Cyclic voltammetric and computational study of a 4-bromophenyl monolayer on a glassy carbon electrode

A glassy carbon (GC) surface modified with monolayer of 4-bromophenyl was examined as voltammetric electrode for some redox systems. The modified electrode exhibited very slow electron transfer in comparison to the unmodified surface by factors which varied with the redox systems. However, after scanning the modified electrode in 0.1 M tetrabutylammonium tetrafluoroborate (TBABF₄) in acetonitrile from 0.4 to −1.1 V vs. Ag/AgCl for 20–25 cycles, the modified electrode showed much faster electron transfer kinetics, e.g., the results for Fe(CN)₆ ^3−/4− were approaching those observed with unmodified surfaces. The effect is attributed to an apparently irreversible structural change in the 4-bromophenyl monolayer, which increases the rate of electron tunneling. The transition to the conducting state is associated with electron injection into the monolayer and causes a significant decrease in the calculated HOMO-LUMO gap for the monolayer molecule. Once the monolayer is switched to the conducting state, it supports rapid electron exchange with the redox system, but not with dopamine, which requires adsorption to the electrode surface. A conductive surface modified electrode may have useful properties for electroanalytical applications and possibly in electrocatalysis. Correspondence: Abbas A. Rostami, Department of Chemistry, Faculty Basic of Science, University of Mazandaran, Babolsar, Iran.     

Impurity and phase compositions of the surface of CdxHg1?xTe solid solutions

The results of our studies of the real surface impurity and phase compositions of Cd _x Hg_{1 − x} Te solid solutions and changes in the compositions induced by thermal evacuation and ion bombardment are presented. The impurity and phase compositions of the surface of CdHgTe solid solutions exposed to air included the gases and vapors (CO, O₂, H₂O) and hydrocarbons adsorbed from the atmosphere. Thermal vacuum treatment of the samples at 615 K led to surface purification from organic impurities, oxygen, water, and mercury microinclusions. The Cd _x Hg_{1 − x} Te sample surface was completely cleaned and its stoichiometric composition achieved by ion etching to a depth of 100 ?.     

Synergistic behavior of sodiumdodecylsulfate and 1,2-diheptanoyl-sn- glycero-3-phosphocholine in an aqueous medium: interfacial and bulk behavior

The synergistic behavior of sodiumdodecylsulfate (SDS) and 1,2-diheptanoyl-sn-glycero-3-phosphocholine (DHPC) binary mixtures has been studied with interfacial and pyrene fluorescence(I ₁/ I ₃) intensity measurements. From the interfacial data, the interfacial parameters; the maximum surface excess (Γ_max), or the minimum area per molecule (A _min), and the surface pressure at the critical micellar concentration (π_cmc) have been evaluated. The cmc value has been used for evaluating the free energies of micellization (ΔG ^o _m). The mixed micelle formation was evaluated with the help of the Clint equation. The SDS plus DHPC mixed micelles showed negative departure from ideality indicating synergistic interactions between the unlike components. The quantitative analysis of mixed micelle, mixed monolayer and the composition of the mixed micelle was carried out with the help of regular solution approximation. The interaction parameters, β and β^σ, in the mixed micelle as well as in the mixed monolayer, respectively showed negative values indicating synergistic behavior of SDS and DHPC molecules.     

Thermodynamic behavior of D-sphingosine/cholesterol monolayers and the topography observed by AFM

Lipid rafts are of a dynamic microdomain structure found in recent years,enriched in sphingolipids,cholesterol and particular proteins.The change of structure and function of lipid rafts could result in many diseases.In this work,the monolayer behavior of mixed systems of D-sphingosine with choles-terol was investigated in terms of the mean surface area per molecule(Am),excess molecular area(Aex),surface excess Gibbs energy(Gex),interaction parameter(ω),activity coefficients(1 and 2) as well as elasticity(C...     

Enabling the Li-ion conductivity of Li-metal fluorosulphates by ionic liquid grafting

Recently unveiled ‘alkali metal fluorosulphate (AMSO₄F)’ class of compounds offers promising electrochemical and transport properties. Registering conductivity value as high as 10⁻⁷ S cm⁻¹ in NaMSO₄F phases, we explored the fluorosulphate group to design novel compounds with high Li-ion conductivity suitable for solid electrolyte applications. In the process, we produced sillimanite-structured LiZnSO₄F by low temperature synthesis (T ≤ 300 °C). Examining this phase, we accidentally discovered the possibility of improving the ionic conductivity of poor conductors by forming a monolayer of ionic liquid at their particle surface. This phenomenon was studied by solid-state NMR, XPS and AC impedance spectroscopy techniques. Further, similar trends were noticed in other fluorosulphate materials like tavorite LiCoSO₄F and triplite LiMnSO₄F. With this study, we propose ‘ionic liquid grafting’ as an interfacial route to enable good Li-ion conductivity in otherwise poor conducting ceramics.     

Thermodynamic surface properties of single crystal faces of xenon calculated by employing the Einstein model of crystalline solids

By broadening the scope of the Einstein statistical-mechanical treatment of a crystalline solid to cover also low-index faces, and using the Lennard-Jones interaction potential and, in addition, adopting an approximate monolayer-nearest-neighbor model, we have calculated the thermodynamic properties of (100) and (111) single crystal faces of Xe(s) in the temperature range 20–80 K. The reversible cleavage work (that corresponds to the Gibbs σ-quantity of interfaces) was found to be on the order of 20–30 mJ m⁻² and is largely due to reduction of the pair-wise dispersion interactions for monolayer atoms as compared with the atoms in the bulk of the crystal. For an unstrained crystal, σ diminishes slightly with temperature for both energetic as well as entropic reasons. On the other hand, the differential work of stretching a solid interface, γ, is a negative quantity (−5 to −30 mN m⁻¹), corresponding to surface pressure, the main reason being that upon (elastic, homogeneous) stretching, the vibration energy levels of the top monolayer are shifted upward, at the same time becoming more closely spaced. It is shown that such a stretching operation causes the T × surface excess entropy term to increase at a faster rate than the corresponding surface energy term, which accounts for the negative sign found for γ. On the same basis, we can also verify that the general, though sometimes questioned, Shuttleworth relation, is necessarily fulfilled for an ideally terminated (metastable) Xe crystal face with a filled monolayer of immobile Xe atoms. As a matter of fact, this equation merely represents an alternative mathematical disguise of the basic energy differential expression for the monolayer.     

Surface modification of CaCO3 filler and its characterization using inverse gas chromatography (IGC)

A CaCO₃ filler was treated by generally used coupling agents and a special one — ethylene-octene copolymer (POE)-g-maleic anhydride (MAH). Fourier transform infrared spectroscopy (FTIR) results show that the special coupling agent POE-g-MAH, in a chemical reaction with CaCO₃, can produce an interfacial layer stronger than simple physical adhesion attained with usual coupling agents. Inverse gas chromatography (IGC) was used to investigate the surface free energy of CaCO₃ after surface modification and to optimize the monolayer content of coupling agents. Based on the IGC results, it can be deduced that the monolayer cover is around 1.9% for CaCO₃ treated with a titanate coupling agent. Scanning electron microscope (SEM) observation results show that the separated morphology existed in the ternary composites containing CaCO₃ after surface treatment with coupling agents, whereas the core-shell morphology was obtained in the ternary composites with POE-g-MAH. The encapsulation of the CaCO₃ filler treated with POE-g-MAH was caused by the strong chemical reaction between the elastomer and CaCO₃ particles. __________ Translated from Journal of Northwestern Polytechnical University, 2007, 25(2): 274–278 [译自: 西北工业大学学报]     

Phase equilibria and isomorphism in the LiVWO<Subscript>6</Subscript>-NaVWO<Subscript>6</Subscript> system

Compounds of composition Li _x Na_{1 − x} VWO₆ (0 ≤ x ≤ 1), which are synthetic analogues of brannerite-type minerals, were produced for the first time by solid-state synthesis at high temperatures. The structure of the compounds and their unlimited miscibility in the solid phase in the LiVWO₆-NaVWO₆ binary system were determined by X-ray diffraction. The phase equilibrium diagram was studied by differential thermal analysis together with thermodynamic modeling. It was found that the system under investigation is described by the regular solid solutions model.     

Electrochemical solid phase micro-extraction and determination of salicylic acid from blood samples by cyclic voltammetry and differential pulse voltammetry

The electrochemical solid phase micro-extraction of salicylic acid (SA) at graphite-epoxy-composed solid electrode surface was studied by cyclic voltammetry. SA was oxidized electrochemically in pH 12.0 aqueous solution at 0.70 V (vs. saturated calomel electrode) for 7 s. The oxidized product shows two surface-controlled reversible redox couples with two proton transferred in the pH range of 1.0∼6.0 and one proton transferred in the pH range of 10.0∼13.0 and is extracted on the electrode surface with a kinetic Boltzman function of i _p = 3.473–4.499/[1 + e^{(t − 7.332)/6.123}] (χ ² = 0.00285 μA). The anodic peak current of the extracted specie in differential pulse voltammograms is proportional to the concentration of SA with regression equation of i _p = −5.913 + 0.4843 c (R = 0.995, SD = 1.6 μA) in the range of 5.00∼200 μM. The detection limit is 5.00 μM with RSD of 1.59% at 60 μM. The method is sensitive and convenient and was applied to the detection of SA in mouse blood samples with satisfactory results.     

Ca2+- and Mg2+-induced molecular interactions in a dehydrocholic acid/didodecyldimethylammonium bromide mixed monolayer

The aim of this article is the evaluation of Ca²⁺ and Mg²⁺ subphases presence effect on mixed monolayers composed by dehydrocholic acid (HDHC) and didodecyldimethylammonium bromide (DDAB). The monolayer stability was analyzed by the evaluation of thermodynamic parameters, ΔG _mix^E and α. At all calcium ion-tested concentration, the mixed systems X _HDHC = 0.6 and 0.8 at π = 30 mJ m⁻² were always the most favored proportions. The X _HDHC = 0.6 system was also stable in magnesium presence, and the X _HDHC = 0.2-mixed monolayer went through a stable to an unstable state as the content of Ca²⁺ or Mg²⁺ augment. Finally, the X _HDHC = 0.4 monolayer showed a particular behavior, i.e., remained stable at low cation concentration, unstable at intermediate concentration and stable again at high concentration. The effect was similar at Mg²⁺ presence.     

Phase equilibria in the Cu-Bi-Se system and thermodynamic properties of copper selenobismuthates

The Cu-Bi-Se system was studied using DTA, X-ray powder diffraction, and electromotive force (e.m.f.) measurements in (−) Cu (solid)|Cu₄RbCl₃I₂ (solid)|(Cu in alloy) (solid) (+) concentration cells in the range 300–430 K. Polythermal sections and a 300-K isothermal section of the phase diagram are constructed, as well as a liquidus surface projection. The existence of ternary compounds CuBi₃Se₅, CuBiSe₂, and Cu₃BiSe₃ is verified, and phase fields involving them are established. Primary separation fields and the types and coordinates of invariant and monovariant equilibria are determined. E.m.f. data were used to calculate partial molar functions $ (\Delta \bar G,\Delta \bar H,\Delta \bar S) $ (\Delta \bar G,\Delta \bar H,\Delta \bar S) of copper in alloys and the standard thermodynamic functions of formation and entropies of the ternary compounds and the end-member (Cu₉BiSe₆) of solid solutions based on the low-temperature Cu₂Se phase.     

Influence of purity on the thermal stability of solid organic compounds

DSC method was used to study thermal stability of nitrocompounds. It was assumed the model to estimate stability of solid phase in which perfect solid phase is totally stable and amorphous-liquid domains connected with impurities decompose according to the kinetic model determined for the liquid phase above the melting point. The influence of sample purity on relative stability, which is k _l/k _s — ratio of decomposition rate constants in liquid and solid phase, at temperature 20 K below the melting point was predicted. The increase of liquid domains in solid phase causes decrease of k _l/k _s ratio (relative stability) at chosen temperature. This revised version was published online in July 2006 with corrections to the Cover Date.     

Isotropic transition behaviour of an amphiphilic di-block copolymer under pressure

The present work deals with the interactions between carbon dioxide, used as pressure medium, either in the gas state (GCO₂) or in the supercritical state (SCCO₂) and amphiphilic di-block copolymers PEO_m-b-PMA(Az)_n. The effect of pressure on the isotropic transition of the PEO_m-b-PMA(Az)_n copolymer was investigated using scanning transitiometry (ST). The experimental results were compared with those measured when using ‘relatively inert’ mercury (Hg) as pressure medium. Morphological observation of a PEO_m-b-PMA(Az)_n thin film submitted to SCCO₂ was performed by atomic force microscopy (AFM) to investigate the nano-structure organization. These results indicate the possibility of modifying the nano-structure in a specific way depending on the CO₂ physical state.     

The surface property and aggregation behavior of a hydrophobically modified cyclodextrin

The surface property of an amphiphilic cyclodextrin 2-O-(hydroxypropyl-N,N-dimethyl-N-dodecylammonio)-β-cyclodextrin (HPDMA-C₁₂-CD) was investigated using oscillating bubble rheometer and electrical conductivity method at different temperatures. The surface tension and dilational viscoelasticity of HPDMA-C₁₂-CD were provided. The results showed that HPDMA-C₁₂-CD could adsorb on the air–water interface, which decreased the surface tension of water efficiently. Critical micelle concentration (cmc) can be clearly defined from the surface tension isotherm. pC₂₀ and π _cmc were derived from the surface tension isotherms as well. The thermodynamic parameters (ΔG   ⁰ _m  , ΔH   ⁰ _m  , −TΔS   ⁰ _m) derived from electrical conductivity indicated that the micellization of HPDMA-C₁₂-CD was entropy-driven at lower temperature, while it was enthalpy-driven at higher temperature. The dilational modulus appeared a maximum value while the phase angle appeared two maxima as a function of HPDMA-C₁₂-CD concentration.     

Calculation of the molecular exchanging energy of binary surfactants system on the surface monolayer of aqueous solution

By using the binary anionic/cationic surfactants system CH3(CH2)nOSO_3/CH3(CH2)nN (CH3)3 as an ex-ample, the molecular exchanging energy (ε) of adsorption on the surface monolayer of aqueous solu-tion has been studied. ε can be obtained with two methods. One is from the relationship between ε and the molecule interaction parameter (β). This relationship is founded by considering that the adsorption of mixed surfactants on the surface monolayer of solution satisfies the dimensional crystal model condition under which β can be obtained by testing the surface tension of solution. The other is directly from the molecular structure of surfactants with the Lennard-Jones formula. The results for the studied system show that these two methods coincide well.     

Complexation and Precipitation of Arsenate and Iron Species in Sodium Perchlorate Solutions at 25∘C

The complexation of As(V) in aqueous solutions in the presence of iron(III) was investigated spectrophotometrically with both variable and constant ionic strengths. The determined thermodynamic and stoichiometric formation constants of the FeHAsO₄⁺ species are log₁₀^∘β = 9.21± 0.01 and log₁₀^Iβ (1.0mol⋅dm⁻³ NaClO₄) = 7.78 ± 0.01, respectively. The numerical treatment of the obtained spectral data was performed with the SPECA program. The analysis required the consideration of the hydrolysis of Fe(III) and the protonation of As(V) in the pH range studied. No significant hydrolysis was observed because of the low pH values (pH < 2.5) involved. The stabilities of the solid Fe(III) arsenates was established by solubility experiments. All of the solubility experiments were performed in aqueous NaClO₄ solutions at constant ionic strength (1.0mol⋅dm⁻³) and at 25^∘C. The experimental data were consistent with FeAsO₄⋅2H₂O being the solid phase (log₁₀ ^∘ K_so = −24.30± 0.08). The corresponding thermodynamic constants were computed by means of the Modified Bromley's Methodology (MBM) that describes the variation of the activity coefficients of all of the ions involved in the complexation and precipitation equilibria with the medium and ionic strength. Finally, the solid phase obtained in this work was also characterized by FT-IR and FT-Raman spectroscopies, and the hydration of the solid iron arsenate was confirmed by X-ray diffraction data.     

Bile salt structural effect on the thermodynamic properties of a catanionic mixed adsorbed monolayer

The interfacial effects of two bile salts (sodium deoxycholate (NaDC) and sodium dehydrocholate (NaDHC)) in a catanionic mixed adsorbed monolayer have been investigated at 25 °C. The surfactant interfacial composition, the interfacial orientation of the molecules and the energy changes are analysed to show a thermodynamic evidence of the hydrophobic BSs effect during its intercalation into interfacial adsorbed didodecyldimethyl ammonium bromide (DDAB) molecules. Both mixed systems (NaDC–DDAB and NaDHC–DDAB) have analogous adsorption efficiencies, which are similar from a pure DDAB monolayer and superior to that obtained for both bile salts molecules. Nevertheless, their adsorption effectiveness is different: NaDC causes an increment of Γ while NaDHC produces the opposite effect. The adsorption efficiency in surface tension reduction is due to the existence of interfacial synergistic interactions (confirmed by the analysis of β ^γ and ΔG _ad ⁰ values). Maximum synergistic interaction is seen for α _BSs = 0.4. The hydrophobic steroid backbone of NaDHC molecule presents a deep interfacial penetration than NaDC. This fact causes a great disturbance of DDAB hydrocarbon tails and conduces to a large separation of molecules (high A _m values) which explains the reduction of adsorption effectiveness (low Γ _m values).     

Relaxation phenomena in phospholipid monolayers at the air–water interface

In this work we are concerned with the study of long-term relaxation phenomena in dipalmitoyl phosphatidylcholine (DPPC) and dioleoyl phosphatidylcholine (DOPC) monolayers spread at the air–water interface as a function of the surface pressure and the aqueous phase pH (pH 5, 7, and 9). Long-term relaxation phenomena were determined in an automated Langmuir-type film balance at constant temperature (20 °C). Two kinds of experiments were performed to analyze relaxation mechanisms. In one, the surface pressure (π) was kept constant, and the area (A) was measured as a function of time (θ). In the second, the area was kept constant at monolayer collapse and the surface pressure was decreased. This decrease was measured as a function of time. Various relaxation mechanisms, including monolayer molecular loss by dissolution, collapse, and/or organization/reorganization changes, can be fitted to the results derived from these experiments. These relaxation mechanisms are pH and phospholipid dependent. In the discussion, special attention will be given to the effect of the relaxation phenomena on the hysteresis in π–A isotherms before and after the relaxation experiment. At π lower than the equilibrium spreading pressure (π_e) the relaxation phenomena are mainly due to the loss of DPPC or DOPC molecules by desorption into the bulk aqueous phase. The formation of interfacial macroscopic vesicles, which are dissolved into the bulk phase, makes the phospholipid monolayer molecular loss irreversible. At the collapse point (at π > π_e), the relaxation phenomena may be due either to collapse for DPPC and/or to a complex mechanism including competition between desorption and monolayer collapse for DOPC.     

Structural features of the formation of La1?xCaxFeO3?δ (0 ≤x ≤ 0.7) hetero valent solid solutions

A synthesis method with the use of polymer-salt compositions (calcination temperature 800°C) provides the preparation of various solid solutions of a La_1−x Ca _x FeO_3−δ series in the 0≤ x≤ 0.7 range, which belong to the perovskite structure type. A morphotropic phase transition occurs from the orthorhombic perovskite modification (0≤ x ≤ 0.4) to the cubic one (0.5 ≤ x≤ 0.7). A growing number of microdistortions in the perovskite structure and the formation of a microblock structure in the morphotropic phase transition region are observed with increasing degree of calcium substitution for lanthanum. Calcination of solid solutions with x = 0.6 and 0.7 at temperatures above 1000°C in the air or under conditions of reduced oxygen partial pressure (laboratory vacuum of 10⁻³ Torr) results in the formation of a nanostructured state with coherently grown blocks of perovskite and Grenier phase, which is due to irreversible oxygen loss.     

Succinic or glutaric anhydride modified linear unsaturated (epoxy) polyesters

A series of N-alkyl-N-alkyl′-pyrrolidinium-bis(trifluoromethanesulfonyl) imide (TFSI⁻) room temperature ionic liquids (RTILs) has been investigated by means of thermogravimetric analysis (TG), differential scanning calorimetry, FT-IR spectroscopy, and X-ray diffraction analysis. These compounds exhibit a thermal stability up to 548–573 K. The mass loss starting temperature, T _ml, falls in a narrow range of temperatures: 578–594 K. FT-IR spectra, performed before and after 24 h isothermal experiments at 553 and 573 K, have confirmed their great thermal stability. Below the ambient temperature, these compounds exhibit a complex behavior. N-methyl-N-propyl-pyrrolidinium-TFSI is the sole liquid which crystallizes without forming any amorphous phase even after quenching in liquid nitrogen. Its crystalline phase has a melting point, T _m, of 283 ± 1 K. When the amorphous solid is heated, the N-butyl-N-ethyl-pyrrolidinium-TFSI presents a glass transition temperature, T _g, at 186 K followed by a cold crystallization, T _cc, at 225 K, and a final T _m at 262 K. The N-butyl-N-methyl-pyrrolidinium-TFSI exhibits a T _g between 186 and 181 K, its cold crystallization leading to two different solid phases. Solid phase I has a melting point T _I,m = 252 K and phase II, T _II,m = 262 K. When the amorphous phase is obtained at a cooling rate of 10 K/min, its T _cc is 204 K, and a metastable solid phase (III) is obtained which transforms into the phase II at 226 K. However, when the sample is quenched, the amorphous phase transforms into phase II at T _cc = 217 K and phase I at 239 K. P₁₅-TFSI exhibits the most complicated pattern as, on cooling, it leads to both a crystallized phase at 237 K and an amorphous phase at 191 K. On heating, after a T _g at 186 K and a T _cc at 217 K, two solid–solid phase transitions are observed at 239 K and 270 K, the final T _m being 279 K.