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Boundary conditions for catalyst performance in the conversion of common precursors such as N2, O2, H2O, and CO2 are governed by linear free energy and scaling relationships. Knowledge of these limits offers an impetus for designing strategies to alter reaction mechanisms to improve performance. Typically, experimental demonstrations of linear trends and deviations from them are composed of a small number of data points constrained by inherent experimental limitations. Herein, high-throughput experimentation on 14 bulk copper bimetallic alloys allowed for data-driven identification of a scaling relationship between the partial current densities of methane and C2+ products. This strict dependence represents an intrinsic limit to the Faradaic efficiency for C–C coupling. We have furthermore demonstrated that coating the electrodes with a molecular film breaks the scaling relationship to promote C2+ product formation., High-throughput experimentation on the reduction of CO2 on copper alloys led to the identification of a scaling relationship between CH4 and C2+ products that can be broken with an organic additive.

Epsilon-near-zero (ENZ) properties have been reported in organic molecular films. In particular, cyanine and squaraine films have been shown to exhibit ENZ properties in the visible spectral region with a strong 3rd order nonlinear optical response near the ENZ spectral region. Noting both cyanine and squaraine belong to the polymethine family, a series of six curcuminoid borondifluoride (Curc) derivatives were developed to examine whether such a polymethine character is positively correlated with the ENZ property of the organic films. Those Curc derivatives possess a Donor–Acceptor–Donor (D–A–D) architecture with acceptor, AcacBF2, located at the molecular center. The backbone of Curc is designed such that the donor strength can be tuned to transit between charge transfer (CT) and polymethine character. This balance between CT and polymethine character of the Curc series is examined based on the Lippert–Mataga plot. As donor strength in the D–A–D structure increases, CT character is less marked resulting in a more dominant polymethine character. The structural and optical properties of the Curc films with a thickness in the order of 30 nm were examined to correlate the polymethine character with the ENZ response. The results obtained in isotropic Curc thin films demonstrate that an increase of polymethine character associated with a stronger donor strength leads to an appearance/enhancement of the ENZ property in the visible spectrum range from 500 to 670 nm. Overall, this study provides useful guidelines to engineer new organic materials showing ENZ properties in a desired spectral range.

For the successful application of boundary lubrication, detailed investigations about the influence of preparation process on molecular films are needed. In this paper, a specially designed device was used for the film preparation. The scanning electron microscope (SEM) combined with atomic force microscope (AFM) was employed to characterize the surface morphology and nanotribological behavior of molecular films. After the liquid phase deposition, molecular films are randomly and densely distributed over Ti-doped diamond-like carbon (Ti-DLC) substrates. Through rigorous surface treatments, island-like molecular films were finally achieved on substrate surfaces. The surface friction of molecular films is obviously lower than that of Ti-DLC surfaces. Then, pin-on-disk tribotests were performed to study the macrofriction behavior of molecular films under different preparation parameters. Based on the orthogonal experiment, the effect of five preparation parameters (solution weight percent, smearing force and processing time of three smearing steps) on initial friction coefficient of molecular films was investigated. The results indicated that the order of significance levels is as follows: processing time of the second smearing step > solution weight percent > processing time of step 1 > processing time of step 3 > smearing force. For the purpose of friction reduction, the appropriate level ranges are 0.75% (Solution), 2.5 N–15 N (Force), 1 min–10 min (Step 1), 1 min–2 min (Step 2) and 1 min, 2 min, 5 min and 15 min (Step 3). The initial friction coefficient under the optimized conditions is around 0.112, and the equilibrium friction coefficient is around 0.162, which is lower than that of unlubricated Ti-DLC substrates.

Combining 2D materials with functional molecular films enables the fabrication of van der Waals bound organic/inorganic hybrids that are of interest for future device architectures. Recently, the 2D dielectric hexagonal boron nitride (hBN) has received particular attention since exfoliation allows the preparation of crystalline layers which have been utilized as ultrathin dielectrics in electronic devices. Here, we have studied the formation and structure of molecular films of the prototypical organic semiconductors pentacene (PEN) and perfluoropentacene (PFP) on hBN. Special attention was paid to the influence of substrate surface defects on the film formation by comparing molecular films that were grown on hBN substrates of various quality, including single crystals (representing the most ideal surface), briefly ion bombarded substrates, and exfoliated flakes. While X-ray diffraction (XRD) yields precise information about the crystalline structure of films grown on (large) single crystals, it is hardly applicable to analyze the films formed on exfoliated flakes because of their small size. Here, we demonstrate that in the case of flakes detailed structural analyses of the molecular films are possible by combining atomic force microscopy (AFM) with microspot UV/vis spectroscopy and optical polarization microscopy. On well-ordered hBN single crystal surfaces both acenes form very smooth and epitaxial crystalline films where molecules adopt a recumbent orientation (even in 100 nm thick films). By contrast, both materials adopt an upright molecular orientation and different polymorphs on defective hBN surfaces and reveal distinctly different film morphologies. On exfoliated flakes, PFP shows a film structure similar to that on the hBN single crystals, while PEN films exhibit a structure as on defective hBN substrates. In addition, a pronounced decoration of defect steps, which are probably created by the exfoliation process, was observed for PEN leading to the formation of tall and extended fibers where molecules adopt a recumbent orientation. The present study reveals different robustness in film growth on exfoliated hBN flakes for various molecules, which has to be considered in their device integration, especially with regard to their optoelectronic properties such as light absorption or charge transport, which depend critically on the molecular orientation and crystalline order.

Holographic grating recording and relaxation is studied in different azobenzene molecular glassy films by circularly orthogonally polarized 532 nm laser beams L and R. The readout was made by circularly polarized (R or L) 632.8 nm laser beam. Sandwich-type samples (glass-film-glass) were also studied. Maximum diffraction efficiency of 81% has been achieved in sandwich-type AR-173 film. The following relaxation features have been found: after reaching diffraction efficiency (DE) maximum no DE decay took place; DE read out by R-polarized beam was always higher than that by L-polarized beam; in sandwich-type samples DE decayed until zero when read out by R-polarization whereas DE was zero when read out by L-polarization. 50% relaxation times varied from 4 to 44 minutes, and they mainly decreased when grating period was increased. The observed relaxation peculiarities can be understood if one assumes that volume birefringence grating (VBG) is recorded followed by volume density grating (VDG) and surface relief grating (SRG) recording. R-polarization "feels" all gratings whereas L-polarization only VDG and SRG. At large exposures VDG and SRG dominate. These results confirm the conclusion made by J.Mikelsone in her 2018 PhD thesis that birefringence grating recording in azobenzene materials is a neccessary condition for SRG appearance.

Perovskite solar cells, as an emerging high-efficiency and low-cost photovoltaic technology1–6, face obstacles on their way towards commercialization. Substantial improvements have been made to device stability7–10, but potential issues with lead toxicity and leaching from devices remain relatively unexplored11–16. The potential for lead leakage could be perceived as an environmental and public health risk when using perovskite solar cells in building-integrated photovoltaics17–23. Here we present a chemical approach for on-device sequestration of more than 96 per cent of lead leakage caused by severe device damage. A coating of lead-absorbing material is applied to the front and back sides of the device stack. On the glass side of the front transparent conducting electrode, we use a transparent lead-absorbing molecular film containing phosphonic acid groups that bind strongly to lead. On the back (metal) electrode side, we place a polymer film blended with lead-chelating agents between the metal electrode and a standard photovoltaic packing film. The lead-absorbing films on both sides swell to absorb the lead, rather than dissolve, when subjected to water soaking, thus retaining structural integrity for easy collection of lead after damage. Using lead-absorbing materials to coat the front and back of perovskite solar cells can prevent lead leaching from damaged devices, without affecting the device performance or long-term operation stability.

Ultrathin molecular films deposited on a substrate are ubiquitously used in electronics, photonics, and additive manufacturing methods. The nanoscale surface instability of these systems under uniaxial compression is investigated here by molecular dynamics simulations. We focus on deviations from the homogeneous macroscopic behavior due to the discrete, disordered nature of the deformed system, which might have critical importance for applications. The instability, which develops in the elastoplastic regime above a finite critical strain, leads to the growth of unidimensional wrinkling up to strains as large as 0.5. We highlight both the dominant wavelength and the amplitude of the wavy structure. The wavelength is found to scale geometrically with the film length, λ∝L, up to a compressive strain of ε≃0.4 at least, depending on the film length. The onset and growth of the wrinkling under small compression are quite well described by an extended version of the familiar square-root law in the strain ε observed in macroscopic systems. Under large compression (ε≳0.25), we find that the wrinkling amplitude increases while leaving the cross section nearly constant, offering a novel interpretation of the instability with a large amplitude. The contour length of the film topography is not constant under compression, which is in disagreement with the simple accordion model. These findings might be highly relevant for the design of novel and effective wrinkling and buckling patterns and architectures in flexible platforms for electronics and photonics.

Mitigating molecular contamination during the assembly, integration, and testing of space systems requires quantitative and qualitative methods to detect the presence of molecular films on sensitive surfaces. Atomic layer deposition (ALD) is a self-limiting deposit of a variety of films layer by layer in the vapor phase on multiple types of substrates. The controlled layer-by-layer deposition enables the user to change orientation, morphology, and grain size in films, which directly impacts optical and electronic responses. In this study, the authors demonstrate the ability to use ALD-grown metal oxide thin films coupled with a Raman spectrometer to provide early detection of molecular films on witness surfaces during the assembly, integration, and testing of space flight hardware.

The use of metallosurfactants to prevent pitting corrosion of aluminum surfaces is discussed based on the behavior of the metallosurfactants [ZnII (LN2O2 )H2 O] (1) and [GaIII (LN2O3 )] (2). These species were deposited as multilayer Langmuir-Blodgett films and characterized by IR reflection absorption spectroscopy and UV/Vis spectroscopy. Scanning electron microscopy images, potentiodynamic polarization experiments, and electrochemical impedance spectroscopy were used to assess corrosion mitigation. Both metallosurfactants demonstrate superior anticorrosion activity due to the presence of redox-inactive 3d10 metal ions that enhance the structural resistance of the ordered molecular films and limit chloride mobility and electron transfer.

Here we report molecular films terminated with diazonium salts moieties at both ends which enables single-molecule contacts between gold and silicon electrodes at open circuit via a radical reaction. We show that the kinetics of film grafting is crystal-facet dependent, being more favorable on ⟨111⟩ than on ⟨100⟩, a finding that adds control over surface chemistry during the device fabrication. The impact of this spontaneous chemistry in single-molecule electronics is demonstrated using STM-break junction approaches by forming metal-single-molecule-semiconductor junctions between silicon and gold source and drain, electrodes. Au-C and Si-C molecule-electrode contacts result in single-molecule wires that are mechanically stable, with an average lifetime at room temperature of 1.1 s, which is 30-400% higher than that reported for conventional molecular junctions formed between gold electrodes using thiol and amine contact groups. The high stability enabled measuring current-voltage properties during the lifetime of the molecular junction. We show that current rectification, which is intrinsic to metal-semiconductor junctions, can be controlled when a single-molecule bridges the gap in the junction. The system changes from being a current rectifier in the absence of a molecular bridge to an ohmic contact when a single molecule is covalently bonded to both silicon and gold electrodes. This study paves the way for the merging of the fields of single-molecule and silicon electronics.

Crown-ether (CR) ring molecules are known as host molecules for capturing guest species inside the ring. So far CR molecular films have only been grown by drop-casting a CR solution on an inert sub...

An elastic recoil detection analysis (ERDA) system in air for hydrogen analysis was developed in the Wakasa Wan Energy Research Center. This system uses a thin silicon–nitride window to separate the air and vacuum regions, and the beam is irradiated through the window. Elements scattered by the beam enter the vacuum region through the same window, and are detected by an ERDA detector located there. The hydrogen sensitivity of the system was investigated by analyzing high molecular films. We used a helium beam and a stopper foil in front of the ERDA detector to ensure that only hydrogen was detected. Hydrogen energy spectra for the high molecular films and background were obtained.

Various electrooptic and magnetooptic effects enable the electric and magnetic field control of the holographic information recording. They can become significant if the frequency of light irradiation is close enough to the absorption line of a material. In this paper, these effects are theoretically considered, and the influence of applied external electric (up to 17 kV/cm) as well as magnetic field (0.15T) is experimentally studied on the transmission holographic grating recording in azobenzene-based molecular films at 632.8 and 532 nm. Recording beam polarizations were s-s, p-p, L-L and L-R . Self-diffraction efficiency (SDE) exposure time dependences were measured with and without the applied fields, and maximum SDE values as well as recording energies corresponding to 0.017% SDE were determined. No effect of electric field was found within the measurement accuracy (1-5%). Some trend to recording efficiency increase by magnetic field was observed. This result is in the agreement with the theoretical analysis. Unfortunately, these results are within experimental errors (usually 15-24%).

The atomic composition of films of a polyphenol antioxidant, namely, resveratrol (RVL), with a thickness of up to 50 nm thermally deposited on an oxidized silicon surface is studied by the method of X-ray photoelectron spectroscopy (XPS). It is found that the surface area of pores in the RVL film is about 15% of the total surface area. The results of studying the stability of the RVL films when their surface is treated with Ar+ ions of 3 keV under the electric current of 1 μA passing through the sample for 30 s are given. The treatment gives rise to an increase in the area of pores to 30–40%, while the ratio of the concentration of C atoms to the concentration of O atoms in the RVL film both before and after the treatment of the surface with ions does not correspond to the chemical formula of RVL molecules. Using the method of atomic force microscopy (AFM) in contact mode with a scanning area size of about 10 × 10 μm, RVL coatings deposited on the oxidized silicon and polycrystalline Au surfaces are studied. It is found that the RVL films produce grainy and porous coatings on the substrate surfaces. The typical size of grains in the sample surface plane is 150–300 nm, and the characteristic elevation reaches 30 nm.

Purpose This paper aims to evaluate the inhibitive effect and adsorption behavior of the 2-amino-5-thiol-1,3,4-thiadiazole vanillin (A) on copper in 3 per cent NaCl solution. Design/methodology/approach A thiazole Schiff bases were synthesized, named, 2-amino-5-thiol-1,3,4-thiadiazole vanillin (A), which was fabricated respectively on copper surface by the molecular self-assembled. Evaluation was carried out by electrochemical measurement and surface analysis techniques. Measurement of static friction coefficient scanning electron microscopy and Contact angle analysis were applied, and it is finally confirmed the existence of the adsorbed film. The inhibitive mechanism of A was evaluated by means of quantitative calculation and molecular dynamics simulation. Findings The electrochemical measurement indicated that the self-assembled molecular film can effectively inhibit the corrosion of copper sheet, when the concentration was 15 mmol⋅L−1 and the assembly time was 6 h, the corrosion inhibition effect was the best, reaching as high as 97.5 per cent. Scanning electron microscopy results showed that the Schiff base compound forms a protective film on the surface of the copper, which effectively blocks the transfer of corrosion particles to the metal substrate, thereby inhibiting the occurrence of corrosion. Adsorption behavior of A followed the Langmuir’s adsorption isotherm and attributed to mixed-type adsorption. The results of Quantitative calculation and molecular dynamics simulation showed that A was adsorbed on Cu (111) surface in parallel. Research limitations/implications In this study, the corrosion inhibition properties of Schiff base film were investigated by combining theory with experiment. Theoretical calculation is helpful to guide the synthesis of efficient and environmentally friendly corrosion inhibitors. Practical implications The damage caused by metal corrosion is great. The self-assembled Schiff base membrane synthesized in this paper is simple and compact, and the corrosion inhibition efficiency of copper in 3 per cent NaCl solution is 97.5 per cent. Social implications Inhibition of metal corrosion can better save energy and reduce economic losses. Originality/value The synthesized Schiff base was prepared on the copper surface by the molecular self-assembled. The Schiff base membrane has a good corrosion inhibition effect on copper in 3 per cent NaCl solution, and the corrosion inhibition efficiency is up to 97.5 per cent.

Spin selectivity in photo-emission from ferromagnetic substrates functionalized with chiral organic films was analyzed by ultraviolet photoelectron spectroscopy at room temperature. Using radiation with photon energy greater than the ionization potential of the adsorbed molecules, photoelectrons were collected that originated from both underlying ferromagnetic substrates and the organic films, with kinetic energies in the range of ca. 0-18 eV. We investigated chiral organic films composed of self-assembled monolayers of α-helical peptides and electrostatically adsorbed films of the protein, bovine serum albumin, with different α-helix and β-sheet contents. Ultraviolet photoelectron spectral widths were found to depend on substrate magnetization orientation and polarization, which we attribute to helicity-dependent molecular ionization cross sections arising from photoelectron impact, possibly resulting in spin-polarized holes. These interactions between spin-polarized photoelectrons and chiral molecules are physically manifested as differences in the measured photoionization energies of the chiral molecular films. Substrate magnetization-dependent ionization energies and work function values were deconvoluted using surface charge neutralization techniques, permitting the measurement of relative spin-dependent energy barriers to transmission through chiral organic films.

Halogen bonding mediated electrochemical anion sensing has very recently been established as a potent platform for the selective and sensitive detection of anions, although the principles that govern binding and subsequent signal transduction remain poorly understood. Herein we address this challenge by providing a comprehensive study of novel redox-active halogen bonding (XB) and hydrogen bonding (HB) ferrocene-isophthalamide-(iodo)triazole receptors in solution and at self-assembled monolayers (SAMs). Under diffusive conditions the sensory performance of the XB sensor was significantly superior. In molecular films the XB and HB binding motifs both display a notably enhanced, but similar, response to specific anions. Importantly, the enhanced response of these films is rationalised by a consideration of the (interfacial) dielectric microenvironment. These effects, and the resolved relationship between anion binding and signal transduction, underpin an improved fundamental understanding of anion sensing at redox-active interfaces which will benefit not just the development of more potent, real-life relevant, sensors but also new tools to study host–guest interactions at interfaces., Surface enhancement effects in the sensing of anions at redox-active molecular films are investigated in detail and rationalised based on a consideration of the dielectric binding microenvironment.

Molecules are fascinating candidates for constructing tunable and electrically conducting devices by assembling either single or ensemble of molecules between two electrical contacts followed by current-voltage (I-V) analysis which is often termed 'molecular electronics'. Recently, there has been also an upsurge of interest in spin-based electronics or spintronics across the molecules offering an additional scope to create ultra-fast responsive devices with less power consumption and lower heat generation using the intrinsic spin property rather than electronic charge. Researchers have been exploring this idea of utilizing organic molecules, organometallics, coordination complexes, polymers, and biomolecules (proteins, enzymes, oligopeptides, DNA) in integrating molecular electronics and spintronics devices. Although several methods exist to prepare molecular-thin films on a suitable electrode, the electrochemical potential-driven technique emerges as highly efficient in various aspects. The key focus of this review is to describe recent advances in the electrochemical potential-driven growth of nanometric molecular films of various molecules on technologically relevant substrates, including non-magnetic and magnetic electrodes to investigate the stimuli-responsive charge and spin transport phenomena. Although there have been several bottlenecks with the scaling-up, fabrication and operational mechanism, still we foresee that the molecular devices can hold the potentials to compete against physical and economic barriers for commercial success soon.

Made available in DSpace on 2021-06-25T10:32:05Z (GMT). No. of bitstreams: 0 Previous issue date: 2021-01-01 Organic electrochemical transistors (OECTs) are technologically relevant devices presenting high susceptibility to physical stimulus, chemical functionalization, and shape changes—jointly to versatility and low production costs. The OECT capability of liquid-gating addresses both electrochemical sensing and signal amplification within a single integrated device unit. However, given the organic semiconductor time-consuming doping process and their usual low field-effect mobility, OECTs are frequently considered low-end category devices. Toward high-performance OECTs, microtubular electrochemical devices based on strain-engineering are presented here by taking advantage of the exclusive shape features of self-curled nanomembranes. Such novel OECTs outperform the state-of-the-art organic liquid-gated transistors, reaching lower operating voltage, improved ion doping, and a signal amplification with a >104 intrinsic gain. The multipurpose OECT concept is validated with different electrolytes and distinct nanometer-thick molecular films, namely, phthalocyanine and thiophene derivatives. The OECTs are also applied as transducers to detect a biomarker related to neurological diseases, the neurotransmitter dopamine. The self-curled OECTs update the premises of electrochemical energy conversion in liquid-gated transistors, yielding a substantial performance improvement and new chemical sensing capabilities within picoliter sampling volumes. Brazilian Nanotechnology National Laboratory (LNNano) Brazilian Center for Research in Energy and Materials (CNPEM), Giuseppe Máximo Scolfaro 10000, Polo II de Alta Tecnologia Institute of Chemistry (IQ) University of Campinas (UNICAMP) Cidade Universitária “Zeferino Vaz” Postgraduate Program in Materials Science and Technology (POSMAT) São Paulo State University (UNESP) Postgraduate Program in Materials Science and Technology (POSMAT) São Paulo State University (UNESP)

International audience; Conspectus. Lanthanide ions are prime ingredients for the design of compounds, materials, and devices with unique magnetic and optical properties. Accordingly, coordination chemistry is one of the best tools for building molecular edifices from these ions because it allows careful control of the ions’ environment and of the dimensionality of the final compound.In this Account, we review our results on lanthanide-based dimers. We show how a pure fundamental study on lanthanide coordination chemistry allows the investigation of a full continuum of results from the compound to materials and then to devices. The conversion of molecules into materials is a tricky task because it requires strong molecular robustness toward the surface deposition processes as well as the preservation and detectability of the molecular properties in the material. Additionally, the passage of a material toward a device implies a material with a given function, for example, a tailored response to an external stimulus.To do so, we targeted neutral and isolated molecules whose transfer on surfaces by chemi- or physisorption is much easier than that of charged molecules or extended coordination networks. Then, we focused on molecules with very strong evaporability to avoid wet chemistry deposition processes that are more likely to damage the molecules and/or distort their geometries.We thus designed lanthanide dimers based on fluorinated β-diketonates and pyridine-N-oxide ligands. As expected, they show remarkable evaporability but also strong luminescence and interesting magnetic behavior because they behave as single-molecule magnets (SMMs). Ligand substitutions and stoichiometric modifications allow the optimization of the geometric organization of the dimers in the crystal packing as well as their evaporability, SMM behavior, luminescent properties, or their ability to be anchored on surfaces. Most of all, this family of molecules shows a strong ability to form thick films on various substrates. This allows converting these molecules to magnetic materials and luminescent devices.Magnetic materials can be designed by creating thick films of the dimers deposited on gold. These films have been designed and investigated with the most advanced techniques of on-surface imaging (atomic force microscopy, AFM), on-surface physicochemical characterization (X-ray photoelectron spectroscopy (XPS), time of flight-secondary ion mass spectroscopy (Tof-SIMS)), and on-surface magnetic investigation (low-energy muon spin relaxation (LE-μSR)). Contrary to what was previously observed on other SMM films, no depth dependence of the SMM behavior was observed. This means that the dimers do not suffer from the vacuum or substrate interface and behave similarly, whatever their localization. This exceptional magnetic robustness is a key ingredient in the creation of materials for molecular magnetic data storage.Luminescent devices can be obtained by layering molecular films of the dimers with a copper-rich solid-state electrolyte between ITO/Pt electrodes. The electromigration of Cu(2+) ions into films of Eu(3+), Tb(3+), and Dy(3+) dimers quenches their luminescence. This luminescence tuning by electromigration is reversible, and this setup can be considered to be a proof of concept of full solid-state luminescent device where reversible coding can be tailored by an electric field. It is envisioned for optical data storage purposes. In the future, it could also benefit from the SMM properties of the molecules to pave the way toward multifunctional molecular data storage devices.

The study of Langmuir monolayers incorporating biomimetic and bioactive substances plays an important role today in assessing the properties and quality of the molecular films for potential biomedical applications. Here, miscibility of binary and ternary monolayers of phospholipid (dioleoyl phosphatidylcholine, DOPC), immunosuppressant (cyclosporine A, CsA), and antioxidant (lauryl gallate, LG) of varying molar fractions was analyzed by means of the Langmuir technique coupled with a surface potential (ΔV) module at the air–water interface. The surface pressure–area per molecule (π–A) isotherms provided information on the physical state of the films at a given surface pressure, the monolayer packing and ordering, and the type and strength of intermolecular interactions. Surface potential–area (ΔV–A) isotherms revealed the molecular orientation changes at the interface upon compression. In addition, the apparent dipole moment of the monolayer-forming molecules was determined from the surface potential isotherms. The obtained results indicated that the film compression provoked subsequent changes of CsA conformation and/or orientation, conferring better affinity for the hydrocarbon environment. The mutual interactions between the components were analyzed here in terms of the excess and total Gibbs energy of mixing, whose values depended on the stoichiometry of the mixed films. The strongest attraction, thus the highest thermodynamic stability, was found for a DOPC–CsA–LG mixture with a 1:1:2 molar ratio. Based on these results, a molecular model for the organization of the molecules within the Langmuir film was proposed. Through this model, we elucidated the significant role of LG in improving the miscibility of CsA in the model DOPC membrane and thus in increasing the stability of self-assembled monolayers by noncovalent interactions, such as H-bonds and Lifshitz–van der Waals forces. The above 1:1:2 combination of three components is revealed as the most promising film composition for the modification of implant device surfaces to improve their biocompatibility. Further insight into mechanisms concerning drug–membrane interactions at the molecular level is provided, which results in great importance for biocoating design and development as well as for drug release at target sites., This study was financially supported by the National Science Centre in Poland, under the research project “Comprehensive physicochemical studies of multicomponent films: phospholipid-immunosuppressant-antioxidant on liquid or solid support,” no. 2019/03/X/ST4/01470. P.C. and S.M. acknowledge DGA/fondos FEDER (construyendo Europa desde Aragón) for funding the research group Platón (E31_20R) and financial assistance from the European MagicCellGene Project (M-ERA.NET COFUND call 2016, Ministerio de Economía y Competitividad from Spain in the framework of project PCIN-2017-127).

Morphologies of adsorbed molecular films are of interest in a wide range of applications. To study the epitaxial growth of these systems in computer simulations requires access to long time and length scales, and one typically resorts to kinetic Monte Carlo (KMC) simulations. However, KMC simulations require as input transition rates and their dependence on external parameters (such as temperature). Experimental data allow only limited and indirect access to these rates, and models are often oversimplified. Here, we follow a bottom-up approach and aim at systematically constructing all relevant rates for an example system that has shown interesting properties in experiments, buckminsterfullerene on a calcium fluoride substrate. We develop classical force fields (both atomistic and coarse-grained) and perform molecular dynamics simulations of the elementary transitions in order to derive explicit expressions for the transition rates with a minimal number of free parameters.

The carbon dioxide reduction reaction (CO2RR) in aqueous electrolytes suffers from efficiency loss due to the competitive hydrogen evolution reaction (HER). Developing efficient methods to suppress...

A model experimental approach, providing molecular scale insight into the build up mechanisms of a corrosion inhibiting interface, is reported. 2-mercaptobenzimidazole (2-MBI), a widely used organic inhibitor, was deposited from the vapor phase at ultra-low pressure on copper surfaces in chemically-controlled state, and X-ray photoelectron spectroscopy was used in situ to characterize the adsorption mechanisms upon formation of the inhibiting film. On copper surfaces prepared clean in the metallic state, the intact molecules lie flat at low exposure, with sulfur and both nitrogen atoms bonded to copper. A fraction of the molecules decomposes upon adsorption, leaving atomic sulfur on copper. At higher exposure, the molecules adsorb in a tilted position with sulfur and only one nitrogen bonded to copper, leading to a densification of 2-MBI in the monolayer. A bilayer is formed at saturation with the outer layer not bonded directly to copper. In the presence of a pre-adsorbed 2D oxide, oxygen is substituted and the molecules adsorb intactly without decomposition. A 3D oxide prevents the bonding of sulfur to copper. The molecular film formed on metallic and 2D oxide pre-covered surfaces partially desorbs and decomposes at temperature above 400 °C, leading to the adsorption of atomic sulfur on copper.

International audience; 2-mercaptobenzimidazole (2-MBI) is considered as an effective corrosion inhibitor for copper. In this study, the adsorption of 2-MBI on pristine and pre-oxidized Cu(111) surfaces was investigated by sublimation at ultra low pressure, using Auger Electron Spectroscopy, Scanning Tunneling Microscopy and X-ray Photoelectron Spectroscopy in order to understand its corrosion inhibition properties. 2-MBI adsorbs with S and N atoms bonded to Cu. On pristine Cu(111) surface, a self-assembled monolayer is formed at about 5 L, with the adsorption of atomic S resulting from molecule decomposition to form a (√ 7 × √ 7)R19.1 • structure, and that of the molecule forming a (8×8) structure. 2-MBI is lying flat in the adsorbed multilayer. Oxidation of copper prior to exposure results in compact and homogeneous molecular films, with dissociation and substitution of 2D oxide by 2-MBI, but much more slower than that for 2-mercaptobenzothiazole (2-MBT). A multilayer of 2-MBI can block the initial stages of oxidation of copper under low oxygen pressure at room temperature , and the molecular layer is stable until 500 • C. The comparison with 2-MBT suggests that the latter is a better corrosion inhibitor for copper at room temperature. Figure 1: 2-MBI chemical structure (thione form) and associated molecular dimensions (the van der Waals surface is presented).

A series of new achiral porphyrins with hydrophobic dodecyl chains and hydrophilic substituents were designed in order to clarify the relationship between molecular geometry and aggregation as well as the supramolecular chirality in Langmuir-Schaefer films. These achiral porphyrins have zero (TPPA0), one (TPPA1), two (TPPA2a, TPPA2b), three (TPPA3) and four (TPPA4) long hydrophobic chains, respectively. Most of the compounds showed good spreading behaviour on a water surface except TPPA4 and could be fabricated into LS films easily. Depending on the number of alkyl chains, the porphyrin derivatives showed different aggregation behaviour in the LS films. The transferred films were characterized by UV-vis, circular dichroism (CD) and FTIR spectroscopy, and atomic force microscopy (AFM). Interestingly, some of the porphyrin assemblies were found to be optically active in the LS films although the compounds themselves are achiral. TPPA3 showed a strong Cotton effect in the LS film and fiber-like morphology on mica surface. Weak supramolecular chirality was detected from the LS films of TPPA0, TPPA1 and TPPA4, but no Cotton effect was observed for the LS films of TPPA2a or TPPA2b. On the other hand, when the LS film of TPPA3 was dipped into hexane or exposed to HCl gas, which altered the hydrophobic effect among the dodecyl chains and destroyed the π-π interactions between the porphyrin macrocyclic rings, the CD signal decreased or disappeared. The different aggregation behaviour and supramolecular chirality in the films was suggested to be related to the molecular structure and subsequent packing in their organized molecular films.

Physical properties of magnetic nanostructures and devices strongly depend on the morphological characteristics of their various components. This is especially true and becomes particularly complex in hybrid nanostructures, where soft organic molecules are at the vicinity of ferromagnetic metallic films. The supramolecular architecture of molecular films embedded between iron (Fe) and cobalt (Co) layers, has been investigated by ferromagnetic nuclear resonance (FNR). In such sample architecture, the presence of pin holes in the organic layers is detected by FNR contributions in a specific spectral range. The methodology that has been developed allows probing the continuity and packing of zinc tetra-phenyl porphyrin (ZnTPP) molecular films between the Co and Fe films. The experimental results suggest that, regardless of the nature of the ferromagnetic under-layer, at least 15 monolayers of ZnTPP are necessary to form continuous and pin-hole free molecular films. In addition, quantitative analyses show that ZnTPP layers exhibit distinct morphologies that are dependent on the nature of the ferromagnetic metallic under-layer.

Made available in DSpace on 2020-12-12T01:30:15Z (GMT). No. of bitstreams: 0 Previous issue date: 2020-07-01 The combination of organic and inorganic materials at the nanoscale to form functional hybrid structures is a powerful strategy to develop novel electronic devices. The knowledge on semiconductor thin-film polarization brings direct benefits to the hybrid organic/inorganic electronics, becoming primordial for the development of devices such as electromechanical logic gates, solar cells, miniaturized valves, organic diodes, and molecular supercapacitors, among others. Here, we report on the dielectric polarization of ultrathin organic semiconducting films-ca. 5 nm thick metal phthalocyanine ensembles (viz., CuPc, CoPc, F16CuPc)-employed to build up hybrid metal/oxide/molecule heterojunctions. Such hybrid heterostructures are fully integrated into self-rolled nanomembrane-based capacitors and further investigated by impedance spectroscopy measurements as a function of temperature (from 6 to 300 K). The dielectric polarization of the metal phthalocyanines is found to be thermally activated above a specific threshold temperature, which depends on the molecular structure. Below this threshold, the current leakage across the system is suppressed, thus evidencing intrinsic-like polarization mechanisms. The temperature-independent permittivities of the ultrathin molecular films are found to be strongly dependent on the organic/inorganic hybrid interfaces, while the calculated relaxation times are more likely related to each single-molecule polarization. Beyond the advances in determining the temperature dependence of the permittivity for ultrathin phthalocyanine films integrated within solid-state electronics, our results also support the deterministic design of novel functional devices based on nanoscale hybrid organic/inorganic heterojunctions. Brazilian Nanotechnology National Laboratory (LNNano) Brazilian Center for Research in Energy and Materials (CNPEM) Postgraduate Program in Materials Science and Technology (POSMAT) São Paulo State University (UNESP) Postgraduate Program in Materials Science and Technology (POSMAT) São Paulo State University (UNESP)

Spatial control of surface functionalization and interactions is essential for microarray-based analysis. This study reports the fabrication of two-dimensional molecular films with site-specific functionalities, forming microarrays at discrete locations. Arrays of microsized gold disks were produced on a silicate membrane using microfabrication. On these arrays, orthogonal self-assembly of molecules was performed that can specifically bind to gold or silicate. The gold array elements were functionalized with a range of alkanethiols and the silicate with polymeric poly-l-lysine-grafted-poly(ethylene glycol) (PLL-PEG). The surface functionalization on the gold disk array and the surrounding substrate was characterized at each step using X-ray photoelectron spectroscopy (XPS) to show that alkanethiols are specifically attached to the gold. PLL-PEG was used to provide resistance against nonspecific protein and cell adsorption and attached exclusively to the silicate. The effectiveness of the surface chemistry was validated by the selective self-assembly of a gold nanoparticle monolayer array on the gold regions. In a more sophisticated example, selective adhesion of MCF-7 cells to anti-EpCAM antibody modified gold areas of the gold-silicate surface was demonstrated to give a cell microarray. This study provides a general approach to fabricate chemical patterns on silicon-based devices with the convergence of microfabrication and material-specific surface modification, which may be useful to expand the functionalities and potential applications for patterned biomolecular films. Importantly, the ability to pattern surfaces with different surface chemistries is not limited to planar surfaces using this orthogonal surface-coupling approach.

The [1]benzothieno[3,2-b][1]benzothiophene (BTBT) planar system was used to functionalize the phthalocyanine ring aiming at synthesizing novel electron-rich π-conjugated macrocycles. The resulting ZnPc-BTBT and ZnPc-(BTBT)4 derivatives are the first two examples of a phthalocyanine subclass having potential use as solution-processable p-type organic semiconductors. In particular, the combination of experimental characterizations and theoretical calculations suggests compatible energy level alignments with mixed halide hybrid perovskite-based devices. Furthermore, ZnPc-(BTBT)4 features a high aggregation tendency, a useful tool to design compact molecular films. When tested as hole transport materials in perovskite solar cells under 100 mA cm-2 standard AM 1.5G solar illumination, ZnPc-(BTBT)4 gave power conversion efficiencies as high as 14.13 %, irrespective of the doping process generally required to achieve high photovoltaic performances. This work is a first step toward a new phthalocyanine core engineerization to obtain robust, yet more efficient and cost-effective materials for organic electronics and optoelectronics.

International audience; In the last few years, hybrid lipid-copolymer assemblies have attracted increasing attention as possible two-dimensional (2D) membrane platforms, combining the biorelevance of the lipid building blocks with the stability and chemical tunability of copolymers. The relevance of these systems varies from fundamental studies on biological membrane-related phenomena to the construction of 2D complex devices for material science and biosensor technology. Both the fundamental understanding and the application of hybrid lipid-copolymer-supported bilayers require thorough physicochemical comprehension and structural control. Herein, we report a comprehensive physicochemical and structural characterization of hybrid monolayers at the air/water interface and of solid-supported hybrid membranes constituted by 1,2-dipalmitoyl-sn-glycero-3-phosphocholine (DPPC) and the block copolymer poly(butadiene-b-ethyleneoxide) (PBD-b-PEO). Hybrid lipid-copolymer supported bilayers (HSLBs) with variable copolymer contents were prepared through spontaneous rupture and fusion of hybrid vesicles onto a hydrophilic substrate. The properties of the thin films and the parent vesicles were probed through dynamic light scattering (DLS), differential scanning calorimetry (DSC), optical ellipsometry, quartz crystal microbalance with dissipation monitoring (QCM-D), and confocal scanning laser microscopy (CSLM). Stable, hybrid lipid/copolymer systems were obtained for a copolymer content of 10−65 mol %. In particular, DSC and CSLM show lateral phase separation in these hybrid systems. These results improve our fundamental understanding of HSLBs, which is necessary for future applications of hybrid systems as biomimetic membranes or as drug delivery systems, with additional properties with respect to phospholipid liposomes.

We demonstrate visible pump soft X-ray probe near-edge X-ray absorption fine structure (NEXAFS) spectroscopy measurements at the carbon K edge on thin molecular films in the laboratory. This opens new opportunities through the use of laboratory equipment for chemical speciation. We investigate the metal-free porphyrin derivative tetra(tert-butyl)porphyrazine as an ideal model system to elucidate electronic properties of tetrapyrroles like chlorophyll or heme. In contrast to measurements in gas or liquid state, the investigation of thin films is of high interest in the field of optoelectronic and photovoltaic devices though challenging due to the low damage thresholds of the samples upon excitation. With a careful pre-characterization using optical techniques, successful measurements were performed using a NEXAFS spectrometer based on a laser-produced plasma source and reflection zone plates with a resolving power of 1000 and a time resolution of 0.5 ns. In combination with density functional theory calculations, first insights into a long-lived excitonic state are gained and discussed. Deutsche Forschungsgemeinschaft 313838950 LASERLAB Europe 654148 Ministerio de Ciencia e Innovación PGC2018-101689-B-I00

2-mercaptobenzothiazole (2-MBT) is used for its corrosion inhibition properties. In this study, the adsorption of 2-MBT on metallic and pre-oxidized Cu(1 1 1) surfaces was investigated using Auger Electron Spectroscopy and Scanning Tunneling Microscopy. Growth and structure of molecular films adsorbed at ultra low pressure and room temperature on clean and pre-oxidized Cu(1 1 1) surfaces were characterized. On clean metallic Cu(1 1 1) surface, local triangular ( 7 × 7 ) R19.1° structures are formed at low exposures (3–4 L), which are assigned to the adsorption of atomic S resulting from partial decomposition of 2-MBT. At 10 L, a full non-ordered monolayer of 2-MBT is formed, and further exposure leads to the formation of a non-ordered multilayer. The thickness of the outermost 2-MBT layer is 1.3 A, which suggests that the outermost molecules of the multilayer are lying flat. Oxidation of the copper surface prior to exposure to 2-MBT results in more compact and homogeneous molecular films. The initial 2D oxide is dissociated and replaced by 2-MBT. Thermal stability at different temperatures was studied on clean and pre-oxidized copper surfaces saturated with 2-MBT. A ( 7 × 7 ) R19.1° structure is observed in both cases for temperatures higher than 100 ° C, indicating the decomposition of 2-MBT and a copper surface covered with atomic S.

The present study provides an experimental and computational insight into amino acid adsorption on a graphite substrate. We investigated two aromatic amino acids, histidine and tyrosine, and their behavior on highly-ordered pyrolytic graphite (HOPG). The study was carried out under ambient conditions, in a 1-octanol solution and at room temperature. We found that both amino acids form well-ordered molecular films on graphite, as opposed to dimer rows found for another amino acid (methionine). Scanning Tunneling Microscopy reveals intermolecular spacings and angular orientations of the individual molecules in the well-ordered molecular layer. Both amino acids arrange themselves into a chevron pattern governed by inter-molecular attractive forces. The configuration consists of adjacent rows of parallel molecules, however, individual molecules in neighboring rows are angled with respect to each other. Additional computational chemistry methods using a Molecular Mechanics approach and the AMBER ff03 force field are employed in support of the experimental findings. These calculations provide suggested molecular geometries and estimated adsorption energies and inter-molecular binding energies for molecules on a graphene sheet.

Chiral plasmonics is a growing field because of its potential to produce high-performance biomolecule sensors and negative refractive index materials. Understanding and controlling molecular properties and their effect on the chiroptical coupling between chiral molecular films and metal nanostructures is thus vital for the future design of devices. Here we develop and apply a theoretical method to study that coupling. We first extend the three-dimensional finite-difference time-domain method to include chiral molecular layers with arbitrarily oriented induced dipole moments relative to the nanostructure’s surface. We then use the methodology to investigate the chiral imprinting response from molecularly coated nanospheres as a test of the method. Finally we study a gold nanocross array to understand how long- and short-range interactions between the chiral molecular layer and the nanoparticles affect their optical response.

As a novel photomechanical behavior, structural changes of azobenzene-based photochromic amorphous molecular films fabricated on the surface of soft materials such as agar gel were found upon irradiation with linearly polarized laser beam. The present photomechanical behavior included two-stage processes, striped pattern formation in the direction perpendicular to the polarization direction of the incident beam and subsequent band-like structure formation aligned in the direction parallel to the polarization direction. Both glass-transition temperature of the photochromic materials and the viscosity of the underlying layers were suggested to be important factors for exhibiting the present photomechanical behavior.

Self-assembled layers, and 2D condensed molecular films as their specific cases, are known to be strongly sensitive to external conditions such as temperature, concentration of self-assembling substance(s) in solution, as well as composition of the supporting electrolyte in terms of the kind and concentration of present ions. In this work we have studied effects of a series of four sodium halides on the 2D condensation of 5-fluorocytosine (5-FC) at the hanging mercury drop electrode. This fluorinated nucleobase was selected for the study with respect to its unique 2D condensation properties (previously described in NaCl), showing remarkable capacitance pits in two potential regions (one around the potential of zero charge and the other within highly negative potential region). NaF electrolyte was not able to support 2D condensation of 5-FC, while in NaI and NaBr the 2D condensation was facilitated in comparison with the NaCl electrolyte. Furthermore, we have studied the formation of the 2D condensed film at different temperatures and ac perturbation frequencies to obtaining a complex view into the 5-FC 2D condensation processes. Our results show great importance of the composition of supporting electrolyte, and/or other experimental conditions on the properties of 2D condensed layers.

In this study, we compare and investigate both microscopic molecular packing and mesoscopic morphogenetic behavior in two-dimensional (2D) organized films/three-dimensional (3D) solids of three kin...

The molecular orientation of π-conjugated molecules has been reported to significantly affect the performance of organic photovoltaic devices (OPVs) based on molecular films. Hence, the control of molecular orientation is a key issue toward the improvement of OPV performance. In this research, oriented thin films of an n-type molecule, 3,4,9,10-Perylenetetracarboxylic Bisbenzimida-zole (PTCBI), were formed by deposition on in-plane oriented polythiophene (PT) films. Orientation of the PTCBI films was evaluated by polarized UV-vis spectroscopy and 2D-Grazing incidence X-ray diffraction. Results indicated that PTCBI molecules on PT film exhibit nearly edge-on and in-plane orientation (with molecular long axis along the substrate), whereas PTCBI molecules without PT film exhibit neither. OPVs composed of PTCBI molecular film with and without PT were fabricated and evaluated for correlation of orientation with performance. The OPVs composed of PTCBI film with PT showed higher power conversion efficiency (PCE) than that of film without PT. The experiment indicated that in-plane orientation of PTCBI molecules absorbs incident light more efficiently, leading to increase in PCE.

In this work, we studied the effect of an applied electric field on the dissociation of acetic acid (AA) at the interface of the acid and ammonia molecular layers using the ice film capacitor method. The dissociation of AA was monitored by reflection absorption infrared spectroscopy, which measured the changes in the intensities of the vibrational modes of AA and the acetate anion. The extent of field-induced dissociation was found to be dependent on the direction of the applied electric field. Interestingly, the extent of acid dissociation was greater when the field was applied in the opposite direction to that of the proton-transfer motion. This suggested that the reaction was aided by the reorientation of the reagent molecules rather than by electrostatic stabilization of the charge-transfer energy. The effect of molecular size was studied by comparing the results for AA with those of formic acid and propionic acid. The dissociation of smaller acids was more strongly enhanced than that of larger acids,...

A physical insight regarding poly(tetrafluoroethylene) (PTFE) is revealed herein. The driving force for the oriented growth of materials on aligned PTFE is investigated. The growth has been reported in numerous publications for a wide range of deposited materials on aligned PTFE layers since its discovery in 1991 because it is a promising method for preparing ordered molecular films. MD model simulations demonstrate herein that the shallow charged atomic grooves between adjacent PTFE chains trap typical two linear molecules, thus explaining the remarkable degrees of uniaxial orientation in their deposited thin films on the layers. Charge modifications to the model demonstrate for the first time that the negative charge of its fluorine atoms is crucial for the remarkable degrees. Hence, such an orientation is only possible with PTFE.

We synthesized a new series of donor–acceptor (D-A) type conjugated copolymers containing two electron-accepting units, namely thienoisoquinoline (TIQO) and benzothiadiazole (BT) (PTIQO-HBT) or fluorinated BT analogs (PTIQO-FBT and PTIQO-FFBT) connected to thiophene-based electron-donating units. The optical and electrochemical properties, planarity of conjugated backbone, molecular crystalline structure, and charge transport characteristics were investigated to comprehensively study the structure–property relationship of these semiconducting copolymers. When the BT unit carries 0, 1, and 2 fluorine, both the highest occupied and the lowest unoccupied molecular orbital energy levels of the conjugated copolymers gradually decrease. DFT calculations showed no significant difference in the energy gap or the copolymer backbone planarity. However, the grazing incidence X-ray diffraction results confirm that the PTIQO-FBT copolymer film has a longer coherence length of π–π stacking between the molecular chains than PTIQO-HBT and PTIQO-FFBT, which may affect the intermolecular charge transport. Organic field-effect transistors (OFETs) employing the three TIQO-based D-A type semiconductor copolymer films as active layer all exhibited ambipolar characteristics that enable both hole and electron transport. Particularly, the PTIQO-FBT based OFETs (hole mobility: 0.030 cm2/V·s, electron mobility: 0.023 cm2/V·s) demonstrate higher performance with well-balanced hole and electron transport, as compared to the other two copolymers in terms of field-effect mobility. Therefore, introducing a single fluorine into the BT unit in the TIQO-based D-A type conjugated copolymers results in the most appropriately controlled ground-state charge transfer for efficient intramolecular charge transport along the polymer backbone, as well as higher molecular film crystallinity.

In this study, interactions of Fe3O4 magnetic nanoparticles with serum albumin biomolecules in aqueous solutions were considered. The studies were conducted with the laser correlation spectroscopy and optical analysis of dehydrated films. It was shown that the addition of magnetite to an albumin solution at low concentrations of up to 10−6 g/L led to the formation of aggregates with sizes of up to 300 nm in the liquid phase and an increase in the number of spiral structures in the dehydrated films, which indicated an increase in their stability. With a further increase in the magnetite concentration in the solution (from 10−4 g/L), the magnetic particles stuck together and to albumin, thus forming aggregates with sizes larger than 1000 nm. At the same time, the formation of morphological structures in molecular films was disturbed, and a characteristic decrease in their stability occurred. Most stable films were formed at low concentrations of magnetic nanoparticles (less than 10−4 g/L) when small albumin–magnetic nanoparticle aggregates were formed. These results are important for characterizing the interaction processes of biomolecules with magnetic nanoparticles and can be useful for predicting the stability of biomolecular films with the inclusion of magnetite particles.

We synthesize three fused-ring electron acceptors (m-ITBr, o-ITBr and IT-2Br) based on indacenodithieno[3,2-b]thiophene as the core unit and 2-(3-oxo-2,3-dihydroinden-1-ylidene)malononitrile with 1 or 2 bromine substituents as the end-capped unit. The effects of bromine atom number and substituted position on molecular film absorption, energy level, photovoltaic performance, charge transport and film morphology are systematically carried out. Compared with ITIC, m-ITBr, o-ITBr and IT-2Br all show red-shifted film absorption (550–750 nm) and downshifted highest occupied molecular orbital (HOMO) and lowest unoccupied molecular orbital (LUMO) energy levels. The PM6:IT-2Br based devices exhibit power conversion efficiency (PCE) of up to 12.92%, which is much higher than the reference devices based on ITIC (8.98%). In addition, all three brominated devices achieve high efficiency over 11% (11.84% for m-ITBr devices and 11.14% for o-ITBr devices). Herein, it is also concluded that bromination on terminal groups plays a vital role in enhancing the photovoltaic performance of IDTT-based FREAs.

Molecular films of octadecyltrichlorosilane (OTS) silanized on silicon substrates were obtained by a succession of fabrication steps consisting in plasma hydroxylation of silicon surface, formation of a water layer adsorbed on hydroxylated surface by substrate exposure to water vapor and OTS vapor deposition. All fabrication steps were realized in the same vacuum chamber to avoid surface contamination and to control the amount of water adsorbed on the hydroxylated surface. It is proved that the amount of water on the substrate surface plays a key role in fabrication of smooth OTS molecular films, large amounts of water on substrates resulting in formation of 3D OTS aggregates. The atomic force microscopy (AFM) investigations of the film surface revealed formation of liquid-expanded and liquid-condensed domains in OTS molecular films. Annealing of the OTS films promotes film dehydration, increases the film hydrophobicity and reduces nanoscopic adhesion and friction forces between silicon AFM tips and film surface.

The uptake and thermal chemistry of cinnamaldehyde on Cu(110) single-crystal surfaces were characterized by temperature-programmed desorption and x-ray photoelectron spectroscopy (XPS). Adsorption at 85 K appears to be initiated by low-temperature decomposition to form styrene, which desorbs at 190 K, followed by the sequential buildup of a molecular monolayer and then a condensed molecular film. Molecular desorption from the monolayer occurs at 410 K, corresponding to a desorption energy of approximately 98 kJ/mol, and further decomposition to produce styrene (again) and other fragmentation products is seen at 550 K. The molecular nature and the quantitation of the low-temperature uptake were corroborated by the XPS data, which also provided hints about the adsorption geometry adopted by the unsaturated aldehyde on the surface. Density functional theory calculations, used to estimate adsorption energies as a function of coverage and coordination mode, pointed to possible η1-O binding, at least at high coverages, and to a stabilizing effect on the surface by the aromatic ring of cinnamaldehyde. Finally, coadsorption of oxygen on the surface was found to weaken the binding of cinnamaldehyde to the Cu substrate at high coverages without enhancing its uptake, but to not modify the decomposition mechanism or energetics in any significant way.

The crystalline packing of polymers with high tendencies to form amorphous materials has been attained by controlling intermolecular interactions. Block copolymers of aromatic polyamides in which hydrogen-bonding moieties are sparing and mostly substituted easily form amorphous materials because of steric hindrance and weak intermolecular affinities. Block copolymers of aromatic polyamides synthesized from 4-(N-methylamino)benzoic acid, terephthalic acid chloride, and poly(propylene glycol)bis(2-aminopropyl ether) are commonly amorphous, regardless of unit length. Despite these copolymers not having distinct hydrophobic groups along the alkyl chain, aromatic rings in the same plane could be packed by π–π stacking by the method of two-dimensional interfacial molecular films. The hard segment responsible for the c-axis length increased the tilted angle depending on the chain length; as a result, the chain length was not dependent on the long spacing value. Actually, the layered period in organized films of aromatic polyamides did not depend on the segment length and always indicated a constant value. Isothermal crystallization was attempted for block copolymers of aromatic polyamides exhibiting potential packing ability by the method of organized molecular films. The analyzed glass transition temperature of the oligomer corresponding only to the block unit was adopted as the crystallization temperature. All amorphous polyamides used in this study crystallized after 24 h. A monoclinic packing structure and interactions between the few remaining hydrogen-bonding moieties were suggested by a reciprocal lattice analysis. POLYM. ENG. SCI., 2017. © 2017 Society of Plastics Engineers

Using Langmuir and Langmuir-Blodgett techniques molecular films of chlorinated perylene derivatives, namely tetra-n-butyl-1,6,7,12-tetrachloroperylene-3,4,9,10-tetracarboxylate (PCn for n = 1, 5, 9) have been studied. The Langmuir films of pure compounds and mixed with liquid crystalline 4-octyl-4′-cyanobiphenyl (8CB) were characterized by surface pressure-mean molecular area isotherms. An additive rule reveals miscibility of all the dyes with 8CB but shows different types of intermolecular interaction forces. The pure and mixed Langmuir films were transferred onto quartz plates and characterized spectroscopically. Absorption and fluorescence spectra were recorded for the samples in form of diluted chloroform solution, the dye with 8CB mixtures in monomolecular Langmuir-Blodgett films and in liquid crystal cells. Different tendency to aggregation of the dye with short and long alkyl chains was observed. It is shown that the dye molecule stacking and aggregation of the chlorinated perylene dyes depend on the dye concentration and are related to the torsion of the perylene core.

Hydrophobins are surface-active fungal proteins that adsorb to the water-air interface and self-assemble into amphiphilic, water-repelling films that have a surface elasticity that is an order of magnitude higher than other molecular films. Here we use surface-specific sum-frequency generation spectroscopy (VSFG) and site-directed mutagenesis to study the properties of class I hydrophobin (HFBI) films from Trichoderma reesei at the molecular level. We identify protein specific HFBI signals in the frequency region 1200-1700 cm-1 that have not been observed in previous VSFG studies on proteins. We find evidence that the aspartic acid residue (D30) next to the hydrophobic patch is involved in lateral intermolecular protein interactions, while the two aspartic acid residues (D40, D43) opposite to the hydrophobic patch are primarily interacting with the water solvent.