Monomer Monolayer Research Articles

In-situ nanospectroscopic imaging of plasmon-induced two-dimensional [4+4]-cycloaddition polymerization on Au(111)

Plasmon-induced chemical reactions (PICRs) have recently become promising approaches for highly efficient light-chemical energy conversion. However, an in-depth understanding of their mechanisms at the nanoscale still remains challenging. Here, we present an in-situ investigation by tip-enhanced Raman spectroscopy (TERS) imaging of the plasmon-induced [4+4]-cycloaddition polymerization within anthracene-based monomer monolayers physisorbed on Au(111), and complement the experimental results with density functional theory (DFT) calculations. This two-dimensional (2D) polymerization can be flexibly triggered and manipulated by the hot carriers, and be monitored simultaneously by TERS in real time and space. TERS imaging provides direct evidence for covalent bond formation with ca. 3.7 nm spatial resolution under ambient conditions. Combined with DFT calculations, the TERS results demonstrate that the lateral polymerization on Au(111) occurs by a hot electron tunneling mechanism, and crosslinks form via a self-stimulating growth mechanism. We show that TERS is promising to be plasmon-induced nanolithography for organic 2D materials.

Photochemical Creation of Covalent Organic 2D Monolayer Objects in Defined Shapes via a Lithographic 2D Polymerization.

In this work we prepare Langmuir-Blodgett monolayers with a trifunctional amphiphilic anthraphane monomer. Upon spreading at the air/water interface, the monomers self-assemble into 1 nm-thin monolayer islands, which are highly fluorescent and can be visualized by the naked eye upon excitation. In situ fluorescence spectroscopy indicates that in the monolayers, all the anthracene units of the monomers are stacked face-to-face forming excimer pairs, whereas at the edges of the monolayers, free anthracenes are present acting as edge groups. Irradiation of the monolayer triggers [4 + 4]-cycloadditions among the excimer pairs, effectively resulting in a two-dimensional (2D) polymerization. The polymerization reaction also completely quenches the fluorescence, allowing to draw patterns on the monomer monolayers. More interestingly, after transferring the monomer monolayer on a solid substrate, by employing masks or the laser of a confocal scanning microscope, it is possible to arbitrarily select the parts of the monolayer that one wants to polymerize. The unpolymerized regions can then be washed away from the substrate, leaving 2D macromolecular monolayer objects of the desired shape. This photolithographic process employs 2D polymerizations and affords 1 nm-thin coatings.

Structural Characterization of a Covalent Monolayer Sheet Obtained by Two‐Dimensional Polymerization at an Air/Water Interface

AbstractThis work describes a two‐dimensional polymerization at an air/water interface and provides, for the first time, direct spectroscopic evidence for the kind of crosslinks formed and for the conversion reached in a covalently bonded monolayer sheet. This evidence was obtained through a combination of a variety of monolayer characterization techniques before and after transfer onto solid substrates, in particular by tip‐enhanced Raman spectroscopy (TERS) and TERS mapping after transfer of both the monomer and polymer monolayer onto Au(111). This work is a major advance for the field of 2D polymers synthesized at the air/water interface as it, in principle, allows estimation of the crystallinity by percolation theory and the location of regions with defects.

Structural Characterization of a Covalent Monolayer Sheet Obtained by Two-Dimensional Polymerization at an Air/Water Interface.

This work describes a two-dimensional polymerization at an air/water interface and provides, for the first time, direct spectroscopic evidence for the kind of crosslinks formed and for the conversion reached in a covalently bonded monolayer sheet. This evidence was obtained through a combination of a variety of monolayer characterization techniques before and after transfer onto solid substrates, in particular by tip-enhanced Raman spectroscopy (TERS) and TERS mapping after transfer of both the monomer and polymer monolayer onto Au(111). This work is a major advance for the field of 2D polymers synthesized at the air/water interface as it, in principle, allows estimation of the crystallinity by percolation theory and the location of regions with defects.

Nano-structural comparison of 2-methacryloyloxyethyl phosphorylcholine- and ethylene glycol-based surface modification for preventing protein and cell adhesion

Polymer brush, owing to its precisely controllable nanostructure, has great potential for surface modification in the biomedical field. In this study, we evaluated the bio-inertness of polymer brush, monomer monolayers, and polymer-coated surfaces based on their structures, to identify the most effective bio-inert modification. We focused on two well-known bio-inert materials, 2-methacryloyloxyethyl phosphorylcholine (MPC) and ethylene glycol (EG). The amount of adsorbed proteins on the surface was found to be dependent on the monomer unit density in the case of MPC, whereas this correlation was not observed in the case of EG. Cell adhesion was suppressed on the brush structure of both MPC and EG units, regardless of their density. The brush structure of MPC and EG units showed better anti-protein- and anti-cell-adhesion than monolayers and polymer-coated surfaces. Thus, the steric repulsion was not only important in EG units-based surface, but also in MPC-based surface. In addition, multiple polymer layers formed by MPC-based polymer coating also displayed similar properties.

Protective role of PEG conjugated phospholipid in reducing ischemic reperfusion injury in two allogeneic pig kidney transplant models

Polymer brush, owing to its precisely controllable nanostructure, has great potential for surface modification in the biomedical field. In this study, we evaluated the bio-inertness of polymer brush, monomer monolayers, and polymer-coated surfaces based on their structures, to identify the most effective bio-inert modification. We focused on two well-known bio-inert materials, 2-methacryloyloxyethyl phosphorylcholine (MPC) and ethylene glycol (EG). The amount of adsorbed proteins on the surface was found to be dependent on the monomer unit density in the case of MPC, whereas this correlation was not observed in the case of EG. Cell adhesion was suppressed on the brush structure of both MPC and EG units, regardless of their density. The brush structure of MPC and EG units showed better anti-protein- and anti-cell-adhesion than monolayers and polymer-coated surfaces. Thus, the steric repulsion was not only important in EG units-based surface, but also in MPC-based surface. In addition, multiple polymer layers formed by MPC-based polymer coating also displayed similar properties.

Minimally invasive characterization of covalent monolayer sheets using tip-enhanced Raman spectroscopy.

Synthetic covalent monolayer sheets and their subclass, two-dimensional polymers are of particular interest in materials science because of their special dimensionality which renders them very different from any bulk matter. However, structural analysis of such entities is rather challenging, and there is a clear need for additional analytical methods. The present study shows how tip-enhanced Raman spectroscopy (TERS) can be performed on monomer monolayers and the covalent sheets prepared from them by [4 + 4]-cycloaddition to explore rather complex structural and mechanistic issues. TERS is a surface analytical method that combines the high lateral resolution of scanning probe microscopy (SPM) with a greatly enhanced Raman scattering intensity. The high spatial resolution (<60 nm) and the significantly improved sensitivity (contrast factor of >4000) compared to confocal Raman microscopy provides new insights into the formation of this new and exciting material, namely significant consumption of the reactive units (anthracenes) and exclusion of the alternative [4 + 2]-cycloaddition. Moreover, due to the high lateral resolution, it was possible to find a first spectroscopic hint for step growth as the dominant mechanism in the formation of these novel monolayer sheets. In addition, TERS was used to get first insights into the phase behavior of a comonomer mixture.

Formation of a stable polymer blue phase under UV irradiation of Langmuir-Schaefer films of diin N-arylcarbamate derivative

Polymerization under UV irradiation is studied in monolayer Langmuir-Schaefer films of diin N-arylcarbamate derivative. The formation of a stable polymer blue phase of diacetylene derivative stable against excess UV light and heating to a temperature of 120 °C was detected. The formation of the structurally ordered Langmuir monolayer of monomers is studied using Brewster angle microscopy.

Simulation of foaming ability, multiplicity, and foam stability of shampoo

Equations for a foam height, multiplicity, and foam stability of shampoo were suggested. Model deriving was based on an assumption that foams was monodispersed systems consisting from cells of gas in the form of pentagonal dodecahedra with liquid films created by two adsorption monolayers of surfactant monomers.

Study of the Aggregation of Human Insulin Langmuir Monolayer

The human insulin (HI) Langmuir monolayer at the air-water interface was systematically investigated in the presence and absence of Zn(II) ions in the subphase. HI samples were dissolved in acidic (pH 2) and basic (pH 9) aqueous solutions and then spread at the air-water interface. Spectroscopic data of aqueous solutions of HI show a difference in HI conformation at different pH values. Moreover, the dynamics of the insulin protein showed a dependence on the concentration of Zn(II) ions. In the absence of Zn(II) ions in the subphase, the acidic and basic solutions showed similar behavior at the air-water interface. In the presence of Zn(II) ions in the subphase, the surface pressure-area and surface potential-area isotherms suggest that HI may aggregate at the air-water interface. It was observed that increasing the concentration of Zn(II) ions in the acidic (pH 2) aqueous solution of HI led to an increase of the area at a specific surface pressure. It was also seen that the conformation of HI in the basic (pH 9) medium had a reverse effect (decrease in the surface area) with the increase of the concentration of Zn(II) ions in solution. From the compression-decompression cycles we can conclude that the aggregated HI film at air-water interface is not stable and tends to restore a monolayer of monomers. These results were confirmed from UV-vis and fluorescence spectroscopy analysis. Infrared reflection-absorption and circular dichroism spectroscopy techniques were used to determine the secondary structure and orientation changes of HI by zinc ions. Generally, the aggregation process leads to a conformation change from α-helix to β-strand and β-turn, and at the air-water interface, the aggregation process was likewise seen to induce specific orientations for HI in the acidic and basic media. A proposed surface orientation model is presented here as an explanation to the experimental data, shedding light for further research on the behavior of insulin as a Langmuir monolayer.

Surface‐Confined Electropolymerization of Methylene Blue on Gold Electrodes

AbstractWe report on the electrochemical behaviour and electropolymerization of self‐assembled monolayers (SAMs) of methylene blue (MB) on gold electrodes. The SAMs of MB on gold electrodes were prepared by immersing the substrates into a solution of 1.0 mM MB in absolute ethanol for different times at room temperature. Cyclic voltammetry experiments exhibited that reductive desorption of MB monolayer takes place at three different potentials on polycrystalline gold electrodes, while reductive desorption of MB monolayer consists of only one peak on single crystal Au(111) substrates. Calculated charge densities for different immersion times indicated that optimal immersion time for self‐assembly of MB is 96 h. Electropolymerization of SAMs of MB on gold electrode was achieved by applying 0.95 V for 1 s in 0.1 M borate buffer solution (pH: 9.0). It was observed that poly(MB) monolayers are highly stable in acidic media. ATR‐FTIR and UV‐vis spectra exhibited differences between monomer and polymer monolayers, which are attributed to surface‐confined electropolymerization. STM image of poly(MB) monolayer on Au(111) substrate revealed a surface that is covered by well‐ordered, collateral nanowires with an average size of 3 nm.

Neutron scattering study of the dynamics of a polymer melt under nanoscopic confinement

Poly(ethylene oxide) confined in an anodic aluminum oxide solid matrix has been studied by different neutron scattering techniques in the momentum transfer (Q) range 0.2<or=Q=/Q/<or=1.9 A(-1). The cylindrical pores of the matrix present a diameter (40 nm) much smaller than their length (150 microm) and are parallel and hexagonally ordered. In particular, we investigated the neutron intensity scattered for two orientations of the sample with respect to the incident beam, for which the Q direction was either parallel or perpendicular to the pores for a scattering angle of 90 degrees . Diffuse neutron scattering at room temperature has shown that the aluminum oxide has amorphous structure and the polymer in the nanoporous matrix is partially crystallized. Concerning the dynamical behavior, for Q<1 A(-1), the spectra show Rouse-like motions indistinguishable from those in the bulk within the uncertainties. In the high-Q limit we observe a slowing down of the dynamics with respect to the bulk behavior that evidences an effect of confinement. This effect is more pronounced for molecular displacements perpendicular to the pore axis than for parallel displacements. Our results clearly rule out the strong corset effect proposed for this polymer from nuclear magnetic resonance (NMR) studies and can be rationalized by assuming that the interactions with the pore walls affect one to two adjacent monomer monolayers.

Membrane nanostructures on the basis of biologically active compounds for bionanotechnological purposes

This paper discusses several works on supramolecular nanosystems such as monolayer, bilayer, and multiple-layer films of various biologically active compounds like surface-active monoand polymers, membrane proteins, enzymes, and ionophores. Special attention is paid to the production and studies of surfaceactive monomer monolayers containing immobilized photosynthetic reaction center proteins, bacteriorhodopsin, glucose oxidase, and new amphiphilic derivatives of crown-containing dyes. Based on the results obtained for such structures by absorption and fluorescence spectroscopy, atomic force and Brewster-angle microscopy, and surface pressure and surface potential isotherm measurements, the possibility of developing bioand nanomaterials possessing a set of specified properties (including biosensor, chemosensor, photochromic, and photorefractive materials) is demonstrated.

V(V) species in supported catalysts: Analysis and performance in oxidative dehydrogenation of ethane

Voltammetry of immobilized microparticles (VMP), diffuse reflectance UV–vis spectroscopy (DRS), X-ray powder diffraction (XRD), and Raman spectroscopy were used to identify V(V) oxidic species in vanadia catalysts supported on titania, alumina, mesoporous silicas, and composites of Al 2O 3 and TiO 2 with montmorillonite (MMT). V 2O 5 was detected by VMP irrespective of its crystallinity at concentrations close to the detection limit of crystalline V 2O 5 by XRD. The interpretation of DRS was re-evaluated after VMP analyses, because detection of lower concentrations of V 2O 5 by DRS is complicated by partial overlap of their absorption bands with rather intense absorption bands of major oligomeric vanadate species, while sensitivity of VMP to V 2O 5 is much better than to less condensed vanadates. VMP selectively identified polyvanadates prevailing on TiO 2 supports and oligomeric vanadate species prevailing on alumina at medium V-loadings. XRD-nanocrystalline V 2O 5 was found as major species on impregnated mesoporous silicas with V loading above 4 wt.%. Al- and Ti-chemically modified MMTs disperse V(V) oxide species preferentially either on the Al 2O 3 or TiO 2 components, or on the aluminosilicate components; these cases are easily distinguished by VMP. VMP, especially if combined with spectral and XRD analyses, can produce detailed information about V(V) oxidic forms at V-loading close to or slightly above the critical monomer monolayer concentration, where 2-D and 3-D condensation of [VO 4] units is initiated. These forms play an important role in functionality of heterogeneous catalysts in oxidative dehydrogenation of ethane.

Polyelectrolyte-mediated adsorption of amelogenin monomers and nanospheres forming mono- or multilayers.

We have applied optical waveguide lightmode spectroscopy combined with streaming potential measurements and Fourier-transformed infrared spectroscopy to investigate adsorption of amelogenin nanospheres onto polyelectrolytes. The long-term objective was to better understand the chemical nature of these assemblies and to gain further insight into the molecular mechanisms involved during self-assembly. It was found that monolayers of monomers and negatively charged nanospheres of a recombinant amelogenin (rM179) irreversibly adsorbed onto a positively charged polyelectrolyte multilayer films. On the basis of measurements performed at different temperatures, it was demonstrated that intermolecular interactions for the formation of nanospheres were not affected by their adsorption onto polyelectrolytes. Consecutive adsorption of nanospheres resulting in the formation of multilayer structures was possible by using cationic poly(l-lysine) as mediators. N-Acetyl-d-glucosamine (GlcNac) did not disturb the nanosphere-assembled protein's structure, and it only affected the adsorption of monomeric amelogenin. Infrared spectroscopy of adsorbed amelogenin revealed conformational differences between the monomeric and assembled forms of rM179. While there was a considerable amount of alpha-helices in the monomers, beta-turn and beta-sheet structures dominated the assembled proteins. Our work constitutes the first report on a structurally controlled in vitro buildup of an rM179 nanosphere monolayer-based matrix. Our data support the notion that amelogenin self-assembly is mostly driven by hydrophobic interactions and that amelogenin/PEM interactions are dominated by electrostatic forces. We suggest that similar forces can govern amelogenin interactions with non-amelogenins or the mineral phase during enamel biomineralization.

Adsorption of human insulin and Asp B28 insulin on a PTFE-like surface

The interactions of human insulin, Zn-free human insulin, and Asp B28 insulin with a hydrophobic surface were studied by ellipsometry. All three insulin types investigated adsorbed with high affinity onto the hydrophobic surface, as the plateau of the adsorption isotherm, represented by the irreversible bound fraction, was reached at concentrations > 10 −3 mg/ml. The plateau values for human insulin and Zn-free human insulin could not be distinguished with statistical significance, whereas the plateau value for Asp B28 insulin was lower than those for the two others, with an adsorbed amount corresponding to a monolayer of insulin monomers. The results observed may be explained by differences in self-association patterns of the insulin types or by enhanced charge repulsion between the Asp B28 analog and the negatively charged surface.

Soluble fibrin augments spreading of fibroblasts by providing RGD sequences of fibrinogen in soluble fibrin

We previously reported that fibroblasts were found to spread far more avidly on NaBr-solubilized fibrin monomer (FM) monolayers than on immobilized fibrinogen (Fbg), indicating that removal of fibrinopeptides by thrombin is a prerequisite for the fibrin-mediated augmentation of cell spreading [J. Biol. Chem. 272 (1997) 8824–8829]. Soluble fibrin (SF), a 1:2 complex of fibrin-monomer and fibrinogen, is known to be present in the circulating blood under the pathological condition in which blood coagulation is activated. However, its physiological roles are still incompletely known. Fibroblasts spread on immobilized purified soluble fibrin. Cells spreading on immobilized soluble fibrin were blocked by the exogenous addition of soluble fibrin and glycine–arginine–glycine–aspartic acid–serine–phenylalanine (GRGDSP)-synthetic peptide but not by the addition of fibrinogen or fibrin monomer. However, cell spreading activity was decreased in the surfaces coated with fragment X, whose Aα-chains lack carboxyl-terminal segments including arginine–glycine–aspartic acid (RGD)-2 domain, fibrin monomer complexes. It suggests that the RGD-2 domain of fibrinogen after being complexed with fibrin monomer plays a pivotal role for soluble fibrin-dependent cell spreading. Soluble fibrin in plasma derived from the patients of disseminated intravascular coagulation (DIC) was immuno-purified using the monoclonal antibody (mAb) which specifically recognizes the Ca ++-dependent conformer of fibrinogen. The purified soluble fibrin consisted of desAA-fibrin monomer and two fibrinogen molecules and did show the cell spreading activity. Thus, soluble fibrin in plasma plays a role as the modulator of thrombogenic process in vivo.

Polymerization of organized monomers

The current explanations of olefin and vinyl monomer polymerization propose that monomer molecules are successively added one by one to the growing polymer chain. This may be true if the monomer molecules exist as individual species in a polymerizing system, e.g. in dilute solutions of monomer. There are cases, however, in which monomer molecules are organized: bulk liquid monomer, solid monomer, a monomer monolayer adsorbed on a support, etc. Various supra-molecular species and particles of monomer exist in such cases. In the 1960-ties, Semenov, Kargin and Kabanov proposed a theory of organized monomer polymerization. In the last 25 years, our research group has further developed and applied that theory to various polymerizing systems: the radical polymerization of compressed ethene gas, the radical polymerization of liquid methyl methacrylate, olefin polymerization by transition metals and by Al-based catalysts. An outline of the main achievements are presented in this article.

Modification of Electrochemically Roughened Au(111) by Underpotentially Deposited Silver and Its Effect on the Subsequent Electrodeposition of Polypyrrole

In this study, electrochemically roughened Au(111) is modified with underpotential deposition (UPD) silver for the first time. The formation of self-assembled monolayers of pyrrole monomers and subsequently further autopolymerization are found on the UPD-Ag-modified gold surfaces. The presence of UPD Ag improves the stability of polypyrrole (PPy) monolayers against desorption in a sonicating bath at elevated temperature. Furthermore, the nucleation and growth mechanism for PPy electropolymerized on UPD-Ag-modified Au is distinguishable from that on unmodified Au. The corresponding conductivity and the Raman intensity of PPy electropolymerized on UPD-Ag-modified Au increase by about 2-fold and 4-fold, respectively.

Solid state photopolymerization of modified amphiphilic diynes in multilayers

Solid state topochemical photopolymerization of amphiphilic diynes modified at hydrophobic part of molecule was under the study. All compounds formed stable monomer monolayers on an aqueous subphase surface and were transferred as multilayers onto quartz substrates by the Langmuir-Blodgett technique. The changes of the multilayer absorption spectra as a function of UV irradiation time have been investigated. It is shown that the insertion of an ester or sulfonyl group into the hydrophobic part of the diyne molecule increased their activity in topochemical photopolymerization reaction. The polymer absorbancies decreased under excess UV irradiation due to the decomposition of polydiacetylenic chains in the multilayer structure.