scholarly journals Alginate-g-PNIPAM-Based Thermo/Shear-Responsive Injectable Hydrogels: Tailoring the Rheological Properties by Adjusting the LCST of the Grafting Chains

2021 ◽  
Vol 22 (8) ◽  
pp. 3824
Author(s):  
Konstantinos Safakas ◽  
Sofia-Falia Saravanou ◽  
Zacharoula Iatridi ◽  
Constantinos Tsitsilianis

Graft copolymers of alginate backbone and N-isopropylacrylamide/N-tert-butylacrylamide random copolymer, P(NIPAMx-co-NtBAMy), side chains (stickers) with various NtBAM content were designed and explored in aqueous media. Self-assembling thermoresponsive hydrogels are formed upon heating, in all cases, through the hydrophobic association of the P(NIPAMx-co-NtBAMy) sticky pendant chains. The rheological properties of the formulations depend remarkably on the NtBAM hydrophobic content, which regulates the lower critical solution temperature (LCST) and, in turn, the stickers’ thermo-responsiveness. The gelation point, Tgel, was shifted to lower temperatures from 38 to 20 °C by enriching the PNIPAM chains with 20 mol % NtBAM, shifting accordingly to the gelation temperature window. The consequences of the Tgel shift to the hydrogels’ rheological properties are significant at room and body temperature. For instance, at 37 °C, the storage modulus increases about two orders of magnitude and the terminal relaxation time increase about 10 orders of magnitude by enriching the stickers with 20 mol % hydrophobic moieties. Two main thermo-induced behaviors were revealed, characterized by a sol–gel and a weak gel–stiff gel transition for the copolymer with stickers of low (0.6 mol %) and high (14, 20 mol %) NtBAM content, respectively. The first type of hydrogels is easily injectable, while for the second one, the injectability is provided by shear-thinning effects. The influence of the type of media (phosphate buffer (PB), phosphate-buffered saline (PBS), Dulbecco’s modified Eagle’s medium (DMEM)) on the hydrogel properties was also explored and discussed. The 4 wt % NaALG-g-P(NIPAM80-co-NtBAM20)/DMEM formulation showed excellent shear-induced injectability at room temperature and instantaneous thermo-induced gel stiffening at body temperature, rendering it a good candidate for cell transplantation potential applications.

2018 ◽  
Vol 36 (2) ◽  
pp. 235-241 ◽  
Author(s):  
Ziaul Raza Khan ◽  
Anver Aziz ◽  
Mohd. Shahid Khan ◽  

Abstract High-quality CdS nanocrystalline thin films were grown by sol-gel spin coating method at different solution temperatures on glass substrates. As-deposited films exhibited nanocrystalline phase with hexagonal wurtzite structure and showed good adhesion and smooth surface morphology. It was clearly observed that the crystallinity of the thin films improved with the increase in solution temperature. Crystallites sizes of the films also increased and were found to be in the range of 10 mm to 17 nm. The influence of the growth mechanism on the band and sub-band gap absorption of the films was investigated using UV-Vis and photothermal deflection spectroscopy (PDS). The band gap values were calculated in the range of 2.52 eV to 2.75 eV. The band gap decreased up to 9 % with the increase in solution temperature from 45 °C to 75 °C. Absorption coefficients estimated by PDS signal showed the significant absorption in low photon energy region of 1.5 eV to 2.0 eV. The dark and illuminated I-V characteristics revealed that the films were highly photosensitive. The results demonstrated the potential applications of sol-gel grown CdS nanocrystalline thin films as photoconductors and optical switches.


2017 ◽  
Vol 2017 ◽  
pp. 1-8 ◽  
Author(s):  
Hiroyuki Takeno ◽  
Mai Kozuka

We investigated effects of cooling rates on self-assembling structures and mechanical and electrochemical properties of 12-hydroxystearic acid (12-HSA) in an ionic liquid (IL), 1-allyl-3-butylimidazolium bis(trifluoromethanesulfonyl) imide ([ABIm][TFSI]). The mixture of 12-HSA with [ABIm][TFSI] had an upper critical solution temperature (UCST) above the sol-gel transition temperature, and the microstructure of the ionogel was significantly affected by cooling rates, where it was prepared. The twisted self-assembling structure was formed during a slow cooling process at a rate of 0.4°C/min, whereas spherical domains caused by the liquid-liquid phase separation and radiate fibrous structure were observed for the quenched gel. The real-time small-angle X-ray scattering (SAXS) measurements for the ionogel during a slow cooling process at a rate of 0.4°C/min presented three different (001) peaks arising from long spacings of 46.5, 42.4, and 39.7 Å, which were also observed for SAXS curves of a neat 12-HSA. These results suggest that three polymorphic forms of 12-HSA are formed in the IL. The polymorphic form significantly affected the mechanical properties of the ionogel, whereas it did not affect the ionic conductivity. The ionic conductivity of the ionogel was close to that of a neat [ABIm][TFSI] irrespective of the polymorphic forms of 12-HSA.


Materials ◽  
2021 ◽  
Vol 14 (5) ◽  
pp. 1212
Author(s):  
Byung Soo Hwang ◽  
Jong Sik Kim ◽  
Ju Min Kim ◽  
Tae Soup Shim

Gelation behaviors of hydrogels have provided an outlook for the development of stimuli-responsive functional materials. Of these materials, the thermogelling behavior of poly(N-isopropylacrylamide) (p(NiPAm))-based microgels exhibits a unique, reverse sol–gel transition by bulk aggregation of microgels at the lower critical solution temperature (LCST). Despite its unique phase transition behaviors, the application of this material has been largely limited to the biomedical field, and the bulk gelation behavior of microgels in the presence of colloidal additives is still open for scrutinization. Here, we provide an in-depth investigation of the unique thermogelling behaviors of p(NiPAm)-based microgels through poly(N-isopropylacrylamide-co-2-hydroxyethyl methacrylate) microgel (p(NiPAm-co-HEMA))–silica nanoparticle composite to expand the application possibilities of the microgel system. Thermogelling behaviors of p(NiPAm-co-HEMA) microgel with different molar ratios of N-isopropylacrylamide (NiPAm) and 2-hydroxyethyl methacrylate (HEMA), their colloidal stability under various microgel concentrations, and the ionic strength of these aqueous solutions were investigated. In addition, sol–gel transition behaviors of various p(NiPAm-co-HEMA) microgel systems were compared by analyzing their rheological properties. Finally, we incorporated silica nanoparticles to the microgel system and investigated the thermogelling behaviors of the microgel–nanoparticle composite system. The composite system exhibited consistent thermogelling behaviors in moderate conditions, which was confirmed by an optical microscope. The composite demonstrated enhanced mechanical strength at gel state, which was confirmed by analyzing rheological properties.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Azam Marjani ◽  
Reza Khan Mohammadi

AbstractHg(II) has been identified to be one of the extremely toxic heavy metals because of its hazardous effects and this fact that it is even more hazardous to animals than other pollutants such as Ag, Au, Cd, Ni, Pb, Co, Cu, and Zn. Accordingly, for the first time, tetrasulfide-functionalized fibrous silica KCC-1 (TS-KCC-1) spheres were synthesized by a facile, conventional ultrasonic-assisted, sol–gel-hydrothermal preparation approach to adsorb Hg(II) from aqueous solution. Tetrasulfide groups (–S–S–S–S–) were chosen as binding sites due to the strong and effective interaction of mercury ions (Hg(II)) with sulfur atoms. Hg(II) uptake onto TS-KCC-1 in a batch system has been carried out. Isotherm and kinetic results showed a very agreed agreement with Langmuir and pseudo-first-order models, respectively, with a Langmuir maximum uptake capacity of 132.55 mg g–1 (volume of the solution = 20.0 mL; adsorbent dose = 5.0 mg; pH = 5.0; temperature: 198 K; contact time = 40 min; shaking speed = 180 rpm). TS-KCC-1was shown to be a promising functional nanoporous material for the uptake of Hg(II) cations from aqueous media. To the best of our knowledge, there has been no report on the uptake of toxic Hg(II) cations by tetrasulfide-functionalized KCC-1 prepared by a conventional ultrasonic-assisted sol–gel-hydrothermal synthesis method.


Molecules ◽  
2021 ◽  
Vol 26 (6) ◽  
pp. 1661
Author(s):  
Katarzyna Adamiak ◽  
Katarzyna Lewandowska ◽  
Alina Sionkowska

Collagen films are widely used as adhesives in medicine and cosmetology. However, its properties require modification. In this work, the influence of salicin on the properties of collagen solution and films was studied. Collagen was extracted from silver carp skin. The rheological properties of collagen solutions with and without salicin were characterized by steady shear tests. Thin collagen films were prepared by solvent evaporation. The structure of films was researched using infrared spectroscopy. The surface properties of films were investigated using Atomic Force Microscopy (AFM). Mechanical properties were measured as well. It was found that the addition of salicin modified the roughness of collagen films and their mechanical and rheological properties. The above-mentioned parameters are very important in potential applications of collagen films containing salicin.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Abbas Khan ◽  
Naila ◽  
Muhammad Humayun ◽  
Muhammad Sufaid Khan ◽  
Luqman Ali Shah ◽  
...  

Abstract To understand the expected mode of action, the physicochemical study on the solution properties of medicinal compounds and their interaction with deoxyribonucleic acid (DNA), under varying experimental conditions, is of prime importance. The present research work illustrates the physicochemical study and interaction of certain medicinal compounds such as; Levofloxacin, Ciprofloxacin, and Ibuprofen with DNA. Density, viscosity and surface tension measurements have been performed in order to determine, in a systematic manner, the physicochemical, volumetric and thermodynamic properties of these compounds; and most of these parameters have shown different behavior with varying concentration of solution, temperature of the medium and chemical nature/structure of the compound. In addition, these drugs showed a spontaneous surface-active and association behavior in aqueous solutions. The flow behavior, surface properties, volumetric behavior and solute–solvent interaction of these drugs were prominently influenced by experimental variables and addition of DNA to their solutions. UV–Visible spectroscopy was also used to examine the interaction of these drugs with DNA in aqueous media in detail. Calculated values of binding constants (Kb) for all complexes of drug-DNA are positive, indicating a fruitful binding process. It is seen that a smaller Kb value reflects weaker binding of the drug with DNA and vise versa. Due to the difference in the chemical structure of drugs the values of binding constant are different for various drug-DNA complexes and follow the order Kb(Levofloxacin-DNA) > Kb(Ciprofloxacin-DNA) > Kb(Ibuprofen-DNA). On the basis of spectral changes and Kb it can be said that the binding of all these drugs with DNA may be of physicochemical nature and the dominating binding force be of hydrogen bonding between oxygen of drugs and hydrogen of DNA units and the drug having more oxygen atoms showed stronger binding ability. The data further suggest a limited possibility of chemical type attachment of these drugs with DNA.


2021 ◽  
Author(s):  
Younes Ziat ◽  
Hamza Belkhanchi ◽  
Maryama Hammi ◽  
Charaf Laghlimi ◽  
A Moutcine

Abstract Recently, the rise of two dimensional amorphous nanostructured thin films have ignited a big interest because of their intriguingly isotropic structural and physical properties leading to potential applications in the nano-optoelectronics. However, according to literature, most of optoelectronic properties are investigated on chalcogenides related heterostructures. This has motivated the present work aiming to provide a new platform for the fabrication, examination of the properties and the applications of 2D nanostructured thin films based on epoxy/silicone blend. Thin films of Epoxy/Silicone loaded with nitrogen doped carbon nanotubes (N-CNTs) were prepared by sol-gel method and deposited on Indium Tin Oxide (ITO) glass substrates at room temperature. Further examination of optical properties aimed the investigation of optical pseudo-gap and Urbach energy and enabled the determination of processed films thickness based on Manifacier and Swanepol method. The results indicated that the unloaded thin films have a direct optical transition with a value of 3.61 eV followed by noticeable shift towards narrowing gaps depending on the loading rate. Urbach's energy is 0.19 eV for the unloaded thin films, and varies from 0.43 to 1.33 eV for the loaded thin films with increasing the rate of N-CNTs. It is inversely variable with the optical pseudo-gap. Finally, Epoxy/Silicone loaded with N-CNTs nanocomposites films can be developed as active layers with specific optical characteristics, giving the possibility to be used in electro-optical applications.


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