Langmuir-Schaefer Method Research Articles

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.

Silk Fibroin Self-Assembly at the Air–Water Interface

Amphiphilic silk fibroin (SF) forms stable adsorption layers at the air–water interface. The range of the investigated protein concentrations can be divided into two parts according to the peculiarities of the surface layer properties. At protein concentrations from 0.0005 to 0.01 mg/mL, the dynamic surface elasticity monotonically increases with the concentration and surface age and reaches values of up to 220 mN/m. In this range, the adsorption layer compression leads to a fast increase of the surface pressure. In the second part (>0.01 mg/mL), the surface elasticity decreases again and the kinetic dependences of the film thickness and adsorbed amount change only a little. In this case, the layer compression leads only to a slight increase of the surface pressure. These two types of behavior can be attributed to the distinctions in the protein aggregation in the surface layer. Atomic force microscopy (AFM) investigations of the layers transferred from the liquid surface onto a mica surface by the Langmuir–Schaefer method show some peculiarities of the layer morphology in the intermediate concentration range (~0.02 mg/mL).

Fabrication of Densely-Packed Janus Gold Nanoparticles Layer by Self-Assembly for a Potential Molecular Sensing Probe

Localized surface plasmon phenomena of metallic nanoparticles could be utilized for sensing applications. As the particles in the vicinity results in a near-field coupling phenomenon, a higher field enhancement factor increases the sensing sensitivity. In this research, we propose a self-assembled and closely-packed Janus gold nanoparticle (AuNP) structure for application in molecular sensing. We utilize three-phase interfacial trapping and Langmuir-Schaefer method for the fabrication of Janus AuNP layer. In our case, dodecylamine (DDA) was used as the analyte for sensing assay. We found that the color of our AuNP changes from red-wine to blue in conjunction with the phase changes from colloidal to closely-packed layer that results in a red-shift absorbance peak. In the application of sensing assay, the absorbance peak is revealed blue-shifted up to ~40 nm from pristine AuNP layer due to the adsorption of DDA on the particle surfaces. Sensitivity enhancement is also expected due to the hotspot arises from the plasmonic particles in vicinity. This research could be further developed to a sensitive and quantitative molecular sensor up to colorimetric specific biosensor.

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.

Proline Enantiomers Discrimination by (L)-Prolinated Porphyrin Derivative Langmuir–Schaefer Films: Proof of Concept for Chiral Sensing Applications

A porphyrin derivative functionalized with the L-enantiomer of proline amino acid was characterized at the air–pure water interface of the Langmuir trough. The porphyrin derivative was dissolved in dichloromethane solution, spread at the air–subphase interface and investigated by acquiring the surface pressure vs. area per molecule Langmuir curves. It is worth observing that the behavior of the molecules of the porphyrin derivative floating film was substantially influenced by the presence of L-proline amino acid dissolved in the subphase (10−5 M); on the contrary, the physical chemical features of the floating molecules were only slightly influenced by the D-proline dissolved in the subphase. Such an interesting chirality-driven selection was preserved when the floating film was transferred onto solid supports by means of the Langmuir–Schaefer method, but it did not emerge when a spin-coating technique was used for the layering of the tetrapyrrolic derivatives. The obtained results represent proof of concept for the realization of active molecular layers for chiral discrimination: porphyrin derivatives, due to their intriguing spectroscopic and supramolecular properties, can be functionalized with the chiral molecule that should be detected. Moreover, the results emphasize the crucial role of the deposition technique on the features of the sensing layers.

Biorecognition Layer Based On Biotin-Containing [1]Benzothieno[3,2-b][1]benzothiophene Derivative for Biosensing by Electrolyte-Gated Organic Field-Effect Transistors.

Requirements of speed and simplicity in testing stimulate the development of modern biosensors. Electrolyte-gated organic field-effect transistors (EGOFETs) are a promising platform for ultrasensitive, fast, and reliable detection of biological molecules for low-cost, point-of-care bioelectronic sensing. Biosensitivity of the EGOFET devices can be achieved by modification with receptors of one of the electronic active interfaces of the transistor gate or organic semiconductor surface. Functionalization of the latter gives the advantage in the creation of a planar architecture and compact devices for lab-on-chip design. Herein, we propose a universal, fast, and simple technique based on doctor blading and Langmuir-Schaefer methods for functionalization of the semiconducting surface of C8-BTBT-C8, allowing the fabrication of a large-scale biorecognition layer based on the novel functional derivative of BTBT-containing biotin fragments as a foundation for further biomodification. The fabricated devices are very efficient and operate stably in phosphate-buffered saline solution with high reproducibility of electrical properties in the EGOFET regime. The development of biorecognition properties of the proposed biolayer is based on the streptavidin-biotin interactions between the consecutive layers and can be used for a wide variety of receptors. As a proof-of-concept, we demonstrate the specific response of the BTBT-based biorecognition layer in EGOFETs to influenza A virus (H7N1 strain). The elaborated approach to biorecognition layer formation is appropriate but not limited to aptamer-based receptor molecules and can be further applied for fabricating several biosensors for various analytes on one substrate and paves the way for "electronic tongue" creation.

Operationally Stable Ultrathin Organic Field Effect Transistors Based on Siloxane Dimers of Benzothieno[3,2‐b][1]Benzothiophene Suitable for Ethanethiol Detection

AbstractUltrathin organic field effect transistors (OFETs) demonstrate great potential as highly sensitive gas sensors since its electrical performance strongly depends on the environment. However, fabrication of high performance OFETs with reliable operational stability for continuous measurements by fast, rather simple, and inexpensive technique is still a challenge. Herein, electrical and sensing properties of ultrathin OFETs based on siloxane dimers of benzothieno[3,2‐b][1]benzothiophene (BTBT) with different aliphatic spacer lengths fabricated by Langmuir–Blodgett, Langmuir–Schaefer (LS) or spin‐coating techniques are studied, compared and optimized. Investigation of the influence of interface dielectric layer on electrical performance and operational stability of the devices allowed obtaining uniform low‐defect ultrathin semiconducting layers responsible for improved electrical performance. Field‐effect mobility up to 0.47 cm2 V−1 s−1 is achieved for the devices based on the dimer with undecylenic spacer between the BTBT core and disiloxane central fragment fabricated by LS method on the top of poly(methyl methacrylate) interface layer. Promising operational stability lead to advanced sensory properties demonstrated by sensing of ethanethiol with the limit of detection of 30 ppb in the humid air, which is a record value for portable sensing technologies.

Enantioselective Discrimination of Histidine by Means of an Achiral Cubane-Bridged Bis-Porphyrin.

A Langmuir film of cubane-bridged bisporphyrin (H2por-cubane-H2por) at the air/water interface was developed and characterized. The floating film was successfully employed for the chiral discrimination between l- and d-histidine. The enantioselective behavior persisted after the deposition of the film on a solid support using the Langmuir–Schaefer method. Distinct absorption and reflection spectra were observed in the presence of l- or d-histidine, revealing that conformational switching was governed by the interaction between H2por-cubane-H2por and the histidine enantiomer. The mechanism of chiral selection was investigated using an ad hoc modified nulling ellipsometer, indicating the anti-conformation was dominant in the presence of l-histidine, whereas the presence of d-histidine promoted the formation of tweezer conformation.

\u03a0-GISANS: probing lateral structures with a fan shaped beam

We have performed grazing incidence neutron small angle scattering using a fan shaped incident beam focused along one dimension. This allows significantly reduced counting times for measurements of lateral correlations parallel to an interface or in a thin film where limited depth resolution is required. We resolve the structure factor of iron inclusions in aluminium oxide and show that the ordering of silica particles deposited on a silicon substrate depends on their size. We report hexagonal packing for 50 nm but not for 200 nm silica spheres deposited by a modified Langmuir-Schaefer method on a silicon substrate. For the 200 nm particles we extract the particles shape from the form factor. Moreover, we report dense packing of the particles spread on a free water surface. We name this method π-GISANS to highlight that it differs from GISANS as it gives lateral information while averaging the in-depth structure.

Helicenes at Air/Water Interface: Spreading Film and Metal Ion Induced a Helical Ring Nanostructure.

Two enantiomeric hydrohelicenes containing a hydroxyl group and a π-conjugated nonplanar structure are assembled at the air/water interface. These molecules are found to form spreading films with well-defined surface pressure-area isotherms. Upon transferring the spreading film onto the mica surface, porous nanostructures are observed. The spreading film can be transferred onto solid substrates by the Langmuir-Schaefer (LS) method and the transferred LS films display optical activity as revealed by the circular dichroism (CD) spectra. The P- and M-hydrohelicene enantiomers showed mirrored CD spectra, suggesting that the chirality of the LS films was controlled by molecular chirality. When these molecules are spread on the aqueous solution containing metal ions such as Ag+, Cu2+, and Zn2+, a clear twisted ring nanostructure, which is similar to the Möbius strip, is observed. It is suggested that the interaction between the hydroxyl groups of helicenes and metal ions induced such a ring nanostructure.

Nano-sheets of two-dimensional polymers with dinuclear (arene)ruthenium nodes, synthesised at a liquid/liquid interface

We developed a new class of mono- or few-layered two-dimensional polymers based on dinuclear (arene)ruthenium nodes, obtained by combining the imine condensation with an interfacial chemistry process, and use a modified Langmuir–Schaefer method to transfer them onto solid surfaces. Robust nano-sheets of two-dimensional polymers including dinuclear complexes of heavy ruthenium atoms as nodes were synthesised. These nano-sheets, whose thickness is of a few tens of nanometers, were suspended onto solid porous membranes. Then, they were thoroughly characterised with a combination of local probes, including Raman spectroscopy, Fourier transform infrared spectroscopy and transmission electron microscopy in imaging and diffraction mode.

Properties of Langmuir and immobilized layers of betulin diphosphate on aqueous solutions of zinc sulfate and on the surface of zinc oxide nanoparticles

This work examines the specific features of interaction of betulin diphosphate (BDP), exhibiting antitumor and wound-healing properties, with zinc cations during its immobilization on ZnO nanoparticles. The properties of Langmuir and transferred BDP monolayers from an aqueous subphase of zinc sulfate onto the surface of a solid substrate (CaF2, quartz) by the Langmuir—Schaefer method are investigated using IR and UV spectroscopy. It is shown that there is a twofold increase of the molecular area in the immobilized layers, while the compressibility modulus decreases by a factor of 1.5. Zinc oxide nanoparticles with immobilized BDP 10–20 nm in size (surface concentration of BDP is 100 mg g−1) retain the original hexagonal wurtzite structure. The efficiency of betulin diphosphate immobilized on the surface of zinc oxide nanoparticles is demonstrated in in vivo experiments for burn wounds in rats.

Ultrathin Langmuir–Schaefer films of slipped-cofacial J-type phthalocyanine dimer: Supramolecular organization, UV/Vis/NIR study and nonlinear absorbance of femtosecond laser radiation

Based on a comprehensive theoretical and experimental approach, a low-defect thin film of stable dimeric phthalocyanine zinc complex (bis-[2-hydroxy-9(10),16(17), 23(24)-tri-tert-butylphthalocyanine]zinc – J-[OHPctZn]2) was prepared. It is shown that the dye forms stable amorphous edge-on monolayers at the air/water interface with an insignificant content of cylindrical 3D aggregates. These floating layers keep their structure when transferred by the Langmuir-Schaefer method onto a solid substrate, demonstrating a tendency towards ordered H-aggregation with preserving their linear molecular properties. Mixed two- and three-photon absorption of femtosecond laser pulses (280 fs) was firstly detected on this sample, as well as the ability of a material to the nonlinear attenuation of the intense irradiation, which is important for optical limiting.

Unmodified Clay Nanosheets at the Air-Water Interface.

Quasi-two-dimensional (2D) nanolayers, such as graphene oxide or clay layers, adhere to gas–liquid or liquid–liquid interfaces. Particularly, clays are of wide general interest in this context because of their extensive and crucial use as Pickering emulsion stabilizers, as well as for their ability to provide colloidosome capsules. So far, clays could only be localized at oil–water or air–saline-water interfaces in aggregated states, while our results now show that clay nanosheets without any modification can be located at air–deionized-water interfaces. The clay mineral used in the present work is synthetic fluorohectorite with a very high aspect ratio and superior quality in homogeneity and charge distribution compared to other clay minerals. This clay mineral is more suitable for achieving unmodified clay anchoring to fluid interfaces compared to other clay minerals used in previous works. In this context, we studied clay nanosheet organization at the air–water interface by combining different experimental methods: Langmuir–Blodgett trough studies, scanning electron microscopy (SEM) studies of film deposits, grazing-incidence X-ray off-specular scattering (GIXOS), and Brewster angle microscopy (BAM). Clay films formed at the air–water interface could be transferred to solid substrates by the Langmuir–Schaefer method. The BAM results indicate a dynamic equilibrium between clay sheets on the interface and in the subphase. Because of this dynamic equilibrium, the Langmuir monolayer surface pressure does not change significantly when pure clay sheets are spread on the liquid surface. However, also, GIXOS results confirm that there are clay nanosheets at the air–water interface. In addition, we find that clay sheets modified by a branched polymer are much more likely to be confined to the interface.

Encapsulation of Graphene in the Hydrophobic Core of a Lipid Bilayer.

Theoretical simulations have predicted that a lipid bilayer forms a stable superstructure when a sheet of graphene is inserted in its hydrophobic core. We experimentally produced for the first time a lipid–graphene–lipid assembly by combining the Langmuir–Blodgett and the Langmuir–Schaefer methods. Graphene is sandwiched and remains flat within the hydrophobic core of the lipid bilayer. Using infrared spectroscopy, ellipsometry, and neutron reflectometry, we characterized the superstructure at every fabrication step. The hybrid superstructure is mechanically stable and graphene does not disturb the natural lipid bilayer structure.

Refined Structure of Langmuir Lysozyme Films on Single-Crystal Silicon Wafers According to X-Ray Reflectivity Data

Thin lysozyme films on single-crystal silicon wafers have been studied by X-ray reflectivity. The films have been formed using the modified Langmuir–Schaefer method with potassium chloride as a precipitant. A layered model of the structure of the investigated films based on the calculated electron density distribution in a lysozyme molecule is proposed. It is shown that the model obtained in this way allows one to refine the structure of investigated films when processing reflectivity data.

Ultra-thin film sensors based on porphyrin-5-ylphosphonate diesters for selective and sensitive dual-channel optical detection of mercury(II) ions

Reusable dual-channel optical sensors for Hg2+ ions were prepared by Langmuir-Schaefer (LS) method from amphiphilic (trans-A2)BC-type porphyrins functionalized at meso-positions of the tetrapyrrolic macrocycle by sterically demanding diethoxyphosphoryl and mesityl groups as well as electron donating RO, RS or RNH substituents (R = n-C8H17). These three novel amphiphilic porphyrin derivatives were synthesized in good yields and their floating films at the air⎯water interface were investigated. In these monolayers, porphyrin molecules display a slipped stack-of-card orientation, but their strong π stacking is prohibited by bulky diethoxyphosphoryl and mesityl groups. The heteroatom substituent plays a key role in the molecular organization of the monolayers because it can participate in intermolecular hydrogen bonding, which influences the monolayer structure. Sensing properties of the porphyrins organized in Langmuir monolayers differ from those in the solution environment. Selective spectrophotometric detection of Hg2+ ions by these floating films is observed because interfering Cu2+, Zn2+, Cd2+, and Pb2+ ions are coordinated to donor centers located at the periphery of the macrocycle. Transfer of these floating films onto a polyvinyl chloride surface by LS technique affords perforated multilayer films with a tight molecular coverage of the solid support. The effect of the heteroatoms on the organization of these films was demonstrated by scanning electron microscopy (SEM) and electrochemical impedance spectroscopy (EIS). Both absorption and emission studies provide a strong evidence that chromophore-chromophore interactions are rather weak in these LS films. Binding of mercury(II) ions by the films and the regeneration of the sensors were explored visually and using reflection absorbance and fluorescence spectroscopies and then confirmed by X-ray fluorescence analysis. Detection limit of these selective and reusable dual-channel (absorbance and fluorescence) thin-film sensors is about 10−8 M (2 ppb), that corresponds to the action level for Hg2+ ions in drinking water recommended by the U.S. Environmental Protection Agency (EPA).

Circularly Polarized Luminescence of Langmuir–Schaefer Films of Amphiphilic Stilbene Enhanced via Interfacial Reaction with Cyclodextrins

Two enantiomeric amphiphiles containing the stilbene moiety (l-StG and d-StG) were assembled into ordered Langmuir-Schaefer (LS) films through the air/water interface and their circularly polarized luminescence (CPL) was investigated. When the molecules were spread at the air/water interface, a monolayer with nanofiber structures was formed, which could be subsequently transferred onto solid substrates by the LS method. The LS films showed both circular dichroism (CD) and CPL, whose handedness was determined by the molecular chirality of the amphiphiles. When the amphiphilic molecules were spread on the aqueous subphases containing cyclodextrins (including α-CyD, β-CyD, or γ-CyD), similar nanofiber-featured films were formed. However, the CD and CPL showed different changes. When l-StG was spread on the cyclodextrins, both CD and CPL were enhanced. When d-StG was reacted with cyclodextrins, the CD signal decreased while the CPL was enhanced. It was suggested that the chirality cooperation and conflict between the point chirality from the amphiphilic stilbene and the cavity chirality of cyclodextrin led to the phenomenon. However, in any case, the immobilization of the stilbene by the cyclodextrins caused the enhancement of CPL.

Langmuir-Scheaffer Technique as a Method for Controlled Alignment of 1D Materials.

A widely applicable method for aligning 1D materials, and in particular carbon nanotubes (CNTs), independent of their preparation would be very useful as the growth methods for these materials are substance-specific. Langmuir-Schaefer (LS) deposition could be such an approach for alignment, as it aligns a large number of 1D materials independently of the desired substrate. However, the mechanism and required conditions for alignment of 1D nanomaterials in a Langmuir trough are still unclear. Here we show, relying on numerical simulations of the Langmuir film compression, that the LS method is a powerful tool to achieve maximal alignment of 1D material in a controllable manner. In particular, 1D materials terminated with a suitable surfactant can align only if the velocity induced by the attraction between individual 1D entities is low enough relative to the flow speed. To validate this model, we achieved an efficient LS alignment of single-walled carbon nanotubes covered with a suitable surfactant relying on the numerical simulations. In situ polarized Raman microspectroscopy during the compression of Langmuir film revealed good quantitative agreement between the numerical simulations and the experiment. This suggests the applicability of the LS technique as a versatile method for the controlled alignment of 1D materials.

Heavy Metal Ion Sensing Using Ultrathin Langmuir–Schaefer Film of Tetraphenylporphyrin Molecule

The exciting properties of porphyrin molecules can be employed for several applications like sensing, catalysis, photovoltaics and energy related fields. The assemblies of the molecules at interfaces can give rise to some unique physicochemical properties which can enhance the device performance. In this article, we report our studies on heavy metal ion sensing in aqueous medium using ultrathin film of tetraphenylporphyrin (TPP) molecules. The TPP molecules were synthesized and used for forming Langmuir monolayer at the air-water interface. The monolayer was transferred onto solid substrates by Langmuir-Schaefer (LS) method at different target surface pressure of deposition ( $\pi _{\text {T}}$ ). The morphological analysis of the films indicated supramolecular assembly of the molecules in the LS film deposited at $\pi _{\text {T}}={30}$ mN/m. The LS films of TPP molecules were employed for sensing heavy metal cations viz. Pb2+, Hg2+, Co2+ and Cd2+ from the aqueous medium by measuring piezoresponse from a quartz crystal microbalance. The sensing performance was found to be the best with LS film deposited at $\pi _{\text {T}}={30}$ mN/m. The sensitivity towards Pb2+ ion is found to be the highest. The sensing of the heavy metal cations using randomly oriented TPP molecules in spin coated thin film was found to be much inferior as compared to that of LS films of the molecule. The enhanced sensing performance by the LS film of TPP molecules may be attributed to the supramolecular assembly of the molecules. We report that the interference of the sensing measurement for the recognition of Cd2+ and Pb2+ ions is least and thus these species can be detected selectively with less errors. The cation species recognition features obtained from scanning electron microscope images and Raman spectroscopy were found to be remarkably different and therefore these cationic heavy metal species can be selectively detected using the LS film of TPP.