Self-assembled Molecular Films Research Articles

Ring-Closing Reactions of Porphyrins on Noble Metal Surfaces

On-surface chemistry protocols provide elegant routes to individual molecular complexes, oligomers, and hybrid structures at confining interfaces, yielding distinct chemical, physical, and structural properties [1]. In this context, porphyrins and other tetrapyrroles represent versatile precursors that can undergo metalation, ring-opening, and ring-closing reactions. Furthermore, they are often used as functional tectons for self-assembled molecular films, metal-organic coordination networks, and covalent architectures at interfaces [2].We will report on temperature-induced ring-closing reactions of porphyrins on single crystalline Ag and Au surfaces in an ultrahigh vacuum environment. Examples covered include dehydrogenative homocoupling as well as intramolecular ring-closing. Specifically, distinct oligomers including square-type porphyrin tetramers featuring a planar, central antiaromatic cyclooctatetraene (COT) moiety were achieved on a Ag(100) support by employing unsubstituted Zn- and free-base porphines (see Figure) as precursors [3]. Low-temperature scanning tunnelling microscopy (STM), spectroscopy (STS), and bond-resolved atomic force microscopy (AFM) supported by complementary theoretical modelling were used to comprehensively characterize chemical structure and electronic properties of the square-type tetramers with sub-molecular resolution. Furthermore, the synthesis of π-extended oxygen-embedded porphyrins via O-annulation on Au(111) will be discussed. This surface chemical approach yields high selectivity and yield for planar porphyrin products with distinct symmetries and oxygen content that is not achieved by solution chemistry. The bond-resolved AFM characterization is complemented by X-ray photoelectron spectroscopy measurements. These studies thus give access, and insights, to novel porphyrinoids with distinct properties on noble metal supports.

Inner and Interfacial Environmental Nanoarchitectonics of Supramolecular Assemblies Formed by Amphiphiles: from Emergence to Application.

The inner and interfacial environments of self-assemblies provide fascinating nano-space for selective and efficient chemical reactions and processes. In biological systems, various chemical reactions, molecular recognition, and transport occur precisely and selectively by virtue of effective molecular interactions on biological membranes and proteins. Considering these advantages and the concept of nanoarchitectonics, we demonstrated that the photochromism of a lophine dimer was accelerated by using confined nano-spaces formed by surfactant micelles. The photoresponsive micelles were used for the rapid controlled release of a model drug upon ultraviolet light irradiation. Furthermore, selective ion recognition inside the self-assembled molecular films at the interfaces was investigated. The anion-π interaction between the anion and an electron-deficient aromatic ring was evaluated on a solid substrate modified with a naphthalenediimide (NDI) analog. Force curve measurements afforded a quantitative analysis of anion-π interactions on the NDI film. The strength of anion-π interactions is regulated by the electric fields on the electrode. An optical probe was developed to visualize the distribution of Cs ions in the soil, plant bodies, and aqueous media using an optode system. Advances in the development of molecular functional systems are expected based not only on molecular structures but also on the spaces and environments produced by them.

Fabricating fluorosilane self-assembled molecular film on Babbitt alloy and its tribological performance

PurposeThis study aims to improve the tribological performance of Babbitt alloy under oil lubricant condition. Thus, the surface was treated into oleophobic state by modifying with low surface energy fluorosilane (1H,1H,2H,2H-perfluorodecyltriethoxysilane). It is believed that the oleophobic surface offered excellent wear resistance of Babbitt-based tribo-pairs.Design/methodology/approachBy modifying the Babbitt alloy with low surface energy fluorosilane and measuring the oil contact angle, the wetting behavior was evaluated. Using Pin on Disk tribometer, the tribological properties of bare Babbitt and modified Babbitt were quantified. The samples after the friction test were characterized by scanning electron microscope (SEM) and the anti-wear performance was evaluated under dry and oil lubrication conditions.FindingsResults showed that oil contact angle of modified Babbitt was109° which was tripled compared to that of prime surface, which indicates the oleophobic behavior was greatly improved. Under dry conditions, the friction coefficient of the modified surface with different load conditions is slightly lower than that of the bare surface, while the friction coefficient of the modified surface under lubrication conditions is significantly decreased compared to that of the bare surface. Interestingly, under low load and high load, the wear rate of the modified Babbitt alloy surface is only 1/4 and 1/3 of that of the bare surface, respectively.Originality/valueThe work proposed an effective method to improve the Babbitt tribological performances and will lighten future ideas for the Babbitt alloy bearing with high wear resistance, which is beneficial to improve the service life of sliding bearings and has huge promotion and application value in the manufacture of sliding bearings.

Grain size control of perovskite films based on β-alanine self-assembled monolayers surface treatment

The grain size of the perovskite layer can be tuned by the surface treatment of Ultraviolet ozone (UVO) with β-alanine self-assembled molecular films (SAMs) on the Nickel oxide (NiOx) substrate. The UVO treatment had been used to control the hydroxy (-OH) end-group on NiOx substrate and the condensation reaction of β-alanine SAMs, in which the end-group of the amino group (-NH2) correlates with the nucleation of the perovskite layer. The difference of surface end-group with/without the UVO treatment on the NiOx substrate was revealed by the shift of the oxidation peak of the SAMs layer in the cyclic voltammetry and the electrochemical impedance spectroscopy. It is found that the wettability of NiOx substrate was enhanced by the SAMs treatment time due to the increment of -NH2 end-group and the UVO treatment. Larger grain size of the perovskite layer was achieved on the NiOx substrate with SAMs 15 minutes treatment. Moreover, the optical absorbance of perovskite films in the short wavelength range was enhanced by the assembling time of SAMs. This study provides a method to control the surface morphology of the perovskite active layer in its solar cell device applications.

Probing Electric Field Distributions in the Double Layer of a Single-Crystal Electrode with Angstrom Spatial Resolution using Raman Spectroscopy.

The electrical double layer (EDL) is the extremely important interfacial region involved in many electrochemical reactions, and it is the subject of significant study in electrochemistry and surface science. However, the direct measurement of interfacial electric fields in the EDL is challenging. In this work, both electrochemical resonant Raman spectroscopy and theoretical calculations were used to study electric field distributions in the EDL of an atomically flat single-crystal Au(111) electrode with self-assembled monolayer molecular films. This was achieved using a series of redox-active molecules containing the 4,4'-bipyridinium moiety as a Raman marker that were located at different precisely controlled distances away from the electrode surface. It was found that the electric field and the dipole moment of the probe molecule both directly affected its Raman signal intensity, which in turn could be used to map the electric field distribution at the interface. Also, by variation of the electrolyte anion concentration, the Raman intensity was found to decrease when the electric field strength increased. Moreover, the distance between adjacent Raman markers was ∼2.1 Å. Thus, angstrom-level spatial resolution in the mapping of electric field distributions at the electrode-electrolyte interface was realized. These results directly evidence the EDL structure, bridging the gap between the theoretical and experimental understandings of the interface.

Metal Nanoparticle Enhancement of Electron Transfer to Tethered Redox Centers through Self-Assembled Molecular Films.

Metal-nanoparticle-mediated electron transfer (ET) across an insulator thin film containing nanoparticles with attached redox centers was studied using electrochemical impedance spectroscopy. Specifically, a gold spherical microelectrode was modified with 16-amino-1-hexa-decanethiol, creating an insulator film. This was followed by the electrostatic adsorption of gold nanoparticles and the covalent attachment of Os2+ redox centers. A variation of the Creager-Wooster method was developed to get quantitative information regarding the ET kinetics of the system. The experimental data obtained from a single measurement was fitted with a model that decouples two or more ET processes with different time constants and considers a Gaussian distribution of tunneling distances. Two parallel ET mechanisms were observed: one in which the electrons flow by tunneling between the surface and the redox couples with a low kET0 = 1.3 s-1 and a second one in which an enhancement of the electron transfer is produced due to the presence of the gold nanoparticles with a kET0 = 7 × 104 s-1. In this study, we demonstrate that the gold nanoparticle electron transfer enhancement is present only in the local environment of the nanoparticle, showing that the nanoscale architecture is crucial to maximize the enhancement effect.

Study on the preparation and corrosion inhibition of Schiff-base self-assembled membranes

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.

Self-Assembled Molecular Films of Alkanethiols on Graphene for Heavy Metal Sensing

We report a comparative study involving the formation of self-assembled molecular films by two types of alkanethiols (1-octadecanethiol and 1-dodecanethiol) on graphene grown via chemical vapor deposition, for heavy metal sensing applications. Scanning tunneling microscopy measurements confirm that the alkanethiol molecules can form localized, ordered molecular films on single-layer graphene despite the presence of structural and chemical irregularities. To test and compare the sensory characteristics associated with graphene functionalized by 1-octadecanethiol and 1-dodecanethiol, graphene-based field effect transistors are fabricated via photolithography on silicon dioxide substrates. Devices based on graphene functionalized with 1-octadecanethiol are successfully employed to demonstrate the detection of mercury and lead ions at the 10 ppm level via Dirac point shifts, with a notable difference in response associated with the use of different heavy metal ions. On the other hand, devices based on graphene functionalized with 1-dodecanethiol exhibit p-type character, before and/or after exposure to heavy metal ions, complicating their use in heavy metal sensing in a straightforward fashion via Dirac point shifts.

Suppression of Phonon Transport in Molecular Christmas Trees.

Minimising the phonon thermal conductance of self-assembled molecular films, whilst preserving their electrical properties, is highly desirable, both for thermal management at the nanoscale and for the design of high-efficiency thermoelectric materials. Here we highlight a new strategy for minimising the phonon thermal conductance of Christmas-tree-like molecules composed of a long trunk, along which phonons can propagate, attached to pendant molecular branches. We demonstrate that phonon transport along the trunk is suppressed by Fano resonances associated with internal vibrational modes of the branches and that thermal conductance is suppressed most-effectively in molecules with pendant branches of different lengths. As examples, we use density functional theory to demonstrate the reduction in phonon transport in tree-like molecules formed from alkane or acene trunks with various pendant branches.

In situ bioconjugation and ambient surface modification using reactive charged droplets.

Molecular ions are generated in induced electrospray ionization, and they can be transported to grounded ambient surfaces in the form of charged microdroplets. Efficient amide bonds formation between amines and carboxylic acids were observed inside charged droplets during transfer to the surface. Biomolecules derivatized using this method were self-assembled on a bare gold surface via Au-S bonds under the charged microdroplet environment. Cyclic voltammetric analysis of the self-assembled molecular film showed accelerated protein derivatization with cysteine, which allowed the covalent immobilization of the protein to the gold surface. Cytochrome C-functionalized electrodes prepared using the induced dual nanoelectrospray process showed bioactivity toward aqueous solutions of hydrogen peroxide below 50 μM. In effect, we have developed a method that allows derivatization of biomolecules and their immobilization at ambient surfaces in a single experimental step.

Highly ordered luminescent calix[4]azacrown films showing an emission response selective to volatile tetrahydrofuran

Sensitive, selective, low-cost, and simply designed detectors for THF among other vapour organic compounds (VOCs) are highly attractive. Self-assembled molecular films with remarkable selective vapoluminescent response to VOC THF were fabricated using drop-casting of calix[4]azacrown-based J-aggregates. The latter, stabilized via C–H⋯π and C–H⋯O hydrogen bond networks, assemble into nanoparticles that exhibit aggregation-induced emission (AIE) effect, which produces violet emission at room temperature in acetonitrile. The films are highly ordered and switch order at high temperature, leading to 2.5-fold luminescence enhancement and responsive behaviour.

Layer-by-layer self assembly of a water-soluble phthalocyanine on gold. Application to the electrochemical determination of hydrogen peroxide

A self-assembled molecular film of a water-soluble cobalt tetrasulfophthalocyanine was deposited on a gold substrate premodified with poly(diallyldimethylammonium chloride). The process of layer-by-layer assembly on the gold substrate was characterized using UV-Vis, Raman spectroscopy, ellipsometry, contact angle measurements, atomic force microscopy and electrochemical methods. Results demonstrate the formation of a completely covered phthalocyanine film on the gold surface. UV-Vis spectra indicated the formation of monolayer film of the phthalocyanine on the surface. The functionalized surface is uniformly covered and becomes hydrophilic after modification. The modified gold surface exhibits a reversible redox behavior and acts as an electronic conductor for the electrochemical reduction of hydrogen peroxide in pH 7.0 phosphate buffer. A linear increase in the catalytic current is observed for the reduction of hydrogen peroxide in the concentration range from 1 to 20μM, with a detection limit of 0.4μM. Hydrogen peroxide spiked pond water sample showed a recovery of 94% indicating the method is selective and can be applied for various applications. The present method is a simple, cost effective and sensitive electrochemical method for the detection and quantification of hydrogen peroxide.

Self Assembled Films of Porphyrins with Amine Groups at Different Positions: Influence of Their Orientation on the Corrosion Inhibition and the Electrocatalytic Activity

Self-assembled molecular films of two cobalt porphyrins with amine groups at different positions—(5,10,15,20-tetrakis-(2-aminophenyl) porphyrin-cobalt(II), [Co(II) (T(o-NH2)PP)] and (5,10,15,20-tetrakis-(4-aminophenyl) porphyrin-cobalt(II), [Co(II)(T(p-NH2)PP)]—were formed on a gold substrate. The functionalized surfaces were characterized using Raman spectroscopy, atomic force microscopy and electrochemical methods. Both modified gold surfaces completely mask the charge transfer of a [Fe(CN)6]3−/4− redox couple in solution, indicating the layer is highly resistive in behavior. Electrochemical impedance spectroscopy analyses revealed that the porphyrin film with amine groups at ortho positions shows a higher charge-transfer resistance with a better protective behavior compared to the para position modified surface. Raman, AFM and EIS data suggests that an ortho amine positioned molecule forms a more compact layer compared to the para-positioned molecule. This can be explained in terms of their orientation on the gold surface. [Co(II)(T(o-NH2)PP)] adopted a saddle shape orientation whereas [Co(II)(T(p-NH2)PP)] adopted a flat orientation on the gold surface. The porphyrin modified gold electrode catalyzes the oxygen reduction at lower potentials compared to the bare gold electrode. The shift in the overvoltage was higher in case of molecules with flat orientation compared to the saddle shaped oriented porphyrin molecules on the surface.

Investigation on growth process and tribological behavior of mixed alkylsilane self-assembled molecular films in aqueous solution

In this paper, we investigated the frictional behaviors of the mixed self-assembled molecular films of the fluoroalkylsilane (FAS) molecules and non-fluoroalkylsilane (n-FAS) molecules with different chain length covalently absorbed on silicon surfaces, characterized by the universal ball-disk UMT-2 experimental tester under aqueous solution conditions. The surfaces of the substrate modified by mixed self-assembled molecular films were examined by X-ray photoelectron spectroscopy (XPS) and contact angle measurements. The formation processes of the molecular films were characterized by quartz crystal microbalance (QCM). The results indicated that it would take a longer time to reach the adsorption equilibrium of the molecular films with the increment of carbon chain length. The measured tribological results showed that the mixing of the fluoroalkylsilane and non-fluoroalkylsilane enhance the lubrication and decrease the friction and wear compared to the one-component thin films. This may be caused by the reduced excitation of the energy dissipation channels.

Altering the Static Dipole on Surfaces through Chemistry: Molecular Films of Zwitterionic Quinonoids

The adsorption of molecular films made of small molecules with a large intrinsic electrical dipole has been explored. The data indicate that such dipolar molecules may be used for altering the interface dipole screening at the metal electrode interface in organic electronics. More specifically, we have investigated the surface electronic spectroscopic properties of zwitterionic molecules containing 12π electrons of the p-benzoquinonemonoimine type, C(6)H(2)(···NHR)(2)(···O)(2)(R = H (1), n-C(4)H(9) (2), C(3)H(6)-S-CH(3) (3), C(3)H(6)-O-CH(3) (4), CH(2)-C(6)H(5) (5)), adsorbed on Au. These molecules are stable zwitterions by virtue of the meta positions occupied by the nitrogen and oxygen substituents on the central ring, respectively. The structures of 2-4 have been determined by single crystal X-ray diffraction and indicate that in these molecules, two chemically connected but electronically not conjugated 6π electron subunits are present, which explains their strong dipolar character. We systematically observed that homogeneous molecular films with thickness as small as 1 nm were formed on Au, which fully cover the surface, even for a variety of R substituents. Preferential adsorption toward the patterned gold areas on SiO(2) substrates was found with 4. Optimum self-assembling of 2 and 5 results in ordered close packed films, which exhibit n-type character, based on the position of the Fermi level close to the conduction band minimum, suggesting high conductivity properties. This new type of self-assembled molecular films offers interesting possibilities for engineering metal-organic interfaces, of critical importance for organic electronics.

Tunable water-based lubrication behavior of alkyl- and fluoroalkyl-silanes

In this paper, we report the tribological properties of self-assembled molecular (SAM) films of fluoroalkylsilanes and non-fluoroalkylsilanes, with different chain-lengths, adsorbed on Si substrate surfaces by covalent bonds. The SAM films were characterized using a universal ball-disk experimental tester in aqueous solutions. The substrate surface was examined by X-ray photoelectron spectroscopy (XPS), and the SAM films adsorbed on the Si surfaces were inspected by contact angle measurements and XPS. Lubrication studies revealed that several kinds of fluoroalkylsilanes had similar friction coefficients; the small differences were attributed to the chain flexibility. In contrast, differences in the aqueous lubrication properties of SAM films of non-fluoroalkylsilanes were clearly identified. It is suggested that substitution with fluorine atoms and the surface affinities of fluoroalkylsilanes contributed to redistribution of surface changes, causing variations in lubrication behaviors.

The Chemistry of the Sulfur–Gold Interface: In Search of a Unified Model

Over the last three decades, self-assembled molecular films on solid surfaces have attracted widespread interest as an intellectual and technological challenge to chemists, physicists, materials scientists, and biologists. A variety of technological applications of nanotechnology rely on the possibility of controlling topological, chemical, and functional features at the molecular level. Self-assembled monolayers (SAMs) composed of chemisorbed species represent fundamental building blocks for creating complex structures by a bottom-up approach. These materials take advantage of the flexibility of organic and supramolecular chemistry to generate synthetic surfaces with well-defined chemical and physical properties. These films already serve as structural or functional parts of sensors, biosensors, drug-delivery systems, molecular electronic devices, protecting capping for nanostructures, and coatings for corrosion protection and tribological applications. Thiol SAMs on gold are the most popular molecular films because the resulting oxide-free, clean, flat surfaces can be easily modified both in the gas phase and in liquid media under ambient conditions. In particular, researchers have extensively studied SAMs on Au(111) because they serve as model systems to understand the basic aspects of the self-assembly of organic molecules on well-defined metal surfaces. Also, great interest has arisen in the surface structure of thiol-capped gold nanoparticles (AuNPs) because of simple synthesis methods that produce highly monodisperse particles with controllable size and a high surface/volume ratio. These features make AuNPs very attractive for technological applications in fields ranging from medicine to heterogeneous catalysis. In many applications, the structure and chemistry of the sulfur-gold interface become crucial since they control the system properties. Therefore, many researchers have focused on understanding of the nature of this interface on both planar and nanoparticle thiol-covered surfaces. However, despite the considerable theoretical and experimental efforts made using various sophisticated techniques, the structure and chemical composition of the sulfur-gold interface at the atomic level remains elusive. In particular, the search for a unified model of the chemistry of the S-Au interface illustrates the difficulty of determining the surface chemistry at the nanoscale. This Account provides a state-of-the-art analysis of this problem and raises some questions that deserve further investigation.

Nanopatterning of Functional Materials by Gas Phase Pattern Deposition of Self-Assembled Molecular Thin Films in Combination with Electrodeposition

We present a general methodology to pattern functional materials on the nanometer scale using self-assembled molecular templates on conducting substrates. A soft lithographic gas phase edge patterning process using poly(dimethylsiloxane) molds was employed to form electrically isolating organosilane patterns of a few nanometer thickness and a line width that could be tuned by varying the time of deposition. Electrodeposition was employed to deposit patterns of Ni and ZnO on these prepatterned substrates. Deposition occurred only on patches of the substrate where no organosilane monolayer was present. The process is simple, inexpensive, and scalable to large areas. We achieved formation of metallic and oxide material patterns with a lateral resolution of 80 nm.

Surface-Driven Porphyrin Self-Assembly on Pre-Activated Si Substrates

Self-assembled molecular thin films of melamine-bridged bis-porphyrin dyad, both in free form, P(H2)P(H2), or as Zn(II) metallated complex, P(Zn)P(Zn), were deposited on crystalline Si(100) by soaking or drop-casting techniques. The influence of the adopted preparation methodology, the substrate surface pre-activation procedure and the used solvent (THF or CHCl3) on the morphology and surface coverage of the resulting films was investigated by FE-SEM (Field Emission-Scanning Electron Microscopy) and AFM (Atomic Force Microscopy). The chemical composition and electronic structure of the most promising systems were also addressed by XPS (X-ray Photoelectron Spectroscopy). The results pointed out that an accurate tuning of porphyrin-porphyrin, porphyrin-substrate and porphyrin-solvent molecular interactions allow to tailor the morphogenesis and chemico-physical properties of the final self-assembled films. In addition, preliminary gas sensing tests evidenced the potential of the present porphyrin-based films for the development of new molecular sensing devices.

Redox-Executed Logic Operations through the Reversible Voltammetric Response Characteristics of Electroactive Self-Assembled Monolayers

We propose charge quantization in electrochemical oxidation–reduction (redox) systems as a route to performing logical operations efficiently and reversibly. The theory is based on the interfacial potential distribution for electrodes coated with electroactive self-assembled molecular films. We monitor the change in the oxidation number by studying the current as a function of the working and reference electrode potentials and of the temperature. Diamond-shaped regions can be defined that delineate the stability of a given redox species as a function of the applied and reference potentials. Using these electrochemical Coulomb diamonds, we then show the principles for the design of a complete set of binary gates and a finite-state set–reset machine. We demonstrate the analogies between these redox systems and nanoscale solid-state systems where the charging energy is finite. Redox systems allow simple logic operations at room temperature because typically the standard potential is higher than the thermal energy.