We present investigations of the kinetics of the colloidal sol-to-gel transition by combining small angle static light scattering (SASLS) and dynamic light scattering (DLS) techniques. Dilute monomer volume fractions were used to allow for a full investigation of the gelation to obtain all possible kinetic regimes. Our data verify the predictions of a kinetic theory, the ideal gel point (IGP) theory, where three regimes of kinetics are expected. We observe the first regime, the well-known cluster-dilute regime, with a kinetic exponent of z = 1. Followed by a cluster-dense regime with an enhanced kinetics and z ’ 2. Finally, a gelation regime is observed where the aggregate growth slows and ceases to grow at the IGP predicted size, Rg,G. These results quantitatively verify the IGP theory. We conclude that kinetic description provides a complete theory of the gelation process from sol to gel.
more »
« less
Kinetics of sol-to-gel transition in irreversible particulate systems
A comprehensive theory encompassing the kinetics of the sol-to-gel transition is yet to be formulated due to break-down of the mean-field Smoluchowski Equation. Using high temporal-resolution Monte Carlo simulation of irreversible aggregation systems, we show that this transition has three distinct regimes with kinetic exponent z 2 1 ½ ; 2Þ corresponding to aggregation of sol clusters proceeding to the ideal gel point (IGP); z 2 ½2; 5:7Þ for gelation of sol clusters beyond IGP; and z 2 ½2; 3:5Þ for a hitherto unidentified regime involving aggregation of gels when monomer-dense. We further establish universal power-law scaling relationships that connect the kinetics of these three regimes. Improved parameterizations are performed on the characteristic timescale parameters that define each regime.
more »
« less
- Award ID(s):
- 1649783
- PAR ID:
- 10160899
- Date Published:
- Journal Name:
- Journal of colloid and interface science
- Volume:
- 550
- ISSN:
- 0021-9797
- Page Range / eLocation ID:
- 57–63
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
-
Soft materials that change form or function in response to environmental or user-applied stimuli have a wide range of biomedical applications ( 1 ). Gels can form in water from weakly interacting molecules but can return to the state of a flowing liquid suspension, known as a sol, upon changes in the concentration of the molecules or the applied temperature. This behavior is known as a reentrant phase transition. A gel-to-sol phase transition typically arises from a reduction in concentration, meaning that a gel becomes a sol upon dilution and a sol becomes a gel with increased concentration. On page 213 of this issue, Su et al. ( 2 ) demonstrate a system that exhibits a sol-to-gel transition when diluted, inverting the common behavior of gels. Their observations offer insight into systems that undergo reentrant phase transitions in biology.more » « less
-
A polypeptide-based hydrogel system, when prepared from a diblock polymer with a ternary copolypeptide as one block, exhibited thermo-, mechano- and enzyme-responsive properties, which enabled the encapsulation of naproxen (Npx) during the sol–gel transition and its release in the gel state. Statistical terpolymerizations of l -alanine (Ala), glycine (Gly) and l -isoleucine (Ile) NCAs at a 1 : 1 : 1 feed ratio initiated by monomethoxy monoamino-terminated poly(ethylene glycol) afforded a series of methoxy poly(ethylene glycol)- block -poly( l -alanine- co -glycine- co - l -isoleucine) (mPEG- b -P(A-G-I)) block polymers. β-Sheets were the dominant secondary structures within the polypeptide segments, which facilitated a heat-induced sol-to-gel transition, resulting from the supramolecular assembly of β-sheets into nanofibrils. Deconstruction of the three-dimensional networks by mechanical force (sonication) triggered the reverse gel-to-sol transition. Certain enzymes could accelerate the breakdown of the hydrogel, as determined by in vitro gel weight loss profiles. The hydrogels were able to encapsulate and release Npx over 6 days, demonstrating the potential application of these polypeptide hydrogels as an injectable local delivery system for small molecule drugs.more » « less
-
null (Ed.)Stimuli-responsive supramolecular gels and metallogels have been widely explored in the past decade, but the fabrication of metallogels with reversible photoresponsive properties remains largely unexplored. In this study, we report the construction of photoresponsive hybrid zinc-based metallohydrogel systems coassembled from an imidazole functionalized phenylalanine derivative gelator (ImF) and carboxylic acid functionalized arylazopyrazole (AzoPz) molecular photoswitches in the presence of Zn 2+ ions. Unlike traditional covalent conjugation, noncovalent introduction of small molecular switches into the gel matrix provides a convenient route to generate photoresponsive functional materials with tunable properties and expands the scope of optically controlled molecular self-assemblies. It has been found that the carboxylic acid functionalized AzoPz derivatives alone or mixed with the ImF moiety could not self-assemble to form any gels. However, in the presence of Zn 2+ ions they readily formed the coassembled hybrid metallogels in an alkaline aqueous solution with various morphologies. These results suggest that the gelation process was triggered by the Zn 2+ ions. In addition, the ImF gelator shows specific response to Zn 2+ ions only. The presence of the AzoPz moiety in the gel matrix makes the metallogel coassemblies photoresponsive and the reversible gel-to-sol phase transition was studied by UV-vis spectroscopy. The gels showed a slow reversible light-induced gel-to-sol phase transition under UV ( λ = 365 nm) and then sol-to-gel transition by green light ( λ = 530) irradiation resulting in the reformation of the original gel state. The morphology and viscoelastic properties of the fibrillar opaque metallogels have been characterized by transmission electron microscopy (TEM) and rheological measurement, respectively.more » « less
-
Cationic glycylalanylglycine (GAG) self-assembles into a gel in a 55 mol% ethanol/45 mol% water mixture. The gel exhibits a network of crystalline fibrils grown to lengths on a 10 −4 –10 −5 m scale (Farrel et al. , Soft Matter , 2016, 12 , 6096–6110). Rheological data are indicative of a rather strong gel with storage moduli in the 10 kPa regime. Spectroscopic data revealed the existence of two gel phases; one forms below T = 15 °C (phase I) while the other one forms in a temperature range between 15 °C and the melting temperature of ca. 35 °C (phase II). We explored the reformation of the cationic GAG gel in 55 mol% ethanol/45 mol% water after thermal annealing by spectroscopic and rheological means. Our data reveal that even a short residence time of 5 minutes in the sol phase at 50 °C produced a delay of the gelation process and a gel of lesser strength. These observations suggest that the residence time at the annealing temperature can be used to adjust the strength of both gel phases. Our spectroscopic data show that the annealing process does not change the chirality of peptide fibrils in the two gel phases and that the initial aggregation state of the reformation process is by far more ordered for phase I than it is for phase II. In the gel phases of GAG/ethanol/water mixtures, ethanol seems to function as a sort of catalyst that enables the self-assembly of the peptide in spite of its low intrinsic propensity for aggregation.more » « less
An official website of the United States government

