Langmuir-Blodgett Research Articles

Structural and viscoelastic properties of floating monolayers of a pectinolytic enzyme and their influence on the catalytic properties

HypothesisThe catalytic activity of enzymes immobilized in self-assembly systems as Langmuir-Blodgett (LB) films is influenced by molecular interactions dictated by the composition and viscoelasticity of the previous floating monolayers. We believe that the insertion of carbon nanotubes (CNT) in mixed polygalacturonase/lipid monolayers may influence intermolecular interactions and viscoelastic properties, being then possible to tune system stability and rheological properties, driving catalytic properties of the films for biosensing. ExperimentsThe physicochemical properties of the monolayers were investigated by tensiometry, surface potential, Brewster angle microscopy, infrared spectroscopy, and dilatational rheology. The monolayers were transferred to solid supports LB films and characterized by atomic force microscopy, quartz crystal microbalance, and fluorescence spectroscopy. The catalytic activity of the LB films was verified by colorimetric assay. FindingsThe enzyme-CNT-lipid film had a catalytic activity at least twice as high as the pure enzyme owing to the synergy between the components, with the lipid acting as a protector matrix for the enzyme and the CNTs acting as an energy transfer facilitator. These results point to a proof-of-concept system, through which we can propose an alternative to achieve enhanced bio-inspired films with high control of the molecular architecture by using the LB approach.

Coating of Conducting and Insulating Threads with Porous MOF Particles through Langmuir-Blodgett Technique.

The Langmuir-Blodgett (LB) method is a well-known deposition technique for the fabrication of ordered monolayer and multilayer thin films of nanomaterials onto different substrates that plays a critical role in the development of functional devices for various applications. This paper describes detailed studies about the best coating configuration for nanoparticles of a porous metal-organic framework (MOF) onto both insulating or conductive threads and nylon fiber. We design and fabricate customized polymethylmethacrylate sheets (PMMA) holders to deposit MOF layers onto the threads or fiber using the LB technique. Two different orientations, namely, horizontal and vertical, are used to deposit MIL-96(Al) monolayer films onto five different types of threads and nylon fiber. These studies show that LB film formation strongly depends on deposition orientation and the type of threads or fiber. Among all the samples tested, cotton thread and nylon fiber with vertical deposition show more homogenous monolayer coverage. In the case of conductive threads, the MOF particles tend to aggregate between the conductive thread’s fibers instead of forming a continuous monolayer coating. Our results show a significant contribution in terms of MOF monolayer deposition onto single fiber and threads that will contribute to the fabrication of single fiber or thread-based devices in the future.

Lipid-matrix effects on tyrosinase immobilization in Langmuir and Langmuir-Blodgett films.

The immobilization of the enzyme tyrosinase (Tyr) in lipid matrices can be explored to produce biosensors for detecting polyphenols, which is relevant for the food industry. Herein, we shall demonstrate the importance of the lipid composition to immobilize the enzyme tyrosinase in Langmuir-Blodgett (LB) films. Tyr could be incorporated into Langmuir monolayers of arachidic acid (AA), 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and 1,2-dipalmitoyl-sn-glycero-3-phospho-(1'-rac-glycerol) (sodium salt) (DPPG), having as the main effect an expansion in the monolayers. Results from polarization-modulated infrared reflection-absorption spectroscopy (PM-IRRAS) pointed to electrostatic interactions between the charged residues of Try and the lipid headgroups, in addition to changes in the order of lipid chains. The interaction between Tyr and DPPC in Langmuir monolayers can be correlated with the superior performance of DPPC/Tyr LB films used as biosensors to detect catechol by cyclic voltammetry. The molecular-level interactions assessed via PM-IRRAS are therefore believed to drive an immobilization process for Tyr in the lipid LB matrix and may serve as a general criterion to identify matrices that preserve enzyme activity.

Micellar effect of CTAB on Phenol red sodium salt: A model system may be used for cell membrane study

This communication reports the effect of micelles on the molecular organisation of an anionic fluorescent dye Phenol Red Sodium salt (PRSS) in Langmuir-Blodgett (LB) film. PRSS is a water soluble anionic fluorescent dye generally used as a pH marker for cell tissue culture. Below and Above CMC of CTAB the spectral characteristics.Of PRSS molecules changes which confirms the interactions of the PRSS molecules with micelles of the CTAB. UV–vis absorption and fluorescence spectroscopic studies confirm this. So we can modified the spectral behavior of the PRSS molecules in solution as well as in LB films which may be useful as an indicator in different biological process.

A Numerical Approach for Space Charge Limited Bipolar Flow in Cylindrical diodes

In this paper, a numerical iteration approach to resolve the space charge limited (SCL) bipolar flow problem in cylindrical geometries has been developed. Such an approach is basis for the simultaneous determination of the unknown current densities and the potential distribution. We employed this method to study the characteristics of the SCL bipolar flow. By considering a cylindrical geometry with a cathode radius Rc and an anode radius Ra, the enhancement over the classical Langmuir-Blodgett (LB) law is investigated as a function of Rc/Ra. It is found that for the bipolar flow model, the SCL current density can be given by F×JLB, where F and JLB represent the enhancement factor on account of the influence of ions and the LB law, respectively. The enhancement factor F follows a Rc/Ra scaling and gradually converges to a constant with increasing Rc/Ra. The planar bipolar flow solution is recovered in the condition where the values of Rc and Ra are much greater than that of the gap spacing.

100 °C-Langmuir–Blodgett Method for Fabricating Highly Oriented, Ultrathin Films of Polymeric Semiconductors

The Langmuir-Blodgett (LB) and Langmuir-Schaefer techniques facilitate thermodynamic favorability at an air-water interface, at which nanoscale molecular aggregations can be manipulated by micrometer- or millimeter-scale mechanics. The customary use of an aqueous subphase has limitations in the available temperature and spread materials. We present a general strategy to replace the aqueous subphase with an inert, low-vapor-pressure liquid, ethylene glycol. As a representative spread material that requires high-temperature processes, a semicrystalline polymeric semiconductor was investigated. We successfully demonstrated that the polymeric semiconductor spreads homogeneously across the entire surface of ethylene glycol heated to 100 °C using an LB trough, and spontaneously forms multilayers. Comprehensive studies such as X-ray diffraction, optical spectroscopy, and charge transport measurements revealed that barrier compression of solid-state polymer thin films during a high-temperature LB process produced uniaxial alignment of the polymer main chain with an averaged dichroic ratio of about 8, by which the electron transport concomitantly became highly anisotropic. The LB method presented in this work could be used to deposit thin films under ultimate environments, e.g., below 0 °C or above 100 °C, minimizing the effects of the vapor pressure of the subphase.

The unique asymmetric nano-cluster formation by the uneven hockey-stick-shaped mesogen based on 1,3,4-oxadiazole in Langmuir–Blodgett thin film

Achiral Bent Core Mesogens (BCMs) are an exciting class of potentially useful material that catch special attention in the last decade. The newly synthetic compound 5-hexadecyloxy-2-[(E)-({4-[5-(4-octyloxyphenyl)-1,3,4-oxadiazol-2-yl] phenyl}imino)methyl]phenol, named as ABC, is a Schiff base derivative. Having both flexible hydrophobic and rigid hydrophilic part it shows a surface-active liquid crystalline property. This study is based on the Langmuir–Blodgett (LB) thin film fabricated with this molecule. The spectral study, showing intense bathochromic shift of characteristic peaks, reveals that the J-aggregation of molecules in the film in comparison to its solution. Atomic force microscopic (AFM) and scanning electron microscopic (SEM) images reveal the occurrence of unique unsymmetrical nano-size cluster formation in pure ABC thin film as well as mixed thin film with Behenic acid (BA) as supporting matrix.

Hydrodynamic Process in the Langmuir-Blodgett Film Method.

Preparing organic coatings in a very controlled manner through the spreading of organic molecules on the water surface is one of the emphases for research in Langmuir-Blodgett (LB) technology. For preparing a homogeneous film and improving the quality of the film, it is our concern to have a deeper understanding of the dynamic process involved in spreading. Here, we present an overview of the hydrodynamic process under the influence of assisting the spreading solvent, which mainly focuses on the mechanical mechanisms of related phenomena. A typical spreading experiment of two-component mixed droplets on water substrate for the purpose of preparing LB films was carried out in this research. We perform the spreading of a liquid of silicone oil and oleic acid mixture on the horizontal surface of another immiscible deep water substrate, where the volatile silicone oil is the assisting spreading solvent with low viscosity. We find that it needs to exceed a certain critical value (60% in our experiment) to achieve a uniform and centrosymmetric spreading process, which is a key factor for getting a homogeneous film. We observe that the evolution of a large droplet into liquid film and then into small droplets under the action of surface tension gradient in experiments. Gravity-viscous and surface tension-viscous dominate successively in the whole spreading process, with its spreading radius r(t) ∝ t1/4 and r(t) ∝ t3/4, respectively. However, we also obtain singular values of scaling exponents -0.033 and -0.180, which is attributed to nonuniform distribution of the Laplace pressure caused by different curvatures near the capillary wave.

Visual Luminescent Probes Constructed by Eu3+ Complex-Functionalized Silica Nanocomposites and Their Langmuir-Blodgett Films at Interfaces.

The trivalent europium ion (Eu3+) has garnered a great deal of interest for the design of luminescent materials possessing compound-independent emission bands, strong luminescent intensity, and long emission lifetimes. We herein introduce a synthetic methodology capable of constructing visual luminescent probes from Eu3+ complex-functionalized silica nanocomposites and their Langmuir-Blodgett (LB) films at interfaces. In order to facilitate the coordinative stabilization of Eu3+ over carrier surfaces, silica nanoparticles (nanoSiO2) were pregrafted with terpyridyl (TPy) to make nanoSiO2TPy linkers. Then, a well-designed coordination reaction of nanoSiO2TPy with EuCl3 and 2,6-pyridinedicarboxylic acid (DPA) was carried out at solid-liquid and air-water interfaces, where our desired material (denoted as nanoSiO2TPy@EuDPA) and its corresponding LB film are obtained. The presence of TPy and DPA interacting with Eu3+ plays a key role in regulating the chemical nature of the particle surface, hence giving rise to closely packed nanocomposite arrays in the film. As a result, the improvement in uniformity and stability is achieved alongside the enhancement in emission intensity and lifetime. With such advantageous optical properties, we find them workable as facile, green, and affordable luminescent sensors, by which a range of common toxic anions (Cr2O72-, MnO4-, and PO43-) can be visually and quantitatively recognized. Notably, the LB film-based material could afford a higher Ksv value (1.53 × 105 M-1), a lower detection limit (0.157 μM), and better recyclability than its original powder analogue, showcasing its utility as a more promising candidate for practical use.

Grafen Kaplı Kimyasal Sensörlerin Şişme Davranışları ve Matematiksel Modelleme

Bu çalışmada, grafen kaplı Langmuir-Blodgett (LB) ince filmlerin şişme davranışları Kuartz Kristal Mikrobalans (KKM) tekniği kullanılarak incelenmiştir. Bu filmler, bazı organik buharların (aseton, etanol ve metanol) difüzyon katsayı değerlerinin hesaplanması (Fick’in erken-zaman difüzyon kanunu kullanılarak) için oda sıcaklığında etkileşmeye bırakılmıştır. Difüzyon katsayı değerleri sırası ile aseton, etanol ve metanol için 20.43 x 10−16, 1.30 x 10−16 ve 0.91 x 10−16 cm2 s−1 olarak hesaplanmıştır. Benzer sıralama grafen kaplı KKM sensörünün tepkisi (frekans değişimi, Δf) için de aseton (342 Hz) > etanol (76 Hz) > metanol (51 Hz) olarak elde edilmiştir.

Fewer-layer conductive metal-organic Langmuir-Blodgett films as electrocatalysts enable an ultralow detection limit of H2O2

The detection of low-concentration hydrogen peroxide (H2O2) has important theoretical-significance and practical value in many fields, such as medical science, biological chemistry, and food safety inspection. Traditional commercial H2O2 test paper and detection technology can only reach the detection limit of 10−3–10−5 (mass fraction). In this paper, we report a simple method to prepare 2D MOF (metal-organic frameworks) [Co3(HOB)2]n films based on Langmuir-Blodgett (LB) method combined with layer-by-layer growth technique. Even 3-layer [Co3(HOB)2]n films can realize the lowest H2O2 detection limit of 1.05 × 10−8 wt% (3.08 nmol·L−1) based on the resultant 2D MOF catalyst. Meanwhile, density functional theory (DFT) calculations revealed that Co2+ ions of the LB films decreased the energy of [HOOH] transforming into [HO2] during the H2O2 reduction reactions, thus speeding up the decomposition of H2O2.

Development of a Schottky barrier diode using molecular network of 1-alkyl-2-(arylazo) imidazole prepared by Langmuir–Blodgett technique

In this paper we report the photophysical and electrical characteristics of our synthesized imidazole derivative namely l-alkyl-2-(arylazo) imidazole (AAI) organized in Langmuir-Blodgett (LB) films towards the development of organic Schottky barrier diode (SBD). Presence of long alkyl chain in the molecule make it suitable for LB technology and may favour aggregations of the molecules in LB films under barrier compression. The interfacial properties of the formation of Langmuir monolayer of AAI at air-water interface have been studied by surface pressure versus area per molecule (π-A) isotherm and compressibility modulus. Hysteresis study of the isotherm confirmed the formation of stable monolayer of AAI molecular assemblies at air-water interface. The aggregation of AAI molecules in LB films is confirmed by Ultraviolet–visible (UV–vis) absorption, fluorescence emission spectroscopy and Atomic force microscopic (AFM) methods. AAI molecules also formed network type morphology in LB films due to their closure association and aggregations or cluster of molecules which were evidenced by AFM technique. The compression induced aggregations of AAI is reflected as broadened nature of monomeric absorption band along with the emergence of a new absorption band at longer wavelength side for LB film deposited at surface pressure of 25 mN/m. The optical absorption bands of AAI and the corresponding transitions between different electronic states have been simulated by density functional theoretical (DFT) analysis and is compared with the experimental results. Nonlinear behaviour of the current-voltage characteristics and various relevant electrical parameters of the LB film device at the interface of metal electrode (gold) satisfy the necessary conditions showing the properties of a Schottky barrier diode.

Crystallization of Poly(ethylene)s with Regular Phosphoester Defects Studied at the Air-Water Interface.

Poly(ethylene) (PE) is a commonly used semi-crystalline polymer which, due to the lack of polar groups in the repeating unit, is not able to form Langmuir or Langmuir–Blodgett (LB) films. This problem can be solved using PEs with hydrophilic groups arranged at regular distances within the polymer backbone. With acyclic diene metathesis (ADMET) polymerization, a tool for precise addition of polar groups after a certain interval of methylene sequence is available. In this study, we demonstrate the formation of Langmuir/LB films from two different PEs with regular phosphoester groups, acting as crystallization defects in the main chain. After spreading the polymers from chloroform solution on the water surface of a Langmuir trough and solvent evaporation, the surface pressure is recorded during compression under isothermal condition. These π-A isotherms, surface pressure π vs. mean area per repeat unit A, show a plateau zone at surface pressures of ~ (6 to 8) mN/m, attributed to the formation of crystalline domains of the PEs as confirmed by Brewster angle and epifluorescence microscopy. PE with ethoxy phosphoester defects (Ethoxy-PPE) forms circular shape domains, whereas Methyl-PPE-co-decadiene with methyl phosphoester defects and two different methylene sequences between the defects exhibits a film-like morphology. The domains/films are examined by atomic force microscopy after transferring them to a solid support. The thickness of the domains/films is found in the range from ~ (2.4 to 3.2) nm depending on the transfer pressure. A necessity of chain tilt in the crystalline domains is also confirmed. Grazing incidence X-ray scattering measurements in LB films show a single Bragg reflection at a scattering vector qxy position of ~ 15.1 nm−1 known from crystalline PE samples.

Fabrication of picoline amide-based calix[4]arene Langmuir-Blodgett thin film for volatile organic vapor sensing application

Picoline amide-based calix[4]arene molecule was the first time deposited onto gold substrate as an active layer by using Langmuir-Blodgett (LB) coating technique. UV-visible, atomic force microscopy, and surface plasmon resonance (SPR) technique were used to control monolayer quality. The sensing properties were investigated by exposing the LB thin film to different percentage of organic VOCs vapors such as acetone, benzene, chloroform, ethyl acetate, and methanol in air-VOCs mixture. SPR results showed that this calix[4]arene molecule is a good candidate with a fast and reversible sensor response for VOCs sensing applications.

Graphenic substrates as modifiers of the emission and vibrational responses of interacting molecules: The case of BODIPY dyes.

Graphenic substrates (GS), such as reduced graphene oxide (rGO) and graphene oxide (GO), are 2D materials known for their unique physicochemical properties such as their ability to enhance vibrational spectroscopic signals and quench the fluorescence of adsorbed molecules. These properties provide an opportunity to develop nanostructured GS-based systems for detecting and identifying different analytes with high sensitivity and reliability through molecular spectroscopic techniques. This work evaluated the capacities of different GS to interact with a highly fluorescent compound, thereby changing its optical emission response (fluorescence quenching) and amplifying its vibrational signal, which is the base of graphene-enhanced Raman scattering (GERS). To test these properties, we used a derivative of highly fluorescent BODIPY (BP) compounds, which cover a wide range of applications from solar energy conversion to photodynamic cancer therapy. GS prepared by using the Langmuir-Blodgett (LB) technique allowed us to quench the fluorescence emission of BP and improve its Raman spectroscopy detection limit due to the GERS effect. These results were interpreted in light of the π-π interactions taking place between the Csp2 domains of GS and the aromatic core of the BP fluorophore.

Electrowetting on Langmuir-Blodgett films from epicuticular wax

Langmuir and Langmuir-Blodgett (LB) films were fabricated from epicuticular wax, that had been extracted from Vitis vinifera. For Langmuir films, the influence of subphase temperature on their structure was examined, whereas for LB films, the surface morphology at various temperatures and the effect of the layer number on electrowetting were investigated. Isotherms of surface pressure revealed no well-defined phase transition or collapse on Langmuir films at 22 °C, whereas Brewster angle microscopy showed that even before starting the compression procedure, there are platelets of epicuticular wax floating on the subphase. Those platelets give rise to the Langmuir films of epicuticular wax during compression. In contrast, for higher temperatures (40 °C and 50 °C), a well-defined phase transition was found – without epicuticular wax platelets, with a behavior close to those found in typical fatty acids. For LB films, atomic force microscopy images indicated a decreasing of roughness as a function of the subphase temperature as a result of greater organization of the epicuticular wax film. A significant modulation of about 20 ° (under applied voltage range of 0 to 100 V) was demonstrated of the electrowetting on LB films, which did not depend on the LB layer number. Our results suggest that epicuticular wax LB films have the potential for being applied in electrowetting-based devices. Furthermore, the Langmuir-Blodgett technique is feasible to fabricate films with various compositions focusing on the electrowetting.

Facile preparation of self-assembled black phosphorus-based composite LB films as new chemical gas sensors

In recent years, the researches on the modification and functionalization of black phosphorus (BP) materials have attracted more and more attention. In this study, few-layers BP nanosheets (BPNS) were prepared by a simple liquid exfoliation method. However, BPNS has the disadvantages of easy oxidation and poor stability, which will also affect the performance of BP. Therefore, 4-azidobenzoic acid was used to modify the BPNS to improve the stability of BP. In addition, 4-azidobenzoic acid modified BPNS (f-BPNS) and dye molecules can form a composite Langmuir-Blodgett (LB) film through electrostatic interaction or π-π stacking forces. UV–vis, Atomic force microscopy (AFM) and other characterizations were used to prove the successful preparation of the f-BPNS-dye composite LB film. It should be noted that the obtained uniform and dense composite films showed good sensitivity to acid and alkali gas. Moreover, the f-BPNS-dye composite films can still maintain high performance after 10 cycles of acid-alkali tests, indicating that the prepared films have high stability. This work provides a new direction for the preparation of new two-dimensional composite materials and their application in gas sensors.

Thermally Stable Nitrothiacalixarene Chromophores: Conformational Study and Aggregation Behavior.

Achieving high thermal stability and control of supramolecular organization of functional dyes in sensors and nonlinear optics remains a demanding task. This study was aimed at the evaluation of thermal behavior and Langmuir monolayer characteristics of topologically varied nitrothiacalixarene multichromophores and phenol monomers. A nitration/azo coupling alkylation synthetic route towards partially O-substituted nitrothiacalixarenes and 4-nitrophenylazo-thiacalixarenes was proposed and realized. Nuclear magnetic resonance (NMR) spectroscopy and X-ray diffractometry of disubstituted nitrothiacalix[4]arene revealed a rare 1,2-alternate conformation. A synchronous thermal analysis indicated higher decomposition temperatures of nitrothiacalixarene macrocycles as compared with monomers. Through surface pressure/potential-molecular area measurements, nitrothiacalixarenes were shown to form Langmuir monolayers at the air–water interface and, through atomic force microscopy (AFM) technique, Langmuir–Blodgett (LB) films on solid substrates. Reflection-absorption spectroscopy of monolayers and electronic absorption spectroscopy of LB films of nitrothiacalixarenes recorded a red-shifted band (290 nm) with a transition from chloroform, indicative of solvatochromism. Additionally, shoulder band at 360 nm was attributed to aggregation and supported by gas-phase density functional theory (DFT) calculations and dynamic light scattering (DLS) analysis in chloroform–methanol solvent in the case of monoalkylated calixarene 3. Excellent thermal stability and monolayer formation of nitrothiacalixarenes suggest their potential as functional dyes.

The effect of fullerene layer on the aggregates formation in amyloid beta Langmuir-Blodgett films

The investigation of the effect of carbon nanomaterials and lipids on the aggregation particularities of the amyloid beta/Aβ(1-42) layers is important for understanding the generation mechanism of neuronal disorder and how it can be inhibited. Additionally, amyloids are nanomaterials with a wide area of potential applications from nanotechnology to biotechnology. This paper presents a study about the preparation of Aβ(1-42) layer by two different methods, Langmuir-Blodgett (L-B) and drop cast (DC), on Si and Si covered by a layer of Buckminster fullerene, C60, and on the effect of fullerene layer or/and cholesterol (Ch) on the generation of Aβ(1-42) secondary structure forms, relevant for specific applications. AFM, SEM FTIR and Raman analysis offered details about the layer surface topography, morphology and particularities of the secondary structure generated in the process of Aβ(1-42) molecules aggregation. This study showed that the presence of Ch inhibited the formation of fibrils in Aβ(1-42) film deposited by L-B on Si covered by C60. The structures developed during aggregation were correlated with the topography and roughness of the films. The presence of Ch determined a decrease in roughness for L-B film and increase in roughness for DC film deposited on Si covered by C60 layer.

Langmuir, Raman, and electrical properties comparison of calixarene and calixarene-rGO using Langmuir Blodgett (LB) technique

A layered composites of calix[4]arene, namely, THC4-rGO, was produced from calix[4]arene-25,26,27,28-tetrol (THC4) and reduced graphene oxide (rGO) using the Langmuir–Blodgett (LB) technique. THC4 and rGO were prepared in a solution form first, then by using the LB technique to form LB films which were then deposited onto a quartz surface for Raman and electrical study. Langmuir property such as surface pressure-area (Π-A) isotherms of THC4 and rGO were used to study the intermolecular interactions at air–water interface. Raman spectroscopy was used to observe the crystallinity of the composites. The electrical properties by using four-point probe, i.e., I–V curves, resistivity, and conductivities of the rGO and THC4-rGO were analyzed to illustrate the enhanced properties. The results from this study can be utilized for the potential application of electronic sensors using calix[4]arene.