites (theophylline and theobromine and doping agents (spironolactone, propranolol, and ephedrine and determination of caffeine in serum sample and propranolol and ephedrine in urine were studied on normal-phase thin layers (“Sorbfil-UV-254”. Aqueous organic solvents and aqueous micellar surfactant solutions were compared as the mobile phases for separation. The acceptable separation of purine bases and doping agents was achieved by micellar Thin Layer Chromatography and normal-phase Thin Layer Chromatography. Anionic surfactant solution with added 1-propanol was the best eluent as for caffeine, theophylline, and theobromine separation, as for doping agents. The best characteristics of caffeine extraction from serum, and propranolol and ephedrine from urine were achieved when micellar eluent based on non-ionic Tween-80 surfactant was used. DOI:

  16. Platelet aggregation secondary to coronary obstruction.

    Moore, S


    From many observations made at autopsy it is apparent that thrombosis in a coronary artery is usually, if not always, associated with rupture of an atheromatous plaque. The sequelae of such rupture include hemorrhage into the plaque with further narrowing of the lumen, formation of an occlusive thrombus or of a non-occlusive thrombus. A developing thrombus in an artery undergoes fragmentation with showering of the distal microcirculation by aggregates of platelets possibly with some admixture of fibrin. In many cases of sudden cardiac death associated with severe atherosclerotic stenosis of the coronary vessels, an occlusive thrombus is not found and the myocardium shows no morphological lesion or else focal patchy early damage in the subendocardial region. One possible mechanism that might explain these findings is microembolism from mural nonobstructing coronary thrombus. Such a mechanism is well established in transient ischemia of the brain and retina related to ulcerated atheroma of the internal carotid artery. Experimental observations indicate that platelet aggregates in the myocardial circulation cause arrhythmias, sudden death, vasculitis, and myocardial ischemic damage. Induction of an occlusive coronary artery thrombus is associated with development of an infarct involving the full thickness of the myocardium. A nonocclusive thrombus is associated with either no myocardial damage or focal subendocardial ischemic injury. It is possible that further aggregation of platelets may facilitate the extension of infarction subsequent to an occlusive event, although there is little evidence on this point. A number of clinical studies show increased platelet reactivity to agents causing aggregation, such as norepinephrine or collagen, in subjects experiencing thromboembolic episodes. It seems unlikely, however, that in vitro tests of platelet function can identify or predict clinical arterial thrombotic disease, although studies of platelet survival and turnover


    T.A. Nelyubina


    Full Text Available In this article, author considers a class of technologies aggregates, which can be present as complex socio-economic systems. The order parameters are chosen as instrument of reflect the system integrity of this technologies aggregates. The analysis of aggregates through order parameters permit: to diagnose the state of the system and its life phase, understand the compatibility extent between the current state of system and the assumed modifications in it, understand the nature of attendant risks. It also allows to compare the systems, track the dynamics of order parameters and forecast the trends of the future changes. Author formulates number and definitions of order parameters for this class of technologies aggregates; proposes the assessment method of condition of order parameters for technologies aggregate of region; makes express-assessment of preparedness level of technologies aggregates of some regions to innovation changes.

  18. Behavior of the aggregate wind resource in the ISO regions in the United States

    Gunturu, Udaya


    The collective behavior of wind farms in seven Independent System Operator (ISO) areas has been studied. The generation duration curves for each ISO show that there is no aggregated power for some fraction of time. Aggregation of wind turbines mitigates intermittency to some extent, but in each ISO there is considerable fraction of time when there is less than 5% capacity. The hourly wind power time series show benefit of aggregation but the high and low wind events are lumped in time, thus indicating that intermittency is synchronized in each region. The timeseries show that there are instances when there is no wind power in most ISOs because of large-scale high pressure systems. An analytical consideration of the collective behavior of aggregated wind turbines shows that the benefit of aggregation saturates beyond a certain number of generating units asymptotically. Also, the benefit of aggregation falls rapidly with temporal correlation between the generating units.

  19. In vivo amyloid aggregation kinetics tracked by time-lapse confocal microscopy in real-time.

    Villar-Piqué, Anna; Espargaró, Alba; Ventura, Salvador; Sabate, Raimon


    Amyloid polymerization underlies an increasing number of human diseases. Despite this process having been studied extensively in vitro, aggregation is a difficult process to track in vivo due to methodological limitations and the slow kinetics of aggregation reactions in cells and tissues. Herein we exploit the amyloid properties of the inclusions bodies (IBs) formed by amyloidogenic proteins in bacteria to address the kinetics of in vivo amyloid aggregation. To this aim we used time-lapse confocal microscopy and a fusion of the amyloid-beta peptide (A β42) with a fluorescent reporter. This strategy allowed us to follow the intracellular kinetics of amyloid-like aggregation in real-time and to discriminate between variants exhibiting different in vivo aggregation propensity. Overall, the approach opens the possibility to assess the impact of point mutations as well as potential anti-aggregation drugs in the process of amyloid formation in living cells.


    Maris Angela


    Full Text Available In the paper the authors present a model aggregate rating based on credit-scoring models, banking models and their rating model. Multi-criteria approach and an aggregate model better capture business risk of the company.

  1. Electrochemical sensors and biosensors based on less aggregated graphene.

    Bo, Xiangjie; Zhou, Ming; Guo, Liping


    As a novel single-atom-thick sheet of sp(2) hybridized carbon atoms, graphene (GR) has attracted extensive attention in recent years because of its unique and remarkable properties, such as excellent electrical conductivity, large theoretical specific surface area, and strong mechanical strength. However, due to the π-π interaction, GR sheets are inclined to stack together, which may seriously degrade the performance of GR with the unique single-atom layer. In recent years, an increasing number of GR-based electrochemical sensors and biosensors are reported, which may reflect that GR has been considered as a kind of hot and promising electrode material for electrochemical sensor and biosensor construction. However, the active sites on GR surface induced by the irreversible GR aggregations would be deeply secluded inside the stacked GR sheets and therefore are not available for the electrocatalysis. So the alleviation or the minimization of the aggregation level for GR sheets would facilitate the exposure of active sites on GR and effectively upgrade the performance of GR-based electrochemical sensors and biosensors. Less aggregated GR with low aggregation and high dispersed structure can be used in improving the electrochemical activity of GR-based electrochemical sensors or biosensors. In this review, we summarize recent advances and new progress for the development of electrochemical sensors based on less aggregated GR. To achieve such goal, many strategies (such as the intercalation of carbon materials, surface modification, and structural engineering) have been applied to alleviate the aggregation level of GR in order to enhance the performance of GR-based electrochemical sensors and biosensors. Finally, the challenges associated with less aggregated GR-based electrochemical sensors and biosensors as well as related future research directions are discussed.

  2. Fundamental factors determining the nature of parasite aggregation in hosts.

    Sébastien Gourbière

    Full Text Available The distribution of parasites in hosts is typically aggregated: a few hosts harbour many parasites, while the remainder of hosts are virtually parasite free. The origin of this almost universal pattern is central to our understanding of host-parasite interactions; it affects many facets of their ecology and evolution. Despite this, the standard statistical framework used to characterize parasite aggregation does not describe the processes generating such a pattern. In this work, we have developed a mathematical framework for the distribution of parasites in hosts, starting from a simple statistical description in terms of two fundamental processes: the exposure of hosts to parasites and the infection success of parasites. This description allows the level of aggregation of parasites in hosts to be related to the random variation in these two processes and to true host heterogeneity. We show that random variation can generate an aggregated distribution and that the common view, that encounters and success are two equivalent filters, applies to the average parasite burden under neutral assumptions but it does not apply to the variance of the parasite burden, and it is not true when heterogeneity between hosts is incorporated in the model. We find that aggregation decreases linearly with the number of encounters, but it depends non-linearly on parasite success. We also find additional terms in the variance of the parasite burden which contribute to the actual level of aggregation in specific biological systems. We have derived the formal expressions of these contributions, and these provide new opportunities to analyse empirical data and tackle the complexity of the origin of aggregation in various host-parasite associations.

  3. Kinetic analysis of the multistep aggregation mechanism of monoclonal antibodies.

    Nicoud, Lucrèce; Arosio, Paolo; Sozo, Margaux; Yates, Andrew; Norrant, Edith; Morbidelli, Massimo


    We investigate by kinetic analysis the aggregation mechanism of two monoclonal antibodies belonging to the IgG1 and IgG2 subclass under thermal stress. For each IgG, we apply a combination of size exclusion chromatography and light scattering techniques to resolve the time evolution of the monomer, dimer, and trimer concentrations, as well as the average molecular weight and the average hydrodynamic radius of the aggregate distribution. By combining the detailed experimental characterization with a theoretical kinetic model based on population balance equations, we extract relevant information on the contribution of the individual elementary steps on the global aggregation process. The analysis shows that the two molecules follow different aggregation pathways under the same operating conditions. In particular, while the monomer depletion of the IgG1 is found to be rate-limited by monomeric conformational changes, bimolecular collision is identified as the rate-limiting step in the IgG2 aggregation process. The measurement of the microscopic rate constants by kinetic analysis allows the quantification of the protein-protein interaction potentials expressed in terms of the Fuchs stability ratio (W). It is found that the antibody solutions exhibit large W values, which are several orders of magnitude larger than the values computed in the frame of the DLVO theory. This indicates that, besides net electrostatic repulsion, additional effects delay the aggregation kinetics of the antibody solutions with respect to diffusion-limited conditions. These effects likely include the limited efficiency of the collision events due to the presence of a limited number of specific aggregation-prone patches on the heterogeneous protein surface, and the contribution of additional repulsive non-DLVO forces to the protein-protein interaction potential, such as hydration forces.

  4. Protein aggregation in salt solutions

    Kastelic, Miha; Kalyuzhnyi, Yurij V.; Hribar-Lee, Barbara; Dill, Ken A.; Vlachy, Vojko


    Protein aggregation is broadly important in diseases and in formulations of biological drugs. Here, we develop a theoretical model for reversible protein–protein aggregation in salt solutions. We treat proteins as hard spheres having square-well-energy binding sites, using Wertheim’s thermodynamic perturbation theory. The necessary condition required for such modeling to be realistic is that proteins in solution during the experiment remain in their compact form. Within this limitation our model gives accurate liquid–liquid coexistence curves for lysozyme and γ IIIa-crystallin solutions in respective buffers. It provides good fits to the cloud-point curves of lysozyme in buffer–salt mixtures as a function of the type and concentration of salt. It than predicts full coexistence curves, osmotic compressibilities, and second virial coefficients under such conditions. This treatment may also be relevant to protein crystallization. PMID:25964322

  5. Acetone:isomedzation and aggregation

    HU Zhan; JIN Ming-xing; XU Xue-song; CHENG Xi-hui; DING Da-jun


    The advanced experimental and theoretical techniques enable us to obtain information on the rearrangement of atoms or molecules in a reaction nowadays.As an example,we report on our research work on acetone isomerization and aggregation to give an insight into the reaction pathways,the products and their structures,and the growth regularity of aggregation.The evidences on the structural change of acetone and the stability of acetone clusters are found by a laser ionization mass spectrometer and the results are interpreted from theoretical analysis based on the DFT/B3LYP method.Various isomerization channels of acetone have been established and the optimal structures of the neutral clusters (CH3COCH3)n and the protonated acetone clusters (CH3COCHa)n H+ for n=1-7 have been determined.

  6. Intuitionistic fuzzy aggregation and clustering

    Xu, Zeshui


    This book offers a systematic introduction to the clustering algorithms for intuitionistic fuzzy values, the latest research results in intuitionistic fuzzy aggregation techniques, the extended results in interval-valued intuitionistic fuzzy environments, and their applications in multi-attribute decision making, such as supply chain management, military system performance evaluation, project management, venture capital, information system selection, building materials classification, and operational plan assessment, etc.

  7. Breakup of small aggregates driven by turbulent hydrodynamic stress

    Babler, Matthaus U; Lanotte, Alessandra S


    Breakup of small solid aggregates in homogeneous and isotropic turbulence is studied theoretically and by using Direct Numerical Simulations at high Reynolds number, Re_{\\lambda} \\simeq 400. We show that turbulent fluctuations of the hydrodynamic stress along the aggregate trajectory play a key role in determining the aggregate mass distribution function. Differences between turbulent and laminar flows are discussed. A novel definition of the fragmentation rate is proposed in terms of the typical frequency at which the hydrodynamic stress becomes sufficiently high to cause breakup along each Lagrangian path. We also define an Eulerian proxy of the real fragmentation rate, based on the joint statistics of the stress and its time derivative, which should be easier to measure in any experimental set-up. Both our Eulerian and Lagrangian formulations define a clear procedure for the computation of the mass distribution function due to fragmentation. Contrary, previous estimates based only on single point statistic...

  8. Molecular Weight and Aggregation of Erwinia Gum in Aqueous Solutions


    Erwinia(E) gum is composed of glucose, fucose, galactose and glucuronic acid. The weight-average molecular weights Mw, number-average molecular weights Mn and intrinsic viscosities[η] of the four fractions and the unfractionated E gum in aqueous solutions at desired temperatures were studied by light scattering, membrane osmometry, size exclusion chromatography(SEC) and viscometry. The experimental results prove that E gum formed aggregates in the aqueous solution at 25 ℃ and the aggregates were broken gradually with increasing temperature. The dissociation of the aggregates of E gum in the aqueous solution started at 36 ℃, and was completed at around 90 ℃. The [η] values of E gum and its fractions are much higher than those of the conventional polymers with the similar molecular weights, and decrease with increasing NaCl concentration.

  9. The Unbalanced Linguistic Aggregation Operator in Group Decision Making

    Li Zou


    Full Text Available Many linguistic aggregation methods have been proposed and applied in the linguistic decision-making problems. In practice, experts need to assess a number of values in a side of reference domain higher than in the other one; that is, experts use unbalanced linguistic values to express their evaluation for problems. In this paper, we propose a new linguistic aggregation operator to deal with unbalanced linguistic values in group decision making, we adopt 2-tuple representation model of linguistic values and linguistic hierarchies to express unbalanced linguistic values, and moreover, we present the unbalanced linguistic ordered weighted geometric operator to aggregate unbalanced linguistic evaluation values; a comparison example is given to show the advantage of our method.

  10. Approximate aggregate nearest neighbor search on moving objects trajectories

    Mohammad; Reza; Abbasifard; Hassan; Naderi; Zohreh; Fallahnejad; Omid; Isfahani; Alamdari


    Aggregate nearest neighbor(ANN) search retrieves for two spatial datasets T and Q, segment(s) of one or more trajectories from the set T having minimum aggregate distance to points in Q. When interacting with large amounts of trajectories, this process would be very time-consuming due to consecutive page loads. An approximate method for finding segments with minimum aggregate distance is proposed which can improve the response time. In order to index large volumes of trajectories, scalable and efficient trajectory index(SETI) structure is used. But some refinements are provided to temporal index of SETI to improve the performance of proposed method. The experiments were performed with different number of query points and percentages of dataset. It is shown that proposed method besides having an acceptable precision, can reduce the computation time significantly. It is also shown that the main fraction of search time among load time, ANN and computing convex and centroid, is related to ANN.

  11. Familial aggregation of cluster headache

    Simao Cruz


    Full Text Available Several studies suggest a strong familial aggregation for cluster headache (CH, but so far none of them have included subjects with probable cluster headache (PCH in accordance with the International Classification of Headache Disorders. Objective To identify cases of probable cluster headache and to assess the familial aggregation of cluster headache by including these subjects. Method Thirty-six patients attending a headache consultation and diagnosed with trigeminal autonomic headaches were subjected to a questionnaire-based interview. A telephone interview was also applied to all the relatives who were pointed out as possibly affected as well as to some of the remaining relatives. Results Twenty-four probands fulfilled the criteria for CH or PCH; they had 142 first-degree relatives, of whom five were found to have CH or PCH, including one case of CH sine headache. The risk for first-degree relatives was observed to be increased by 35- to 46-fold. Conclusion Our results suggest a familial aggregation of cluster headache in the Portuguese population.

  12. Network Provisioning Using Multimedia Aggregates

    Joan Vila-Carbó


    Full Text Available Multimedia traffic makes network provisioning a key issue. Optimal provisioning of network resources is crucial for reducing the service cost of multimedia transmission. Multimedia traffic requires not only provisioning bandwidth and buffer resources in the network but also guaranteeing a given maximum end-to-end delay. In this paper we present methods and tools for the optimal dimensioning of networks based on multimedia aggregates. The proposed method minimises the network resources reservations of traffic aggregates providing a bounded delay. The paper also introduces several methods to generate multimedia traffic aggregation using real video traces. The method is evaluated using a network topology based on the European GÉANT network. The results of these simulations allow us to discover the relationship between a required delay and the necessary bandwidth reservation (or the achievable utilisation limit. An interesting conclusion of these scenarios is that, following several recommendations, the network utilisation can reach values of around 80% or higher.

  13. Stability of an ophthalmic micellar formulation of cyclosporine A in unopened multidose eyedroppers and in simulated use conditions.

    Chennell, P; Delaborde, L; Wasiak, M; Jouannet, M; Feschet-Chassot, E; Chiambaretta, F; Sautou, V


    Cyclosporine A eye drops are used at concentrations ranging from 0.5 to 20mg/mL to treat a variety of ophthalmic diseases. Cyclosporine A formulations at high concentrations are difficult to manufacture because of cyclosporine's lipophilicity, and generally require an oil based vector. In this study, we investigated the physicochemical and microbiological stability of two high concentrations (10mg/mL and 20mg/mL) of an ophthalmic cyclosporine A micellar solution in a low density polyethylene multidose eyedropper, at two conservation conditions (5°C and 25°C), before and with simulated use. Analyses used were the following: visual inspection, cyclosporine quantification by a stability-indicating liquid chromatography method, osmolality and pH measurements and turbidity. A complementary analysis by dynamic light scattering was implemented to evaluate potential particle formation or micelle size change. In the in-use study, cyclosporine quantification was also performed on the drops emitted from the multidose eyedroppers. Our results show that the cyclosporine micellar formulation retains good physicochemical and microbiological stability, as all parameters stayed within acceptable range limits, however a higher variability in cyclosporine concentrations was observed for 20mg/mL units stored at 25°C. The in-use study showed that cyclosporine concentrations in the emitted drops were also within acceptable range limits. The micellar formulation presented in this study can therefore be stored at 5°C or at ≤25°C for up to 6months. Copyright © 2017 Elsevier B.V. All rights reserved.

  14. Influence of Phosphatidylcholine and Calcium on Self-Association and Bile Salt Mixed Micellar Binding of the Natural Bile Pigment, Bilirubin Ditaurate.

    Neubrand, Michael W; Carey, Martin C; Laue, Thomas M


    Recently [Neubrand, M. W., et al. (2015) Biochemistry 54, 1542-1557], we determined a concentration-dependent monomer-dimer-tetramer equilibrium in aqueous bilirubin ditaurate (BDT) solutions and explored the nature of high-affinity binding of BDT monomers with monomers and micelles of the common taurine-conjugated bile salts (BS). We now investigate, employing complementary physicochemical methods, including fluorescence emission spectrophotometry and quasi-elastic light scattering spectroscopy, the influence of phosphatidylcholine (PC), the predominant phospholipid of bile and calcium, the major divalent biliary cation, on these self-interactions and heterointeractions. We have used short-chain, lyso and long-chain PC species as models and contrasted our results with those of parallel studies employing unconjugated bilirubin (UCB) as the fully charged dianion. Both bile pigments interacted with the zwitterionic headgroup of short-chain lecithins, forming water-soluble (BDT) and insoluble ion-pair complexes (UCB), respectively. Upon micelle formation, BDT monomers apparently remained at the headgroup mantle of short-chain PCs, but the ion pairs with UCB became internalized within the micelle's hydrophobic core. BDT interacted with the headgroups of unilamellar egg yolk (EY) PC vesicles; however, with the simultaneous addition of CaCl2, a reversible aggregation took place, but not vesicle fusion. With mixed EYPC/BS micelles, BDT became bound to the hydrophilic surface (as with simple BS micelles), and in turn, both BDT and BS bound calcium, but not other divalent cations. The calcium complexation of BDT and BS was enhanced strongly with increases in micellar EYPC, suggesting calcium-mediated cross-bridging of hydrophilic headgroups at the micelle's surface. Therefore, the physicochemical binding of BDT to BS in an artificial bile medium is influenced not only by BS species and concentration but also by long-chain PCs and calcium ions that exert a specific rather

  15. pH-Regulated Reversible Transition Between Polyion Complexes (PIC) and Hydrogen-Bonding Complexes (HBC) with Tunable Aggregation-Induced Emission.

    Tian, Sidan; Liu, Guhuan; Wang, Xiaorui; Wu, Tao; Yang, Jinxian; Ye, Xiaodong; Zhang, Guoying; Hu, Jinming; Liu, Shiyong


    The mimicking of biological supramolecular interactions and their mutual transitions to fabricate intelligent artificial systems has been of increasing interest. Herein, we report the fabrication of supramolecular micellar nanoparticles consisting of quaternized poly(ethylene oxide)-b-poly(2-dimethylaminoethyl methacrylate) (PEO-b-PQDMA) and tetrakis(4-carboxylmethoxyphenyl)ethene (TPE-4COOH), which was capable of reversible transition between polyion complexes (PIC) and hydrogen bonding complexes (HBC) with tunable aggregation-induced emission (AIE) mediated by solution pH. At pH 8, TPE-4COOH chromophores can be directly dissolved in aqueous milieu without evident fluorescence emission. However, upon mixing with PEO-b-PQDMA, polyion complexes were formed by taking advantage of electrostatic interaction between carboxylate anions and quaternary ammonium cations and the most compact PIC micelles were achieved at the isoelectric point (i.e., [QDMA(+)]/[COO(-)] = 1), as confirmed by dynamic light scattering (DLS) measurement. Simultaneously, fluorescence spectroscopy revealed an evident emission turn-on and the maximum fluorescence intensity was observed near the isoelectric point due to the restriction of intramolecular rotation of TPE moieties within the PIC cores. The kinetic study supported a micelle fusion/fission mechanism on the formation of PIC micelles at varying charge ratios, exhibiting a quick time constant (τ1) relating to the formation of quasi-equilibrium micelles and a slow time constant (τ2) corresponding to the formation of final equilibrium micelles. Upon deceasing the pH of PIC micelles from 8 to 2 at the [QDMA(+)]/[COO(-)] molar ratio of 1, TPE-4COOH chromophores became gradually protonated and hydrophobic. The size of micellar nanoparticles underwent a remarkable decrease, whereas the fluorescence intensity exhibited a further increase by approximately 7.35-fold, presumably because of the formation of HBC micelles comprising cationic PQDMA

  16. Unusual subterranean aggregations of the California Giant Salamander, Dicamptodon ensatus

    Fellers, Gary M.; Wood, Leslie L.; Carlisle, Sarah; Pratt, David


    Larval Dicamptodon are one of the most abundant vertebrates in headwater streams in the Pacific Northwest. Their numbers and biomass can exceed those of all other amphibians, and of salmonid fishes. By contrast, metamorphosed Dicamptodon are only found infrequently, usually during formal surveys using pitfall traps, cover boards, or time constrained surveys However, we found two aggregations (23 and 27 individuals) of metamorphosed Dicamptodon ensatus during a culvert removal project at Point Reyes National Seashore, California. Furthermore, we found an additional 23 terrestrial D. ensatus in terrestrial habitat adjacent to the culverts. We did not expect these aggregations because metamorphosed individuals are so rarely encountered, and aggregations are likely to increase competition and predation in a species known to feed regularly on vertebrate prey. Deteriorating culverts might provide an unusually high-quality habitat that leads to aggregations such as we describe. Our observations may provide insight into the natural haunts of D. ensatus—underground burrows or caverns—and if so, then aggregations may be normal, but rarely seen.

  17. A simple spectrophotometric method for the determination of trace level lead in biological samples in the presence of aqueous micellar solutions

    Khan, Humaira; Ahmed, M. Jamaluddin; Bhanger, M. Iqbal


    A very simple, ultra-sensitive and fairly selective new spectrophotometric method has been developed for the rapid determination of lead(II) at ultra-trace level using 1,5-diphenylthiocarbazone (dithizone) in presence of aqueous micellar solutions. The proposed method enabled the determination of lead down to µg l−1 in human blood and urine in aqueous media without resource of any “clean-up” step. The most remarkable point of this method is that the presence of micellar system avoids the prev...

  18. Fast relaxation of a hexagonal Poiseuille shear-induced near-surface phase in a threadlike micellar solution.

    Hamilton, W A; Butler, P D; Magid, L J; Han, Z; Slawecki, T M


    The dynamics of near-surface conformations in complex fluids under flow should dramatically affect their rheological properties. We have made the first measurements resolving the decay kinetics of a hexagonal phase induced in a threadlike polyionic micellar system under Poiseuille shear near a quartz surface. Upon cessation of shearing flow, this minimum interference crystalline phase formed within approximately 20 microm of the surface "melts" to a metastable two-dimensional liquid of aligned micelles in approximately 0.7 s. This is some three orders of magnitude shorter than the time required for bulk (Couette) shear-aligned micelles in this system to reach a fully entangled state.

  19. Determination of ephedrine and codeine in human urine by cation-selective exhaustive injection and sweeping micellar electrokinetic chromatography

    Li Jun Li; Si Guang Li; Hai Yan Li; Zhuo Cai; Hao Cheng


    A sensitive method for the determination of ephedrine and codeine in human urine by capillary electrophoresis (CE) was described. In order to improve the sensitivity, two online concentration techniques including cation-selective exhaustive injection (CSEI) and sweeping micellar electrokinetic chromatography (sweeping-MEKC) were used. Under the optimum conditions, the detection limits (S/N = 3) were 0.10 μg/L for ephedrine and 0.80 μg/L for codeine. This method was successfully applied to real urine sample analysis.

  20. Study of interaction of proflavin with triethylamine in homogeneous and micellar media: Photoinduced electron transfer probed by magnetic field effect

    Chakraborty, Brotati; Basu, Samita


    Interaction of triethylamine (TEA) with cationic proflavin (PF +) in homogeneous and micellar media is studied using absorption spectroscopy, steady-state as well as time-resolved fluorescence spectroscopy and laser flash photolysis in conjunction with an external magnetic field. The two prime phenomena that have been highlighted in this study are photoinduced electron transfer (PET) and ground-state complex formation. This study shows that it is the medium which determines the reaction pathways to be followed. Magnetic field effect (MFE) helps to elucidate the reaction mechanism involved and this work also highlights the distance dependence factor associated with MFE.