skip to main content


Title: Activation Energy for Dissociation of Hydrogen‐Bonding Crosslinkers in Phase‐Change Salogels: Dynamic Light Scattering versus Rheological Studies
Abstract

Dissociation energy of dynamic bonds in thermoresponsive phase‐change salogels is explored using rheology and dynamic light scattering (DLS). The salogels are formed by polyvinyl alcohol (PVA) reversibly crosslinked by hydrogen‐bonding amine‐terminated molecules in an inorganic phase‐change material—lithium nitrate trihydrate (LNH) salt—as a solvent. The crosslinker geometry (linear vs branched) has a strong effect on both the gelation temperature (Tgel) and the crosslinker to polymer ratio at which the gelation occurs. Due to their higher functionality, dendritic crosslinkers are more efficient gelators as compared to their linear counterparts, inducing PVA gelation at a lower concentration of a crosslinker and resulting in salogels with higherTgel. Both stress relaxation and DLS data can be fitted by the exponential functions with temperature‐independent exponents of ≈0.5 and 2, respectively. For the first time, it is reported that the crosslinker dissociation activation energy determined from the rheological stress relaxation time and DLS slow mode decay time are in very good agreement, comprising ≈130–140 kJ mol−1for salogels with both linear and dendritic crosslinkers.

 
more » « less
NSF-PAR ID:
10459583
Author(s) / Creator(s):
 ;  
Publisher / Repository:
Wiley Blackwell (John Wiley & Sons)
Date Published:
Journal Name:
Macromolecular Chemistry and Physics
Volume:
220
Issue:
22
ISSN:
1022-1352
Format(s):
Medium: X
Sponsoring Org:
National Science Foundation
More Like this
  1. Abstract

    Rheological modifiers are added to formulations to tune rheology, enable function and drive phase changes requiring an understanding of material structure and properties. We characterize two colloidal rod systems during phase transitions using multiple particle tracking microrheology, which measures the Brownian motion of probes embedded in a sample. These systems include a colloid (monodisperse polyamide or polydisperse hydrogenated castor oil), surfactant (linear alkylbenzene sulfonate [LAS]), and nonabsorbing polymer (polyethylene oxide [PEO]) which drives gelation by depletion interactions. Phase transitions are characterized at all concentrations using time‐cure superposition. We determine that rheological evolution depends onLAS:colloid. The critical PEO concentration required to form a gel,cc/c*, is independent ofLAS:colloid, critical relaxation exponent,n, is dependent onLAS:colloid, and both are independent of colloid polydispersity.nindicates the material structure at the phase transition. AtLAS:colloid > 16, the scaffold is a tightly associated network and atLAS:colloid = 16 a loosely associated network.

     
    more » « less
  2. Abstract Purpose

    One standard method, proton resonance frequency shift, for measuring temperature using magnetic resonance imaging (MRI), in MRI‐guided surgeries, fails completely below the freezing point of water. Because of this, we have developed a new methodology for monitoring temperature with MRI below freezing. The purpose of this paper is to show that a strong temperature dependence of the nuclear relaxation timeT1in soft silicone polymers can lead to temperature‐dependent changes of MRI intensity acquired withT1weighting. We propose the use of silicone filaments inserted in tissue for measuring temperature during MRI‐guided cryoablations.

    Methods

    The temperature dependence ofT1in bio‐compatible soft silicone polymers was measured using nuclear magnetic resonance spectroscopy and MRI. Phantoms, made of bulk silicone materials and put in an MRI‐compatible thermal container with dry ice, allowed temperature measurements ranging from –60°C to + 20°C.T1‐weighted gradient echo images of the phantoms were acquired at spatially uniform temperatures and with a gradient in temperature to determine the efficacy of using these materials as temperature indicators in MRI. Ex vivo experiments on silicone rods, 4 mm in diameter, inserted in animal tissue were conducted to assess the practical feasibility of the method.

    Results

    Measurements of nuclear relaxation times of protons in soft silicone polymers show a monotonic, nearly linear, change with temperature (R2 > 0.98) and have a significant correlation with temperature (Pearson'sr > 0.99,p < 0.01). Similarly, the intensity of the MR images in these materials, taken with a gradient echo sequence, are also temperature dependent. There is again a monotonic change in MRI intensity that correlates well with the measured temperature (Pearson'sr < ‐0.98 andp < 0.01). The MRI experiments show that a temperature change of 3°C can be resolved in a distance of about 2.5 mm. Based on MRI images and external sensor calibrations for a sample with a gradient in temperature, temperature maps with 3°C isotherms are created for a bulk phantom. Experiments demonstrate that these changes in MRI intensity with temperature can also be seen in 4 mm silicone rods embedded in ex vivo animal tissue.

    Conclusions

    We have developed a new method for measuring temperature in MRI that potentially could be used during MRI‐guided cryoablation operations, reducing both procedure time and cost, and making these surgeries safer.

     
    more » « less
  3. Abstract

    Herein, this work reports the first synthetic vaccine adjuvants that attenuate potency in response to small, 1–2 °C changes in temperature about their lower critical solution temperature (LCST). Adjuvant additives significantly increase vaccine efficacy. However, adjuvants also cause inflammatory side effects, such as pyrexia, which currently limits their use. To address this, a thermophobic vaccine adjuvant engineered to attenuate potency at temperatures correlating to pyrexia is created. Thermophobic adjuvants are synthesized by combining a rationally designed trehalose glycolipid vaccine adjuvant with thermoresponsive poly‐N‐isoporpylacrylamide (NIPAM) via reversible addition fragmentation chain transfer (RAFT) polymerization. The resulting thermophobic adjuvants exhibit LCSTs near 37 °C, and self‐assembled into nanoparticles with temperature‐dependent sizes (90–270 nm). Thermophobic adjuvants activate HEK‐mMINCLE and other innate immune cell lines as well as primary mouse bone marrow derived dendritic cells (BMDCs) and bone marrow derived macrophages (BMDMs). Inflammatory cytokine production is attenuated under conditions mimicking pyrexia (above the LCST) relative to homeostasis (37 °C) or below the LCST. This thermophobic behavior correlated with decreased adjuvantRgis observed by DLS, as well as glycolipid‐NIPAM shielding interactions are observed by NOESY‐NMR. In vivo, thermophobic adjuvants enhance efficacy of a whole inactivated influenza A/California/04/2009 virus vaccine, by increasing neutralizing antibody titers and CD4+/44+/62L+lung and lymph node central memory T cells, as well as providing better protection from morbidity after viral challenge relative to unadjuvanted control vaccine. Together, these results demonstrate the first adjuvants with potency regulated by temperature. This work envisions that with further investigation, this approach can enhance vaccine efficacy while maintaining safety.

     
    more » « less
  4. Abstract

    Poly(caprolactone) networks are well‐studied shape‐memory polymers owing to their high fixity and recovery, their ability to store large amounts of elastic energy, and their tunable shape‐triggering temperature. To elucidate the influence of network structure on shape‐memory features, poly(caprolactone) networks are prepared by reacting different molecular weight diacrylate prepolymers with trifunctional (trimethylolpropane tris(3‐mercaptopropionate),3T) or tetrafunctional (pentaerythritol tetrakis(3‐mercaptopropionate),4T) crosslinkers. Networks from4Tcrosslinkers generally exhibit higher gel fractions, more elastically active strands, and superior shape‐memory properties compared with networks from3T. Melted elastomers exhibit stress–strain behavior well described by the neo‐Hookean model. How the state of crystallization during the cold‐drawing process has a large effect on the draw stress, the network's shape fixity, and its elastic storage capacity is shown. Finally, the working strain range of networks is evaluated. Cured elastomers prepared from prepolymers with different molecular weights can store and release large amounts of elastic energy (>2 MJ m−3), over different ranges of tensile strain.

     
    more » « less
  5. Supramolecular polymer gels are an evolving class of soft materials with a vast number of properties that can be tuned to desired applications. Despite continuous advances concerning polymer synthesis, sustainability or adaptability, a consistent understanding of the interplay between structure, dynamics, and diffusion processes within transient networks is lacking. In this study, the hierarchy of several relaxation processes is investigated, starting from a microscopic perspective of a single sticker dissociation event up to the center-of-mass diffusion of a star-shaped polymer building block on different length scales, as well as the resulting macroscopic mechanical response to applied external stress. In addition to that, a second focus is placed on the gel micro-structure that is analyzed by light scattering. Conversion of the dynamic light scattering (DLS) inverse length scale into real space allows for a combination of relaxation times with those obtained by forced Rayleigh scattering (FRS). For these investigations, a model-type metallo-supramolecular network consisting of narrowly dispersed tetra-arm poly(ethylene glycol)-terpyridine macromolecules that are interconnected via complexation with zinc ions is chosen. Assembling the obtained activation energies reveals that all complex dissociation-governed relaxation processes exhibit similar activation energies. 
    more » « less