Study of Langmuir monolayers and Langmuir-Schaefer films based on symmetrical meso-aryl-substituted porphyrin derivative

This paper presents the results of a study of meso-aryl-substituted porphyrin Langmuir monolayers by the method of compression isotherms. Experimental data were used to plot the dependences of the compression modulus (C−1) on the specific area. Monolayers at specific surface pressure were transferred to solid substrates and investigated. The monolayers were transferred to the surface of monocrystalline silicon at surface pressures of 8, 25, and 60 mN/m and examined them by atomic force microscopy (AFM) in a semi-contact mode. It was found that with an increase in the transfer pressure, the coarsening of molecular aggregates occurs. The smallest roughness is observed for a porphyrin film formed and transferred at a pressure of 8 mN/m.

Interfacial Behavior of Oligo(Ethylene Glycol) Dendrons Spread Alone and in Combination with a Phospholipid as Langmuir Monolayers at the Air/Water Interface

Dendrons consisting of two phosphonate functions and three oligo(ethylene glycol) (OEG) chains grafted on a central phenoxyethylcarbamoylphenoxy group were synthesized and investigated as Langmuir monolayers at the surface of water. The OEG chain in the para position was grafted with a t-Bu end-group, a hydrocarbon chain, or a partially fluorinated chain. These dendrons are models of structurally related OEG dendrons that were found to significantly improve the stability of aqueous dispersions of iron oxide nanoparticles when grafted on their surface. Compression isotherms showed that all OEG dendrons formed liquid-expanded Langmuir monolayers at large molecular areas. Further compression led to a transition ascribed to the solubilization of the OEG chains in the aqueous phase. Brewster angle microscopy (BAM) provided evidence that the dendrons fitted with hydrocarbon chains formed liquid-expanded monolayers throughout compression, whilst those fitted with fluorinated end-groups formed crystalline-like domains, even at large molecular areas. Dimyristoylphosphatidylcholine and dendron molecules were partially miscible in monolayers. The deviations to ideality were larger for the dendrons fitted with a fluorocarbon end-group chain than for those fitted with a hydrocarbon chain. Brewster angle microscopy and atomic force microscopy supported the view that the dendrons were ejected from the phospholipid monolayer during the OEG conformational transition and formed crystalline domains on the surface of the monolayer.

Effects of Lipid Saturation on the Surface Properties of Human Meibum Films

Elevated levels of acyl chain saturation of meibomian lipids are associated with vastly different effects: from enhanced tear film (TF) stability in infants to shortened TF breakup time in meibomian gland disease patients. Thus it is important to study the effect of saturation on the surface properties of human meibum (MGS). Therefore, MGS films (1, 2, 3, 4, 5, 10, 25, 50, 67, and 100% saturation) were spread at the air/water interface of a Langmuir surface balance. The layers’ capability to reorganize during dynamic area changes was accessed via the surface pressure (π)-area (A) compression isotherms and step/relaxation dilatational rheology studies. Film structure was monitored with Brewster angle microscopy. The raise in the % (at ≥10%) of saturation resulted in the formation of stiffer, thicker, and more elastic films at π ≥ 12 mN/m with the effects being proportional to the saturation level. At the same time, at low (≤10 mN/m) π the raise in saturation resulted in altered spreading and heterogeneous structure of MGS layers. The strong impact of saturation on MGS surface properties correlates with our recent spectroscopy study, which demonstrated that saturation induced increase of MGS acyl chain order, phase transition temperature, and cooperativity.

Physicochemical characterization of colored soluble protein fractions extracted from Spirulina (Spirulina platensis)

The aim of this study was to evaluate the physicochemical properties of Spirulina colored soluble protein fractions extracted from spray-dried Spirulina powder. Three fractions, including the blue soluble Spirulina protein, the green soluble Spirulina protein, and the total soluble Spirulina protein fractions were obtained. Investigations on their behavior at air/water interface were carried out using dynamic methods of drop volume and bubble pressure surface tension measurements. Evaluation of their monolayer films’ mechanical behavior was done via compression isotherms using Langmuir film balance. The protein contents of the fractions were 82.76, 82.29, and 74.53% for the blue, the green, and the total fractions, respectively. Surface tension decay increased with increasing concentration for all the fractions. No significant difference in surface tension decay was observed between the samples at 0.3% (w/w). Surface tension decay was less important at pH 3 for all the fractions. The total fraction and the blue fraction appeared to form more elastic films than the green fraction. The blue soluble fraction also presented the highest collapse pressure and initial expansion area.

Aggregation behavior of unsubstituted magnesium porphyrazine in monolayers at air–water interface and in Langmuir–Schaefer films

The aggregation behavior of unsubstituted magnesium porphyrazine (MgPz) was studied in layers at the water–air interface and in Langmuir–Schaefer films. Regions of existence and characteristics of the structure and properties of stable nanostructured monolayers of MgPz were determined with the method of quantitative analysis of compression isotherms of floating layers in a wide range of initial surface coverage degrees (ISCD). MgPz on the water surface forms monolayers of three types: a face-on type and two edge-on types that differ in the structure. The specific feature of the monolayers of the second type is the independence of the structure of two-dimensional MgPz nanoparticles formed on water on the ISCD. A mathematical model and a state diagram of the monolayer were constructed and a passport of MgPz monolayers was compiled. For the first time, the state diagram contains boundary isotherms based on data obtained from the model. Langmuir–Schaefer films of MgPz formed from layers of various types were prepared and studied by UV-vis absorption spectroscopy.

Humidity-dependent compression-induced glass transition of the air–water interfacial Langmuir films of poly(d,l-lactic acid-ran-glycolic acid) (PLGA)

Constant rate compression isotherms of the air–water interfacial Langmuir PLGA films show a distinct feature of an exponential increase in surface pressure in the high surface polymer concentration regime.