Formation Of Self-assembled Structures Research Articles

Precursor‐involved and Conversion Rate‐controlled Self‐assembly of a 'Super Gelator' in Thixotropic Hydrogels for Drug Delivery

AbstractEnzymatic hydrogelation is a totally different process to the heating‐cooling gelation process, in which the precursors of the gelators can be involved during the formation of self‐assembled structures. Using thixotropic hydrogels formed by a super gelator as our studied system, we demonstrated that the enzyme concentration/conversion rate of enzymatic reaction had a strong influence on the morphology of resulting self‐assembled nanostructures and the property of resulting hydrogels. The principle demonstrated in this study not only helps to understand and elucidate the phenomenon of self‐assembly triggered by enzymes in biological systems, but also offers a unique methodology to control the morphology of self‐assembled structures for specific applications such as controlled drug release.

Self-assembled structure formation from interactions between polyhedral oligomeric silsesquioxane and sorbitol in preparation of polymer compounds

This study investigated the factors responsible for molecular interactions leading to self-assembly between the molecules of sorbitol and polyhedral oligomeric silsesquioxane (POSS) carrying organic and inorganic side groups. The study also assessed the utility of such molecular adducts as processing aids which will aid preparation of polymer compounds, films, and spun fibers. Several POSS molecules containing silanol functionalities and alkyl and phenyl substituents were used to separately evaluate the effects of hydrogen bonding and π−π interactions on formation of molecular adducts. The molecular adducts were studied using differential scanning calorimetry, wide angle X-ray diffraction, scanning electron microscopy, mass spectrometry, oscillatory shear rheology, and molecular dynamics simulation. The study revealed that POSS-sorbitol self-assembled structures were formed only when hydrogen bonding and π−π interactions worked cooperatively. In addition, self-assembled molecules were of amorphous nature although POSS and sorbitol were crystalline.

Acid-directed synthesis of SERS-active hierarchical assemblies of silver nanostructures

SERS-active silver hierarchical assemblies are synthesized in solution by the assistance of small acid molecules. We here demonstrate the acid-directed self-assembly of metal nanoparticles (MNPs) into large systems with complex structures, without the application of any polymer surfactant or capping agent. It is verified that small acid molecules (citric acid, mandelic acid, etc.) incorporated into conventional solution chemistry can direct the assembly of MNPs into well-defined hierarchical structures. The constructed assembled structures with highly roughened surfaces can be highly sensitive SERS platforms, and the fabricated core–shell Ag wires show especially high SERS sensitivity toward the analyte melamine. The prepared Ag particles with hierarchical structures show no evident polarization-dependent SERS behavior, and this isotropic feature may be an advantage for highly sensitive SERS tags, since no certain incident polarization is required for molecule detection. We believe the subsequent addition of acid to induce formation of self-assembled structures can be a general synthetic platform to fabricate metal structures with complex morphologies.

Self-Assembly of Hierarchical Microstructures and Their Ring Patterns in Evaporating Droplets

Urchin-like and tree-shaped hierarchical microstructures were prepared within a solution droplet through drying-mediated self-assembly of organic molecules. The hierarchical architectures inside the droplet can orderly arrange into irregular ring patterns. The morphology evolvement of the hierarchical microstructures and the formation of the ring patterns were captured and studies with the assistance of optical microscopy. Their formation mechanisms were discussed on the basis of the results of time-dependent experiments. The amount of organic molecules in the solution had an obvious effect on the size and morphology of hierarchical microstructures and ring pattern formation. The optical properties of the hierarchical microstructures were investigated in detail and the formation of self-assembled structures resulted in significant changes in optical properties. The formation of the complex superstructures and generation of the ring patterns not only enriched synthesis science but also provided new blocks in future architectures of functional devices.

Energy Transfer between Confined Dye and Surface Attached Au Nanoparticles of Mesoporous Silica

Nanoscale architectures have been designed by entrapping rhodamine 6G dye molecules into the channels of mesoporous silica and Au nanoparticles anchor onto the surface of the mesoporous matrix. The surface energy transfer between confined dye and Au nanoparticles has been studied by steady state and time-resolved spectroscopy. The appearance of second surface plasmon band at 680 nm with increasing the concentration of mesoporous silica indicates the formation of self-assembled structure of Au nanoparticles which is established by TEM and DLS studies. A mechanism for self-assembled Au nanoparticles is proposed. The PL quenching (76.3% to 27.4%) and energy transfer efficiency (51.8% to 17.4%) can be tuned with changing the arrangement of Au nanoparticles. Analysis reveals that the energy transfer from dye to Au nanoparticles is a surface energy transfer process and it follows 1/d4 distance dependence. This anisotropy decay reveals that the dye molecules are aligned inside the channels of mesoporous silica. Such energy transfer between confined dye and Au nanoparticles could pave the way for designing new optical based materials for the application in chemical sensing or light harvesting system.

Formation of extended straight molecular chains by pairing of thymine molecules on the Ag–Si(111) surface

Here, we report on the assembly of thymine molecules into extended straight chains of single and multiple dimer rows on a Si(111)/Ag \(\sqrt{3}\times \sqrt{3}\) R30° surface. Using variable temperature scanning tunneling microscopy, we follow the nucleation process and formation of self-assembled structures. Submonolayer coverages at 120 K are disordered and exhibit a high density of thymine dimers. Upon annealing the dimers assemble into extended dimer chains along three equivalent high-symmetry surface directions. At low coverages single dimer rows are favored. At increased coverage chains with multiple dimer rows are observed, with a preference to an even multiplicity. We show that a complex cross-talk between H-bond thymine–thymine interactions and commensurization of dimer chains to the Ag/Si surface leads to this specific layout.

Self-assembly structure formation on patterned InP surfaces

Self-assembly of polystyrene spheres guided by patterned n-type InP substrates has been investigated. InP surfaces were patterned using a variety of methods including wet chemical etching, sputter coating, thermal evaporation, and photo lithography. The self-assembly of polystyrene spheres depended on the appearance of patterns and was affected by the deposition techniques (sputter coating and thermal evaporation) of Au micro-squares. SEM and AFM were used to characterize the surface morphologies.

SWNT-DNA and SWNT-polyC Hybrids: AFM Study and Computer Modeling

Hybrids of carbon single-walled nanotubes (SWNT) with fragmented single or double-stranded DNA (fss- or fds-DNA) or polyC were studied by Atom Force Microscopy (AFM) and computer modeling. It was found that fragments of the polymer wrap in several layers around the nanotube, forming a strand-like spindle. In contrast to the fss-DNA, the fds-DNA also forms compact structures near the tube surface due to the formation of self-assembly structures consisting of a few DNA fragments. The hybrids of SWNT with wrapped single-, double- or triple strands of the biopolymer were simulated, and it was shown that such structures are stable. To explain the reason of multi-layer polymeric coating of the nanotube surface, the energy of the intermolecular interactions between different components of polyC was calculated at the MP2/6-31++G** level as well as the interaction energy in the SWNT-cytosine complex.

Complexity in the Self-Assembly of Bifunctional Molecules on HOPG: The Influence of Solvent Functionality on Self-Assembled Structures

Self-assembled monolayers of bifunctional molecules HOOC(CH2)nCOOH (n = 20, 18, 16, 14, 12, 10), HOOC(CH2)nCH2OH (n = 13, 14), and HOCH2(CH2)14CH2OH dissolved in octanoic acid were investigated using scanning tunneling microscopy, to understand the self-assembly of bifunctional molecules and the influence of a carboxylic acid solvent on the formation of self-assembled structures on HOPG. In the series of di-acids (HOOC(CH2)nCOOH), only HOOC(CH2)20COOH forms stable coadsorption structures with the solvent octanoic acid. The remaining di-acids form stable single-component monolayers and do not coadsorb with solvent octanoic acid. Coadsorption structures involving mixtures of di-acids were observed. This result suggests that coadsorption with acid solvent or with other di-acids occurs to maximize hydrogen-bond density in the overlayer. A quantitative model based on this concept is proposed. For hetero-bifunctional molecules HOOC(CH2)nCH2OH (n = 13, 14), the coadsorption of HOOC(CH2)14CH2OH and octanoic acid at the molecular level produces a microscopic mesh made of homogeneously arranged openings with a dimension of approximately 12.5 A x approximately 5.0 A x approximately 1.8 A. For the hetero-bifunctional molecule HOOC(CH2)13CH2OH, hydroxyl groups of two adjacent lamellae assemble to form a herringbone geometry, and the two carboxylic acid groups assemble with a straight head-to-head configuration. In addition, a new mixed hydrogen-bonding network of COOH...O-H was observed in another self-assembled structure of this molecule. The bifunctional molecule HOCH2(CH2)14CH2OH exhibits multiple packing patterns on HOPG via different hydrogen-bonding networks. HOCH2(CH2)14CH2OH self-assembles using the H-O...O-H network typical of the n-alcohol herringbone structure, forming an asymmetric adsorbate on HOPG. It also forms domains with another hydrogen-bonding network, in which molecules in adjacent lamellae are parallel to each other. This investigation demonstrates the complexity and diversity of self-assembled structures formed from bifunctional molecules on solid surfaces. It also indicates that a solvent with the same functional group as the solute can significantly impact the formation of the self-assembled structures of these bifunctional molecules.

Nanocrystalline Ag from Supramolecular Stabilization of Metals in 4‐tert‐Butylcalix[4]arene Lattices

Competition between intermolecular forces is a prime method for directing the formation of self-assembled structures without resorting to the use of covalently modified host molecules. In this study, we demonstrate how the competition between hydrogen bonding, coordinate bonding, and van der Waals interactions guides the formation of a complex crystalline clathrate based on a Ag-ethylenediamine coordination complex and 4-tert-butylcalix[4]arene. Owing to the coordinative flexibility of Ag and the stabilizing interactions with the calixarene framework, a four-coordinate Ag complex is included in the structure. Subsequent removal of the amine by heating the crystalline inclusion compound results in reduction of the Ag+ ion such that metallic Ag nanocrystals are formed, thus indicating that this self-assembly approach is a viable method for obtaining simple calixarene frameworks loaded with silver. In the light of the experimental evidence, we comment on how this process relates to the reduction of silver in other systems.

Self-assembled carboxylate complexes of zinc, nickel and copper

A metallo-organic hybrid acid namely tetra-aquo bis-4-carboxy- N-phthaloylglycinato zinc(II) dihydrate is prepared and characterised. In this complex the hydrogen bonding by free carboxylic acid group and π–π interactions between the rings in crystal lattice contributes to the formation of self-assembled structure. A monomeric nickel complex from 2-carbomethoxy benzoic acid ( L2H) and pyridine [Ni( L2)(py) 3(H 2O) 2] L2 is prepared (where py = pyridine). This complex has ionic as well as monodentate carboxylates. It forms self-assembly by C–H⋯π as well as hydrogen-bonding interactions. The 2-carbomethoxy benzoic acid ( L2H) forms dimeric copper complex [Cu 2( L2) 4(H 2O) 2]2H 2O which has an extended chain structure through hydrogen-bond interactions.

Correlation between Chain Packing and Photoluminescence for PPV/PPE in Macroscopically Oriented State: Side Chain Effects

Self-organization features of poly(p-phenylene-vinylene)/poly(p-phenylene-ethynylene)s (PPV/PPE)s polymers of constitutional structure (−PhC⋮CPhC⋮CPhCHCHPhCHCH−)n and bearing two alkoxy side chains on either every one (1) or every second (2) phenylene moieties are presented. Formation of self-assembled structures on various size scales has been examined using a combination of experimental methods. Initial investigations performed for macroscopically isotropic samples by means of DSC, POM, and 2D SALS have revealed a strong dependence of the thermal behavior and related morphologies on the side chain densities. The existence of organizational features in macroscopically oriented bulk samples (extruded filaments) was also demonstrated using 2D WAXS. Self-organization of (PPV/PPE)s into biphasic structures made of spatially segregated main chain layers with the side chains filling the space between layers was postulated. The local arrangement of the macromolecular subunits was strongly dependent on the macro...

Whey Protein Coating Efficiency on Surfactant-Modified Hydrophobic Surfaces

Whey protein oxygen-barrier coatings on peanuts are not effective, due to incomplete peanut-surface coverage, as well as some cracking and flaking of the coating. Addition of sorbitan laurate (Span 20) in the whey protein coating solution up to the critical micelle concentration (cmc) of 0.05% (w/w) significantly improved coating coverage to 88% of the peanut surface. Increasing the Span 20 concentration in the coating solution to 3 times the cmc (0.15% w/w) produced a substantial increase in peanut surface energy (>70 dyn/cm), indicating adsorption of the surfactant to the peanut surface. With this level of Span 20, the whey protein coating coverage on peanuts increased to 95%. These results suggest that a concentration of surfactant above the cmc in the coating solution is required for formation of self-assembled structures of surfactant molecules on peanut surfaces, which significantly increases the hydrophilicity, and thus coatability, of peanut surfaces.

Supramolecular self-assembly of d(TGG)4, synergistic effects of K+ and Mg2+

Spectral evidence indicates that molar concentrations of K+ can induce aggregate formation in d(TGG)4. The 320-nm turbidity monitoring indicates that more than 1 M KCl is needed for the onset of aggregation to occur at 20 degrees C within the time span of 24 h. The kinetic profile is reminiscent of autocatalytic reactions that consist of a lag period followed by accelerative and levelling phases. Progressive shortening of lag periods and more rapid accelerative phases accompany further increases in [K+]. Interestingly, the presence of Mg2+ greatly facilitates the aggregate formation and results in the prominent appearance of an intense psi-type CD. For example, whereas 1 M K+ fails to induce aggregate formation of d(TGG)4 within 24 h, the addition of 1 mM Mg2+ to a 1 M K+ solution is sufficient to induce the onset of aggregation in approximately 12 h. Furthermore, adjustment of the buffer to 16 mM Mg2+/1 M KCl reduces the lag time to less than 10 min and aggregation is nearly complete in 2 h. The requirement of [K+] for aggregation is reduced to 2 mM in the presence of 16 mM Mg2+, a reduction of nearly three orders of magnitude when compared to solutions without Mg2+. The effects of K+ and Mg2+ ions are synergistic, because the presence of 16 mM Mg2+ alone does not induce aggregate formation in this oligomer. Thermal stabilities of the aggregates are strongly dependent on the concentrations of these two ions. Although aggregates formed in the presence of 2 M KCl alone melt around 55 degrees C, those formed with added 16 mM Mg2+ melt at approximately 90 degrees C, with some aggregates remaining unmelted even at 95 degrees C. The slow kinetics of aggregate formation led to the appearance of gross hystereses in the cooling profiles. The interplay of these two ions appears to be specific, because the replacement of K+ by Na+ or the replacement of Mg2+ by other divalent cations does not lead to the observed self-assembly phenomenon, although Sr2+ can substitute for K+. A possible mechanism for the formation of self-assembled structures is suggested.