Spectroscopic studies of molecular interaction at the liquid–liquid interface

The development of techniques to study the liquid–liquid interface is a major challenge. Spectroscopy in all its forms provides a powerful method of investigation, especially when combined with other optical techniques. Over the last 30 years, there have been significant developments in the methods for studying heterogeneous interfaces. As technology progresses, the sensitivity of existing techniques has been improved but there are major challenges still to be met, such as the measurement of interfacial dielectric constant and viscosity. This paper aims to summarise the use of spectroscopy to study molecular interactions at the liquid–liquid interface.     

Chiral complexation and aggregation of bilirubin with serum albumin at a liquid/liquid interface

The chiral complexation of bilirubin (BR) with bovine and human serum albumin (BSA and HSA), and the aggregation of the complexes at the heptane+chloroform(5:1)/water interface were studied via UV/Vis absorption and circular dichroism (CD) measurements in combination with the centrifugal liquid membrane (CLM) method. The interfacial adsorptivities of BR, BSA and their complexes were also studied by performing interfacial tension measurements at the interface. The changes in the absorbances and the induced CD amplitudes of the interfacial BR-BSA complex provided insights into the mechanism of the conformational enantioselective complexation at the interface, and indicated that the chiral conversion induced by the complexation with BSA was from the P(+) form to the M(-) form of BR. The broadening of the 450 nm band and the appearance of a new shoulder at 474 nm further supported the formation of aggregates of the complexes at the interface. The dependence of the CD amplitude on the molar ratio of BSA to BR revealed that the composition of the complex was 1:1 BSA:BR. The probable interfacial reaction scheme was proposed, and the affinity constant of BR-BSA at the interface was found to be 4.67 x 10(8) M(-2). The interfacial complexation and aggregation of BR and HSA were weaker than those of the BR-BSA complex due to the different BR binding positions adopted for BSA and HSA and the binding effect of chloroform.     

Molecular dynamics studies on octadecylammonium chloride at the air/liquid interface

Molecular dynamics simulations on surfactant octadecylammonium chloride at the air/liquid interface were performed. It was found that the alkyl chains of octadecylammonium would change to order with increasing the concentration of octadecylammonium at the air/liquid interface. Some functions, such as the concentration distributions, the radial distribution function and the mean squared displacement (MSD) were evaluated to investigate the structural properties of interface. We found that the salts can affect octadecylammonium aggregate at the interface: (1) univalent ions, such as chloride and sodium ions, affect slightly the structure of monolayer and (2) bivalent ions, such as sulfate or calcium ions, affect greatly, especially for the bivalent negative ions.     

Spectroscopic studies and normal coordinate analysis of bilirubin

The infrared spectrum of bilirubin has been recorded in the spectral region 200-4000 cm(-1). The Raman spectrum has also been recorded using the second harmonic (530 nm) radiation of a 200 mW Nd-YAG laser. In order to confirm the vibrational assignment of the bands obtained from experimental observation, a normal coordinate analysis has been carried out using the semi-empirical AM1 method through MOPAC 5.1 computer program. Electronic absorption spectrum of bilirubin dissolved in CHCl3 has been recorded in the spectral region 300-600 nm. A broad spectrum is observed with peak maxima at 454.2 nm. The photoacoustic spectrum of this molecule (in the powder form) has also been recorded for the first time which shows certain discrete features.     

Glycoprotein adsorption into bilirubin/cholesterol mixed monolayers at the air-water interface

The adsorption of α₁-acid glycoprotein into bilirubin/cholesterol mixed monolayers with various component molar ratios is investigated using surface pressure-area (π-A) isotherms and (dπ/dA)-A curves. The results showed that the surface area per molecule increased after the adsorption/insertion of glycoprotein molecules into the monolayers. The compressibility of mixed monolayers increased as a result of hydrogen bonding between bilirubin and glycoprotein molecules, while the interactions between bilirubin and cholesterol are weakened. The adsorption of glycoprotein into a monolayer induced changes in molecular surface area depending on the surface pressure and molar fraction of bilirubin. The transmission electron microscopy of mixed monolayers confirmed the insertion of glycoprotein particles of spherical shape with an average diameter of about 80 nm into the monolayer. The text was submitted by the authors in English.     

Graphene oxide hydrogel at solid/liquid interface

A strong solid/liquid interfacial interaction is found between porous alumina and graphene oxide (GO) aqueous dispersion, which promotes a fast enrichment of GO on the alumina surface and results in the formation of a GO hydrogel.     

Protein adsorption at liquid/liquid interface with low interfacial tension

Adsorption of proteins at the interface of two-liquid systems composed of aqueous ammonium sulfate solution and tert-butanol by phase separation was investigated by drop shape tensiometry. The change of interfacial tension with time and protein concentration as well as upon compression of the adsorbed layer were compared for bovine serum albumin, ovalbumin, β-lactoglobulin, lysozyme, trypsin and horse radish peroxidase. A correlation between the dilatational moduli of various protein films and the partitioning of proteins in the two-liquid system was found, which provides evidence to the role of emulsion stability in protein separation by three-phase partitioning.     

Spectroscopic studies of the stability of monolayers of 2-docosylamino-5-nitropyridine at the air/water interface

Monolayers of 2-docosylamino-5-nitropyridine (DCANP) at the air/water interface were investigated by UV/Vis spectroscopy. The combination of this method with the classic constant-area relaxation technique yields insight into the longtime stability and the collapse behavior of monolayers. We have demonstrated that monolayers of DCANP are certainly stable under standard deposition conditions. At surface pressures above 20 mN/m monolayer instabilities lead to the formation of a three-dimensional head-to-head multilayered structure.     

Salt effect on molecular orientation at air/liquid methanol interface

The salt effects on molecular orientation at air/liquid methanol interface were investigated by the polarization-dependent sum frequency generation vibrational spectroscopy(SFG-VS). We clarified that the average tilting angle of the methyl group to be u = 308 58 at the air/pure methanol surface assuming a d-function orientational distribution. Upon the addition of 3 mol/L Na I, the methyl group tilts further away from the surface normal with a new u = 418 38. This orientational change does not explain the enhancement of the SFG-VS intensities when adding Na I, implying the number density of the methanol molecules with a net polar ordering in the surface region also changed with the Na I concentrations. These spectroscopic findings shed new light on the salt effects on the surfaces structures of the polar organic solutions. It was also shown that the accurate determination of the bulk refractive indices and Raman depolarization ratios for different salt concentrations is crucial to quantitatively interpret the SFG-VS data.     

Investigation of the oxidation of hydroquinone at the liquid/liquid interface

<正>The oxidation of hydroquinone(QH_2) was investigated for the first time at liquid/liquid(L/L) interface by scanning electrochemical microscopy(SECM).In this study,electron transfer(ET) from QH_2 in aqueous to ferrocene(Fc) in nitrobenzene (NB) was probed.The apparent heterogeneous rate constants for ET reactions were obtained by fitting the experimental approach curves to the theoretical values.The results showed that the rate constants for oxidation reaction of QH_2 were sensitive to the changes of the driving force,which increased as the driving force increased.In addition,factors that would affect ET of QH_2 were studied.Experimental results indicated ion situation around QH_2 molecule could change the magnitude of the rate constants because the capability of oxidation of QH_2 would be affected by them.     

Selective silver ion transfer voltammetry at the polarised liquid/liquid interface

Transfer of silver ions across the water/1,2-dichloroethane interface was studied by cyclic voltammetry (CV). In the absence of added neutral ionophore, Ag+ transferred across the interface when the organic phase contained either tetraphenylborate or tetrakis(4-chloro)phenylborate anions, but this transfer was not possible in the presence of organic phase hexafluorophosphate or perchlorate anions. The ion transfer processes observed were independent of the nature of the organic phase cation. The CV in the presence of tetraphenylborate exhibited a shape consistent with an ion transfer followed by chemical reaction; the rate constant for the following chemical reaction was 0.016 s(-1). In the presence of tetrakis(4-chloro)phenylborate, a return peak equivalent in magnitude to the forward peak was observed, indicative of a simple ion transfer reaction uncomplicated by accompanying chemical reactions. The selectivity of the transfer was assessed with respect to other metal cations: no transfers for copper, cadmium, lead, bismuth, cobalt, nickel, palladium or zinc were observed. The selectivity of the transfer suggests this can form the basis of a selective voltammetric methodology for the determination of silver ions.     

Topography of bent-core liquid crystals at the air/liquid crystal interface

Bent-core liquid crystals show a variety of novel structures involving the interplay of molecular bend, tilt and polarisation. Here we investigate the microstructures of the B4, B7 and the dark conglomerate (DC) phases at the air/liquid crystal interface. In these phases, bent-core molecules undergo complex self-assembly, forming helical nanofilaments (the B4 phase), layer undulations (the B7 phase) and disordered focal conics (the DC phase) in the bulk. However, due to the fluidity of the phases and the homeotropic alignment at the interface, several different topographies are observed at the air/liquid crystal interface. We will discuss the surface structures discovered so far in the B4, B7 and DC phases and show how they help us to understand the microstructure and the self-assembly of the liquid crystal phases of bent-core molecules.     

磷钼钒杂多阴离子的液/液界面电化学研究

用循环伏安法研究了V^vMo11-V5^vMo7杂多阴离子在水/硝基苯界面的转移行为, 观察了溶液酸度对转移行为的影响及杂多阴离子稳定存在的pH范围, 钒取代的杂多阴离子稳定性较12-磷钼杂多酸显著提高, 但随钒原子数增加离子稳定性降低, 在"电位窗"内转移的离子主要为-4价, 转移过程为扩散控制, 由循环伏安实验得到了杂多阴离子的表观转移电位△0^wψ^0和转移自由能△Gtr^0^w^-^0,对于不同钒数的杂多阴离子, 其半波电位E1/2与pH关系均可用E1/2=A-37pH(mV)描述。     

Electron transfer mediated by glucose oxidase at the liquid/liquid interface

In order to establish an experimental basis for exploring the reactivity of membrane-bound redox enzymes using electrochemistry at an organic/aqueous interface, the reactivity of glucose oxidase adsorbed at the dichloroethane/water interface has been studied. Turnover of glucose in the aqueous phase mediated by dimethyl ferricenium electrogenerated in the organic phase was measured by measuring the feedback current caused by recycling the mediator as the generator electrode approached close to the interface from the organic side. An unexpected self-exchange reaction of the ferrocene at the interface was suppressed by adsorption of a surfactant. The interfacial enzyme reaction could be distinguished from reaction within the bulk of the aqueous phase. Reaction within a protein-surfactant film formed at the interface is conjectured.     

Hydrogen evolution catalyzed by electrodeposited nanoparticles at the liquid/liquid interface

Aqueous protons reduction by decamethylferrocene in 1,2-dichloroethane can be catalyzed efficiently by platinum and palladium nanoparticles electrogenerated in situ at the liquid-liquid interface.     

Alkane/Alcohol mixed monolayers at the solid/liquid interface

In this work, we present the behavior of solid monolayers of binary mixtures of alkanes and alcohols adsorbed on the surface of graphite from their liquid mixtures. We demonstrate that solid monolayers form for all the combinations investigated here. Differential scanning calorimetry (DSC) is used to identify the surface phase behavior of these mixtures, and elastic neutron incoherent scattering has been used to determine the composition of the mixed monolayers inferred by the calorimetry. The mixing behavior of the alcohol/alkane monolayer mixtures is compared quantitatively with alkane/alkane and alcohol/alcohol mixtures using a regular solution approach to model the incomplete mixing in the solid monolayer with preferential adsorption determining the surface composition. This analysis indicates the preferential adsorption of alcohols over alkanes of comparable alkyl chain length and even preferential adsorption of shorter alcohols over longer alkanes, which contrasts strongly with mixtures of alkane/alkane and alcohol/alcohol of different alkyl chain lengths where the longer homologue is always found to preferentially adsorb over the shorter. The alcohol/alkane mixtures are all found to phase separate to a significant extent in the adsorbed layer mixtures even when molecules are of a similar size. Again, this contrasts strongly with alkane/alkane and alcohol/alcohol mixtures where, although phase separation is found for molecules of significantly different size, good mixing is found for similar size species.     

Solubilization of bilirubin by cholate micelles. Spectroscopic and gel permeation studies

The interactions of bilirubin with bile salts have been studied using fluorescence, circular dichroism and¹H NMR methods. Enhancement of bilirubin fluorescence and induction of optical activity in bilirubin in the presence of cholate has been observed. Fluorescence enhancement is pronounced above the critical micelle concentration, while induced CD bands are detectable even in the premicellar region. Dehydrocholate and deoxycholate did not cause a fluorescence increase, but induced CD bands were observed for bilirubin in these cases. Gel permeation chromatography on Sephadex G-50 yielded a single bilirubin-cholate species at alkaline pH, while two species were obtained at neutral pH.¹H NMR and CD spectral characterizations of these complexes are reported. A 4∶1 cholate-bilirubin mixture has been analysed by difference (nuclear Overhauser effect) NOE spectroscopy. Observation of strong, negative NOE, both intermolecular and intramolecular leads to the conclusion that specific methyl groups on bilirubin and cholate are proximal in the mixed micelle.     

Recent analytical methodologies on equilibrium, kinetics, and dynamics at liquid/liquid interface

The form of liquid/liquid interface is flexible and it cannot be fixed at a spatial position. Also the interface is prevented from any physical contact by the organic phase and aqueous phase. In addition, analytical methods operated in vacuo cannot be applied. These restrictions depressed the development of liquid/liquid interfacial chemistry. However, the modification of liquid/liquid interfacial form and original analytical methods have been invented interdependently. The present review classifies the forms of liquid/liquid interface first, and it arrays the related analytical methods with brief explanations. It dominantly deals with recent reports of analytical methodologies, which were published in 2001-2004, on equilibrium, kinetics, and dynamics of substances at liquid/liquid interface, but it also includes historically important studies.     

Surface-enhanced Raman spectroscopy of dodecanethiol-bound silver nanoparticles at the liquid/liquid interface

Adsorption and domain formation of dodecanethiol (DT)-bound silver nanoparticles (SNPs) at the cyclohexane/water interface were studied by means of total internal reflection (TIR) light scattering microscopy and TIR surface-enhanced Raman scattering (SERS). By the TIR light scattering microscopy, the extent of the interfacial adsorption and domain formation of SNP was observed, which was produced by the reaction between citrate-reduced SNPs in the aqueous phase and DT in the cyclohexane phase. The Raman spectra of DT on SNP showed that the relative intensity ratios of gauche to trans conformers in the nu(C-S) band region decreased with the increase of the initial concentration of DT, suggesting the change from the liquidlike structure to the solidlike structure of the DT. The residue of the negative charges on the SNPs at the interface was detected by the resonance SERS (SERRS) peaks of the adsorbed cationic porphyrin, 5,10,15,20-tetrakis(N-methylpyridinium-4-yl)-21H,23H-porphine (TMPyP). The efficiency of the interfacial SNPs domains as a SERS substrate for TMPyP strongly depended on the adsorption state of the DT.