scholarly journals Gamma Radiation- and Ultraviolet-Induced Polymerization of Bis(amino acid)fumaramide Gel Assemblies

Polymers ◽  
2022 ◽  
Vol 14 (1) ◽  
pp. 214
Author(s):  
Tomislav Gregorić ◽  
Janja Makarević ◽  
Zoran Štefanić ◽  
Mladen Žinić ◽  
Leo Frkanec
Keyword(s):  
Amino Acid ◽  
Ultraviolet Radiation ◽  
Self Assembly ◽  
Gamma Ray ◽  
Methyl Esters ◽  
Three Dimensional ◽  
Soft Materials ◽  
Polymerization Reaction ◽  
Vinyl Esters ◽  
Gel Network

Controlling the polymerization of supramolecular self-assembly through external stimuli holds great potential for the development of responsive soft materials and manipulation at the nanoscale. Vinyl esters of bis(leu or val)fumaramide (1a and 2a) have been found to be gelators of various organic solvents and were applied in this investigation of the influence of organogelators’ self-assembly on solid-state polymerization induced by gamma and ultraviolet irradiation. Here, we report our investigation into the influences of self-assemblies of bis(amino acid vinyl ester)fumaramides on gamma-ray- and ultraviolet-induced polymerization. The gelator molecules self-assembled by non-covalent interactions, mainly through hydrogen bonds between the amide group (CONH) and the carboxyl group (COO), thus forming a gel network. NMR and FTIR spectroscopy were used to investigate and characterize supramolecular gels. TEM and SEM microscopy were used to investigate the morphology of gels and polymers. Morphology studies showed that the gels contained a filamentous structure of nanometer dimensions that was exhaustive in a three-dimensional network. The prepared derivatives contained reactive alkyl groups suitable for carrying out the polymerization reaction initiated by gamma or ultraviolet radiation in the supramolecular aggregates of selected gels. It was found that the polymerization reaction occurred only in the network of the gel and was dependent on the structure of aggregates or the proximity and orientation of double bonds in the gel network. Polymers were formed by the gels exposure to gamma and ultraviolet radiation in toluene, and water/DMF gels with transcripts of their gel structure into polymers. The polymeric material was able to immobilize various solvents by swelling. Furthermore, methyl esters of bis(leu and val)fumaramide (1b and 2b) were synthesized; these compounds showed no gelling properties, and the crystal structure of the valine derivative 2b was determined.

Spatiotemporal Control of Supramolecular Polymerization and Gelation of Metal-Organic Polyhedra

2020 ◽  
Author(s):  
alexandre legrand ◽  
Li-Hao Liu ◽  
Philipp Royla ◽  
Takuma Aoyama ◽  
Gavin Craig ◽  
...  
Keyword(s):  
Acid Concentration ◽  
Self Assembly ◽  
Colloidal Particles ◽  
Soft Materials ◽  
Supramolecular Materials ◽  
Time Resolved ◽  
Colloidal Gel ◽  
Metal Organic ◽  
Spatiotemporal Control ◽  
Gel Network

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA), and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption and <sup>1</sup>H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

scholarly journals Mimosa Origami: A nanostructure-enabled directional self-organization regime of materials

2016 ◽  
Vol 2 (6) ◽  
pp. e1600417 ◽  
Author(s):  
William S. Y. Wong ◽  
Minfei Li ◽  
David R. Nisbet ◽  
Vincent S. J. Craig ◽  
Zuankai Wang ◽  
...  
Keyword(s):  
Self Assembly ◽  
Three Dimensional ◽  
Soft Materials ◽  
Inorganic Materials ◽  
Living Systems ◽  
Self Organization ◽  
Mimosa Pudica ◽  
Flow Rates ◽  
Immense Potential ◽  
Spontaneous Motion

One of the innate fundamentals of living systems is their ability to respond toward distinct stimuli by various self-organization behaviors. Despite extensive progress, the engineering of spontaneous motion in man-made inorganic materials still lacks the directionality and scale observed in nature. We report the directional self-organization of soft materials into three-dimensional geometries by the rapid propagation of a folding stimulus along a predetermined path. We engineer a unique Janus bilayer architecture with superior chemical and mechanical properties that enables the efficient transformation of surface energy into directional kinetic and elastic energies. This Janus bilayer can respond to pinpoint water stimuli by a rapid, several-centimeters-long self-assembly that is reminiscent of the Mimosa pudica’s leaflet folding. The Janus bilayers also shuttle water at flow rates up to two orders of magnitude higher than traditional wicking-based devices, reaching velocities of 8 cm/s and flow rates of 4.7 μl/s. This self-organization regime enables the ease of fabricating curved, bent, and split flexible channels with lengths greater than 10 cm, demonstrating immense potential for microfluidics, biosensors, and water purification applications.

scholarly journals Stimuli-Responsive Nucleotide–Amino Acid Hybrid Supramolecular Hydrogels

Gels ◽  
2021 ◽  
Vol 7 (3) ◽  
pp. 146
Author(s):  
Matthew Mulvee ◽  
Natasa Vasiljevic ◽  
Stephen Mann ◽  
Avinash J. Patil
Keyword(s):  
Mechanical Properties ◽  
Amino Acid ◽  
Self Assembly ◽  
Soft Materials ◽  
Guanosine Monophosphate ◽  
Molar Ratio ◽  
Stimuli Responsive ◽  
Molar Ratios ◽  
Hybrid Hydrogels ◽  
Guanine Residue

The ability to assemble chemically different gelator molecules into complex supramolecular hydrogels provides excellent opportunities to construct functional soft materials. Herein, we demonstrate the formation of hybrid nucleotide–amino acid supramolecular hydrogels. These are generated by the silver ion (Ag+)-triggered formation of silver–guanosine monophosphate (GMP) dimers, which undergo self-assembly through non-covalent interactions to produce nanofilaments. This process results in a concomitant pH reduction due to the abstraction of a proton from the guanine residue, which triggers the in situ gelation of a pH-sensitive amino acid, N-fluorenylmethyloxycarbonyl tyrosine (FY), to form nucleotide–amino acid hybrid hydrogels. Alterations in the supramolecular structures due to changes in the assembly process are observed, with the molar ratio of Ag:GMP:FY affecting the assembly kinetics, and the resulting supramolecular organisation and mechanical properties of the hydrogels. Higher Ag:GMP stoichiometries result in almost instantaneous gelation with non-orthogonal assembly of the gelators, while at lower molar ratios, orthogonal assembly is observed. Significantly, by increasing the pH as an external stimulus, nanofilaments comprising FY can be selectively disassembled from the hybrid hydrogels. Our results demonstrate a simple approach for the construction of multicomponent stimuli-responsive supramolecular hydrogels with adaptable network and mechanical properties.

Polymerization-induced self-assembly driving chiral nanostructured materials

2015 ◽  
Vol 6 (34) ◽  
pp. 6152-6162 ◽  
Author(s):  
Kamal Bauri ◽  
Amal Narayanan ◽  
Ujjal Haldar ◽  
Priyadarsi De
Keyword(s):  
Amino Acid ◽  
Nanostructured Materials ◽  
Self Assembly ◽  
Soft Materials ◽  
Morphological Transition ◽  
Group Transformation

Amino acid coated chiral nanostructured soft materials are made by the polymerization induced self-assembly (PISA) technique, where the post-polymerization chemical group transformation leads to a morphological transition.

scholarly journals Spatiotemporal Control of Supramolecular Polymerization and Gelation of Metal-Organic Polyhedra

2020 ◽  
Author(s):  
alexandre legrand ◽  
Li-Hao Liu ◽  
Philipp Royla ◽  
Takuma Aoyama ◽  
Gavin Craig ◽  
...  
Keyword(s):  
Acid Concentration ◽  
Self Assembly ◽  
Colloidal Particles ◽  
Soft Materials ◽  
Supramolecular Materials ◽  
Time Resolved ◽  
Colloidal Gel ◽  
Metal Organic ◽  
Spatiotemporal Control ◽  
Gel Network

In coordination-based supramolecular materials such as metallogels, simultaneous temporal and spatial control of their assembly remains challenging. Here, we demonstrate that the combination of light with acids as stimuli allows for the spatiotemporal control over the architectures, mechanical properties, and shape of porous soft materials based on metal-organic polyhedra (MOPs). First, we show that the formation of a colloidal gel network from a preformed kinetically trapped MOP solution can be triggered upon addition of trifluoroacetic acid (TFA), and that acid concentration determines the reaction kinetics. As determined by time-resolved dynamic light scattering, UV-vis absorption and <sup>1</sup>H NMR spectroscopies and rheology measurements, the consequences of the increase in acid concentration are (i) an increase in the cross-linking between MOPs; (ii) a growth in the size of the colloidal particles forming the gel network; (iii) an increase in the density of the colloidal network; and (iv) a decrease in the ductility and stiffness of the resulting gel. We then demonstrate that irradiation of a dispersed photoacid generator, pyranine, allows the spatiotemporal control of the gel formation by locally triggering the self-assembly process. Using this methodology, we show that the gel can be patterned into a desired shape. Such precise positioning of the assembled structures, combined with the stable and permanent porosity of MOPs, could allow their integration into devices for applications such as sensing, separation, catalysis, or drug release.

scholarly journals Graphene Oxide-Chitosan Aerogels: Synthesis, Characterization, and Use as Adsorbent Material for Water Contaminants

Gels ◽  
2021 ◽  
Vol 7 (4) ◽  
pp. 149
Author(s):  
Filippo Pinelli ◽  
Tommaso Nespoli ◽  
Filippo Rossi
Keyword(s):  
Graphene Oxide ◽  
Self Assembly ◽  
Three Dimensional ◽  
Soft Materials ◽  
Complete Removal ◽  
Mechanical Analysis ◽  
Anionic Dyes ◽  
Water Contaminants ◽  
High Sorption ◽  
The Stability

Porous aerogels, formed by subjecting precursor hydrogels using a freeze-drying process, are certainly one of the most studied and synthetized soft materials, thanks to their important features such as elasticity, swelling behavior, softness, and micro and nanosized pores, which guarantee their applicability in various fields. Typically, these systems are synthetized working with natural or synthetic polymers, but in the last years great interest has been given to proper formulated aerogels able to combine polymeric structures with other moieties such as graphene or graphene oxide. This working strategy can be pivotal in many cases to tune important properties of the final system such as toughness, porosity, elasticity, electrical conductivity, or responsive behavior. In this work we propose the synthesis of chitosan graphene oxide aerogels obtained through self-assembly of graphene oxide sheets and chitosan chains. These three-dimensional systems were chemically characterized with IR and XRD technique and their inner structure was investigated through the scanning electron microscopy (SEM). Moreover, we mechanically characterized the material through dynamic mechanical analysis, showing the stability of these systems. Finally, the adsorption ability of these soft materials has been demonstrated using model molecules to simulate water contaminants showing the efficacy of those graphene-based systems even for the removal of anionic dyes. Complete removal of contaminants was obtained at low concentration of dyes in solution (100 mg/L), while with a higher amount of pollutant in the solution (350 mg/L) high sorption capacity (q > 200 mg/g) was observed.

scholarly journals Controlled molecular self-assembly of complex three-dimensional structures in soft materials

2017 ◽  
Vol 115 (1) ◽  
pp. 70-74 ◽  
Author(s):  
Changjin Huang ◽  
David Quinn ◽  
Subra Suresh ◽  
K. Jimmy Hsia
Keyword(s):  
Flexible Electronics ◽  
Self Assembly ◽  
Polymer Network ◽  
Three Dimensional ◽  
Soft Materials ◽  
Tissue Growth ◽  
Tissue Morphogenesis ◽  
Material Transport ◽  
Essential Components ◽  
Living Tissues

Many applications in tissue engineering, flexible electronics, and soft robotics call for approaches that are capable of producing complex 3D architectures in soft materials. Here we present a method using molecular self-assembly to generate hydrogel-based 3D architectures that resembles the appealing features of the bottom-up process in morphogenesis of living tissues. Our strategy effectively utilizes the three essential components dictating living tissue morphogenesis to produce complex 3D architectures: modulation of local chemistry, material transport, and mechanics, which can be engineered by controlling the local distribution of polymerization inhibitor (i.e., oxygen), diffusion of monomers/cross-linkers through the porous structures of cross-linked polymer network, and mechanical constraints, respectively. We show that oxygen plays a role in hydrogel polymerization which is mechanistically similar to the role of growth factors in tissue growth, and the continued growth of hydrogel enabled by diffusion of monomers/cross-linkers into the porous hydrogel similar to the mechanisms of tissue growth enabled by material transport. The capability and versatility of our strategy are demonstrated through biomimetics of tissue morphogenesis for both plants and animals, and its application to generate other complex 3D architectures. Our technique opens avenues to studying many growth phenomena found in nature and generating complex 3D structures to benefit diverse applications.

In vitro and in vivo polysaccharides assembly: ultrastructural and cytochemical study of growing plant cell wall components.

1978 ◽  
Vol 36 (2) ◽  
pp. 434-435
Author(s):  
D. Reis ◽  
B. Vian ◽  
J. C. Roland
Keyword(s):  
Cell Wall ◽  
Self Assembly ◽  
Plant Cell Wall ◽  
Higher Plants ◽  
Three Dimensional ◽  
Cytochemical Study ◽  
Wall Components

Wall morphogenesis in higher plants is a problem still open to controversy. Until now the possibility of a transmembrane control and the involvement of microtubules were mostly envisaged. Self-assembly processes have been observed in the case of walls of Chlamydomonas and bacteria. Spontaneous gelling interactions between xanthan and galactomannan from Ceratonia have been analyzed very recently. The present work provides indications that some processes of spontaneous aggregation could occur in higher plants during the formation and expansion of cell wall.Observations were performed on hypocotyl of mung bean (Phaseolus aureus) for which growth characteristics and wall composition have been previously defined.In situ, the walls of actively growing cells (primary walls) show an ordered three-dimensional organization (fig. 1). The wall is typically polylamellate with multifibrillar layers alternately transverse and longitudinal. Between these layers intermediate strata exist in which the orientation of microfibrils progressively rotates. Thus a progressive change in the morphogenetic activity occurs.

Nanoscale Self-Assembly Using Ion and Electron Beam Techniques: A Rapid Review

MRS Advances ◽  
2020 ◽  
Vol 5 (64) ◽  
pp. 3507-3520
Author(s):  
Chunhui Dai ◽  
Kriti Agarwal ◽  
Jeong-Hyun Cho
Keyword(s):  
Electron Beam ◽  
Self Assembly ◽  
Ion Beam ◽  
Three Dimensional ◽  
The Self ◽  
Stress Generation ◽  
Rapid Review ◽  
High Yield ◽  
3D Nanostructures ◽  
Self Assembled

AbstractNanoscale self-assembly, as a technique to transform two-dimensional (2D) planar patterns into three-dimensional (3D) nanoscale architectures, has achieved tremendous success in the past decade. However, an assembly process at nanoscale is easily affected by small unavoidable variations in sample conditions and reaction environment, resulting in a low yield. Recently, in-situ monitored self-assembly based on ion and electron irradiation has stood out as a promising candidate to overcome this limitation. The usage of ion and electron beam allows stress generation and real-time observation simultaneously, which significantly enhances the controllability of self-assembly. This enables the realization of various complex 3D nanostructures with a high yield. The additional dimension of the self-assembled 3D nanostructures opens the possibility to explore novel properties that cannot be demonstrated in 2D planar patterns. Here, we present a rapid review on the recent achievements and challenges in nanoscale self-assembly using electron and ion beam techniques, followed by a discussion of the novel optical properties achieved in the self-assembled 3D nanostructures.

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