Monolayers Of Derivatives Research Articles

Optical anisotropy and surface phases of cholesterol derivative monolayer at air–water interface

Cholesterol and its derivatives play crucial roles in regulating processes of biological membranes. Langmuir monolayer can mimic a bio-membrane which can be used to investigate the molecular interaction governing the important physical phenomena. The cholesterol derivative exhibiting mesophases (CHLC molecules) was synthesized and spread at the air–water (A/W) interface to investigate the surface behavior. The monolayer exhibited a variety of surface phases such as gas, liquid expanded (LE), low density liquid like (L1) and liquid condensed (L2) phases. Treating the CHLC molecules to be rod-like, the average tilt of the molecules with respect to the surface normal in these phases are found to be different. The tilt angle decreases systematically from LE to L2 phase. The optical anisotropy of the ultrathin Langmuir-Blodgett (LB) films of CHLC molecules in these phases was measured using the surface plasmon resonance (SPR) spectroscopy. The high tilted molecules in the ultrathin LB film displayed a high value of optical anisotropy. The ultrathin film of CHLC molecules at different interfaces was investigated using Brewster angle microscopy, X-ray reflectivity (XRR), SPR spectroscopy and atomic force microscopy. This study is useful for the systems where the physical phenomena are governed by tilt of the molecules.

Orientation Dependent Interlayer Coupling in Organic–Inorganic Heterostructures

AbstractOrganic–inorganic 2D heterostructures combine the high optical absorption of organic molecules with exciton‐dominated optical properties in layered transition metal dichalcogenides (TMDs) such as MoS2. Critical to the interaction and the optical response in such hybrid systems is the electronic band alignment at the interface between the two species. Here, the coupling of monolayers of perylene derivatives is investigated with bilayer MoS2. In particular, variation in the perylene orientation on the MoS2 surface is identified using Raman spectroscopy and scanning probe microscopy. Low‐temperature optical spectroscopy reveals orientation‐dependent interlayer exciton formation. Furthermore, power‐dependent photoluminescence measurements provide insight into the modified interlayer charge transfer in these heterostructures. A saturation of interlayer states is found under high excitation power when the perylene molecules are in a perpendicular orientation to the surface that leads to electron accumulation in the MoS2, whereas parallel alignment of the perylene molecules leads to enhanced populations of organic–inorganic interlayer excitons. This work provides insights into the optimization of organic–inorganic heterostructures, with particular relevance to applications for optoelectronic and excitonic devices.

A Sustainable Method for Removal of the Full Range of Liquid and Solid Hydrocarbons from Water Including Up- and Recycling.

Beyond their CO2 emittance when burned as fuels, hydrocarbons (HCs) serve as omnipresent raw materials and commodities. No matter if as liquid oil spills or the endless amounts of plastic roaming the oceans, HCs behave as persistent pollutants with water as main carrier to distribute. Even if their general chemical structure [-(CH2 )n -] is quite simple, the endless range of n leads to contaminations of different appearances and properties. A water remediation method based on superparamagnetic iron oxide nanoparticles (SPIONs) modified with self-assembled monolayers of alkyl phosphonic acid derivatives is presented. These molecules enable the SPIONs to non-covalently bind HCs, independently from the molecular weight, size and morphology. The attractive interaction is mainly based on hydrophobic and Coulomb interaction, which allows recycling of the SPIONs. The superparamagnetic core allows a simple magnetic collection and separation from the water phase which makes it a promising addition to wastewater treatment. Agglomerates of collected plastic "waste" even exhibit superior adsorption properties for crude oil, another hydrocarbon waste which gives these collected wastes a second life. This upcycling approach combined with presented recycling methods enables a complete recycling loop.

Molecular Orientations of Myristic Acid Derivatives with Different Perfluoroalkyl Chain Lengths at the Air/Water Interface Evaluated by Heterodyne-Detected Sum Frequency Generation Spectroscopy

Surface-related properties of perfluoroalkyl compounds such as hydrophobicity and adhesion force can have a close relationship with the orientational order of the molecules at the surface. Myristic acid (MA) derivatives with perfluoroalkyl (Rf) groups have been known to form a well-ordered monolayer at the air/gold substrate interface. In this study, molecular orientations of the MA derivative monolayers at the air/water interface were investigated by heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. We estimated the molecular orientation of MA derivative monolayers with a marker band observed at around 1370 cm–1. The Rf chain length and the surface pressure dependence of the molecular orientation of four MA derivatives were examined. The marker bands were observed except for the derivative with the shortest Rf chain at the higher surface pressure, whereas the marker bands were observed only for the two derivatives with relatively longer Rf chain lengths at the lower surface pressure. The observation indicates that the longer the Rf chain is and the higher the surface pressure is, MA derivatives tend to adopt a standing orientation closer to perpendicular to the interface.

Effect of Ester Moiety on Structural Properties of Binary Mixed Monolayers of Alpha-Tocopherol Derivatives with DPPC.

Phospholipid membranes are ubiquitous components of cells involved in physiological processes; thus, knowledge regarding their interactions with other molecules, including tocopherol ester derivatives, is of great importance. The surface pressure–area isotherms of pure α-tocopherol (Toc) and its derivatives (oxalate (OT), malonate (MT), succinate (ST), and carbo analog (CT)) were studied in Langmuir monolayers in order to evaluate phase formation, compressibility, packing, and ordering. The isotherms and compressibility results indicate that, under pressure, the ester derivatives and CT are able to form two-dimensional liquid-condensed (LC) ordered structures with collapse pressures ranging from 27 mN/m for CT to 44 mN/m for OT. Next, the effect of length of ester moiety on the surface behavior of DPPC/Toc derivatives’ binary monolayers at air–water interface was investigated. The average molecular area, elastic modulus, compressibility, and miscibility were calculated as a function of molar fraction of derivatives. Increasing the presence of Toc derivatives in DPPC monolayer induces expansion of isotherms, increased monolayer elasticity, interrupted packing, and lowered ordering in monolayer, leading to its fluidization. Decreasing collapse pressure with increasing molar ratio of derivatives indicates on the miscibility of Toc esters in DPPC monolayer. The interactions between components were analyzed using additivity rule and thermodynamic calculations of excess and total Gibbs energy of mixing. Calculated excess area and Gibbs energy indicated repulsion between components, confirming their partial mixing. In summary, the mechanism of the observed phenomena is mainly connected with interactions of ionized carboxyl groups of ester moieties with DPPC headgroup moieties where formed conformations perturb alignment of acyl chains, resulting in increasing mean area per molecule, leading to disordering and fluidization of mixed monolayer.

Improving Orientation, Packing Density, and Molecular Arrangement in Self-Assembled Monolayers of Bianchoring Ferrocene-Triazole Derivatives by "Click" Chemistry.

This work describes the self-assembled monolayers (SAMs) of two ferrocene derivatives with two anchoring groups (at the bottom and at the top of the SAM) deposited on ultraflat template-stripped gold substrates by cyclic voltammetry and analyzed by complementary surface characterization techniques. The SAM of each molecule is deposited by three different protocols: direct deposition (one step), click reaction on the surface (two steps), and reverse click reaction on the surface (two steps). The SAM structure is well studied to determine the SAM orientation, SAM arrangement, and ferrocene position within the SAM. Electron transfer kinetics have also been studied, which agree with the quality of each SAM. With the help of two anchoring groups and click-chemistry active functional groups, we have shown that the two molecules can be deposited by controlling the position of ferrocene at either end. We further investigated the involvement of the triazole five-membered ring in the electron transfer mechanism. We have found that a carbon spacer between ferrocene and triazole improves the SAM packing. This study enhances the understanding of tethering thiol and thiol acetate anchoring groups on gold by a controlled orientation, which may help in the development of functional molecular devices requiring two anchoring groups.

Construction and Characterizations of Antibacterial Surfaces Based on Self-Assembled Monolayer of Antimicrobial Peptides (Pac-525) Derivatives on Gold

Background: Infection that is related to implanted biomaterials is a serious issue in the clinic. Antimicrobial peptides (AMPs) have been considered as an ideal alternative to traditional antibiotic drugs, for the treatment of infections, while some problems, such as aggregation and protein hydrolysis, are still the dominant concerns that compromise their antimicrobial efficiency in vivo. Methods: In this study, antimicrobial peptides underwent self-assembly on gold substrates, forming good antibacterial surfaces, with stable antibacterial behavior. The antimicrobial ability of AMPs grafted on the surfaces, with or without glycine spaces or a primer layer, was evaluated. Results: Specifically, three Pac-525 derivatives, namely, Ac-CGn-KWRRWVRWI-NH2 (n = 0, 2, or 6) were covalently grafted onto gold substrates via the self-assembling process for inhibiting the growth of Staphylococcus aureus (S. aureus) and Escherichia coli (E. coli). Furthermore, the alkanethiols HS(CH)10SH were firstly self-assembled into monolayers, as a primer layer (SAM-SH) for the secondary self-assembly of Pac-525 derivatives, to effectively enhance the bactericidal performance of the grafted AMPs. The -(CH)10-S-S-G6Pac derivative was highly effective against S. aureus and E. coli, and reduced the viable amount of E. coli and S. aureus to 0.4% and 33.2%, respectively, after 24 h of contact. In addition, the immobilized AMPs showed good biocompatibility, promoting bone marrow stem cell proliferation. Conclusion: the self-assembled monolayers of the Pac-525 derivatives have great potential as a novel therapeutic method for the treatment of implanted biomaterial infections.

Steric Effects on the Formation of Self‐Assembled Monolayers of Alicyclic Thiol Derivatives on Au(111)

To understand the steric effects on the formation of alicyclic thiolate self‐assembled monolayers on Au(111), the surface structures and reductive desorption behaviors of self‐assembled monolayers on Au(111) derived from cyclohexanethiol (CHT) and 1‐methylcyclohexanethiols (MCHT) were characterized using scanning tunneling microscopy (STM) and cyclic voltammetry. STM observations showed that the adsorption of CHT on Au(111) resulted in the formation of well‐organized monolayers with an unit cell of a = 14.5 ± 0.3 Å and b = 10.2 ± 0.3 Å, while the adsorption of MCHT with a methyl substituent bonded to the 1‐position of the cyclohexyl ring resulted in the formation of a disordered phase. The reductive desorption potentials for CHT and MCHT monolayers on Au electrodes were observed at −0.984 and −0.974 V, respectively. This difference in potentials can be attributed to the difference in lateral interactions, which depend on the structural order of monolayers.

Features of formation of Langmuir monolayers of porphyrin derivatives on the surface of aqueous solutions of copper nanoparticles

Meso-aryl-substituted porphyrin monolayers were obtained by the Langmuir method depending on the aliquots applied to the water surface and the composition of the subphase. Regardless of the composition of the subphase (pure water or a solution with copper nanoparticles stabilized by surfactant) porphyrin compression isotherms showed the formation of monolayers until a film collapse state is reached. The presence in the subphase volume of copper nanoparticles stabilized by a surfactant (sodium dodecyl sulfate) contributed to the formation of a more stable porphyrin monolayer. A significant difference in the values of the surface potential at the end of porphyrin monolayer compression depending on the composition of the subphase is established. This fact is very promising in the context of creating film heterostructures with improved operational properties.

Structures and Dynamics in Thiolated Diamantane Derivative Monolayers

Self-assembled monolayers (SAMs) of isomeric 1-diamantantyl thiol (1SH) and 4-diamantantyl thiol (4SH) on Au(111) surfaces were characterized using scanning tunneling microscopy (STM) in air. The 4...

Rational construction of self-assembly azobenzene derivative monolayers with photoswitchable surface properties

Photo-responsive azobenzene (ABZ) derivatives with different end groups (R) as photoswitchable molecules were employed to construct self-assembled monolayers (SAMs) on silicon substrate by using 3-glycidoxypropyltrimethoxysilane (GPTS) as the bridging molecules. The assembly process was optimized by changing various parameters, including the type and concentration of ABZ derivatives, reaction time, etc. The obtained SAMs were fully characterized and evaluated using UV spectroscopy, atomic force microscope (AFM), elllipsometer, static contact angle and X-ray photoelectron spectroscopy (XPS). It is found that the end group property of azobenzene derivatives is critical to the obtained SAMs’ photoresponsive properties. Compared with hydrophobic compounds (4-(4′-aminophenylazo) benzoic acid, ABZ-CF3), the hydrophilic compounds (4-(4′-aminophenylazo) benzoic acid, ABZ-COOH) show excellent reversible photoswitching performance with a large contact angle change of 35° under optimized process, and the SAMs are removable by thermal treatment at 240°C in air for only 5min.

THz SERS Observation of Benzenethiol Monolayers on Electrode Surfaces

Surface-selective vibrational spectroscopy is a powerful tool to study various interfacial phenomena such as electrochemical reactions at electrode/electrolyte interfaces. Among various spectroscopic methods, surface enhanced Raman scattering (SERS) is a promising method to conduct in-situ observation in IR- and THz-opaque media. According to recent technological advancements in fabrication of optical filters, elimination of Rayleigh scattering has become highly efficient. Thus, it is now expected that very low-frequency vibrations such as THz vibrations can be observed even in aqueous solutions [1]. Figure shows that an extramolecular vibration of benzenethiol monolayers with ultra-low frequency is indeed observable using this method. We will discuss charge transfer resonances at metal/molecule interfaces based on this low frequency vibration. Figure caption THz-SERS spectra of monolayers of benzenethiol derivatives on a roughened Au substrate Reference [1] M Inagaki, K. Motobayashi, K. Ikeda, J. Phys. Chem. Lett., 8, 2017, pp. 4236-4240. Figure 1

Label-free impedimetric glycosensor based on β-galactose-functionalized gold electrode for the determination of cholera toxin

A label-free impedimetric glycosensor has been developed for the direct detection of cholera toxin (CT). The glycosensor has been fabricated by forming the self-assembled monolayers of β-galactose derivatives containing poly-ethyleneglycol (PEG) spacer on gold electrode surfaces. The selective binding of CT to the β-galactose receptors on the fabricated glycosensor has been directly monitored by electrochemical impedance spectroscopy in the presence of 5.0mM K3Fe(CN)6/K4Fe(CN)6 (1:1, v/v) redox couple. gmonolayers on gold electrode surface has been determined to be ca. 2.53×1010M−1, indicating that the present glycosensor can selectively capture the target CT from sample solutions. Therefore, the present monosaccharide β-galactose derivative can be used as a receptor for CT as an alternative to CT-specific antibodies or pentasaccharide ganglioside GM1, most widely used in conventional CT assays. The present glycosensor can detect CT in the concentration range from 1.18×10−12M to 1.18×10−9M (r2=0.963) with a limit of detection (S/N=3) down to 7.83×10−13M, which is much lower than those obtained with other detection methods. Since the present glycosensor-based CT assay does not require complex and time-consuming signal amplification steps generally employed in sandwich-type immunoassays, it enables the simple and rapid detection of CT.

Time-Lapse Single-Biomolecule Atomic Force Microscopy Investigation on Modified Graphite in Solution.

Atomic force microscopy (AFM) of biomolecular processes at the single-molecule level can provide unique information for understanding molecular function. In AFM studies of biomolecular processes in solution, mica surfaces are predominantly used as substrates. However, owing to its high surface charge, mica may induce high local ionic strength in the vicinity of its surface, which may shift the equilibrium of studied biomolecular processes such as biopolymer adsorption or protein-DNA interaction. In the search for alternative substrates, we have investigated the behavior of adsorbed biomolecules, such as plasmid DNA and E. coli RNA polymerase σ70 subunit holoenzyme (RNAP), on highly oriented pyrolytic graphite (HOPG) surfaces modified with stearylamine and oligoglycine-hydrocarbon derivative (GM) monolayers using AFM in solution. We have demonstrated ionic-strength-dependent DNA mobility on GM HOPG and nativelike dimensions of RNAP molecules adsorbed on modified HOPG surfaces. We propose an approach to the real-time AFM investigation of transcription on stearylamine monolayers on graphite. We conclude that modified graphite allows us to study biomolecules and biomolecular processes on its surface at controlled ionic strength and may be used as a complement to mica in AFM investigations.

Methylene Blue Location in (Hydroperoxized) Cardiolipin Monolayer: Implication in Membrane Photodegradation.

We present molecular dynamics simulations of cardiolipin (CL) and CL monohydroperoxized derivative (CLOOH) monolayers to investigate the initial steps of phospholipid oxidation induced by methylene blue (MB) photoexcitation under continuous illumination. We considered different MB atomic charge distributions to simulate the MB electronic distribution in the singlet ground and triplet excited states. Simulation results allied to experimental data revealed that initial CL photooxidation probably occurs via a type II mechanism, to produce lipid hydroperoxide by singlet oxygen attack to the alkyl chain unsaturations. The resulting hydroperoxide group prefers to reside near the aqueous interface, to increase the membrane surface area and to decrease lipid packing. Interestingly, MB orientation changes from nearly parallel to the water-monolayer interface in the ground state to normal to the interface in its triplet excited state. The latter orientation favors oxidative chain reaction continuity via a type I mechanism, during which the hydrogen atom must be transferred from the hydroperoxide group to triplet MB. Taken together, the present results can be extrapolated to improve our understanding of how oxidation progresses in lipidic biomembrane, which will lead to the formation of oxidized species with shortened chains and will cause severe photodamage to self-organized systems.

Self-assembled monolayers of aromatic pyrrole derivatives: Electropolymerization and electrocopolymerization with pyrrole

Four different 4-(pyrrol-1-yl)-benzenethiol derivatives with/without methyl groups in the 2,5-position of the pyrrole ring and the 3,5-position of the phenyl ring as well as 4-(carbazole-9-yl)-benzenethiol were deposited as self-assembled monolayers on gold to improve the properties of (co)polymerized poly(pyrrole) layers. To understand the behavior of the different systems, the electrochemical properties of the dissolved molecules as well as of the respective monolayers were studied in detail before the copolymerization with pyrrole. As expected, the derivatives without methyl groups at the pyrrole ring as well as the carbazole derivative showed reproducible polymerization from solution and within the monolayer. Infrared reflection-absorption spectroscopy was employed to study the chemical situation within the films before and after electropolymerization. Copolymerization with pyrrole was very effective for 4-(pyrrol-1-yl)-benzenethiol and 4-(pyrrol-1-yl)-3,5-dimethylbenzenethiol monolayers. The poly(pyrrole) films were characterized by scanning electron microscopy and by atomic force microscopy, which revealed significantly smoother and more homogenous surface structures for the films copolymerized onto monolayers of the derivatives without methyl groups at the pyrrole ring as compared to poly(pyrrole) films deposited on bare gold. As evidenced by electrochemical impedance spectroscopy, the capacity at the copolymerized films is decreased as a consequence of the reduction in roughness, while the conductivity at the metal/polymer interface increases due to the covalent attachment through an aromatic system. For the 2,5-dimethylated pyrrole derivatives and for the carbazole derivative there were no such observations.

Anomalously Rapid Tunneling: Charge Transport across Self-Assembled Monolayers of Oligo(ethylene glycol).

This paper describes charge transport by tunneling across self-assembled monolayers (SAMs) of thiol-terminated derivatives of oligo(ethylene glycol) (HS(CH2CH2O)nCH3; HS(EG)nCH3); these SAMs are positioned between gold bottom electrodes and Ga2O3/EGaIn top electrodes. Comparison of the attenuation factor (β of the simplified Simmons equation) across these SAMs with the corresponding value obtained with length-matched SAMs of oligophenyls (HS(Ph)nH) and n-alkanethiols (HS(CH2)nH) demonstrates that SAMs of oligo(ethylene glycol) have values of β (β(EG)n = 0.29 ± 0.02 natom-1 and β = 0.24 ± 0.01 Å-1) indistinguishable from values for SAMs of oligophenyls (β(Ph)n = 0.28 ± 0.03 Å-1), and significantly lower than those of SAMs of n-alkanethiolates (β(CH2)n = 0.94 ± 0.02 natom-1 and 0.77 ± 0.03 Å-1). There are two possible origins for this low value of β. The more probable involves hole tunneling by superexchange, which rationalizes the weak dependence of the rate of charge transport on the length of the molecules of HS(EG)nCH3 using interactions among the high-energy, occupied orbitals associated with the lone-pair electrons on oxygen. Based on this mechanism, SAMs of oligo(ethylene glycol)s are good conductors (by hole tunneling) but good insulators (by electron and/or hole drift conduction). This observation suggests SAMs derived from these or electronically similar molecules are a new class of electronic materials. A second but less probable mechanism for this unexpectedly low value of β for SAMs of S(EG)nCH3 rests on the possibility of disorder in the SAM and a systematic discrepancy between different estimates of the thickness of these SAMs.

Effect of acidity on morphologies and photodimerization kinetics in Langmuir-Blodgett monolayers of styrylquinoline derivatives

The real-time second harmonic generation was employed to investigate the [2+2] photodimerization of styrylquinoline (SQ) derivatives in Langmuir-Blodgett (LB) monolayers deposited from aqueous subphases with different acidity. It was discovered that the photodimerization rate constant significantly decreased upon the addition of acid. The additional atomic force microscopy measurements revealed that surface morphologies were correlated to the photodimerization kinetics. These experimental results provide direct evidence for the topo-chemical mechanisms of [2+2] photodimerization in LB films. The current study demonstrates that the intermolecular interactions and aggregation structures play important roles in the photochemical properties at surfaces.

On-Surface Synthesis of Self-Assembled Monolayers of Benzothiazole Derivatives Studied by STM and XPS.

On-surface synthesis has gradually become a prevalent approach to constructing two-dimensional functional monolayers on various substrates. In the present work, the synthesis of self-assembled monolayers (SAMs) of benzothiazole derivatives was conducted at the liquid/solid interface for the first time. Two kinds of nanostructures were achieved on the highly oriented pyrolytic graphite (HOPG) surface via the condensation reaction between aromatic aldehyde derivatives and 2-aminothiophenol (ATP). The formation of thiazole-based self-assemblies was revealed by scanning tunneling microscopy (STM) and further confirmed by X-ray photoelectron spectroscopy (XPS). The successful synthesis of the benzothiazole derivatives not only extends the scope of on-surface reactions but also can be applied in designing multifunctional SAMs at the interface.

Analysis of the Hysteresis Behavior of Perovskite Solar Cells with Interfacial Fullerene Self-Assembled Monolayers.

The use of self-assembled monolayers (SAMs) of fullerene derivatives reduces the hysteresis of perovskite solar cells (PSCs). We have investigated three different fullerene derivatives observing a decrease on hysteresis for all the cases. Several processes can contribute to the hysteresis behavior on PSCs. We have determined that the reduced hysteresis observed for devices with SAMs is produced by a decrease of the capacitive hysteresis. In addition, with an appropriated functionalization, SAMs can increase photocurrent even when no electron selective contact (ESC) is present and a SAM is deposited just on top of the transparent conductive oxide. Appropriated functionalization of the fullerene derivative, as introducing -CN groups, can enhance cell performance and reduce hysteresis. This work paves the way for a future enhancement of PSCs by a tailored design of the fullerene molecules that could actuate as an ESC by themselves.