Dispersive liquid–liquid microextraction using a surfactant as disperser agent

A novel and efficient surfactant-assisted dispersive liquid–liquid microextraction combined with high-performance liquid chromatography–photodiode array detection was developed for the determination of phenylurea herbicides in water samples. Based on this procedure, which is a dispersive-solvent-free technique, the extractant is dispersed in the aqueous sample using methyltrialkylammonium chloride. Compared with the conventional dispersive liquid–liquid microextraction, the new extraction method has many advantages such as higher extraction efficiency, low cost, reduced environmental hazards, and consumption of less extracting solvent. A few microliters of chloroform containing an appropriate amount of methyltrialkylammonium chloride (mixture of C8–C10) was used to extract the analytes from water samples. The main parameters relevant to the extraction process (namely, type of surfactant, selection of extractant solvent, extractant volume, surfactant concentration, ionic strength, and extraction time) were investigated. The performed analytical procedure showed limits of detection ranging from 2.3 to 18 ng/L, and precision ranges from 0.6% to 2.0% (as intra-day relative standard deviation, RSD) and from 1.3% to 8.3% (as inter-day RSD) depending on the analyte. The method showed good linearity between 0.04 and 40 μg/L with squared correlation coefficients better than 0.9920. This newly established approach was successfully applied to spiked real water samples.     

Topology change by screening the electrostatic interactions in a polymer–surfactant system

We show that a neutral polymer (PEG) induces a topology transition of the bilayers of an ionic surfactant system (SDS–hexanol–brine), provided that the electrostatic interactions between membranes are screened. Hexanol is used as a cosurfactant in order to get a lamellar or a sponge phase, depending on the cosurfactant/surfactant mass ratio. Using brine as solvent, the addition of polymer triggers a transformation between flat or saddle-like bilayers into vesicles. This modification is not observed in pure water because of the electrostatic repulsion between membranes. The effect can be understood in terms of the modification of the membrane Gaussian modulus due to polymer adsorption and of the entropy gain of the adsorbed polymer when the membrane bends to form a vesicle.     

Surfactant presence in a multilayer polyelectrolyte–enzyme system improves its catalytic response

Self-assembling of poly(allylamine) containing an osmium polypyridil complex (PAOs) alternatively with sodium dodecyl sulfate (SDS) and glucose oxidase (GOx) generates a ternary multilayer system, (PAOs/SDS/PAOs/GOx)_n. The introduction of this anionic surfactant allows a sensitive increase of the polyelectrolyte and the enzyme uptake at pH 7.0, enhancing its catalytic behavior in presence of glucose more than 5 times, compared to the system (PAOs/GOx)_n constructed at the same pH. The balance between ionic and hydrophobic interactions in the construction of this system is discussed.     

Gelatin and starch as stabilizers of the coupled enzyme system of luminous bacteria NADH:FMN–oxidoreductase–luciferase

We have studied the effects of a gel-like environment on the characteristics of enzyme preparations based on the coupled enzyme system of luminous bacteria, NADH:FMN–oxidoreductase–luciferase, to design a stable immobilizing reagent for bioluminescent analysis. Natural polymers, gelatin and starch, were used to create a viscous, structured microenvironment. The stability of the coupled enzyme system to such physical and chemical environmental factors as temperature, pH, and ionic strength in gelatin and starch-containing media was examined. It was shown that both gelatin and starch have a stabilizing effect on the enzymes of luminous bacteria under specific conditions. In particular, the enzymes’ activity is increased twofold in the presence of 1 and 5 % of gelatin at 20 °C and 25 °C, respectively (temperatures lower than the gel point). Also, the acceptable pH range of the coupled enzyme system expands into the alkaline region and becomes 6.8–8.1. Stabilization at low ionic strength (0.01–0.06 mol L^?1) is observed. At the same time, microenvironments based on either gelatin or starch do not change the enzymes’ thermal inactivation rate constants in the temperature range from 25 to 43 °C. Finally, gelatin and starch are suitable for development of a reagent for immobilization of enzymes which would be stable and resistant to physical and chemical environmental conditions.     

The shear hysteresis in lamellar structure of surfactant–water binary system

We study the shear effect on the lamellar structure of surfactants in water using dissipative particle dynamics simulations. Starting from a lamellar structure without shear flow, we increase the shear rate and then decrease it stepwisely. A weak shear changes the lamellar plane to be parallel to the shear direction though the lamellar normal has no specific direction on the plane normal to the shear direction. By increasing the shear rate, the lamellar normal eventually flips to the vorticity direction regardless of the initial configuration. Lamellar normal would stay along the vorticity direction on decreasing the shear rate. The hysteresis is also found in shear-stress. By varying the shear rate, the time needed to reach the final unique state is significantly shortened compared with that observed with a constant shear rate. We find a correlation between the excess shear-stress and the tilt angle of surfactant in lamellar.     

An intimately bonded titanate nanotube–polyaniline–gold nanoparticle ternary composite as a scaffold for electrochemical enzyme biosensors

In this work, titanate nanotubes (TNTs), polyaniline (PANI) and gold nanoparticles (GNPs) were assembled to form a ternary composite, which was then applied on an electrode as a scaffold of an electrochemical enzyme biosensor. The scaffold was constructed by oxidatively polymerising aniline to produce an emeraldine salt of PANI on TNTs, followed by gold nanoparticle deposition. A novel aspect of this scaffold lies in the use of the emeraldine salt of PANI as a molecular wire between TNTs and GNPs. Using horseradish peroxidase (HRP) as a model enzyme, voltammetric results demonstrated that direct electron transfer of HRP was achieved at both TNT-PANI and TNT-PANI-GNP-modified electrodes. More significantly, the catalytic reduction current of H₂O₂ by HRP was ∼75% enhanced at the TNT-PANI-GNP-modified electrode, compared to that at the TNT-PANI-modified electrode. The heterogeneous electron transfer rate constant of HRP was found to be ∼3 times larger at the TNT-PANI-GNP-modified electrode than that at the TNT-PANI-modified electrode. Based on chronoamperometric detection of H₂O₂, a linear range from 1 to 1200 μM, a sensitivity of 22.7 μA mM⁻¹ and a detection limit of 0.13 μM were obtained at the TNT-PANI-GNP-modified electrode. The performance of the biosensor can be ascribed to the superior synergistic properties of the ternary composite.     

Phase diagrams of a condensed decane–eicosane–cyclododecane system

An n-eicosane–cyclododecane–n-decane system related to eutectic-type systems is investigated by means of differential thermal analysis. The eutectic alloy with melting point of–33.8°C contains 2.8 wt % of n-eicosane, 89.2 wt % of n-decane, and 8.0 wt % of cyclododecane.     

A concise synthesis of Ni-didecarboxysirohydrochlorin hexamethylester—a model compound for key intermediates in heme d1 and heme biosynthesis

An efficient synthesis of Ni-didecarboxysirohydrochlorin hexamethylester rac-13 was achieved by Barton olefination starting from a readily available dioxo-isobacteriochlorin rac-9. The synthetic route should open a general facile access to this type of naturally occurring hydroporphyrins. Isobacteriochlorins 3–6 are key intermediates in heme d₁ and heme biosynthesis of sulfate reducing and denitrifying bacteria as well as in archaebacteria.     

A note on Li–Yorke chaos in a coupled lattice system related with Belusov–Zhabotinskii reaction

This paper is concerned with the following system which comes from a lattice dynamical system stated by Kaneko in (Phys Rev Lett 65:1391–1394, 1990) and is related to the Belusov–Zhabotinskii reaction: $$\begin{aligned} x_{n}^{m+1}=(1-\varepsilon )f(x_{n}^{m})+\frac{1}{2}\varepsilon \left[ f(x_{n-1}^{m})+f(x_{n+1}^{m})\right] , \end{aligned}$$ x n m + 1 = ( 1 ? ε ) f ( x n m ) + 1 2 ε [ f ( x n ? 1 m ) + f ( x n + 1 m ) ] , where $m$ m is discrete time index, $n$ n is lattice side index with system size $L$ L (i.e., $n=1, 2, \ldots , L$ n = 1 , 2 , … , L ), $\varepsilon $ ε is coupling constant, and $f(x)$ f ( x ) is the unimodal map on $I$ I (i.e., $f(0)=f(1)=0$ f ( 0 ) = f ( 1 ) = 0 and $f$ f has unique critical point $c$ c with $0<c<1$ 0 < c < 1 and $f(c)=1$ f ( c ) = 1 ). It is proved that for coupling constant $\varepsilon =1$ ε = 1 , this CML (Coupled Map Lattice) system is chaotic in the sense of Li–Yorke for each unimodal selfmap on the interval $I=[0, 1]$ I = [ 0 , 1 ] .     

Dimethylditetradecylammonium bromide (2C14DAB) as a self-assembled surfactant coating for detection of protein–dye complexes by CE-LIF

A self-assembled column coating for capillary electrophoresis in conjunction with laser-induced fluorescence detection (CE-LIF) has been evaluated for the separation and quantitation of protein–dye complexes. This semi-permanent coating, composed of dimethylditetradecyl-ammonium bromide (2C₁₄DAB), is inexpensive and easily assembled onto the column and it allows for better peak resolution and greater control over electroosmotic flow. The versatility of long-chained surfactant coatings was determined particularly with respect to their use with fluorescent probes, different pH buffers, and different proteins. Studies were performed to determine the stability of the coating under various pH and buffer conditions. Red-1c, a red luminescent squarylium dye, was used for on-column protein labeling concurrently with the surfactant coating and LIF detection. Protein–Red-1c complexes were excited with a 650-nm diode laser and their emission detected by a photomultiplier tube with a 664-nm filter. A comparison of pre-column labeling and on-column labeling of a two-model protein system (human serum albumin and β-lactoglobulin A) revealed higher efficiencies and greater sensitivities for both proteins using on-column labeling and coated columns. A linear relationship between peak height and protein concentration was obtained by CE-LIF for this on-column labeling method with 2C₁₄DAB-coated columns and the Red-1c probe.     

Cationic–anionic fluorinated surfactant mixtures based on short fluorocarbon chains as potential aqueous film-forming foam

A strategy for aqueous film-forming foam (AFFF) using cationic-anionic surfactant mixtures with short fluorocarbon chains (≤C₄) in both cationic and anionic surfactants was proposed. The minimum surface tension (γ_min) of mixtures of C₄F₉SO₂NH(CH₂)₃N(CH₃)₃I (C₄FI) and C_nF_2n+1COONa (n?=?1, 2, 3, 4) with different molar ratios (5:1, 2:1, 1:1, 1:2, 1:5) was measured at 25?°C. The γ_min for all mixtures of C₄FI–C_nF_2n+1COONa were remarkably lower than that of pure C₄FI. Among these mixtures, the equimolar mixture of C₄FI–C₃F₇COONa was chosen because of the low γ_min, qualified solubility and relatively high fluorine efficiency. The spreading coefficients of its aqueous solution on n-heptane, toluene, benzene, cyclohexane and gasoline were all positive, indicative of its potential in AFFF. The film spreading, sealability and foaming were also tested. The influences of ‘green’ additives (alkyl glucose amide, xanthan gum and sodium carboxymethylcellulose) on foaming performance were studied, in which small dosage of xanthan gum could greatly retard the drainage of foam. It was confirmed that the mixing of oppositely charged surfactants both possessing short fluorocarbon chains was a valuable thought to design AFFF. In application, the quaternary ammonium surfactant likewise can be bromide or chloride rather than iodide for reasons of cost-reduction and stability.     

ICP–MS trace-element analysis as a forensic tool

Careful tracing of evidence at the site of a crime must be performed before suspects can be convicted of a crime or homicide. Fingerprints and ballistic control samples are important evidence. A common method used to examine lead bullets is comparison of physical properties such as weight, dimensions, shape, and distinctive markings. However ballistic investigations, for example comparison of characteristic scratches and marks left on fired bullets, do not always give sufficient information. Ballistic abrasion patterns can change for a variety of reasons, e.g. deformation or mechanical strain. Sometimes only particles remain in a victims body. In such cases trace-element composition and lead-isotope ratios can be compared with those of controls. Elemental composition of particles and deformed bullets have been compared with the elemental fingerprints and isotope ratios of potential bullet types found on suspects. The applicability of the method was studied for two different cases. Data interpretation and several limitations of the technique are also discussed in this paper.     

A phenyl imidazole dicarboxylate-based 3D terbium–organic framework for selective sensing of nitrobenzene

A novel lanthanide(III)–organic framework, {(Tb(μ₃-HPhIDC)(μ₂-C₂O₄)_0.5(H₂O))·2H₂O}_n (1) (H₃PhIDC = 2-phenyl-1H-imidazole-4,5-dicarboxylic acid) has been solvothermally synthesised and structurally characterised, which exhibits selective detection of nitrobenzene via a photoinduced electron transfer quenching mechanism. The high efficiency, stability and recyclability of 1 make it a potential chemosensor for nitrobenzene.     

JR 400–NaAOT interaction: a detailed thermodynamic study of polymer–surfactant interaction bearing opposite charges

The present study entails interaction between the cationic polymer N,N-dimethylhydroxyethyl cellulose (JR 400) and the double-tailed anionic surfactant Na-bis-2-ethyhexylsulphosuccinate (NaAOT). This oppositely charged polymer and surfactant are expected to cause coacervation and precipitation; hence, we have observed formation of thick solution similar to diluted gel at [JR 400]?~?0.01 and 0.10 %?w/v in aqueous solution. Viscometry, conductometry, tensiometry, and microcalorimetry techniques are used to monitor the interaction process. The results are explained in the light of both intrachain and interchain linking by way of NaAOT reverse micelle formation. Adsorption of NaAOT monomers onto the charged side chains of the polymer shields interchain electrostatic repulsion, leading to the formation of hydrophobic microdomains and microscopic heterogeneity in the solution. The morphologies of the domains depend on the level of addition of NaAOT in the system. The different stages of physiochemical changes that arise in solution have been identified by the use of different techniques, and correlations of the results have been attempted in terms of pragmatic models.     

Emergence of a Radical-Stabilizing Metal–Organic Framework as a Radio-photoluminescence Dosimeter

Radio-photoluminescence (RPL) materials display a distinct radiation-induced permanent luminescence center, and therefore find application in the detection of ionizing radiation. The current inventory of RPL materials, which were discovered by serendipity, has been limited to a small number of metal-ion-doped inorganic materials. Here we document the RPL of a metal–organic framework (MOF) for the first time: X-ray induced free radicals are accumulated on the organic linker and are subsequently stabilized in the conjugated fragment in the structure, while the metal center acts as the X-ray attenuator. These radicals afford new emission features in both UV-excited and X-ray excited luminescence spectra, making it possible to establish linear relationships between the radiation dose and the normalized intensity of the new emission feature. The MOF-based RPL materials exhibit advantages in terms of the dose detection range, reusability, emission stability, and energy threshold. Based on a comprehensive electronic structure and energy diagram study, the rational design and a substantial expansion of candidate RPL materials can be anticipated.     

Liquid–liquid equilibrium of aqueous two-phase system (PEG 2000-Sodium Citrate–Water) using potential difference as a key tool

The present work involves an attempt to demonstrate the application of potential difference, existing across the interface of the aqueous two-phase system (ATPS), as a tool for the prediction of the phase equilibrium. The contribution due to long-range interaction for the potential difference and its variation with the composition is studied for the polyethylene glycol (PEG) 2000-Sodium Citrate–Water-based ATPS (Merck, Germany). The developed correlation for the potential difference with concentration shows a satisfactory prediction of the phase equilibrium for the present system.     

Bromoperoxidases and functional enzyme mimics as catalysts for oxidative bromination—A sustainable synthetic approach

The discovery of enzymes that utilize hydrogen peroxide to oxidize bromide under physiological conditions provided a strong stimulus to the field of oxidative bromination. A synthetically useful enzyme, to catalyze the oxidation of bromide, for bromofunctionalization of donor-substituted arenes in solutions of hydrogen peroxide and sodium bromide, is a vanadate(V)-dependent bromoperoxidase from the brown alga Ascophyllum nodosum. This enzyme operates in homogeneous solutions of buffered aqueous tert-butanol (pH 6.2), or, to simplify repetitive use, in a two-phase system after immobilization onto magnetic beads. Synthesis of cyclic bromohydrin ethers (tetrahydrofurans and tetrahydropyrans) and vicinal dibromides from unsaturated hydrocarbons, on the other hand, occurs more effectively in polar aprotic solvents. Under such conditions the more lipophilic tert-butyl hydroperoxide serves as oxidant, which is activated by oxovanadium(V) complexes (functional bromoperoxidase mimics). Protons and bromide ions, which are consumed for in situ generation of bromine, are supplied in organic solution by fragmentation of 3-bromopropionic acids. The structure-reactivity data obtained from oxidations catalyzed by bromoperoxidases and functional enzyme mimics pose a valuable guideline for predicting selectivity in biomimetic synthesis of organobromines from terpenes, acetogenins, and pyrrole alkaloids.     

A biofriendly sol–gel route to new hybrid gels for enzyme encapsulation

New hybrid gels were prepared from the gelation of glycol-modified tetraethoxysilane (TEOS) in the presence of O-2-hydroxy-3-(trimethylammonio)propyl guar gum (HTPG), and were then used for the in situ encapsulation of papain. Different from the sol–gel process based on commonly used TEOS, the biofriendly sol–gel process developed in this study could be conducted rapidly at ambient temperature without the addition of any organic solvent or acidic catalyst. In particular, the mechanical strength and microstructure of resultant hybrid gel matrix could be modulated by HTPG amount. In comparison with free papain, the encapsulated papain is characteristic of improved enzymatic activity, thermal and storage stability as well as good reusability.