Photocatalytic decomposition of an alkylammonium cation in a Langmuir-Blodgett film of a titania nanosheet

The formation of inorganic-organic hybrid films of a titania nanosheet and an amphiphilic alkylammonium cation has been investigated, and the photocatalytic decomposition of the alkylammonium cation in the film has been pursued. When a solution of the amphiphilic alkylammonium salt (octadecylammonium chloride: ODAH+ Cl-) was spread on an interface between the air and a titania nanosheet suspension, the negatively charged nanosheets were adsorbed onto the floating monolayer of ODAH+ to form a hybrid monolayer. The hybridization was confirmed by pi-A isotherm measurements, atomic force microscopy, and X-ray photoelectron spectroscopy. Multilayered films were fabricated in a layer-by-layer way by transferring the hybrid monolayers onto glass plates. Areas per ODAH+ cation in the films were estimated from the infrared (IR) spectra of the films, but these areas were smaller than those estimated from the pi-A isotherm curves. The orientation of the alkyl chain of ODAH+ in the hybrid film was determined by means of polarized IR spectroscopy. The alkyl chains were tilted 41 +/- 1 degrees and 47 +/- 1 degrees from the surface normal for the films prepared from the 8 and 20 ppm (ppm = mg dm(-3)) suspensions, respectively. Together with X-ray diffraction data of the films, the structure of the hybrid film was discussed. When the films were illuminated with a UV light, the absorption intensities due to the alkyl chain of ODAH+ decreased exponentially, indicating the photocatalytic decomposition of ODAH+ by the titania nanosheets in the films. Deviation from the exponential trend in the decomposition rate was observed in the initial period for the hybrid films prepared from the suspensions at low concentrations. Interestingly, the layered structure of the hybrid film was disturbed significantly after the ODAH+ cations were decomposed.     

Langmuir-Blodgett films of a clay mineral and ruthenium(II) complexes with a noncentrosymmetric structure

Mono- and multilayers of amphiphilic [Ru(phen)(2)(dcC12bpy)](2+) (phen = 1,10-phenanthroline, dcC12bpy = 4,4'-caboxyl-2,2'-bipyridyl didodecyl ester) hybridized with a clay mineral have been prepared by a modified Langmuir-Blodgett method, and their structures and properties have been investigated. Formation of a hybrid monolayer of the Ru(II) complex cations and the clay platelets at an air-clay suspension interface was confirmed by surface pressure-molecular area (pi-A) isotherm measurement and atomic force microscopic (AFM) observation. Multilayers were fabricated by depositing the hybrid monolayers onto glass substrates. The absorbance at 492 nm due to the Ru(II) complex cation in the multilayer increased linearly with the increase in the layer number, indicating layer-by-layer deposition of the hybrid monolayers. Because no increase in the second-harmonic generation (SHG) signal from the multilayers against the layer number was observed, the orientation of the Ru(II) complex cations in the layer would be disturbed. The hydrophilic surface of the transferred hybrid monolayer can be converted to a hydrophobic surface by dipping it in an aqueous solution of octadecylammonium chloride (ODAH(+)Cl(-)). The multilayers modified with ODAH(+) showed a quadratic relation between the SHG intensity and the layer number. This means that the Ru(II) complex cations in the multilayer are successfully oriented in a noncentrosymmetric way by the conversion of the surface property. Both a racemic mixture and an enantiomer of the Ru(II) complex cations were employed to examine the chiral effect on the film properties. The chiral contribution to the SHG signal was enhanced in the multilayer modified with ODAH(+).     

Organization and properties of a conjugated poly(heteroarylene methines) at the air-water interface and in the Langmuir-Blodgett films

A poly(heteroarylene methine) derivative, poly[(2,5-thiophenediyl) (p-n-methyl, n-octylaminobenzylidene) (2,5-thiophenequinodimethaneiyl)] (PTABQ), has been synthesized and spread at the air-water interface. The influences of three kinds of solutions on PTABQ monolayer behavior at the air-water interface have been investigated via the measurements of the pi-A isotherm and film stability. The results show that all three kinds of PTABQ solutions are apt to form the stable and transferable monolayer film organized with the plane of its pi-system nearly perpendicular to the air-water interface. Moreover, the monolayer-forming ability of PTABQ can be improved by introducing a water-soluble amphiphilie as an extractable spread-aiding component, which is further proved by the AFM images and FTIR spectra of the transferred films. UV-visible absorption spectra indicate that the well-ordered layer-by-layer structure is successfully controlled in the LB films. The optical bandgap of PTABQ is reduced for the ordered arrangement of its molecules in LB films. The intrinsic electrical conductivity of PTABQ LB films is 8.1 x 10(-8) S/cm and the conductivity of iodine-doped films is 5.7 x 10(-7) S/cm.     

Metal ion-induced H-aggregation of a water-soluble anionic dye Congo red (CR) in Langmuir–Blodgett (LB) film

Present communication reports the preparation of Langmuir monolayer of water-soluble anionic dye Congo red (CR) by allowing it to adsorb from the aqueous subphase onto the preformed Langmuir monolayer of anionic stearic acid using divalent metal cations Mg²⁺ as mediator. Isotherm and compressibility studies of SA-Mg-CR hybrid monolayer gave valuable information about the molecular organisation in the Langmuir monolayer. Absorption spectroscopic studies revealed the formation of H-aggregates in the hybrid Langmuir–Blodgett (LB) films fabricated at lower salt concentration in the subphase. Atomic Force Microscopic image gave visual evidence of distinct nanocrystalline domains in the LB monolayer film.     

Structural and topographical characteristics of adsorbed WPI and monoglyceride mixed monolayers at the air-water interface

In this work we have analyzed the structural and topographical characteristics of mixed monolayers formed by an adsorbed whey protein isolate (WPI) and a spread monoglyceride monolayer (monopalmitin or monoolein) on the previously adsorbed protein film. Measurements of the surface pressure (pi)-area (A) isotherm were obtained at 20 degrees C and at pH 7 for protein-adsorbed films from water in a Wilhelmy-type film balance. Since the surface concentration (1/A) is actually unknown for the adsorbed monolayer, the values were derived by assuming that the A values for adsorbed and spread monolayers were equal at the collapse point of the mixed film. The pi-A isotherm deduced for adsorbed WPI monolayer in this work is practically the same as that obtained directly by spreading. For WPI-monoglyceride mixed films, the pi-A isotherms for adsorbed and spread monolayers at pi higher than the equilibrium surface pressure of WPI are practically coincident, a phenomenon which may be attributed to the protein displacement by the monoglyceride from the interface. At lower surface pressures, WPI and monoglyceride coexist at the interface and the adsorbed and spread pi-A isotherms (i.e., the monolayer structure of the mixed films) are different. Monopalmitin has a higher capacity than monoolein for the displacement of protein from the air-water interface. However, some degree of interactions exists between proteins and monoglycerides and these interactions are higher for adsorbed than for spread films. The topography of the monolayer corroborates these conclusions.     

Equilibrium structure and dynamics of (2R, 3R)-(+)-bis(decyloxy)succinic acid at the air-water interface

A twin-tailed, twin-chiral fatty acid, (2R,3R)-(+)-bis(decyloxy)succinic acid was synthesized and its two dimensional behavior at the air-water interface was examined. The pH of the subphase had a profound effect on the monolayer formation. On acidic subphase, stable monolayers with increased area per molecule due to hydrogen bonding and bilayers at collapse pressures were observed. Highly compressible films were formed at 40 degrees C, while stable monolayers with increased area were observed at sub-room temperatures. Langmuir monolayers formed on subphases containing 1 mM ZnCl2 and CaCl2 revealed two dimensional metal complex formation with Zn2+ forming a chelate-type complex, while Ca2+ formed an ionic-type complex. Monolayers transferred from the condensed phase onto hydrophilic Si(100) and quartz substrates revealed the formation of bilayers through transfer-induced monolayer buckling. Compression induced crystallites in 2D from monolayers and vesicle-like supramolecular structures from multilayers were the noted LB film characteristics, adopting optical imaging and electron microscopy. The interfacial monolayer structure studied through molecular dynamics simulation revealed the order and packing at a molecular level; monolayers adsorbed at various simulated specific areas of the molecule corroborated the (pi-A) isotherm and the formation of a hexagonal lattice at the air-water interface.     

Morphological investigation of hybrid Langmuir-Blodgett films of arachidic acid with a hydrotalcite/dendrimer nanocomposite

A hydrotalcite clay/dendrimer nanocomposite prepared by the ionic exchange process was adsorbed from suspension of the nanocomposite on a Langmuir monolayer of arachidic acid at the air/water interface, followed by compressing and transferring onto an arachidic acid monolayer Langmuir-Blodgett (LB) film on mica. For comparison, the hydrotalcite-adsorbed hybrid film was also prepared. The morphology of hydrotalcite and the nanocomposite studied by transmission electron microscopy indicated the layered structures with respectively 1.2 +/- 0.3 and 3.2 +/- 0.5 nm repeating distances. The hybrid Langmuir films displayed the occupied surface area of 0.24 nm2 for both hydrotalcite and the nanocomposite. The formation of hybrid Langmuir films was confirmed by Brewster angle microscopy. Atomic force microscopic images of hybrid LB films revealed the formation of plateau domains with the height difference of 6 nm for hydrotalcite and 12 nm for the nanocomposite and the presence of dendrimers adsorbed on the clay surface of the nanocomposite.     

Formation of langmuir-blodgett films containing two-dimensional monoatomic arrays of rare-earth cations

The work is focused on the preparation and characterisation of rare-earth containing stearic acid Langmuir-Blodgett (LB) films. Stearic acid monolayer behavior on the rare-earth containing aqueous subphase have been analyzed by thermodynamic measurements. The compression isotherm shape changed substantially under varying the anion type at the constant rare-earth cation content in aqueous subphase. The structure of formed multilayer rare-earth containing LB films was studied using small angle X-rays diffraction. The considerable structural defects in multilayer films were found when rare-earth chloride solution was exploited as aqueous subphase, caused presumably by electrostatic interactions at the monolayer surface under high binding of rare-earth cations. The use of monodentate complexones like acetic acid was proposed to form bulk phase quasi-neutral rare-earth complexes. The electroneutral ligand exchange reactions of such complexes with stearic acid monolayer allowed to neutralise monolayer surface under rare-earth cations binding and to form condenced monolayer below the triple-point temperature. The compression of such monolayer to the state of minimal compressibility and subsequent monolayer deposition resulted in the formation of high ordered LB films with high content of adsorbed multivalent rare-earth cations arranged in two-dimensional monoatomic arrays.     

Magnetic Langmuir-Blodgett films of ferritin with different iron contents

Magnetic Langmuir-Blodgett films of four ferritin derivatives with different iron contents containing 4220, 3062, 2200, and 1200 iron atoms, respectively, have been prepared by using the adsorption properties of a 6/1 mixed monolayer of methyl stearate (SME) and dioctadecyldimethylammonium bromide (DODA). The molecular organization of the mixed SME/DODA monolayer is strongly affected by the presence of the water-soluble protein in the subphase as shown by pi-A isotherms, BAM images, and imaging ellipsometry at the water-air interface. BAM images reveal the heterogeneity of this mixed monolayer at the air-water interface. We propose that the ferritin is located under the mixed matrix in those regions where the reflectivity is higher whereas the dark regions correspond to the matrix. Ellipsometric angle measurements performed in zones of different brightness of the mixed monolayer confirm such a heterogeneous distribution of the protein under the lipid matrix. Transfer of the monolayer onto different substrates allowed the preparation of multilayer LB films of ferritin. Both infrared and UV-vis spectroscopy indicate that ferritin molecules are incorporated within the LB films. AFM measurements show that the heterogeneous distribution of the ferritin at the water-air interface is maintained when it is transferred onto solid substrates. Magnetic measurements show that the superparamagnetic properties of these molecules are preserved. Thus, marked hysteresis loops of magnetization are obtained below 20 K with coercive fields that depend on the number of iron atoms of the ferritin derivative.     

Study of molecular aggregation of artificial amyloid in a langmuir monolayer by infrared spectroscopy

A synthesized peptidolipid (C18IIGLM-NH2) comprised of a single C18-saturated hydrocarbon chain connected to the amino acid sequence IIGLM terminated with the NH2 group was spread on water, which formed a stable Langmuir monolayer. The Langmuir and Langmuir-Blodgett (LB) films have been characterized by measurements of surface pressure-area (pi-A) and surface potential-area (DeltaV-A) isotherms and infrared multiple-angle incidence resolution spectrometry (MAIRS). The Langmuir monolayer had a significantly larger limiting molecular area than that of a similar molecule of C18IIGLM-OH, which was reported in our previous study. The surface dipole moment analysis coupled with the pi-A isotherm suggested that the C18IIGLM-NH2 monolayer was extraordinarily stiff and the fundamental structure of the monolayer was brought about before the monolayer compression. The infrared MAIRS analysis of the C18IIGLM-NH2 LB film revealed that the backbone structure of the monolayer was the 'antiparallel' beta sheet aligned parallel to the substrate. Since the C18IIGLM-OH LB film was made of 'parallel' beta sheet with a random orientation, it has been found that the present C18IIGLM-NH2 Langmuir monolayer has a largely different monolayer structure, although the chemical structures are slightly different from each other by the terminal group only.     

Formation of complex films with water-soluble CTAB molecules

This communication reports the formation of complex Langmuir monolayer at the air-water interface with the water-soluble N-cetyl N,N,N-trimethyl ammonium bromide (CTAB) molecules when interacted with the stearic acid (SA) molecules. The reaction kinetics of the formation of the CTAB-SA complex was monitored by observing the surface pressure versus time graph. Multilayered LB films of this complex doped with Congo red was successfully formed onto a quartz substrate. UV-Vis absorption and steady-state fluorescence spectroscopic characteristics of this doped LB films confirms the successful incorporation of Congo red molecules in to the CTAB-SA complex films.     

Time-dependent complexation of glucose-reduced gold nanoparticles with octadecylamine Langmuir monolayers

We report on the reduction of aqueous chloroaurate ions by glucose to form gold nanoparticles of uniform size. We further demonstrate the complexation of these particles with octadecylamine (ODA) monolayers at the air-water interface. Pressure-area (pi-A) isotherms as a function of time of complexation revealed a significant expansion of the monolayer. Surface pressure variation with time for constant areas after spreading of the monolayer was carried out to observe the kinetics of complexation of the colloidal particles at the interface. The kinetics of complexation of the particles at the interface was also monitored by Brewster angle microscopy (BAM) measurements. Langmuir-Blodgett films of the particles complexed with ODA were formed at a subphase pH of 9 onto different substrates. Quartz crystal microgravimetry (QCM) was used to quantify the amount of particles deposited per immersion cycle of the quartz crystal. The LB films were further characterized by UV-vis and transmission electron microscopy (TEM) measurements. TEM measurements indicate a close packed and equidistant arrangement of colloidal particles in the LB film, probably due to hydrogen-bonding interactions.     

小分子盐对盐酸十八胺单层膜影响的研究

利用Langmuir单层膜模拟生物矿化过程或者是利用LB膜技术构筑层状固体模板来制备与组装纳米材料已成为新的研究热点~([1,2]),因为通过变换成膜材料及制备条件,可以调控生成材料的性质.Langmuir单分子膜的成膜性能直接决定着LB膜的沉积质量、结构和性能~([3,4]).     

Adsorption isotherms of homologous alkyldimethylbenzylammonium bromides on sodium montmorillonite

The adsorption of homologous alkyldimethylbenzylammonium bromides, [C(6)H(5)CH(2)N(CH(3))(2)R]Br, on sodium montmorillonite from aqueous NaCl solutions at room temperature has been studied. R stands for the methyl-, butyl-, hexyl-, octyl-, decyl-, and dodecyl-group, and the corresponding ammonium cations will be denoted as C1+, C4+, C6+, C8+, C10+, and C12+, respectively. C1+, the reference cation, attains the plateau region of adsorption at a level close to the cation exchange capacity (CEC) of the clay. The chain-length dependence on adsorptivity of the homologous cations exhibits an unexpected peculiarity. In the case of short-chain homologues of C1+ their adsorption onto sodium montmorillonite decreases in the order C1+>C4+>C6+. This behavior is due, presumably, to the growing steric hindrances at the surface of clay, which occur because of the limited area available for the bulky organic cations at the exchange sites. These limitations appear to be out-balanced in the case of higher homologues for which the increasingly growing hydrophobic effects lead to the expected sequence of adsorptivity of the cations, i.e., C1+相似文献   

Electron transfer through clay monolayer films fabricated by the Langmuir-Blodgett technique

Hybrid films composed of amphiphilic molecules and clay particles were constructed by the modified Langmuir-Blodgett (LB) method. Clays used were sodium montmorillonite (denoted as mont) and synthetic smectite containing Co(II) ions in the octahedral sites (denoted as Co). Two kinds of amphiphilic molecules were used-[Ru(dC(18)bpy)(phen)2](ClO4)2 (dC(18)bpy = 4,4'-dioctadecyl-2,2'-bipyridyl and phen = 1,10-phenanthroline) (denoted as Ru) and octadecylammonium choloride (ODAH+Cl- or denoted as ODAH). Three kinds of hybrid films (denoted as Ru-mont, Ru-Co, and ODAH-Co films) were prepared by spreading an amphiphilic molecule onto an aqueous suspension of a clay. Atomic force microscopy (AFM) analyses of the films deposited on silicon wafers indicated that closely packed films were obtained at 20 ppm for all the above three cases. Cyclic voltammetry (CV) was measured on an ITO electrode modified with a hybrid film or a monolayer film of pure Ru(II) complex salt (denoted as Ru film). The Ru(II) complexes incorporated in the Ru-mont film lost their redox activity, indicating that montmorillonite layers acted as a barrier against electron transfer. In contrast, the same complexes in the Ru-Co film were electrochemically active with the simultaneous appearance of the redox peaks due to the Co(II)/Co(III) (or Co(II)/Co(IV)) couple. The results implied that electron transfer through cobalt clay layers was possible via mediation by Co(II) ions in a clay sheet. For an aqueous solution containing nitrite ions (NO2-) at pH 3.0, a large catalytic oxidation current was observed for both the electrodes modified with the Ru-mont and Ru-Co films. The results were interpreted in terms of the mechanisms that the charge separation of an incorporated Ru(II) complex took place to produce a pair of a Ru(III) complex and an electron and that the generated Ru(III) complex was reduced by a nitrite ion before it recombined with the electron.     

A study of the interaction between polyelectrolyte-coated nanostructured CaCO<Subscript>3</Subscript> particles and a stearic acid monolayer spread at the water/air interface

The influence of nanostructured CaCO₃ particles, both uncoated and coated with a polyelectrolyte (poly(diallyldimethylammonium chloride), polyethyleneimine, fluorescein-5-isothiocyanate-labeled poly(allylamine hydrochloride), or sodium polystyrene sulfonate), on a stearic acid monolayer spread on the surface of an aqueous subphase has been studied. The interaction of the particles present in the subphase with the monolayer as depending on the presence and composition of a polymer coating has been estimated with the help of compression isotherms and the Brewster angle microscopy. The monolayers were transferred from the aqueous subphase onto a solid substrate and studied by scanning electron microscopy. Strong interaction has been revealed between the calcium carbonate particles and the stearic acid monolayer. It has been shown that the transfer of the monolayer from the aqueous suspension surface onto the solid substrate may be accompanied by the detachment of the polymer coating from the surface of CaCO₃ particles or their transfer together with the monolayer.     

Determination of inorganic cations and anions by ion-exchange chromatography with evaporative light-scattering detection

Evaporative light-scattering detection (ELSD) was investigated for the direct determination of alkali and alkaline-earth cations by cation-exchange chromatography. Successful single run analysis of Na+, K+, Mg2+ and Ca2+ was achieved in 11 min on the Hamilton PRP-X200 column using an aqueous solution of ammonium formate as mobile phase under a salt concentration step gradient mode (20 mM and 100 mM). Surprisingly the use of ELSD reveals a weak retention of inorganic anions (Cl-, NO3-, SO4(2-)) onto the polymeric cation exchanger, which enables the simultaneous determination of inorganic anions (C1- and NO3-) associated with the cations analysed (Na+ and K+).     

Sequence-specific control of azobenzene assemblies by molecular recognition of DNA

We investigated the molecular recognition between the amphiphile AzoAde, which is composed of azobenzene in the hydrophobic and adenine in the hydrophilic portion of the molecule, and oligonucleotides having a homogeneous base (dA30, dT30, dG30, and dC30) at the air-water interface. On the basis of the complementary base-pairing of DNA in the duplex, orderly arrangement of AzoAde on templated dT30 was examined using pi-A isotherm, UV-vis RAS, FT-IR RAS, and XPS measurements. Although there was little interaction between AzoAde and mismatched oligonucleotides (dA30, dG30, and dC30), AzoAde prepared on a dT30 subphase stoichiometrically assembled and interacted with dT30, subsequently forming a J-form assembly at the air-water interface. AFM observation of the LB films revealed the nanostructure of the J-formed AzoAde monolayer on the dT30 subphase as well as the domain structures of the H-formed monolayers on the other oligonucleotide subphases. Therefore, dT30 has a potential application as a template for assembling AzoAde at the air-water interface.     

Adsorption of carboxylate-modified gold nanoparticles on an octadecylamine monolayer at the air/liquid interface

Gold nanoparticles (Au NPs) were prepared and surface-modified by mercaptosuccinic acid (MSA) to render a surface with carboxylic acid groups (MSA-Au). Octadecylamine (ODA) was used as a template monolayer to adsorb the Au NPs dispersed in the subphase. The effect of MSA concentration on the incorporation of Au NPs on the ODA monolayer and the relevant behavior of the mixed monolayer were studied using the pressure-area (pi-A) isotherm and transmission electron microscopy (TEM) observations. The experimental results showed that the adsorbed density of Au NPs is low without the surface modification by MSA. When MSA was added into the Au NP-containing subphase, the incorporation amount of Au NPs increased with increasing MSA concentration up to approximately 1 x 10-5 M for the particle density of 1.3 x 1011 particles/mL. With a further increase in the MSA concentration, the adsorbed particle density decreases due to competitive adsorption between the free MSA molecules and the MSA-Au NPs. It is inferred that free MSA molecules adsorb more easily than the MSA-Au NPs on the ODA monolayer. Therefore, an excess amount of MSA present in the subphase is detrimental to the incorporation of gold particles. The study on the monolayer behavior also shows that the pi-A isotherm of the ODA monolayer shifts right when small amounts of Au NPs or free MSA molecules are incorporated. However, when larger amounts of particles are adsorbed at the air/liquid interface, a left shift of the pi-A isotherm appears, probably due to the adsorption of ODA molecules onto the particle surface and the transferring of the particles from beneath the ODA monolayer to the air/water interface. According to the present method, it is possible to prepare uniform particulate films of controlled densities by controlling the particle concentration in the subphase, the MSA concentration, and the surface pressure of a mixed monolayer.     

Flat orientation of hydrophobic cores induced by two-dimensional confinement of flexible bolaamphiphiles at the air-water interface

We designed and synthesized a new bolaamphiphile consisting of a biphenyl core, flexible trisiloxane spacers, and terminal ammonium groups. The compression of the trisiloxane-containing bolaamphiphile at the air-water interface led to the formation of monolayer films with the hydrophobic rigid core lying flat on the film surface. Such monolayer structures were formed through the compression-induced conformational change of the flexible bolaamphiphile from an extended state to a folded one as confirmed by surface pressure-area isotherm measurements, water contact angle measurements, atomic force microscopy, and UV-vis spectroscopy.