Formation of colloidal suspension of hydrophobic compounds with an amphiphilic self-assembling peptide

The amphiphilic self-assembling peptide EAK16-II was found to be able to stabilize hydrophobic compounds in aqueous solution. Micro/nanocrystals of a hydrophobic compound, pyrene, and a hydrophobic anticancer agent, ellipticine, were stabilized by EAK16-II to form colloidal suspensions in water. Initial evidence of the association between EAK16-II and hydrophobic compounds was the observation of a clouding phenomenon and a difference in fluorescence spectra of the solution. A further investigation on the interaction between EAK16-II and pyrene was carried out using fluorescence spectroscopy and scanning electron microscopy (SEM). It was found that the pyrene–peptide complex formation required mechanical stirring, and the freshly prepared peptide solution (containing peptide monomers and/or peptide protofibrils) was more effective at stabilizing pyrene than the mature fibrils in aged peptide solutions. The time duration over which the complex formed was about 22 h. The data on the complexation of pyrene and EAK16-II at various concentrations suggested that the maximum amount of stabilized pyrene was concentration dependent. SEM images showed that peptide concentration did not significantly affect the size of the complexes/suspensions but altered the structures of the peptide coating on the surface of the complex. Atomic force microscopy (AFM) was conducted to study the interaction of EAK16-II with a model hydrophobic surface, which provided some detailed information of how peptide adsorbed onto the hydrophobic compounds and stabilize them. This study shows the potential of self-assembling peptides for encapsulation of hydrophobic compounds.     

Effect of NaCl and peptide concentration on the self-assembly of an ionic-complementary peptide EAK16-II

Previous work has examined the effects of such factors as pH and peptide concentration on the self-assembly of ionic-complementary peptides. This work focused on the effect of sodium chloride on the molecular self-assembly of an ionic-complementary peptide EAK16-II (AEAEAKAKAEAEAKAK). Surface tensions and dimensions of the self-assembled nanostructures were determined for a wide range of peptide and sodium chloride concentrations using axisymmetric drop shape analysis-profile (ADSA-P) and atomic force microscopy (AFM), respectively. The critical aggregation concentration, or critical self-assembly concentration (CSAC), of EAK16-II was not significantly affected by the presence of NaCl. However, the analysis of size variations in self-assembled nanostructures in response to changes in NaCl concentration indicated that the presence of NaCl does influence the resulting dimensions of the peptide nanostructures when the peptide concentration is below its CSAC. A critical NaCl concentration was identified at approximately 20mM, below which the equivalent radius of the peptide fibrils increased with increasing salt concentration, and above which the opposite response was observed. This critical NaCl concentration was further confirmed in the surface tension measurements, where the equilibrium surface tension and induction time of the peptide at low concentrations (相似文献   

Epitaxially guided assembly of collagen layers on mica surfaces

Ordered assembly of collagen molecules on flat substrates has potential for various applications and serves as a model system for studying the assembly process. While previous studies demonstrated self-assembly of collagen on muscovite mica into highly ordered layers, the mechanism by which different conditions affect the resulting morphology remains to be elucidated. Using atomic force microscopy, we follow the assembly of collagen on muscovite mica at a concentration lower than the critical fibrillogenesis concentration in bulk. Initially, individual collagen molecules adsorb to mica and subsequently nucleate into fibrils possessing the 67 nm D-periodic bands. Emergence of fibrils aligned in parallel despite large interfibril distances agrees with an alignment mechanism guided by the underlying mica. The epitaxial growth was further confirmed by the formation of novel triangular networks of collagen fibrils on phlogopite mica, whose surface lattice is known to have a hexagonal symmetry, whereas the more widely used muscovite does not. Comparing collagen assembly on the two types of mica at different potassium concentrations revealed that potassium binds to the negatively charged mica surface and neutralizes it, thereby reducing the binding affinity of collagen and enhancing surface diffusion. These results suggest that collagen assembly on mica follows the surface adsorption, diffusion, nucleation, and growth pathway, where the growth direction is determined at the nucleation step. Comparison with other molecules that assemble similarly on mica supports generality of the proposed assembly mechanism, the knowledge of which will be useful for controlling the resulting surface morphologies.     

Characterization of poly(methyl methacrylate) nanofiber mats by electrospinning process

In this study, the aim is to describe the influence of electrospinning parameters on the morphology, the water wetting property and dye adsorption property of poly(methyl methacrylate) nanofiber mats. Specifically, the effects of solution concentration, solvent type, applied voltage, distance between the electrodes and particulate reinforcement on the diameter and shape of the nanofibers were investigated. All poly(methyl methacrylate) nanofiber mats contained beaded nanofiber structures. With increasing the polymer solution concentration, the average fiber diameter also increased. Poly(methyl methacrylate) nanofiber mat electrospun from dimethylformamide solution resulted in thicker fibers when compared with the mat electrospun from acetone solution. Increasing the electric potential difference between the collector and the syringe tip did not increase the average fiber diameter. Besides increasing the distance between the electrodes resulted in a decrease in the average fiber diameter. When compared with PMMA nanofiber mat, thicker fibers were obtained with silica nanoparticles reinforced nanofiber mat. According to the water contact angle measurements, all poly(methyl methacrylate) nanofiber mats revealed hydrophobic surface property. PMMA nanofiber mat with the highest water contact angle gave rise to the highest dye adsorption capacity.     

Surface-tuned assembly of porphyrin coordination oligomers

Two self-complementary phenanthroline-strapped porphyrins bearing imidazole arms and C 12 or C 18 alkyl chains were synthesized, and their surface self-assembly was investigated by atomic force microscopy (AFM) on mica and highly ordered pyrrolitic graphite (HOPG). Upon zinc(II) complexation, stable porphyrin dimers formed, as confirmed by DOSY (1)H NMR and UV-visible spectroscopy. In solution, the dimers formed J-aggregates. AFM studies of the solutions dip-coated onto mica or drop-casted onto HOPG revealed that the morphologies of the assemblies formed were surface-tuned. On mica, fiber-like assemblies of short stacks of J-aggregates were observed. The strong influence of the mica's epitaxy on the orientation of the fibers suggested a surface-assisted assembly process. On HOPG, interactions between the alkyl chains and the graphite surface resulted in the stabilization and trapping of monomer species followed by their subsequent association into coordination polymers on the surface. Interdigitation of the alkyl chains of separate polymer strands induced lateral association of wires to form islands that grew preferentially upon drop-casting and slow evaporation. Clusters of laterally assembled wires were observed for the more mobile functionalized porphyrins bearing C 12 chains.     

Peptide/TiO2 surface interaction: a theoretical and experimental study on the structure of adsorbed ALA-GLU and ALA-LYS

The adsorption on the TiO(2) surface of two dipeptides AE (L-alanine-L-glutamic acid) and AK (L-alanine-L-lysine), that are "building blocks" of the more complex oligopeptide EAK16, has been investigated both theoretically and experimentally. Classical molecular dynamics simulations have been used to study the adsorption of H-Ala-Glu-NH(2) and H-Ala-Lys-NH(2) dipeptides onto a rutile TiO(2) (110) surface in water solution. Several peptide conformers have been considered simultaneously upon the surface. The most probable contact points between the molecules and the surface have been identified. Carbonyl oxygens as well as nitrogen atoms are possible Ti coordination points. Local effects are responsible for adsorption and desorption events. Self-interaction effects can induce molecular reorientations giving less strongly adsorbed species. The chemical structure and composition of thin films of the two dipeptides AE and AK on TiO(2) were investigated by XPS (X-ray photoelectron spectroscopy) measurements at both O and N K-edges. Theoretical ab initio calculations (DeltaSCF) were also performed to simulate the spectra, allowing for a direct comparison between experiment and theory.     

Polysiloxane nanofibers via surface initiated polymerization of vapor phase reagents: a mechanism of formation and variable wettability of fiber-bearing substrates

A detailed study of polysiloxane nanofiber formation by surface initiated polymerization of vapor phase organotrichlorosilane reagents is presented. Substrate composition, substrate activation, reagent quantity, reaction pressure, and reaction time are parameters shown to influence nanofiber synthesis. Stepwise variation of the parameters isolates the role of each on polysiloxane nanofiber growth, and a mechanism for fiber formation is proposed based on these findings. Tunable aqueous wettability of the fibers is also demonstrated in this report, with contact angles varying from 85 degrees to 130 degrees +/- 2 degrees depending upon fiber surface density and length. Aqueous contact angles are further increased to >150 degrees by either solution functionalization of calcined fibers or copolymerization with an organofluorosilane     

Adsorption and desorption of polymer/surfactant mixtures at solid-liquid interfaces: substitution experiments

The adsorption of mixtures of aqueous solutions of cationic hydroxyethylcellulose polymer JR400 and anionic surfactant, sodium dodecyl sulfate, using atomic force microscopy (AFM) has been studied. Samples with various compositions from different regions of the ternary phase diagram presented in our previous work were imaged by atomic force microscopy on freshly cleaved mica, and hydrophobically modified mica and silica in soft-contact mode. A series of "washing" (subsequent injection of compositions with gradually decreasing polymer/surfactant ratio) and "scratching" (mechanical agitation of the surface material with an AFM tip) experiments were performed. It was revealed that the morphology of the adsorbed layer altered in a manner following the changes in morphology in the bulk solution. These changes were evidenced in cluster formation in the layer. The results suggest that the influence of the surface was limited to the formation of the adsorbed layer where the local concentrations of polymer and surfactant were higher than those in the bulk. All further modifications were driven by changes in the mixture composition in bulk. Force measurements upon retraction reveal the formation of network structures within the surface aggregates that will greatly slow structural reequilibration.     

Nucleation of bulk phases in the HCl/H2O system

We report experimental results on the low-temperature uptake of HCl on H(2)O ice (ice). HCl was deposited on the surface at greater than monolayer amounts at 85 K, and the ice substrate was heated. The temperature dependence of the HCl vapor pressure from this phase was measured from 110 to 150 K, with the nucleation of a bulk hydrate phase observed at 150 K. Measurements were conducted in a closed system by simultaneous application of gas phase mass spectrometry and surface spectroscopy to characterize vapor/solid equilibrium and the nucleation of bulk hydrate phases. Combining the nucleation data reported here with data we reported previously (180 to 200 K) and data from two other laboratories (165 and 170 K), the thermodynamic boundaries for the nucleation of both the metastable bulk solution and bulk hydrate phases subsequent to monolayer adsorption of HCl have been determined. The nucleation of the metastable bulk solution phase occurs promptly at monolayer coverage at the ice/liquid coexistence boundary on the binary bulk phase diagram. The nucleation of the bulk hexahydrate occurs from this metastable solution along a locus of points defining a state of constant solution free energy. This measured free energy is -51.2 +/- 0.9 kJ/mol. Finally, the temperature dependence of the HCl vapor pressure from the low-temperature phase is reported here for the first time and is consistent with that of the metastable solution predicted by this thermodynamic model of uptake, extending the range of validity of this model of adsorption followed by bulk solution and hydrate nucleation to a lower bound in temperature of 110 K.     

A Simple Method for Cell Sheet Fabrication Using Mica Surfaces Grafted with Peptide Detergent A6K

Cell sheet technology is a very important strategy for scaffold‐free tissue engineering. In order to fabricate cell sheets by a simple method, peptide detergent A₆K was grafted on mica surfaces by dropping its aqueous solution at different concentrations on the surface. As revealed by surface topographical observation and water contact angle measurement, the most hydrophobic surface was obtained using peptide solution at the concentration of 0.2 mg · mL^?1. The peptide‐grafted mica surface was used to culture mouse preosteoblast cell MC3T3‐E1. After the cells reached confluence and the peptide was biodegraded, an intact cell sheet was peeled from the mica. This simple method does not need any non‐biological reagents or complicated procedures, and may have great potential in tissue engineering based on cell sheet technology.

     

From clusters to fibers: parameters for discontinuous para-hexaphenylene thin film growth

All relevant steps of discontinuous thin film growth of para-hexaphenylene on muscovite mica (0 0 1) from wetting layer over small and large clusters to nanofibers are observed and investigated in detail by a combined polarized fluorescence and atomic force microscopy study. From a variation of film thickness and surface temperature, we determine effective activation energies for cluster growth of 0.17 eV, for nanofiber length growth of 0.46 eV, for width growth of 0.19 eV, and for height growth of 0.07 eV. The corresponding exponential prefactors for the nanofiber growth are 1 x 10(9), 6 x 10(4), and 3 x 10(2) nm. Polarized fluorescence studies reveal that nanofibers grow along the grooves of the mica surface and that they do not change direction if they cross an even number of mica surface steps, while they change direction by 120 degrees for an odd number of steps. These results are taken as an input for a model of the unidirectional growth process on mica. Absolute parameters allowing one to grow nanofibers of predetermined morphology via organic molecular beam epitaxy are also given.     

Dispersion of multiwalled carbon nanotubes in water using ionic-complementary peptides

We demonstrate the noncovalent modification of multiwalled carbon nanotubes (MWNTs) immersed in aqueous solution using the ionic-complementary peptide EFK16-II. This modification presumably arises through the interaction between the hydrophobic side of the EFK16-II and MWNT sidewalls and orients hydrophilic functional groups toward the solution phase and enables them to form highly stable dispersions in water. This stability can be attributed to the electrostatic repulsion between self-assembled peptides on the MWNTs. This repulsion as determined by ζ potential measurements increases as the pH diverges from the isoelectric point of ～6.7 for EFK16-II. This trend is confirmed by dynamic light scattering measurements of the suspensions showing a decrease in their particle size as the ζ potential increases. These EFK16-II-MWNT suspensions have been used to modify mica surfaces. Atomic force microscopy and scanning electron microscopy images show that this leads to a uniform distribution of individual modified MWNTs on the mica surfaces. Transmission electron microscopy reveals images of well-dispersed fibers with dimensions similar to those of individual MWNTs. Tissue culture plates previously contacted with EFK16-II-modified MWNTs have been shown to have enough biocompatibility for growth and attachment of cells. The biocompatibility and enhanced electrical conductivity that should result from the modification with these EFK16-II-MWNT suspensions opens up their use in a number of potential biomedical applications such as the design of bioelectrode interfaces and fabrication of biosensors with high sensitivity.     

Nanomechanical stimulus accelerates and directs the self-assembly of silk-elastin-like nanofibers

One-dimensional nanostructures are ideal building blocks for functional nanoscale assembly. Peptide-based nanofibers have great potential in building smart hierarchical structures due to their tunable structures at the single residue level and their ability to reconfigure themselves in response to environmental stimuli. We observed that pre-adsorbed silk-elastin-based protein polymers self-assemble into nanofibers through conformational changes on a mica substrate. Furthermore, we demonstrate that the rate of self-assembly was significantly enhanced by applying a nanomechanical stimulus using atomic force microscopy. The orientation of the newly grown nanofibers was mostly perpendicular to the scanning direction, implying that the new fiber assembly was locally activated with directional control. Our method provides a novel way to prepare nanofiber patterned substrates using a bottom-up approach.     

Adsorption behavior of hexadecyltrimethylammonium bromide (CTAB) to mica substrates as observed by atomic force microscopy

The study of the adsorption behavior of surfac-which makes people further study the adsorptiontants to interfaces is very important in colloid and in-mechanism at the molecular level.terface science[1]owing to the important applications In situ AFM measur…     

Flow injection method for sulfide determination by the methylene blue method

Flow injection determination of sodium sulfide and hydrogen sulfide in solution through the methylene blue spectrophotometric procedure is described. The carrier streams are N,N-dimethylaniline sulfate (5.4 mM, HCl solution) and iron(m) ammonium sulfate (14.2 mM, HCl solution) and are merged before injection of sulfide (in 0.01 M NaOH). The sampling rate is 210 per hour. The effect of reagent concentrations and interferents on the determination has been investigated.     

Molecular modeling of oligopeptide adsorption onto functionalized quartz surfaces

The adsorption of an EAK 16-II oligopeptide sequence in aqueous medium onto functionalized quartz surfaces has been studied by using force field calculations and molecular dynamics methods. Two different surfaces have been simulated respectively involving fully methylated and fully silanolic quartz surfaces. Geometry optimization and molecular dynamics simulations showed that the adsorption process is mainly governed by the electrostatic interactions between SiO- surface groups and the charged residues of the oligopeptide sequence. In particular, it was found that strong electrostatic interactions (a) prompt the parallel orientation of the oligopeptide with respect to the hydrophilic charged surface, resulting in an effective physisorption process and (b) stabilize the beta-sheet configuration of the physisorbed molecules. In particular, the end-on oligopeptide orientations are demonstrated to progressively lie back onto the hydrophilic surface, but this does not happen onto the hydrophobic surface. In any case, no physisorption process was observed for the fully methylated surface, where the molecule is seen to move away from the surface during the simulation time.     

Anion effect on the nanostructure of a metal ion binding self-assembling peptide

Effects of copper salts containing different anions (SO(4)(2)(-), Cl(-), and NO(3)(-)) on the self-assembly of a designed peptide EAK16(II)GGH with affinity for Cu(2+) have been investigated. The peptide secondary structure, self-assembled nanostructures, and surface activity were observed to depend strongly on the type of anion. Over a salt concentration range from 0.05 to 10.0 mM, SO(4)(2)(-) induced long fiber formation, whereas Cl(-) and NO(3)(-) caused short fiber formation. The fiber length increased with copper sulfate concentration, but the concentration of copper chloride and copper nitrate did not affect the peptide nanostructures significantly. Analysis by Fourier transform infrared spectroscopy (FTIR) revealed that the addition of the copper salts tended to cause the peptide conformation to change from alpha-helix/random coil to beta-sheet, the extent to which depended on the anion type. This evidence of the anion effect was also supported by surface tension measurements using the axisymmetric drop shape analysis-profile (ADSA-P) technique. An explanation for the effect of anions on the peptide self-assembly was proposed. The divalent anion SO(4)(2)(-) might serve as a bridge by electrostatically interacting with two lysine residues from different peptide molecules, promoting beta-sheet formation. The extensive beta-sheet formation may further promote peptide self-assembly into long fibers. On the other hand, monovalent anions Cl(-) and NO(3)(-) may only electrostatically interact with one charged residue of the peptide; hence, a mixed secondary structure of alpha-helix/random coil and beta-sheet was observed. This observation might explain the predominant formation of short fibers in copper chloride and copper nitrate solutions.     

Adsorption and redox processes at carbon nanofiber electrodes grown onto a ceramic fiber backbone

The adsorption of aromatic compounds onto activated carbons and carbon nanofibers is of considerable technical importance and beneficial in electroanalytical procedures. Here, effects due to the strong adsorption of hydroquinone, benzoquinone, and phenol onto carbon nanofiber electrodes immersed in aqueous media are reported. Carbon nanofiber materials (fiber diameter approximately 100 nm) are grown onto ceramic fiber substrates by employing an ambient pressure chemical vapour deposition process. The resulting composite electrode material is sufficiently electrically conducting due to the high carbon content and mechanically robust due to the ceramic backbone. It is shown that the voltammetric signal obtained for the one electron reduction of Ru(NH₃)₆³⁺ is dominated by solution trapped in the three-dimensional electrode structure. In contrast, for the hydroquinone/benzoquinone redox system in aqueous phosphate buffer (pH 7) strong adsorption onto the carbon nanofiber material is observed. In the presence of phenol also strong adsorption is detected. In the course of the chemically irreversible oxidation of phenol in aqueous phosphate buffer (pH 7), the formation of multi-electron oxidation products related to benzoquinone is observed. The pathway for the oxidation process is attributed to (i) the high surface area of the carbon nanofiber electrode and (ii) the adsorption of intermediates.     

Experimental isotherms of HCl on H2O ice under stratospheric conditions: connections between bulk and interfacial thermodynamics

The adsorption of HCl on the surface of H(2)O ice has been measured at temperatures and pressures relevant to the upper troposphere and lower stratosphere. The measured HCl surface coverage is found to be at least 100 times lower than currently assumed in models of chlorine catalyzed ozone destruction in cold regions of the upper atmosphere. Measurements were conducted in a closed system by simultaneous application of surface spectroscopy and gas phase mass spectrometry to fully characterize vapor/solid equilibrium. Surface adsorption is clearly distinguished from bulk liquid or solid phases. From 180 to 200 K, submonolayer adsorption of HCl is well described by a Bragg-Williams modified Langmuir model which includes the dissociation of HCl into H(+) and Cl(-) ions. Furthermore, adsorption is consistent with two distinct states on the ice substrate, one in which the ions only weakly adsorb on separate sites, and another where the ions adsorb as an H(+)-Cl(-) pair on a single site with adsorption energy comparable to the bulk trihydrate. The number of substrate H(2)O molecules per adsorption site is also consistent with the stoichiometry of bulk hydrates under these conditions. The ionic states exist in equilibrium, and the total adsorption energy is a function of the relative population of both states. These observations and model provide a quantitative connection between the thermodynamics of the bulk and interfacial phases of HCl/H(2)O, and represent a consistent physicochemical model of the equilibrium system.