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Despite significant efforts to limit the use of fossil fuels, SO2 remains a major air pollutant that adversely affects human health and the environment, especially in heavily industrialized regions of developing countries. Consequently, effective and sustainable methods of SO2 monitoring remain vital issues for detector development. However, despite decades of progress, current solutions based on resistive sensors remain limited by poor sensing performance of semiconducting materials when operated at room temperature and thus suffer from high power consumption due to heating. One solution could be to employ novel 2D semiconductor nanomaterials like MoS2, which have shown good room-temperature performance for gases such as NO2 and NH3. However, they have also shown limited response to other gases, which on the other hand, can be improved by substitutional doping. Consequently, this work investigates, employing density functional theory, the doping of MoS2 with Si, P, Cl, Ge, and Se to improve its SO2 sensing capability. The results show that P doping facilitates all desired effects with the electronic bandgap of MoS2 preserved at 0.72 nm–2 doping concentration, molecule-sheet charge transfers enhanced by 300%, and moderate binding energies that enable effective surface diffusion of SO2 at 300 K.

Understanding the mechanism of interactions between magnetite nanoparticles and phospholipids that form cellular membranes at the molecular level is of crucial importance for their safe and effective application in medicine (e.g., magnetic resonance imaging, targeted drug delivery, and hyperthermia-based anticancer therapy). In these interactions, their surface coating plays a crucial role because even a small modification to its structure can cause significant changes to the behaviour of the magnetite nanoparticles that come in contact with a biomembrane. In this work, the influence of the magnetite nanoparticles functionalized with native and aminated starch on the thermodynamics, morphology, and dilatational elasticity of the model cell membranes was studied. The model cell membranes constituted the Langmuir monolayers formed at the air–water interface of dipalmitoylphosphatidylcholine (DPPC). The surface of the aminated starch-coated nanoparticles was enriched in highly reactive amino groups, which allowed more effective binding of drugs and biomolecules suitable for specific nano–bio applications. The studies indicated that the presence of these groups also reduced to some extent the disruptive effect of the magnetite nanoparticles on the model membranes and improved their adsorption.

An adsorption process of magnetite nanoparticles functionalized with aminated chitosan (Fe3O4-AChit) showing application potential in nanomedicine into cell membrane models was studied. The cell membrane models were formed using a Langmuir technique from three selected phospholipids with different polar head-groups as well as length and carbon saturation of alkyl chains. The research presented in this work reveals the existence of membrane model composition-dependent regulation of phospholipid-nanoparticle interactions. The influence of the positively charged Fe3O4-AChit nanoparticles on a Langmuir film stability, phase state, and textures is much greater in the case of these formed by negatively charged 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DPPG) than those created by zwitterionic 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (POPC). The adsorption kinetics recorded during penetration experiments show that this effect is caused by the strongest adsorption of the investigated nanoparticles into the DPPG monolayer driven very likely by the electrostatic attraction. The differences in the adsorption strength of the Fe3O4-AChit nanoparticles into the Langmuir films formed by the phosphatidylcholines were also observed. The nanoparticles adsorbed more easily into more loosely packed POPC monolayer.

An adsorption process of magnetite nanoparticles functionalized with aminated chitosan (Fe3O4-AChit) showing application potential in nanomedicine into cell membrane models was studied. The cell membrane models were formed using a Langmuir technique from three selected phospholipids with different polar head-groups as well as length and carbon saturation of alkyl chains. The research presented in this work reveals the existence of membrane model composition-dependent regulation of phospholipid-nanoparticle interactions. The influence of the positively charged Fe3O4-AChit nanoparticles on a Langmuir film stability, phase state, and textures is much greater in the case of these formed by negatively charged 1,2-dipalmitoyl-sn-glycero-3-phospho-rac-(1-glycerol) (DPPG) than those created by zwitterionic 1,2-distearoyl-sn-glycero-3-phosphocholine (DSPC) and 2-oleoyl-1-palmitoyl-sn-glycero-3-phosphocholine (POPC). The adsorption kinetics recorded during penetration experiments show that this effect is caused by the strongest adsorption of the investigated nanoparticles into the DPPG monolayer driven very likely by the electrostatic attraction. The differences in the adsorption strength of the Fe3O4-AChit nanoparticles into the Langmuir films formed by the phosphatidylcholines were also observed. The nanoparticles adsorbed more easily into more loosely packed POPC monolayer.

Molecular organization of non-chlorinated (Pn) and chlorinated (PCln) esters of perylene tetracarboxylic acid with four lateral alkyl chains composed of n carbon atoms (n = 4, 10) in spin-coated films has been studied. The Pn dyes have shown a strong tendency for aggregation in the ground and excited state, which can be limited by long alkyl chains. Fluorescence quantum yield (FQY) of their film does not exceed the value of 0.04 and is far below that of the strongly diluted toluene solution (0.87). Chlorine atoms attached in the bay positions of the PCln dyes caused twisting of the perylene skeleton, which resulted in longer intermolecular distances and weaker interactions between molecules in films. In this way, an aggregation process was reduced and the role of the alkyl chains length as a steric hindrance was suppressed. However, FQY of the PCln films is below 0.24, because of its low value measured for the monomeric form in diluted solution (0.35). Furthermore, the concentration effect of the Pn and PCln dyes dispersed in poly (methyl methacrylate) (PMMA) on types of aggregates formed by them and on FQY value has been studied. FQY of the Pn derivatives increased with the drop of their concentration in PMMA up to the values of 0.59 and 0.69 for the dyes with shorter and longer alkyl chains, respectively. This makes them promising materials for application in organic light emitting diodes. In turn, FQY of the PCln derivatives in PMMA matrix was in the range of 0.17–0.37 and does not change in a regular way with dyes concentration.

The photoisomerization and thermal relaxation processes of three amphiphilic azobenzene derivatives (LCAn) showing liquid-crystalline properties were studied in solutions and in monomolecular films formed using Langmuir and Langmuir-Blodgett techniques. The well-controlled isomeric state of LCAn in chloroform during the UV irradiation allowed to prepare spreading solutions containing trans isomers, cis isomers or their mixture and to investigate molecular organization in the Langmuir films made of them. Surface pressure-mean molecular area isotherms and compression modulus-surface pressure dependences delivered information on a thermodynamic state, phase transitions and intermolecular interaction in the monolayers. LCAn in the trans state create densely-packed films, in which the photoisomerization do not occur due to the lack of free volume for the change of the molecules conformation and their strong tendency for the H-type aggregation. However, the reversible switching of the LCAn conformation during cyclic photoisomerization and thermal relaxation processes was observed in the LB films initially deposited onto quartz substrates in the cis state, where molecules are loosely-packed and exist in the monomeric form. Kinetics and rate constants of the photoisomerization and thermal relaxation were determined based on the recorded absorption spectra in order to obtain information on their efficiency and on the impact of the replacement of the alkyl chain attached in the LCAn para position with the alkyloxy chain. Our research show that LCAn are promising materials for application in optical memories, logic gates and holographic gratings.

Magnetite nanoparticles are promising materials for application in magnetic resonance imaging, targeted drug delivery, enzyme immobilization and cancer therapies based on hyperthermia thanks to their biocompatibility, wide chemical affinity and superparamagnetic properties. However, there is still the lack of the knowledge of interactions between magnetite nanoparticles covered with the bioactive polymers and biological cells. In order to fulfil this gap, we have investigated interactions of newly synthetized magnetite nanoparticles functionalized with aminated chitosan (Fe3O4-aminated chitosan) and a model biological membrane made of dipalmitoylphosphatidylcholine (DPPC) using a Langmuir technique. Surface pressure-mean area per DPPC molecule isotherms and Brewster angle microscope images (BAM) recorded during compression of the two-component Fe3O4-aminated chitosan:DPPC films revealed the strong influence of the Fe3O4-aminated chitosan nanoparticles on the stability, phase state and structure of the phospholipid membrane. The studies on the adsorption/incorporation process of the Fe3O4-aminated chitosan nanoparticles showed that they can adsorb/incorporate into the DPPC model membrane at the surface pressure corresponding to this present in the cellular membrane under the biological conditions (35 mN·m−1). The number of the adsorbed/incorporated Fe3O4-aminated chitosan nanoparticles can be regulated by the nanoparticles concentration in the neighbourhood of the DPPC model membrane even at high surface pressure of 35 mN·m−1.

The concept of programmable and reconfigurable soft matter has emerged in science in the last few decades and can be realized by photoisomerization of azobenzene derivatives. This possibility results in great application potential of these compounds in optical storage devices, molecular junctions of electronic devices, command layers of liquid crystal displays or holographic gratings. In this paper, we present the results of a study on the organization and isomerization of the non-ionic and amphiphilic methyl 4-[(E)-2-[4-(nonyloxy)phenyl]diazen-1-yl]benzoate (LCA) in a 2D layer architecture of Langmuir and Langmuir-Blodgett (LB) films supported by spectroscopic studies on LCA chloroform solutions. Our investigation has shown a significantly different molecular organization of LCA depending on the ratio of trans and cis isomers in the monolayers. Taking advantage of a relatively low packing density and aggregation strength in the cis-LCA monolayer, we demonstrated the reversible isomerization in the LB film initially formed of LCA molecules in the cis form, while in the trans-LCA monolayer this effect was not observed. Our approach allows the formation of a switchable monolayer made of the amphiphilic LCA showing liquid crystalline properties without introducing an ionic group into the molecule structure, mixing with another compound or changing the subphase pH to provide free space for the molecules' isomerization.

Langmuir films formed of some fluorescent dyes, 3,4-bis-pentyl ester of 9,10-N-(n-pentylimide)-perylenetetracarboxylic acid, as well as their mixtures with arachidic acid, were studied. Surface pressure versus mean molecular area isotherms for Langmuir films were reordered and the alignment of molecules at the air–water interface was estimated. The isotherms show that the dye molecules do not lie flat onto the water surface but are tilted with respect to the normal to the interface. The surface pressure–area isotherms of Langmuir films formed from the dye/arachidic acid mixture provide evidence for phase separation of the components within almost the entire range of mole fractions. A repulsive interaction between molecules was observed in all two components of Langmuir films.

The influence of chlorine atoms in the bay positions of the perylene-3,4,9,10-tetracarboxylic acids with the different alkyl chains length on their spectral properties in monomolecular films has been studied. The chlorinated (PCln) and for comparison non-chlorinated (Pn) perylene derivatives were deposited onto quartz plates using a Langmuir-Blodgett (LB) technique. The absorption spectra showed that the PCln and Pn dyes form in monolayers the I- and J-type aggregates, respectively. In turn, their steady-state and time-resolved emission spectra revealed presence of two emitter types, which we assigned to monomers and excimers. The luminescence lifetimes of the PCln monomers and excimers determined with a time-correlated single photon counting method (TCSPC) are significantly shorter than these obtained for the same emitter types in the Pn monolayers. In the case of the chlorinated dyes, the contribution of the monomer emission dominates over the excimer emission and is almost independent from the alkyl chain length. By contrast, the share of the Pn monomer emission increases strongly with a number of carbon atoms in their hydrocarbon chains. The luminescence quantum yields (LQY) of the Pn and PCln monolayers measured in an integrating sphere are in the range of 0.06-0.11. The presented results reveal that the PCln dyes exhibit lower tendency for aggregation than the non-chlorinated derivatives. It can be explained by limited intermolecular interaction between neighbouring PCln molecules caused by deformation of the perylene core as a result of strongly electronegative chlorine atoms in the bay positions of these dyes. Moreover, the strong influence of the alkyl chain length on the Pn aggregation contrary to the case of the PCln derivatives was observed.

The Langmuir and Langmuir–Blodgett films formed of tetra-n-butyl-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylate and its binary mixtures with 4-octyl-4′-cyanobiphenyl and arachidic acid have been studied. The Langmuir films were characterized by surface pressure versus mean molecular area isotherms and the films morphology observations were made by means of a Brewster angle microscope. The miscibility of the compounds was determined. Subsequently, the Langmuir films were transferred onto hydrophilic quartz substrates forming the monolayer Langmuir–Blodgett films. The electronic absorption and fluorescence spectra reveal aggregation of the chromophores in ground state driven by π–π molecular orbitals interactions. Perylene-like dye aggregation depends upon the dye concentration in the dye/liquid crystal mixed films and is concentration-independent in dye/arachidic acid one.

The role of newly synthesized tocopherol glycosidic derivative in modifying molecular organization and phase transitions of phospholipid monolayer at the air/water interface has been investigated. Two-component Langmuir films of dl-α-tocopheryl β-D-glucopyranoside (BG) mixed with dipalmitoyl phosphatidylcholine (DPPC) in the whole range of mole fractions were formed at the water surface. An analysis of surface pressure versus mean molecular area (π-A) isotherms and Brewster angle microscope images showed that the presence of BG molecules changes the structure and packing of the DPPC monolayer in a BG concentration dependent manner. BG molecules incorporated into DPPC monolayer inhibit its liquid expanded to liquid condensed phase transition proportionally to the BG concentration. The monolayers were also transferred onto solid substrates and visualized using an atomic force microscope. The results obtained indicate almost complete miscibility of BG and DPPC in the monolayers at surface pressures present in the biological cell membrane (30-35·10(-3) N·m(-1)) for a BG mole fraction as high as 0.3. This makes the monolayer less packed and more disordered, leading to an increased permeability. The results support our previous molecular dynamics simulation data.