Induced Collapse in the Formation of Alternating Langmuir–Blodgett Films

Two compounds whose molecules have large dipole moments, strereoregular perfluorinated alkylmethacrylate-co-methacrylic acid (A) and p-octadecylaminoazobenzene-p"-sulfamide (B), were used to assemble Langmuir–Blodgett polar films by the alternating method to achieve high polarization. According to estimates, the dipole moment of the dimeric unit of copolymer A is equal to about 4 D, the dipole moment of compound B, to 12 D. Unusually high (several units) transfer ratio was observed for the monolayer B when preparing the structures of (AB) _n type. The monolayers were stable during their formation process. Upon the pause of a substrate when passing through the monolayer B, the monolayer area remained strictly constant. According to the model proposed, the monolayer looses its stability and locally collapses in the meniscus zone at the contact line of the monolayer B and substrate due to an increase in the electrostatic repulsion between the dipoles of molecules B. The validity of this model is confirmed by the data of small-angle X-ray diffraction and atomic force microscopy for various alternating Langmuir–Blodgett films.     

Monolayers and Langmuir–Blodgett films of amphiphilic tetramethylsulphonatocalix[4]resorcinarene and their interactions with polyethyleneimine and caeruloplasmin

The paper deals with the surface films of amphiphilic tetramethylsulphonatocalixresorcinarene (R = C₁₁H₂₃) 1 insoluble in water but forms rigid stable non-collapsing films at the water–air interface. Compression isotherms were used to investigate the interactions of the macrocycle films with two polymers fed to the aqueous subphases: synthetic – polyethyleneimine (PEI) and natural – an oxidase enzyme caeruloplasmin (CP). The interactions of the surface films of 1 with these substrates are predominantly dictated by the nature of the macromolecules and not by macrocycle interactions with their individual fragments. CP having retained its globular structure was extracted in the layer of 1 and became the dominating component of the film. The synthetic macromolecule of PEI, six times lower in its weight than CP, did not affect the morphology of the interfacial film, involved in the interactions only with its hydrophilic part directed inside the water.     

Interactions between Langmuir–Blodgett Polymer Monolayers Studied with the Surface Force Apparatus

Langmuir–Blodgett monolayers from end-functionalized polyisoprene (PI–X) were studied in a surface force apparatus (SFA) as a model of a highly stretched brush melt. After deposition on a freshly cleaved mica, two identical brush monolayers (with surface area per molecule of about 170 Ų) were brought into adhesive contact in the SFA; then kinetic changes in the film thickness and the topography of the contact were continuously monitored. We observed spontaneous thinning of the brush melt bilayer. This effect can be attributed to the enhanced lateral motion of the sticking end-groups under the contact induced pressure. The possible model describing kinetic changes in the film thickness is presented. The behavior of the two opposing brush melts and a single brush monolayer in contact with two mica surfaces was compared. Molecular mechanisms involved in the rearrangements of brush melts are proposed for both systems.     

Fabrication and Efficient Acidichromism of Langmuir‐Blodgett Films of Azo Group‐Modified Phthalocyanines

Langmuir‐Blodgett thin films of the azo group‐modified phthalocyanines were successfully prepared, and the aggregated and acidichromic properties of their Langmuir‐Blodgett films were investigated.     

Microcrystalline domains of monolayer and multilayer BDN-SA Langmuir–Blodgett films

Monolayer and multilayer BDN(Bis(4-diethyannodithiobenzil)nickel)-SA(stearyl alcohol) LB (Langmuir–Blodgett) films were prepared and the characteristics of microcrystalline domains were studied using UV–vis.–NIR and AFM. The results indicate that BDN-SA LB films consist of numerous ball-like microcrystalline domains at size scales from a few tens to a few hundreds of nm. AFM images of a multilayer LB film show that well-ordered molecular arrangements exist on the surface of domains which resemble a mosaic structure. The relationship between the mean size of the domain of a BDN-SA LB film with the thickness of the film was also shown.     

Chirality-Controlled Self-Assembly of Amphiphilic Dibenzo[6]helicenes into Langmuir–Blodgett Thin Films

Racemic and highly enantioenriched 3-methoxycarbonyl, 3-carboxy, and 3-hydroxymethyl derivatives of dibenzo[6]helicene were prepared. The Langmuir layers of these helicenes were formed at the air–water interface and transferred onto solid substrates to afford Langmuir–Blodgett films, which were then studied by ambient atomic force microscopy and (chir)optical spectroscopy. Significant differences were found in the behaviour of the Langmuir layers as well as in the morphology, UV/Vis, electronic circular dichroism (ECD), and fluorescence spectra of the Langmuir–Blodgett thin films depending on the molecular chirality and nature of the polar group. The experimental results were supported by molecular dynamics simulations.     

In situ Coordination and Surface Morphology of Langmuir Films of Non－amphiphilic Dithizone with Metal Ions on Air／Water Interface

A spread Langmuir film on the air/water in-terface can serve as a basic model for the under-standing of organized molecular systems[1] .Gener-ally,it is considered that only those compoundsthat possess simultaneously a hydrophilic headgroup and a long- alkyl chain can be spread on theair/water interface[2— 4] .Therefore,researches onthe organized molecular films are mainly concernedwith typical amphiphiles.In order to expand thechoice in molecular film to form materials and omitthe tedious sy…     

Synthesis and photoreaction of Schiff bases derived from p-nitro cinnamaldehyde and diamines in Langmuir and Langmuir–Blodgett films

Monolayers of Schiff bases derived from ethylene diamine and o-phenylene diamine with p-nitro cinnamaldehyde, (compounds 1 and 2) at air/water interface have been studied. Photolysis of 1 in chloroform solution undergoes cis–trans isomerization on irradiation of white light while compound 2 does not undergo isomerization under photolytic conditions. The photolysis of 1 and 2 in Langmuir–Blodgett films (LB films) transferred to quartz plates form dimers. The change in product distribution is attributed to the influence of bridging group of the cinnamaldehyde moieties, molecular configuration and mobility of the compounds in solution, solid state and the aggregation of molecules in monolayer assemblies.     

Nonradiative energy transfer in mixed Langmuir monolayers and Langmuir–Blodgett films of compounds of different chemical composition and structure

Russian Chemical Bulletin - The efficiency of the Förster resonance energy transfer (FRET) in a monolayer film containing the energy donor and energy acceptor fluorophores is low since the...     

Composite Langmuir–Blodgett (LB) films of polyaniline and cadmium stearate

Composite monolayers of cadmium stearate and polyaniline processed with camphor sulphonic acid have been obtained at the air–water interface and subsequently transferred onto substrates as uniform Langmuir–Blodgett multilayers. Pressure–area (Π-A) isotherm studies indicated that polyaniline molecules are not squeezed out of the cadmium stearate matrix during compression or in the compressed state. Monolayer stability is seen to decrease when the polymer content is increased beyond 60% (in weight) which is probably associated with the formation of microaggregates that also affected the monolayer surface potential at large areas per molecule. With increasing amount of polyaniline in the mixture, a transition from Y-type to Z-type deposition has been observed. Transferred multilayer LB films were characterized by UV-vis, FTIR, XRD, surface potential, and dc electrical conductivity measurements. UV-vis results indicated that though the polyaniline was in the doped state in the spreading solution, the transferred films were in the emeraldine base state. FTIR studies revealed that the transferred films mainly contained cadmium stearate salt in addition to polyaniline. XRD results indicated that the stacking order is dependent on the polyaniline content in the composite films, the order was found to decrease upon increasing the polymer amount. The uniformity of transferred films was confirmed by surface potential studies. A possible packing arrangement in these composite Langmuir and Langmuir–Blodgett films has been proposed.     

Synthesis of Iron,Cobalt, Nickel,and Copper Hexacyanoferrates Nanoparticles Stabilized with Sodium Hexametaphosphate,and Their Use for Modification of Langmuir—Blodgett Films

Russian Journal of General Chemistry - Langmuir-Blodgett films were obtained on the basis of octadecylamine monolayers containing nanoparticles of various metals hexacyanoferrates. Nanoparticles...     

Optical,electrical, and thermochromic properties of polyazothiophene Langmuir–Blodgett films

The conductivity and luminescence of conjugated polymers may be combined with the photoisomerization capability of azobenzene materials to achieve unique properties for a variety of applications, particularly if conjugated polymers with azobenzene side chains are processed as nanostructured films. In this study, we report on Langmuir–Blodgett (LB) films of a polythiophene-bearing azobenzene moieties, which displayed photoluminescence, thermochromism, electroactivity, and photoinduced birefringence. The latter three properties were enhanced in the LB films, as compared to spin-coated films of the polyazothiophene, and this has been attributed to differences in film morphology that could be probed with atomic force microscopy.     

Langmuir–Blodgett films of octadecanethiol on gold sols subphase

An octadecanethiol monolayer was formed on an aqueous gold sols subphase, it’s LB films were characterized by means of π-A isotherms, TEM (transmission electron microscopy), XRD (X-ray diffraction) and UV–Vis spectroscopy.     

Interactions of α-Lactalbumin and Cytochrome c with Langmuir Monolayers of Glycerophospholipids

Interaction of cytochrome c (Cyt c), α-lactalbumin III (α-La III) with Langmuir monolayers of pure and mixed glycerophospholipids was investigated using surface pressure-area (Π-A) isotherms. The general trend was that maximum interaction between protein and phospholipid is observed for mixed (1:1 molar ratio) phospholipid monolayers. Interaction between the protein and the charged phospholipid films was found to be independent of global protein charge. Our data indicate that the proteins interact with the phospholipid films by inserting themselves into the monolayer rather than anchoring to the phospholipid head groups.     

Preparation and characterisation of monolayers and Langmuir–Blodgett films of liquid crystal mixed with cubic silsesquioxanes

Polyhedral oligomeric silesquioxanes (POSS) with eight polyether substituents were mixed with the liquid crystal (LC) 4-octyloxy-4′-cyanobiphenyl and spread at the air/water interface. The surface pressure-area and surface potential-area isotherms were recorded for different weight ratios of both components. The obtained results showed that POSS molecules had beneficial influence on LC monolayer improving its stability and rigidity. Moreover, it was found that some LC–POSS mixtures collapse reversibly and form multilayer films on the top of LC monolayer. On the other hand, interfacial dilatational and shear rheology indicated decrease of elasticity of the films after mixing. Brewster angle microscopy revealed multilayer structure of the condensed film and formation of net-like structures in the expanded film. These films were successfully transferred on solid substrates using the Langmuir–Blodgett technique. The scanning electron microscopy images confirmed the film deposition and formation of networks by POSS–LC mixtures. These findings may be useful in the fabrication of electronic devices based on LCs.     

Formation and tribological properties of composite Langmuir–Blodgett films of stearic acid with molybdenum disulfide and amorphous carbon

The morphology and tribological properties of Langmuir–Blodgett mono- and bilayers of stearic acid with particles of molybdenum disulfide (MoS₂) and amorphous carbon (С), prepared on silicon and steel substrates by horizontal deposition (stearic acid–MoS₂ and stearic acid–С monolayers) and by the “roll” technique (stearic acid–MoS₂/stearic acid–С bilayers), were studied. Incorporation of C and MoS₂ particles into the structure of a stearic acid film enhances its wear resistance by a factor of 2.8 and 5.5, respectively. The presence of MoS₂ and С particles and of their aggregates of size from ~220 nm to 16.3 μm in stearic acid layers was confirmed by atomic force microscopy.     

Effects of silver nanoparticles doping on morphology and luminescence behaviour of ferroelectric liquid crystals Langmuir–Blodgett films

We report the deposition of Langmuir–Blodgett (LB) thin films of low-weight dispersed composite systems of ferroelectric liquid crystals (FLCs)–functionalised silver (Ag) nanoparticles. Because of their amphiphilic nature the molecules form stable Langmuir monolayers, which were transferred to silicon substrates. We noticed that absorption wave numbers are present for each bond constituting FLC–nanoparticles composite system, ensuring a complete transfer of molecules from water sub-phase. XRD showed intense peaks at 2θ = 3.2° due to the layer structure of FLC molecules. We infer from the morphology of LB films that doping of nanoparticles do not provide any hindrance to SmC* layer structure of FLC molecules. The photoluminescence study indicates blue shift in emission spectra and peak intensity increases with Ag nanoparticles concentration.     

Effects of substrate on the melting behavior of Cd arachidate Langmuir–Blodgett films

Nineteen monolayered Cd arachidate films were deposited on float glass substrate coated with Si and Ni over-layers. Two layers have been chosen with very different surface free energies. Melting behavior of films were studied using variable temperature X-ray specular reflectivity and Fourier transform infrared spectroscopy measurements. In conformity with earlier studies, melting of the multilayer precede by a transition from distorted hexagonal to hexaticlike phase. However, the transition temperature to hexaticlike phase as well as the melting temperature depend significantly on the type of layer. Both the transition temperatures are higher for the multilayer deposited on Ni layer as compared to those for the film deposited on Si layer. These results can be understood in terms of different surface free energies of Ni and Si layers. Further, in case of Ni layer, transition to hexaticlike phase is relatively sharper. Even in the molten state there is a significant difference in the structure of the Cd arachidate film on two layers; packing density of molecules in molten state is lower in case of substrate with higher surface free energy. These results suggest that the surface free energy of substrate plays a significant role in melting behavior of Langmuir–Blodgett films.     

Electric Field-Controlled Synthesis and Characterisation of Single Metal–Organic-Framework (MOF) Nanoparticles

Achieving control over the size distribution of metal–organic-framework (MOF) nanoparticles is key to biomedical applications and seeding techniques. Electrochemical control over the nanoparticle synthesis of the MOF, HKUST-1, is achieved using a nanopipette injection method to locally mix Cu²⁺ salt precursor and benzene-1,3,5-tricarboxylate (BTC³⁻) ligand reagents, to form MOF nanocrystals, and collect and characterise them on a TEM grid. In situ analysis of the size and translocation frequency of HKUST-1 nanoparticles is demonstrated, using the nanopipette to detect resistive pulses as nanoparticles form. Complementary modelling of mass transport in the electric field, enables particle size to be estimated and explains the feasibility of particular reaction conditions, including inhibitory effects of excess BTC³⁻. These new methods should be applicable to a variety of MOFs, and scaling up synthesis possible via arrays of nanoscale reaction centres, for example using nanopore membranes.