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1. Characterization of Calcium Silicate Hydrate Gels with Different Calcium to Silica Ratios and Polymer Modifications

   https://doi.org/10.3390/gels8020075  

   Madadi, Amirhossein; Wei, Jianqiang (February 2022, Gels)

   Calcium silicate hydrate (CSH) gels, the main binding phases of hydrated cement, are the most widely utilized synthetic materials. To understand the influences of composition and polymers on the reaction kinetics and phase formation, CSH gels with varying Ca/Si ratios and amounts of poly (acrylamide-co-acrylic acid) partial sodium salt (PAAm-co-PAA) were synthesized via a direct method. The CSH gels were characterized through isothermal calorimetry, thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier-transform infrared spectroscopy (FTIR), and Raman spectroscopy at different ages. By increasing the Ca/Si ratio from 0.8 to 1.0, the formation of CSH was enhanced with a 5.4% lower activation energy, whereas the incorporation of PAAm-co-PAA increased the temperature sensitivity of the reactions with an 83.3% higher activation energy. In the presence of PAAm-co-PAA, the reaction rate was retarded at an early age and the negative impact faded over time. The results of an XRD analysis indicated the formation of tobermorite as the main phase of the CSH gels, while the addition of PAAm-co-PAA resulted in a postponed calcium hydroxide consumption and CSH formation, which was confirmed by the decreased FTIR intensity of the C=O bond, Si–O stretching and Si–O bonds. The increased Raman vibrations of Si–O–Si bending Q2, Ca–O bonds, O–Si–O and asymmetric bending vibrations of SiO4 tetrahedra in the presence of PAAm-co-PAA indicate the intercalation of the polymeric phase and internal deformation of CSH gels. 

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2. Rational hydrogel design to improve brain modulus matching for implantation

   https://doi.org/10.1016/j.matlet.2025.138187  

   Garifo, Molli; Bethel, Keturah; Davis, Eric M; Larsen, Jessica (April 2025, Materials Letters)

   Treating the brain is challenging due to the restrictive blood–brain barrier, and modulus-mismatched implants often cause problems. Herein, we have fabricated copolymer hydrogels from thermoresponsive polymer, poly(N-isopropylacrylamide) (PNIPAAm), -r-hydrophilic polymer, poly(acrylic acid) (PAA), which are injectable and transform into soft implants above their lower critical solution temperature (LCST). PAA concentration can be leveraged to tune the LCST and viscosity of the PNIPAAm–r–PAA hydrogel in solution. Furthermore, the Young’s moduli of these materials, ranging from 1-4 kPa, are close to rat and human brain tissue, potentially leading to less inflammation and rejection due to significant modulus mismatch. 

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3. Hydronium‐Crosslinked Inorganic Hydrogel Comprised of 1D Lepidocrocite Titanate Nanofilaments

   https://doi.org/10.1002/adma.202409897  

   Mieles, Matthew; Walter, Adam_D; Wu, Simeng; Zheng, Yue; Schwenk, Gregory_R; Barsoum, Michel_W; Ji, Hai‐Feng (November 2024, Advanced Materials)

   Abstract When a few drops of acid (hydrochloric, acrylic, propionic, acetic, or formic) are added to a colloid comprised of 1D lepidocrocite titanate nanofilaments (1DLs)–2 × 2 TiO₆octahedra in cross‐section–a hydrogel forms, in many cases, within seconds. The 1DL synthesis process requires the reaction between titanium diboride with tetramethylammonium (TMA⁺), hydroxide. Using quantitative nuclear magnetic resonance (qNMR), thermogravimetric analysis (TGA), and differential scanning calorimetry (DSC), the mass percent of TMA⁺after synthesis is determined to be ≈ 13.1 ± 0.1%. The TMA⁺is completely removed from the gels after 2 water soak cycles, resulting in the first completely inorganic, TiO₂‐based hydrogels. Ion exchanging the TMA⁺with hydronium results in gels with relatively strong hydrogen bonds. The hydrogels' compression strengths increased linearly with 1DL colloid concentration. At a 1DL concentration of 45 g L⁻¹, the compressive strength, at 80% deformation when acrylic acid is used, is ≈325 kPa. The strengths are ≈ 50% greater after the TMA⁺is removed. The removal of all residual organic components in the hydrogels, including TMA⁺, is confirmed by qNMR, Fourier‐transformed infrared spectroscopy (FTIR), and TGA/DSC. The 1DL phase is retained after gelation, TMA⁺removal, and 80% compression. 

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4. Microcapillary Reactors via Coaxial Electrospinning: Fabrication of Small Poly(Acrylic Acid) Gel Beads and Thin Threads of Biological Cell Dimensions

   https://doi.org/10.3390/gels7020037  

   Kozawa, Susan K.; Lord, Audrey; Scott-McKean, Jonah J.; Walker, Anne Y.; Costa, Alberto C.; Wnek, Gary E. (June 2021, Gels)

   null (Ed.)

   Poly(acrylic acid) (PAA) bulk gels and threads, typically derived via free-radical polymerization, are of interest as anionic polyelectrolyte mimics of cellular cytosol and as models for early protocells. The thread dimensions have been limited by the diameters of readily-available glass or plastic capillaries, and threads with diameters of less than 50 µm have been difficult to achieve. Here, we report a useful approach for achieving crosslinked, partially neutralized PAA, namely poly(acrylate), gel threads with diameters of a few microns when dry. This technique utilizes coaxial electrospinning to effectively produce capillaries (shells) of polystyrene loaded with a gel-forming precursor mixture composed of 3 M acrylic acid, methylene-bisacrylamide, potassium persulfate and 2.2 M NaOH in the core, followed by thermally-induced polymerization and then the removal of the polystyrene shell. Relatively long (up to 5 mm), continuous PAA threads with thicknesses of 5–15 µm are readily obtained, along with a multitude of PAA gel particles, which result from the occasional break-up of the fluid core prior to gel formation during the electrospinning process. The threads and beads are of the sizes of interest to model ancient protocells, certain functional aspects of excitable cells, such as myocytes and neurons, and various membraneless organelles. 

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5. Salt- and pH-induced swelling of a poly(acrylic acid) brush via quartz crystal microbalance w/dissipation (QCM-D)

   https://doi.org/10.1039/c9sm01289c  

   Hollingsworth, Nisha R.; Wilkanowicz, Sabina I.; Larson, Ronald G. (October 2019, Soft Matter)

   We infer the swelling/de-swelling behavior of weakly ionizable poly(acrylic acid) (PAA) brushes of 2–39 kDa molar mass in the presence of KCl concentrations from 0.1–1000 mM, pH = 3, 7, and 9, and grafting densities σ = 0.12–2.15 chains per nm 2 using a Quartz Crystal Microbalance with Dissipation (QCM-D), confirming and extending the work of Wu et al. to multiple chain lengths. At pH 7 and 9 (above the p K a ∼ 5), the brush initially swells at low KCl ionic strength (<10 mM) in the “osmotic brush” regime, and de-swells at higher salt concentrations, in the “salted brush” regime, and is relatively unaffected at pH 3, below the p K a , as expected. At pH 7, at low and moderate grafting densities, our results in the high-salt “salted brush” regime ( C s > 10 mM salt) agree with the predicted scaling H ∼ Nσ +1/3 C s −1/3 of brush height H , while in the low-salt “osmotic brush” regime ( C s < 10 mM salt), we find H ∼ Nσ +1/3 C s +0.28–0.38 , whose dependence on C s agrees with scaling theory for this regime, but the dependence on σ strongly disagrees with it. The predicted linearity in the degree of polymerization N is confirmed. The new results partially confirm scaling theory and clarify where improved theories and additional data are needed. 

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