Langmuir-Schaefer Films Research Articles

Symmetrical diynylic N-arylcarbamate molecules with different numbers of CH2 groups in spacers

The photopolymerization of Langmuir-Schaefer films of diacetylene N-arylcarbamate symmetrical molecules containing different numbers of methylene groups in the molecules was studied. The result of diyne films UV irradiation was the effective transition of the films into the stable state of blue phase polydiacetylene. The number of CH2 groups in the molecules affected the efficiency of the monomers film transition into the polymer and the conjugation length of the polymer chains. Studying the morphology of the films using scanning electron microscopy showed the horizontal position of diyne molecules on the substrates in the state of domains, the sizes of which depended on the number of CH2 groups in the molecules.

Photopolymerization of the Langmuir‒Schaefer Films of Symmetrical Diynylic N-Arylcarbamate Molecules with Different Numbers of СН2 Groups in Spacers

Photopolymerization of the Langmuir‒Schaefer Films of Symmetrical Diynylic N-Arylcarbamate Molecules with Different Numbers of СН2 Groups in Spacers

Tetrapyrrolic macrocycles self-organization into floating layers and sensory properties of their Langmuir-Schaefer films

The influence of the chemical structure of the 5,10,15,20-tetraphenylporphyrin (I) and 2-aza-21-carba-5,10,15,20-tetraphenylporphyrin (II) on their supramolecular organization in floating layers at the air/water interface and sensor properties in Langmuir-Schaefer films has been investigated. It was shown that a minor change in the macrocycle structure (namely, the replacement of a single nitrogen atom from the center to the periphery of macrocycle) has a considerable effect on the surface properties and hysteresis processes of the floating layers. Using the Bruster angle microscopy, it was established that both porphyrins aggregate even before the compression of their floating layers begins. The aggregation is more pronounced in porphyrin I. The analysis of hysteresis loops showed that the formation of a floating layer by the modified porphyrin II requires approximately 100 times more energy than for the unmodified porphyrin I. Using the Langmuir-Schaefer (LS) method, the floating layers were transferred onto solid substrates and the resulting thin films were analyzed by atomic force microscopy, scanning electron microscopy, polarization optical microscopy, and spectrophotometry. The combination of these methods revealed a general tendency of the porphyrins to form 3D structures on the surface of LS-films. The study of the basic properties of the porphyrin's LS-films showed that both porphyrins are diprotonated. The protonation process in porphyrin II occurs at a concentration of HClO4 that is 1000 times lower than that observed in porphyrin I. The greater tendency to protonation of porphyrin II is caused by the availability of both nitrogen atoms (the external nitrogen atom located at the macrocycle periphery and the internal nitrogen atom, which becomes more assesible to interactions due to the distortion of the macrocycle). As for the sensor properties of LS-films for iodide ion in aqueous solutions, it was observed that the diprotonated form of porphyrin I exhibited higher sensitivity due to a more developed film surface because of the presence of a greater number of 3D aggregates. The data obtained can be used in the development of efficient pH-controlled thin-film sensor materials for halide ions.

Thin-film polydiacetylenes of a stable blue phase based on symmetrical and unsymmetrical diacetylene <i>N</i>-arylcarbamates

The conditions and features of the formation of Langmuir monolayers of symmetrical and asymmetrical diacetylene N-arylcarbamates and the structural organization of Langmuir-Schaefer films based on them were studied. Photopolymerization of monolayer solid films of two types of molecules was monitored using absorption spectroscopy and showed the transition of diyne molecules to the blue phase polydiacetylene state. The efficiency of the solid-phase topochemical polymerization reaction in a film of symmetrical diynes turned out to be 5 times higher than in a film of asymmetrical diyne molecules. The morphology of monolayer surfaces before and after UV irradiation was studied using scanning electron microscopy.

Nanostructured films of PM6 and Y6 and their assembly using Langmuir–Schaefer technique

This study investigates the molecular-level assembly and electronic properties of Langmuir and Langmuir–Schaefer (LS) films formed from Y6 (a non-fullerene electron acceptor) and PM6 (a wide bandgap electron donor polymer). We employ a variety of techniques including surface pressure-area isotherms, Brewster angle microscopy, ultraviolet-visible spectroscopy, Raman spectroscopy, and electrical characterizations to explore the behavior of these films. Our findings reveal that the films exhibit a tendency to aggregate and form non-homogeneous layers, which impacts their optical and electrical properties. The LS films show a significant sensitivity to solar radiation, which is evident from the changes in conductivity under illumination. This study highlights the potential of these materials in the development of photovoltaic applications, emphasizing the importance of molecular packing and film morphology in optimizing device performance.

Redox behavior of unsubstituted cobalt phthalocyanine in nanostructured Langmuir-Schaefer films

Although the properties of unsubstituted metal tetrapyrroles in solutions have received attention in numerous work, the physico-chemistry of their thin films remains poorly investigated. In this work, we constructed thin films of unsubstituted cobalt phthalocyanine on the surface of quartz plates and indium tin oxide (ITO) electrodes using the Langmuir-Schaefer (LS) and drop casting techniques. In LS films, CoPc species are involved in strong intermolecular interactions, which result in formation of CoPc nanostructures and prominent changes in the ultraviolet-visible spectrum. Electrochemical reduction of CoPc in LS films at −0.9 V (versus silver chloride electrode) results in formation of Co(I) species. In contrast to the highly reactive nature of Co(I)Pc in solution, these species generated in thin films are relatively resistant to dioxygen due to the dense packing of CoPc units. These findings can further the development of CoPc-based resistive sensors utilizing not only common Co(II), but also Co(I) species, which may possess different sensitivity toward analytes.

Solution Processed Hybrid Lead Perovskite Films for White Light Emission and Lasing Applications

Abstract2D organic–inorganic hybrid lead halide perovskite films are fascinating optoelectronic materials for white‐light emission and lasing applications. Here, it is demonstrated that nano‐meter‐thick films of perovskites can be formed at room temperature using Langmuir–Schaefer (LS) deposition technique. In situ X‐ray measurements reveal a self‐assembly process of the 2D perovskite formation at the air–water interface. This formation process requires the presence of stearic acid monolayer on the water subphase having a solution of lead‐perovskite in dimethylformamide. Microscopy and X‐ray measurements of these nanofilms transferred onto substrates show crystalline phase formation that deviates from the known orthorhombic structure of the bulk crystals. The nanofilms exhibit novel broad optical emission with sharp band‐edge transition in temperature‐dependent photoluminescence studies. Also, their band‐edge emission is distinctly blue‐shifted compared to that of thicker 2D perovskite flakes prepared by the slow‐cooling chemical synthesis process. 2D flakes exhibit lasing that cannot be obtained in the LS nanofilms as their thicknesses are lower than the lasing wavelength prohibiting wave‐guide formation. The results show that the 2D single‐crystalline nature of the LS films and flakes are suitable materials to develop broad‐band white light emission across the entire visible range and to obtain lasing without external cavities, respectively.

Keplerate {Mo132}-Stearic Acid Conjugates: Supramolecular Synthons for the Design of Dye-Loaded Nanovesicles, Langmuir-Schaefer Films, and Infochemical Applications.

Self-assembly gives rise to the versatile strategies of smart material design but requires precise control on the supramolecular level. Here, inorganic-organic synthons (conjugates) are produced by covalently grafting stearic acid tails to giant polyoxometalate (POM) Keplerate-type {Mo132} through an organosilicon linker (3-aminopropyltrimethoxysilane, APTMS). Using the liposome production approach, the synthons self-assemble to form hollow nanosized vesicles (100-200 nm in diameter), which can be loaded with organic dyes─eriochrome black T (ErChB) and fluorescein (FL)─where the POM layer serves as a membrane with subnanopores for cell-like communication. The dye structure plays an essential role in embedding dyes into the vesicle's shell, which opens the way to control the colloidal stability of the system. The produced vesicles are moved by an electric field and used for the creation of an infochemistry scheme with three types of logic gates (AND, OR, and IMP). To design 2D materials, synthons can form spread films, from simple addition on the water-air interface to lateral compression in the Langmuir bath, and highly ordered structures appear, demonstrating electron diffraction in Langmuir-Schaefer (LS) films. These results show the significant potential of POM-based synthons and nanosized vesicles to supramolecular design the diversity of smart materials.

Influence of the Porphyrin Structures on the Contact Angle of Water Wetting by Langmuir-Schaefer Films

Studying the contact angle of water droplets on the surfaces of thin films formed by organic compounds allows to establish hydrophilic/hydrophobic properties of the films. Knowledge of hydrophilicity/hydrophobicity makes it possible to optimize the composition and increase the adhesive properties of films, improving their functionality. In this study, the dependence of the contact angle of Langmuir-Schaefer films (LS-films) of three compounds: 5,10,15,20-tetraphenylporphyrin (I), 2-aza-21-carba-5,10,15,20-tetraphenyl-porphyrin (II), and 5,15-bis(2,6-bis(dodecycloxy)phenyl)porphyrin (III) was examined. Contact angle data were obtained for LS-films with different transfer numbers of floating layers of the studied porphyrins and different surface roughness. It was found that LS-films of compounds I and II are hydrophobic and their hydrophobicity increases with an increasing of transfer number. In addition, an increase in the surface roughness of the LS film of compound I compared to compound II reduces the value of the contact angle. Unlike porphyrins I and II, LS-films of compound III displayed hydrophilic properties. The obtained data can be used for the targeted design of compounds to create thin film materials of various purposes.

Construction of calixarene-based sensor: Multilayer Langmuir–Schaefer film and first-principles studies for 4-aminobenzoic acid sensing application

Calixarenes, being well-known macrocyclic structures, have attracted considerable interest in the field of nanosensors due to their diverse advantages. 4-Aminobenzoic acid (PABA) was aimed to be detected by both calix[4]arene (C4) and calix[6]arene (C6) in this host-guest investigation. This study investigated the development of C4-PABA and C6-PABA complexes using the Langmuir–Schaefer (LS) method and first-principles density functional theory (DFT). All of the LS films formed were characterised by field emission scanning electron microscopy (FESEM), energy dispersive X-ray (EDX), carbon, hydrogen, nitrogen, oxygen elemental analyser (CHNS), ultraviolet-visible spectroscopy (UV-Vis), and Fourier-transform infrared spectroscopy (FTIR). Additionally, this work applied DFT to compute the binding energy and band gap. Morphological and elemental analysis based on the conducted characterisations indicated the incorporation of PABA via lower rims into both C4 and C6. The computed binding energy and band gap validated the experiment's findings that promising reactivity existed between calixarenes and PABA with the formation of stable complexes. The sensing of PABA by both C4 and C6 was proven. In the near future, the outcomes of this research can be applied to drug delivery systems for pharmaceutical and medical purposes.

Selective fluoride ion sensing in aqueous medium using ultrathin film of functionalized single-walled carbon nanotubes

The presence of fluoride ion (F - ) in potable water above its permissible limit (1–4 ppm) poses serious health hazards. Hence, detection of fluoride in potable water is essential. The π-electron rich single-walled carbon nanotubes can interact with F- to form semi-covalent C-F bond which can act as a basis for F - sensing in aqueous medium. Here, a single layer of octadecylamine functionalized single-walled carbon nanotubes (ODA-SWCNTs) was transferred onto solid substrates by the Langmuir–Schaefer (LS) method and employed for sensing of F- in aqueous medium by recording piezo and electrochemical responses, simultaneously using an electrochemical quartz crystal microbalance. The lowest detectable concentration and range of detectable concentration of fluoride ion were found to be 0.5 ppm and 0.5–145 ppm, respectively. The analysis of the LS film of ODA-SWCNTs before and after interaction with fluoride ion by Raman spectroscopy and grazing angle x-ray diffraction measurement reveals perturbation of π-electrons of the SWCNTs due to semi-covalent binding of the fluoride with the carbon atom of the nanotubes. The sensor showed a good selectivity towards the F- in the presence of some heavy metal ions. Testing of the sensor towards F- in tap water obtained from some local region showed a good accuracy.

High Reactivity of Supermolecular Nanoentities of a Vitamin B12 Derivative in Langmuir-Schaefer Films Toward Gaseous Toxins.

Recently, we have described the first supermolecular nanoentities (SMEs) of a vitamin B12 derivative, viz., a monocyano form of heptabutyl cobyrinate ((CN-)BuCby), unique nanoparticles with strong noncovalent intermolecular interactions, and emerging optical and redox properties. In this work, the fast response of thin films based on the SMEs of the B12 derivative to gaseous toxins (viz., hydrogen cyanide, ammonia, sulfur dioxide, and hydrogen sulfide) particularly dangerous for humans was demonstrated. The reaction between SMEs of (CN-)BuCby in Langmuir-Schaefer (LS) films and HCN generates dicyano species and proceeds ca. 5-fold more rapidly than the process involving drop-coated films that contain (CN-)BuCby in molecular form. The highest sensitivity toward HCN was achieved by using thicker LS films. The reaction proceeds reversibly: upon exposure to air, the dicyano complex undergoes partial decyanation. The decyanated complex retains reactivity toward HCN for at least four subsequent cycles. The processes involving SMEs of (CN-)BuCby and NH3, SO2, and H2S are irreversible, and the sensitivity of the films toward these gases is lower in comparison with HCN. Presented data provides mechanistic information on the reactions involving solid vitamin B12 derivatives and gaseous toxins. In the case of NH3, deprotonation of the coordinated Co(III)-ion water molecule occurs, and the generated hydroxocyano species exhibit high air stability. After binding of SO2, a mixture of sulfito and dicyano species is produced, and the regenerated film contains aquacyano and diaqua or aquahydroxo species, which possess high reactivity toward gaseous toxins. Reaction with H2S produces a mixture of the Co(III)-dicyano form and Co(II)-species containing sulfide oxidation products, which are resistant to aerobic oxidation. Our findings can be used for the development of naked-eye, electronic optic, and chemiresistive sensors toward gaseous toxins with improved reactivity for prompt cyanide detection in air, blood, and plant samples and for analysis of exhaled gases for the diagnosis of diseases.

Solvent Impact on Langmuir and Langmuir–Schaefer Films of Soluble Main‐Chain Poly(fullerene)s Based on C60

Understanding the morphology and electronic properties of poly(fullerene)s is crucial for the development of new organic devices. This work addresses the fabrication and characterization of Langmuir–Schaefer (LS) films of poly(fullerene)s based on C60 with short (HSS8) and long (HSS16) sidechains, solubilized in chloroform or xylene. In addition, density functional theory (DFT) calculations are used to optimize the molecular geometries, determine energies, and investigate the influence of solvent applied. Depending on the organic solvent, floating material isotherms indicate the formation of disordered aggregates in the aqueous subphase. The influence of solvent in LS films is also evidenced by way of atomic force microscopy (AFM), UV‐vis, and cyclic voltammetry (CV) measurements. From DFT calculations, the arms of the poly(fullerene)s start to extend from an initial position of surrounding the fullerene sphere. In AFM measurements, depending on the organic solvent, the roughness significantly reduces, while the homogeneity is much higher. In UV‐vis and CV measurements, the propensity to form aggregates depends mainly on the polarization of the solvent and is directly related to the maximum absorption, oxidation, and reduction peaks. From the optical bandgap energy values, the poly(fullerene)s studied here present high potential for application in organic electronic devices.

Photochemical outcomes triggered by gold shell-isolated nanorods on bioinspired nanoarchitectonics for bacterial membranes

Boosted by the indiscriminate use of antibiotics, multidrug-resistance (MDR) demands new strategies to combat bacterial infections, such as photothermal therapy (PTT) based on plasmonic nanostructures. PTT efficiency relies on photoinduced damage caused to the bacterial machinery, for which nanostructure incorporation into the cell envelope is key. Herein, we shall unveil the binding and photochemical mechanisms of gold shell-isolated nanorods (AuSHINRs) on bioinspired bacterial membranes assembled as Langmuir and Langmuir-Schaefer (LS) monolayers of DOPE, Lysyl-PG, DOPG and CL. AuSHINRs incorporation expanded the isotherms, with stronger effect on the anionic DOPG and CL. Indeed, FTIR of LS films revealed more modifications for DOPG and CL owing to stronger attractive electrostatic interactions between anionic phosphates and the positively charged AuSHINRs, while electrostatic repulsions with the cationic ethanolamine (DOPE) and lysyl (Lysyl-PG) polar groups might have weakened their interactions with AuSHINRs. No statistical difference was observed in the surface area of irradiated DOPE and Lysyl-PG monolayers on AuSHINRs, which is evidence of the restricted nanostructures insertion. In contrast, irradiated DOPG monolayer on AuSHINRs decreased 4.0 % in surface area, while irradiated CL monolayer increased 3.7 %. Such results agree with oxidative reactions prompted by ROS generated by AuSHINRs photoactivation. The deepest AuSHINRs insertion into DOPG may have favored chain cleavage while hydroperoxidation is the mostly like outcome in CL, where AuSHINRs are surrounding the polar groups. Furthermore, preliminary experiments on Escherichia coli culture demonstrated that the electrostatic interactions with AuSHINRs do not inhibit bacterial growth, but the photoinduced effects are highly toxic, resulting in microbial inactivation.

Single-Wall Carbon Nanohorn Langmuir-Schaefer Films.

A suspension of single-walled carbon nanohorn (SWCNH) aggregates with a size of approx. 50 nm was used to create a floating film at the water-air interface. The film was then transferred onto large-area quartz substrates using the Langmuir-Schaefer technique at varied surface pressures. The packaging and arrangement of SWCNHs in the film can be controlled during the process. The resulting films' optical and electrical properties were investigated, and the highest electrical conductivity and figure of merit parameter values were observed for the film transferred at surface pressure near the collapse point. These films had a surface density of less than 5 μg cm-2, making them ideal for use in ultra-light sensors, supercapacitors, and photovoltaic cell electrodes. The preparation and properties of the Langmuir-Schaefer films of carbon nanohorns are reported for the first time.

Unveiling the mechanisms underlying photothermal efficiency of gold shell-isolated nanoparticles (AuSHINs) on ductal mammary carcinoma cells (BT-474)

Gold nanoparticles are valuable photothermal agents owing to their efficient photothermal conversion, photobleaching resistance, and potential surface functionalization. Herein, we combined bioinspired membranes with in vitro assays to elicit the molecular mechanisms of gold shell-isolated nanoparticles (AuSHINs) on ductal mammary carcinoma cells (BT-474). Langmuir and Langmuir-Schaefer (LS) films were handled to build biomembranes from BT-474 lipid extract. AuSHINs incorporation led to surface pressure-area (π-A) isotherms expansion, increasing membrane flexibility. Fourier-transform infrared spectroscopy (FTIR) of LS multilayers revealed electrostatic AuSHINs interaction with head portions of BT-474 lipid extract, causing lipid chain disorganization. Limited AuSHINs insertion into monolayer contributed to hydroperoxidation of the unsaturated lipids upon irradiation, consistently with the surface area increments of ca. 2.0%. In fact, membrane disruption of irradiated BT-474 cells containing AuSHINs was confirmed by confocal microscopy and LDH leakage, with greater damage at 2.2 × 1013 AuSHINs/mL. Furthermore, the decrease in nuclei dimensions indicates cell death through photoinduced damage.

Langmuir-Schaefer films based on cyclotriphosphazene-substituted phthalocyanines: Supramolecular organization, UV/Vis study, and laser-induced nonlinear absorption

Low-defective thin films of 2-hydroxy-9(10),16(17),23(24)-tri-tert-butylphthalocyanine (1), as well as its cyclotriphosphazene-substituted derivatives, monomer (2) and clamshell-like dimer (3), have been obtained and extensively studied. It is shown that these dyes produce stable floating layers with a certain number of three-dimensional aggregates at the air/water interface. The floating layers retain their structure when transferred to a glass substrate by the Langmuir-Schaefer method, demonstrating the H-aggregation of the dyes. In contrast to the initial monohydroxyphthalocyanine 1, thin films of its derivatives, cyclotriphosphazene-substituted monomer 2 and dimer 3, show a slight increase in absorption when the number of deposited layers exceeds 100. It is shown that thin films of the studied dyes 1–3 can be used in the technology of optical limitation of laser radiation, demonstrating a good cutting efficiency of dangerous nanosecond pulses.

Nanoarchitectonic approaches for measuring the catalytic behavior of a membrane anchored enzyme. From Langmuir-Blodgett to a novel Langmuir-Schaefer based nanofilm building device

Self-organized lipid monolayers at the air-water interface (Langmuir films, LF) are commonly used for measuring the catalytic properties of membrane-bound enzymes. This methodology allows to provide a consistent flat topography molecular density, packing defects and thickness. The aim of the present work was to show the methodological advantages of using the horizontal transfer method (Langmuir-Schaefer) with respect to the vertical transfer method (Langmuir-Blodgett) when mounting a device to measure catalytic activity of membrane enzymes. Based on the results obtained we can conclude that it is possible to prepare stable Langmuir-Blodgett (LB) and Langmuir-Schaefer (LS) films from Bovine Erythrocyte Membranes (BEM) preserving the catalytic activity of its native Acetylcholinesterase (BEA). In comparison, the LS films showed Vmax values more similar to the enzyme present in the vesicles of natural membranes. In addition, it was much easier to produce large amounts of transferred areas with the horizontal transfer methodology. It was possible to decrease the time required to mount an assay with numerous activity points, such as building activity curves as a function of substrate concentration. The present results show that LSBEM provides a proof of concept for the development of biosensors based on transferred purified membrane for the screening of new products acting on an enzyme embedded on its natural milieu. In the case of BEA, the application of these enzymatic sensors could have medical interest, providing drug screening tools for the treatment of Alzheimer's disease.

Perylene nanostructured films optimization for organic electronics: Molecular, structural, and electrochemical characterization

The deposition technique, structure, and thermal treatment can influence the optical and electrical properties of perylene derivatives films. In this work, the nanostructured Langmuir-Schaefer films of bis(n-propylimide) perylene (PTCD-Pr) with thermal treatment were optimized for an electrochemical application. The PTCD-Pr film before and after thermal treatment was characterized by ultraviolet-visible absorption, infrared absorption spectroscopy, micro-Raman scattering, and voltammetry. Brewster angle microscopy images confirmed the higher aggregation degree of molecules on Langmuir film. The PTCD-Pr deposition showed a linear growth, forming H, J, and null aggregates. The infrared absorption spectroscopy indicates a preferential head-on orientation with a slight chromophore deviation. After thermal treatment (200 °C for 2 h), the PTCD-Pr film showed a decrease in the contribution of null aggregates while maintaining the same molecular orientation. The Raman and surface-enhanced Raman spectroscopy measurements also confirmed the presence of PTCD-Pr molecules distributed throughout the substrate surface, and the thermal treatment conditions did not degrade the PTCD-Pr molecule. Moreover, thermal treatment contributes to the increase of stability of the film at the electrode surface for electrochemical measurements. In the presence of active species (paraquat in this case), the thermally treated film showed promising electrocatalytic properties compared to the unmodified electrode.

P(VDF-TrFE)/BaTiO3 nanocomposite Langmuir-Schaefer thin film for piezoelectric nanogenerator

In this study, a piezoelectric nanogenerator (PENG) was fabricated based on nanocomposite thin films comprising piezoelectric poly(vinylidenefluoride-co-trifluoroethylene) (P(VDF-TrFE)) as a matrix and BaTiO3 (BTO) nanoparticles (NPs) as a nanofiller. The Langmuir-Schaefer (LS) technique was employed to prepare the films. A mixed solution of the polymer and ceramic NPs was spread on the surface of water subphase at a predetermined surface pressure, and thin films were then prepared by transferring the spread monolayer onto indium tin oxide-coated polyethylene terephthalate (ITO-PET) substrate multiple times at a constant surface pressure. Microstructure, crystallinity, β-phase content, dielectric constant, and piezoelectric coefficient (d33) of the thin films were measured with SEM, XRD, FT-IR, LCR meter, and Quasi-static meter, respectively. Six different PENG devices with different BTO contents were fabricated by arranging the thin film-coated substrates in sandwich structure, and they were subject to measurements of piezoelectric characteristics such as open-circuit output voltage (VOC) and short-circuit current (ISC). As results, it was found that the PENG with 4 wt% BTO with ten layers of monolayer deposited at the surface pressure of 15 mN/m yielded the highest VOC of 71.4 V, which was higher than pristine polymer LS film’s 66.2 V at the same conditions, and power density of 35.7 μW/cm2 at 2.5 Hz bending-releasing frequency. This optimum piezoelectric performance was explained in terms of the highest crystallinity, β-phase content, and dielectric properties at the specific BTO content. The optimum PENG coupled with a capacitor and several light emitting demonstrated that it is possibly used to supply power with large energy storage capability of 470 µJ with a 1 µF capacitor for 3 min. This PENG of improved performance is promising as a supply power for a self-powered microelectronics because it has additional advantages of facile fabrication and coating a large area.