scholarly journals Unravelling a Novel Sol-Gel Transition Mechanism in Polymer Self-Assemblies: An Order-Order Transition Based on Specific Molecular Interactions Between Hydrophilic and Hydrophobic Polymer Blocks

Author(s):  
Lukas Hahn ◽  
Theresa Zorn ◽  
Josef Kehrrein ◽  
Tobias Kielholz ◽  
Benedikt Sochor ◽  
...  

Using a wide range of state-of-the art analytical techniques and molecular dynamics simulation, a novel mechanism for macromolecular interactions are described. Distinct interactions between the hydrophilic and hydrophobic blocks in amphiphilic triblock copolymers lead to an order-order transition from spherical micelles to worm-like micelles upon cooling the aqueous polymer solutions below room temperature. Macroscopically, this this leads to reversible gelation. This novel mechanism represent a novel building block to better understand polymer self-assembly.<br>

2021 ◽  
Author(s):  
Lukas Hahn ◽  
Theresa Zorn ◽  
Josef Kehrrein ◽  
Tobias Kielholz ◽  
Benedikt Sochor ◽  
...  

Using a wide range of state-of-the art analytical techniques and molecular dynamics simulation, a novel mechanism for macromolecular interactions are described. Distinct interactions between the hydrophilic and hydrophobic blocks in amphiphilic triblock copolymers lead to an order-order transition from spherical micelles to worm-like micelles upon cooling the aqueous polymer solutions below room temperature. Macroscopically, this this leads to reversible gelation. This novel mechanism represent a novel building block to better understand polymer self-assembly.<br>


Foods ◽  
2019 ◽  
Vol 8 (12) ◽  
pp. 652
Author(s):  
Floriane Doudiès ◽  
Anne-Sophie Arsène ◽  
Fabienne Garnier-Lambrouin ◽  
Marie-Hélène Famelart ◽  
Antoine Bouchoux ◽  
...  

The objective of this work is to bring new information about the influence of temperatures (7 °C and 20 °C) on the equation of state and sol–gel transition behavior of casein micelle dispersions. Casein micelle dispersions have been concentrated and equilibrated at different osmotic pressures using equilibrium dialysis at 7 °C and 20 °C. The osmotic stress technique measured the osmotic pressures of the dispersions over a wide range of concentrations. Rheological properties of concentrated dispersions were then characterized, respectively at 7 °C and at 20 °C. The essential result is that casein micelle dispersions are less compressible at 7 °C than at 20 °C and that concentration of sol–gel transition is lower at 7 °C than at 20 °C, with compressibility defined as the inverse to the resistance to the compression, and that is proportional to the cost to remove water from structure. From our interpretations, these two features were fully consistent with a release of soluble β-casein and nanoclusters CaP and an increased casein micelle hydration and apparent voluminosity at 7 °C as compared with 20 °C.


Polymers ◽  
2020 ◽  
Vol 12 (3) ◽  
pp. 698 ◽  
Author(s):  
Alina Amirova ◽  
Serafim Rodchenko ◽  
Mikhail Kurlykin ◽  
Andrey Tenkovtsev ◽  
Illia Krasnou ◽  
...  

Water-soluble, partially cross-linked poly-2-isopropyl-2-oxazoline combining the properties of chemical and physical gels was synthesized by a two-step procedure. Thermally induced sol-gel transition in its aqueous solution was studied by rheology, light scattering, and turbidimetry. It was demonstrated that the synthesized product is bimodal; it consists of linear and cross-linked components. The cross-linked components are responsible for the gelation, while the linear ones abate the viscosity growth. Heating the solution above the phase transition temperature leads to the self-assembly of the particles into a physical gel. The combination of chemical and physical cross-linking was found to be a prospective route for thermosensitive gel development.


2011 ◽  
Vol 189-193 ◽  
pp. 2986-2992 ◽  
Author(s):  
Hai Xia Liu ◽  
Sheng Jie Li ◽  
Yong Nian Yan

Through analyzing cell direct assembly process requirements and existing hydrogel materials properties, employing the discrete/deposit rapid prototyping technique, developed a cell direct assembly technology adopting the hybrid of gelatin-based hydrogels. The cell assembly technology skillfully combined with the sol/gel transition mechanism about chemical and physical crosslink of gelatin-based hydrogels, in consideration of the main forming factors, through controlling the extruded materials rheological properties and optimizing the forming process, thereby achieved a promising assembling process with high cell survival rate and its corresponding biological viability. The technology can form a predefined three-dimensional structure with certain shape and size, suitable for variety of natural polymer materials (the most similar with extracellular matrix, such as fibrin, sodium alginate, chitosan, hyaluronic acid) with gelatin coupling forming; therefore, it satisfied majority cells needs of choosing the gelatin-based composite hydrogels reasonably. With the limitative extrusion pressure, more than 90% of the cells survived through this process and performed metabolic functions during a long term culture. This technology is a front research of biotechnology manufacturing science, is an important expansion of manufacturing technology.


2021 ◽  
Author(s):  
Aroa Duro-Castano ◽  
Laura Rodriguez-Arco ◽  
Lorena Ruiz-Perez ◽  
Cesare De Pace ◽  
Gabriele Marchello ◽  
...  

Polypeptide-based nanoparticles offer unique advantages from a nanomedicine perspective such as biocompatibility, biodegradability and stimuli-responsive properties to (patho)physiological conditions. Conventionally, self-assembled polypeptide nanostructures are prepared by first synthesizing their constituent amphiphilic polypeptides followed by post-polymerization self-assembly. Herein, we describe the one-pot synthesis of oxidation-sensitive supramolecular micelles and vesicles. This was achieved by polymerization-induced self-assembly (PISA) of the N-carboxyanhydride (NCA) precursor of methionine using polyethylene oxide as stabilizing and hydrophilic block in dimethyl sulfoxide (DMSO). By adjusting the hydrophobic block length and concentration we obtained a range of morphologies from spherical to worm-like micelles, to vesicles. Remarkably, the secondary structure of polypeptides greatly influenced the final morphology of the assemblies. Surprisingly, worm-like micellar morphologies were obtained for a wide range of methionine block lengths and solid contents, with spherical micelles restricted to very short hydrophobic lengths. Worm-like micelles further assembled into oxidation-sensitive, self-standing gels in the reaction pot. Both vesicles and worm-like micelles obtained using this method demonstrated to degrade under controlled oxidant conditions which would expand their biomedical applications such as in sustained drug release or as cellular scaffolds in tissue engineering.


2020 ◽  
Vol 15 (1) ◽  
pp. 137-150
Author(s):  
Darshana Tushar Bhatti ◽  
Sachin Prakashbhai Parikh ◽  
◽  

A wide range of active pharmaceutical ingredients (API) is found in various water streams. These synthetic non-biodegradable organics create trouble in conventional wastewater treatment due to toxicity. There is a strong need to develop substitute technology such as visible light driven photocatalysis with a reusable photocatalyst to completely oxidize these substances into carbon dioxide and water. Sol-gel method was used for synthesis of Fe doped TiO2 and Ag-Fe codoped TiO2 nanoparticles with 0.5 wt% Fe and Ti/Ag molar ratio 30 (Ag-Fe CT 30). The morphology and structure of nanoparticles were studied using various analytical techniques. Ag-Fe CT 30 photocatalyst has exhibited excellent photocatalytic activity compared to commercial TiO2, undoped TiO2 and Fe doped TiO2 nanophotocatalysts under solar and UV irradiation for removal of an antifungal drug intermediate, Difloro triazole acetophenone (DFTA) from water. COD reduction efficiency was highest with Ag-Fe CT 30 under solar and UV irradiation proves the potential of Ag-Fe CT 30 photocatalyst to absorb both UV as well as visible radiations. Ag-Fe CT 30 has shown good stability for 4 runs without much decline in the efficacy. This study provides insights on the solar application of a reusable Ag-Fe CT 30 photocatalyst for the treatment of high strength COD wastewater. Kinetics of COD reduction by photocatalysis has been determined.


2007 ◽  
Vol 1037 ◽  
Author(s):  
Joseph S. Fragala ◽  
R. Roger Shile ◽  
Jason Haaheim

AbstractDepositing a wide range of materials as nanoscale features onto diverse surfaces with nanometer registration and resolution are challenging requirements for any nanoscale processing system. Dip Pen Nanolithography® (DPN®), a high resolution, scanning probe-based direct-write technology, has emerged as a promising solution for these requirements. Many different materials can be deposited directly using DPN, including alkane thiols, metal salts and nanoparticles, metal oxides, polymers, DNA, and proteins. Indirect deposition allows the creation of many interesting nanostructures. For instance, using MHA may be used to create arrays of antibodies, which then bond specifically to antigens on the surface of viruses or cells, to create cell or virus arrays. The DPN system is designed to allow registration to existing features on a writing substrate via optical alignment or nanoscale alignment using the core AFM platform. This allows, for instance, the nanoscale deposition of sensor materials directly onto monolithic electronic chips with both sensing and circuit features.To enable the DPN process, novel pen and ink delivery systems have been designed and fabricated using MEMS technology. These MEMS devices bridge the gap between the macro world (instrument) and the nano world (nanoscale patterns). The initial MEMS devices were simple and robust both in design and fabrication to get products into the marketplace quickly. The first MEMS-based DPN device was a passive pen array based on silicon nitride AFM probe technology from Cal Quate's group at Stanford. The next two devices (an inkwell chip and a thermal bimorph active pen) were more complicated and took considerable effort to commercialize. In this work, some of the difficulties in bringing brand new MEMS devices from the prototype stage into production will be shared. The subsequent MEMS products have become even more complicated both in design and fabrication, but the development process has improved as well. For example, the 2D nanoPrintArray has 55,000 pens in one square centimeter for high throughput writing over large areas. The 2D arrays enable templated self assembly of nanostructures giving researchers the ability to control the placement of self assembled features rather than allowing the self assembly to occur randomly.Applications of DPN technology vary from deposition of DNA or proteins in nanoarrays for disease detection or drug discovery, to deposition of Sol-gel metal oxides for gas sensors, and to additive repair of advanced phase-shifting photomasks.


Materials ◽  
2019 ◽  
Vol 12 (2) ◽  
pp. 226 ◽  
Author(s):  
Veronica Vanzanella ◽  
Marco Scatto ◽  
Erwin Zant ◽  
Michele Sisani ◽  
Maria Bastianini ◽  
...  

Poly(ethyleneoxideterephthalate)/poly(butyleneterephthalate) (PEOT/PBT) segmented block copolymers are widely used for the manufacturing of 3D-printed bio-scaffolds, due to a combination of several properties, such as cell viability, bio-compatibility, and bio-degradability. Furthermore, they are characterized by a relatively low viscosity at high temperatures, which is desired during the injection stages of the printing process. At the same time, the microphase separated morphology generated by the demixing of hard and soft segments at intermediate temperatures allows for a quick transition from a liquid-like to a solid-like behavior, thus favoring the shaping and the dimensional stability of the scaffold. In this work, for the first time, the rheology of a commercial PEOT/PBT material is studied over a wide range of temperatures encompassing both the melt state and the phase transition regime. Non-isothermal viscoelastic measurements under oscillatory shear flow allow for a quantitative determination of the material processability in the melt state. Additionally, isothermal experiments below the order–disorder temperature are used to determine the temperature dependence of the phase transition kinetics. The importance of the rheological characterization when designing the 3D-printing scaffold process is also discussed.


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