On the extraction of MoO x photothermally active nanoparticles by gel filtration from a byproduct of few-layer MoS2 exfoliation.

Gel filtration is a versatile technique employed for biological molecules and nanoparticles, offering their reproducible classification based on size and shape. Colloidal nanoparticles are of significant interest in biomedical applications due to a large number of solution-based bioconjugation procedures. Nevertheless, the inherent polydispersity of the nanoparticles produced by various techniques necessitates the employment of high yield separation and purification techniques. Here we demonstrate the employment of gel filtration on non-stoichiometric plasmonic MoO x nanoparticles, prepared by an oxidation process during liquid-phase exfoliation of few-layer MoS2 nanosheets. This resulted in the separation of two types of MoO x particles, in the form of two different chromatographic fractions. They showed different sizes, morphological and optical properties. The fraction containing smaller particles with diameters of 1-4 nm, exhibited an increased absorbance peak in the near IR region and responded with a significant temperature increase to laser irradiation at the wavelength close to the maximal absorption. The fraction with the larger particles from 3 up to 10 nm, showed weak photoluminescence and a preferred orientation upon the deposition on a planar substrate. However, it had no absorbance in the near IR compared to the former fraction. According to our knowledge, this is the first time that the gel filtration was applied to the separation of molybdenum oxide nanomaterials. This step ensured the isolation of plasmonic MoO x nanoparticles suitable for further bioconjugation and target photothermal treatment.

An elevated concentration of MoS2 lowers the efficacy of liquid-phase exfoliation and triggers the production of MoOx nanoparticles.

It is generally accepted that liquid-phase exfoliation (LPE) enables large-scale production of few-layer MoS2 flakes. In our work, we studied in detail few-layer MoS2 oxidation in the course of standard LPE in a water/ethanol solution. We demonstrate that an increase of the initial MoS2 concentration above a certain threshold triggers a pronounced oxidation and the exfoliation process starts to produce MoOx nanoparticles. A subsequent decrease of the water pH along with an increased content of SO42- suggests an oxidation scenario of few-layer MoS2 oxidation towards MoOx nanoparticles. Moreover, the lowered pH leads to agglomeration and sedimentation of the few-layer MoS2 flakes, which significantly lowers their production yield. We employed a large number of physico-chemical techniques to study the MoS2-to-MoOx transformation and found a threshold value of 10 mg ml-1 of the initial MoS2 concentration to trigger this transformation.

The effect of polyethylene glycol-modified lipids on the interaction of HIV-1 derived peptide-dendrimer complexes with lipid membranes.

In this study, dendrimers have been purposed as an alternative approach for delivery of HIV peptides to dendritic cells. We have investigated the interaction of dendriplexes formed from polyanionic HIV peptide Nef and cationic carbosilane dendrimer (CBD) with model lipid membranes - large unilamellar vesicles (LUVs), Langmuir monolayers and supported lipid membranes (sBLMs) containing various molar ratio of zwitterionic 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) and 1,2-distearoyl-sn-glycero-3-phosphoethanolamine-N-[methoxy (polyethylene glycol)-2000] (DSPE-PEG2000). In our experiments, the lipid membranes represented the model of the plasma membrane of the cell. PEGylated lipids were used in order to model glycocalyx which constitutes the outer leaflet of cellular membranes. The presence of PEGylated lipids resulted in an increase of the phase transition temperature of the lipid bilayer of LUVs, in a decrease of specific volume and adiabatic compressibility. Fluorescence anisotropy study suggests that PEGylated LUVs possessed higher lipid order and decreased fluidity when compared to zwitterionic DMPC vesicles. The interaction of dendriplexes with monolayers was accompanied by the formation of the aggregates as revealed by BAM experiments. This conclusion has been confirmed also by AFM imaging of sBLMs. We have demonstrated that dendriplexes interact with lipid membranes for all types of lipid composition. Moreover, the stronger interaction of cationic dendrimer/peptide complexes with lipid monolayers, vesicles and sBLMs was observed for membranes composed of zwitterionic lipids than for PEGylated lipid membranes. Increased concentration of PEGylated lipids made this interaction weaker.

Control of single-electron charging of metallic nanoparticles onto amorphous silicon surface.

Sequential single-electron charging of iron oxide nanoparticles encapsulated in oleic acid/oleyl amine envelope and deposited by the Langmuir-Blodgett technique onto Pt electrode covered with undoped hydrogenated amorphous silicon film is reported. Single-electron charging (so-called quantized double-layer charging) of nanoparticles is detected by cyclic voltammetry as current peaks and the charging effect can be switched on/off by the electric field in the surface region induced by the excess of negative/positive charged defect states in the amorphous silicon layer. The particular charge states in amorphous silicon are created by the simultaneous application of a suitable bias voltage and illumination before the measurement. The influence of charged states on the electric field in the surface region is evaluated by the finite element method. The single-electron charging is analyzed by the standard quantized double layer model as well as two weak-link junctions model. Both approaches are in accordance with experiment and confirm single-electron charging by tunnelling process at room temperature. This experiment illustrates the possibility of the creation of a voltage-controlled capacitor for nanotechnology.

Study of the Calix[4]resorcinarene--dopamine interactions in monolayers by measurement of pressure--area isotherms and Maxwell displacement currents.

The mechanisms of interactions between calix[4]resorcinarene and dopamine in monolayers formed at the air-water interface were studied by analyzing their mechanical, thermodynamic, and electrical properties evaluated from measurements of pressure-area isotherms and Maxwell displacement currents (MDCs). An increased concentration of dopamine in the water subphase resulted in an increase in the area per calix[4]resorcinarene molecule, an increase in the collapse pressure, and a shift in the monolayer phase transitions from the gaseous to the liquid state and from the liquid to the solid state toward higher molecular areas. A contactless method of recording MDCs enabled the monitoring of changes in the charge state of the monolayer-constituting molecules and the determination of a relationship between the phase state of the monolayer and the structural transitions of calix[4]resorcinarene. The changes of the MDC recordings started already in the gaseous state of the monolayer. On the basis of MDC values, we determined the normal component of the dipole moment of calix[4]resorcinarene, as well as that of its complex with dopamine. The dipole moment reached a maximum value of 1040 mD in the region of the phase transition from the liquid to the solid state of the monolayer. The results obtained suggest that the binding of dopamine with calix[4]resorcinarene depends on the orientation of the calixarene molecules in the monolayer. The calix[4]resorcinarene-dopamine interactions were also quantified in terms of the excess of Gibbs free energy, thereby allowing the evaluation of the energy of the calix [4]resorcinarene-dopamine bond, which was in the range from 1.95 to 8.54 kJ/mol depending on the surface pressure. This value implies weak interactions between these molecules.

Maxwell displacement current allows to study structural changes of gramicidin A in monolayers at the air-water interface.

We applied methods of measurement Maxwell displacement current (MDC) pressure-area isotherms and dipole potential for analysis of the properties of gramicidin A (gA) and mixed gA/DMPC monolayers at an air-water interface. The MDC method allowed us to observe the kinetics of formation of secondary structure of gA in monolayers at an air-water interface. We showed, that secondary structure starts to form at rather low area per molecule at which gA monolayers are in gaseous state. Changes of the MDC during compression can be attributed to the reorientation of dipole moments in a gA double helix at area 7 nm(2)/molecule, followed by the formation of intertwined double helix of gA. The properties of gA in mixed monolayers depend on the molar fraction of gA/DMPC. At higher molar fractions of gA (around 0.5) the shape of the changes of dipole moment of mixed monolayer was similar to that for pure gA. The analysis of excess free energy in a gel (18( ) degrees C) and in a liquid-crystalline phase (28( ) degrees C) allowed us to show influence of the monolayer structural state on the interaction between gA and the phospholipids. In a gel state and at the gA/DMPC molar ratio below 0.17 the aggregates of gA were formed, while above this molar ratio gA interacts favorably with DMPC. In contrast, for DMPC in a liquid-crystalline state aggregation of gA was observed for all molar fractions studied. The effect of formation ordered structures between gA and DMPC is more pronounced at low temperatures.

Ion selectivity of a poly(3-pentylmethoxythiophene) LB-layer modified carbon-fiber microelectrode as a consequence of the second order filtering in voltcoulometry.

Ion selective properties of poly(3-pentylmethoxythiophene) Langmuir-Blodgett film modified carbon-fiber microelectrode are described. The study of the electrode behavior indicates that important features occur if two electrochemical methods, one of them being kinetics sensitive, are used. While in case of the typical steady-state voltammetry the electrode remains sensitive to both the cations and anions, the kinetics-sensitive properties of voltcoulometry based on the second-order filtering scheme disable the observation of anions. As a model system a mixture of copper and dopamine ions is used.

Study of gramicidin A--phospholipid interactions in Langmuir monolayers: analysis of their mechanical, thermodynamical, and electrical properties.

The mechanisms of interactions between gramicidin A (gA) and dimyristoylphosphatidylcholine (DMPC) in monolayers formed at the air-water interface were studied by analyzing their mechanical, thermodynamical, and electrical properties evaluated from measurements of pressure-area isotherms and of Maxwell displacement currents (MDC). A contactless method of recording MDC enabled us to monitor changes in the charge state of the monolayer-constituting molecules and to find the relation between a phase state of the monolayer and structural transitions of gA. The peptide-lipid interactions were quantified in terms of the excess of Gibbs free energy, excess entropy, as well as the molecular dipole moments at various gA/DMPC molar ratios, at various temperatures (in the gel phase and also in the liquid-crystalline phase of DMPC molecule), and at various surface pressures. It was found that the strongest interactions between gA and DMPC took place at the gA/DMPC molar ratio at around 0.25. At this monolayer composition, the phospholipids, via their carbonyl moieties, dominantly interact with the single helical gA, which mostly stands upright on the surface and is anchored by its C-terminus to the water surface, and prevent the formation of the intertwined helical gA dimers. The optimum ratio was confirmed also by anomalous electrical behavior of electrical dipole moments derived from MDC measurements.