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DMSO dipole structure and resonance forms from charge delocalization. (b) A simple illustrative model of the major interactions involved in solvation of poly (AMPS) gel in DMSO/water mixture.
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The present article deals with super-swelling behavior of crosslinked homopolymer of 2-acrylamido-2-methylpropane sulfonic acid, poly(AMPS), in binary mixtures of dimethyl sulfoxide (DMSO) and various polar solvents including water, mono-, and polyhydric alcohols, and amide solvents such as N-methyl pyrrolidone. Extraordinary phase transition seque...
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... explain the strange behavior, we have to pre- liminarily focus on DMSO and its properties in aqueous medium. DMSO is a simple highly polar molecule with a S¼ ¼O group and two hydrophobic CH 3 groups [ Fig. ...
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... the number of major polymer-solvent interac- tions can preliminarily give a rough prediction about the swelling extent 14 considering additional CAHÁÁÁO hydrogen bonding interactions in DMSO may lead us to order of DMSO/water mixture > water > DMSO, which is in agreement with the experimental results (Fig. 1). To roughly illustrate the solvent specificity, we employed a simple solvation model 27 of poly (AMPS) sites shown in Figure 2(b). Meanwhile, it seems that even solvent-solvent interactions, particu- larly well-known CAHÁÁÁO hydrogen bonding, are not ineffective in the solvation promotion. ...
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... wide-ranged overentrant behavior of poly (AMPS) gel may be explained by the solvent capabil- ity to form hydrogel bonding with the solute and the scheme of its swelling in aqueous DMSO media given in Figure 2. Glycerol possesses three OH groups, so it has great capability for hydrogen bond- ing. ...
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... should be considered that this behavior was not observed for poly(APMS) in DMSO-free solvent mix- tures. Conventional continuous VPT had already been observed for poly(AMPS) in different water- solvent mixtures. This also indicated the importance of polymer-solvent interactions for poly(AMPS) in DMSO-solvent mixtures [ Fig. ...
Similar publications
Novel copolymeric gels of poly(AMPS–TEA-co-AAm) with superabsorbency in both water and alcohols were synthesized by neutralizing 2-acrylamido-2-methyl-1-propane sulfonic acid (AMPS) with triethylamine (TEA) followed by copolymerizing the resulted salt with acrylamide (AAm) in aqueous solutions using N,N′-methylenebisacrylamide (MBAm) as a crosslink...
Citations
... There will always exist a noticeable overlap between organogels and hydrogels in the case of binary solvent systems. [5,32,33] For such cases, we define a gel according to the nature of the predominant or the most functional solvent. For gels, where 3D networks and solvents of opposite polarity can co-exist in one material with a clear interface, the term "bigel" or "organohydrogel" is appropriate (Figure 1). ...
Organogels are an important class of gels, and are comparable to hydrogels owing to their properties as liquid‐infused soft materials. Despite the extensive choice of liquid media and compatible networks that can provide a broader range of properties, relatively few studies are reported in this area. This review presents the applicability of organogels concerning their choice of components, unique properties, and applications. Their distinctive features compared to other gels are discussed, including multi‐stimuli responses, affinity to a broad range of substances, thermal and environmental stability, electronic and ionic conductivity, and actuation. The active role of solvents is highlighted in the versatility of organogel properties. To differentiate between organogels and other gels, these are classified as gels filled with different organic liquids, including highly polar organic solvents and binary solvent systems. Most promising applications of organogels as sophisticated multifunctional materials are discussed in light of their unique features.
... This behavior could be explained by the presence of DMSO in the coatings, as shown by FTIR and XPS, as the formation of miscible DMSO-H 2 O clusters could be formed, as reported by Zohuriaan et. al. [41]. The above observed variations could also be explained by the fact that it is generally accepted that contact angle measurements are commonly applied to analyze the surface wettability of materials, but they are generally not useful for porous surfaces owing to the heterogeneity, capillary force in pores, and surface reconstruction [36]. ...
Designing and obtaining new synthetic smart biointerfaces with specific and controlled characteristics relevant for applications in biomedical and bioengineering domains represents one of the main challenges in these fields. In this work, Matrix-Assisted Pulsed Laser Evaporation (MAPLE) is used to obtain synthetic biointerfaces of poly(N-isopropyl acrylamide-butyl acrylate) p(NIPAM-BA) copolymer with different characteristics (i.e., roughness, porosity, wettability), and their effect on normal HEK 293 T and murine melanoma B16-F1 cells is studied. For this, the influence of various solvents (chloroform, dimethylsulfoxide, water) and fluence variation (250-450 mJ/cm2) on the morphological, roughness, wettability, and physico–chemical characteristics of the coatings are evaluated by atomic force microscopy, scanning electron microscopy, contact angle measurements, Fourier-transform-IR spectroscopy, and X-ray photoelectron spectroscopy. Coatings obtained by the spin coating method are used for reference. No significant alteration in the chemistry of the surfaces is observed for the coatings obtained by both methods. All p(NIPAM-BA) coatings show hydrophilic character, with the exception of those obtained with chloroform at 250 mJ/cm2. The surface morphology is shown to depend on both solvent type and laser fluence and it ranges from smooth surfaces to rough and porous ones. Physico–chemical and biological analysis reveal that the MAPLE deposition method with fluences of 350-450 mJ/cm2 when using DMSO solvent is more appropriate for bioengineering applications due to the surface characteristics (i.e., pore presence) and to the good compatibility with normal cells and cytotoxicity against melanoma cells.
... Physical signals such as light, temperature, electric field, magnetic field and mechanical stress modify the energies of chain dynamics and molecular interactions. These environmentally responsive microgels show non-linear response to an external signal and therefore, large varieties of different approaches made to develop smart applications in biology, medicine, and nanotechnologies [8][9][10][11][12][13][14][15][16]. ...
The temperature sensitive copolymer of microsize hydrogels consist of N-isopropylacrylamide (NIPAM) and 2- acrylamido-2 methylpropanesulphonic acid (AMPS) have been synthesized by soap free emulsion polymerization method in the presence of polyethylene glycol (PEG) as macro initiator and N, N´-methylenebisacrylamide (NMBA) as crosslinker. In this work, Dynamic Light Scattering (DLS), Transmission Electron Microscope (TEM) and Atomic Force Microscope (AFM) technique were used for structural analysis of microgels. It was found that particle size observed by TEM and AFM were spherical with a diameter around 103.0 nm to 133.1 nm and 121.1 nm to 189.0 nm. While DLS measurement shows narrow particle size distribution with hydrodynamic diameter from 343.6nm to 528 nm at a temperature 25°C and 132.5nm to 414.4nm at temperature 50°C depending on the AMPS content in Microgels samples. The surface roughnesses of particles were observed to be increasing with increased AMPS content. Moreover, decrease in hydrodynamic diameter from 25°C to 50°C revealed the temperature sensitivityproperty of microgels.
... So, after photoexcitation, these two states are populated (originating the LE and ICT states) being depopulated very rapidly through a radiative channel. Although isopropanol is a protic solvent, only a long component (τ ∼ 1.20 ns) was observed, due to its steric effects which difficult the H-bond formation [70]. For (1) the profiles of emission maps (excitation vs emission) clearly showed the excitationindependent behavior in hexane, toluene, ACN, and MeOH solutions ( Supporting Information, Fig. S9). ...
Curcumin and its dyes have attracted attention due to their environment-sensitivity and optical properties. However, the free molecule has low photoactivity, which is a limitation for use in photodynamic therapy. To overcome this limitation, we proposed the chelation of a D-π-A-π-D curcumin dye (1) with the metals Cu (II) and Pd (II). The photophysical properties of the curcumin dyes were investigated in different solvents, using UV–vis spectroscopy and time-resolved/steady-state fluorescence techniques. In our results, all curcumin dyes exhibited a positive solvatochromism from non-polar to polar solvents, with the Stokes’ shift in the range of 1895–4970 cm⁻¹. The acidochromism studies were performed in chloroform solution and TLC plates using trifluoroacetic acid (TFA). The results exhibited a negative acidochromism and fluorescence quenching upon gradual addition of TFA, demonstrating reversibility upon addition of triethylamine (TEA). The main mechanism which influences the solvatochromism/acidochromism is the ICT system and fluorescence lifetime decays exhibited mono-exponential fit for aprotic solvents and bi-exponential fit for protic solvents (EtOH and MeOH). Compared to the curcumin ligand (1), the metal complexes (1a-b) exhibited higher singlet oxygen quantum yields (ΦΔ = 0.36 and 0.54, respectively). The in vitro antimicrobial photoactivity of the compounds was evaluated against six different microorganisms. The results showed that the metal complexes (1a-b) exhibited both antileishmanial (MIC = 2.29 μM against Leishmania amazonensis promastigotes) and antifungal (IC50 = 10 μM against Sporothrix brasiliensis yeasts) activities, while the ligand showed no activity, suggesting the chelation with the metals Cu (II) and Pd (II) may improve its photoactivity.
... Absorbent polymers respond to electrical or chemical potential (9), radiative light or energy (9), temperature (10), solvent composition (11)(12)(13), pH (14)(15)(16), and salt concentrations (17). They can also respond to external stimuli when their molecular composition is modified or when their polarity or ionic properties are altered through functionalization (18). ...
This chapter describes the synthesis, characterization and absorption capacities of three types of biobased absorbent polymers. The three absorbent polymers described in this chapter are all produced from renewable products such as starch, glycerol, monglyceride, and chitosan. Each of the absorbent polymers were successfully synthesized and absorbed varying amounts of solvent dependent on their molecular composition.
... However, the MOF complexity order is DMAC 4 DMF 4 DMSO 4 NMP, which could be related to the electrophilic properties (i.e., acceptor number, AN) of the solution. 19 The order of the number of receptors induced by the solution system was NMP o DMAC o DMF o DMSO (AN or electrophilic). The lower the AN, the more favorable the formation of contact ion pairs. ...
... The lower the AN, the more favorable the formation of contact ion pairs. 19 In other words, the suitable polarity of mixed solvents can enhance the ionization and coordination of Hmim, and the corresponding electrophilic properties can accelerate the forward reaction efficiency of the complex. Therefore, the surface topography diversity of MOF-based microrobots is due to the synergistic effect of solution polarity and electrophilic properties. ...
... With the addition of aprotic polar solvents, the hydrogen bond between Hmim and the tight stacking state between imidazole rings will be destroyed immediately. However, due to the steric hindrance effect, 19 i.e., NMP 4 DMAC 4 DMF, the MOF structures begin to change from cubes to sheets as the concentration of NMP increases. However, the steric hindrance of DMAC becomes weaker, which makes the morphology of MOFs maintain the cubic shape in a wide range of concentrations. ...
Magnetically driven mobile micro/nanorobots have a significant influence on the application and development of intelligent targeted drug delivery. However, the potential risk of biological toxicity is one of the major problems in drug-loaded micro/nanorobot fabrication. Therefore, there is an urgent need to combine the features (high cargo-loading, low biotoxicity, and good biodegradability) of metal-organic frameworks (MOFs) with micro/nanorobot mobility. In this paper, the concept of green chemical synthesis is used to prepare mass-manufactured biodegradable MOF-based microrobots with low biotoxicity and high drug loading for the targeted treatment of cancer cells. Based on the solvation principle of the binary solvent system, the two-component solvent will be mixed with aprotic polar solvents (X = DMAC, DMF, DMSO, NMP) and proton polar solvents (MeOH) to reduce original aprotic polar solvent toxicity. This can adjust the electrophilicity and polarity of the solution environment, change the configuration of organic ligands, and directly affect the nucleation and growth of MOF crystallites. The results show that five different MOF crystal structures can be synthesized on the surface of microrobots. The MOFs synthesized in a DMAC/MeOH solvent system have cubic structures with good biocompatibility and drug delivery properties. Furthermore, the magnetically actuated motion of MOF-based microrobots with different geometries was systematically tested to obtain the best swimming performance. Subsequently, the microrobots were guided through vascular-like microfluidic channels and can be precisely controlled. Thus, this establishes a foundation to create mass-manufactured microrobotic systems that provide a new direction for small-scale medical robots with low toxicity, high drug loading capacity, biodegradability, and precise motion control.
... It was observed that the S% of organo-hydrogels decreased with the increase in essential oil ratio in the organo-hydrogel composition. These observations are consistent with the literature [49,50]. ...
The very recent Covid-19 pandemic has made the need to understand biocompatible polymers as support material in drug delivery systems and controlled release clearer, especially for organo-hydrogels. This study aims to synthesize various new polymeric materials called gels, hydrogels, and organo-hydrogels according to the monomer used and to investigate their use as drug release systems. The agar-glycerol (AG) pair was used to synthesize the polymers, N, N, methylene bisacrylamide (MBA, m) and glutaraldehyde (GA, g) were used as cross-linkers and peppermint oil (PmO) was included to obtain the organo-hydrogels. Therefore, one AG gel and two p (AG-m) and p (GA-g) hydrogels were synthesized within the scope of the study. Six different organo-hydrogels based on p(AG-m-PmO) or p (AG-g-PmO) were also synthesized by varying the amount of peppermint oil. Paracetamol and carboplatin were selected as the sample drugs. Synthesized gels, hydrogels and organo-hydrogels were characterized by FTIR and SEM analysis. Additionally, swelling behaviors of the synthesized gels were investigated in different media (ID water, tap water, ethanol, acetone, ethanol/ID water (1:1), acetone/ID water (1:1) and gasoline) and at different pHs. Moreover, it was determined that organo-hydrogels were blood compatible and had antioxidant properties based on hemolysis, blood clotting and antioxidant analysis. Therefore, the release of paracetamol (a known antipyretic-painkiller, recommended and used in the treatment of Covid-19) and carboplatin (widely used in cancer treatment) were studied. Evidently, as the amount of PMO oil increases, the -OH groups in organo-hydrogels will increase and the chemical and physical bonding rates will increase; therefore it was observed that increasing peppermint oil in the organo-hydrogels structure to 0.3 mL stimulated the release of the drugs. For instance, maximum paracetamol release amount from p(AG-g-PmO) and p(AG-m-PmO) organo-hydrogels was calculated to be 72.3% at pH 7.4 and 69.8% at pH 2.0, respectively. The maximum carboplatin release amount from p(AG-g-PmO) and p(AG-m-PmO) organo-hydrogels was calculated to be 99.7% at pH 7.4 and 100% at pH 7.4, respectively. It was concluded that the synthesized organo-hydrogels might easily be used as drug carrier and controlled drug release materials.
... As a result, the swelling of organo-hydrogels in different organic solvent-water mixtures can be controlled by the solvent composition. Those observations were consistent with the literature [41,42]. ...
In this study, it was aimed to investigate the synthesis, characterization and drug release behaviors of organo-hydrogels containing pH-sensitive Agar (A), Glycerol (G), Thyme Oil (TO). The novel organo-hydrogels containing TO were prepared in an emulsion media by the free-radical polymerization and crosslinking reactions among Agar (A), Glycerol (G), TO, N, N, methylenebisacrylamide (MBA) or glutaraldehyde (GA) reagent. Swelling ability (ethanol, acetone, ethanol/ID water (1:1), acetone/ID water (1:1) and gasoline environments and different pH), Fourier Transform Infrared Spectroscopy (FTIR) analysis and 5-Fluorouracil (5-Flu) drug release of the organo-hydrogels were profoundly determined and some structural parameters for organo-hydrogels such as blood clotting, hemolysis analysis, antioxidant analysis were also evaluated in this study. The FTIR spectra confirmed that the TO was bonded onto the organo-hydrogel structure, and the A, G and TO macromolecular chains interpenetrated through the MBA or GA reagent. When swelling analyzes were examined, it was determined that organo-hydrogels, which added thyme oil to the structure, swelled not only in pure water and tap water but also in organic solvents such as ethanol, acetone, ethanol/ID water (1:1), acetone/ID water (1:1) and gasoline. All of the organo-hydrogels synthesized in the light of blood clotting, hemolysis analysis, antioxidant analysis were hemocompatible and could be used within the body. The release results indicated that the organo-hydrogel p(AG-m-TO)³ and p(AG-g-TO)³ had the highest 84.3% and 73.3% release capacity. In addition, it was reported that the release capacities of organo-hydrogels were inversely proportional to the increased amount of TO. When 5-Flu drug release was examined in terms of kinetic models, it was observed that the release adapted to the Korsmeyer-Peppas (KPKM) model. And it was also determined that organo-hydrogels based on p(AG-m-TO) comply with the non-Fick law and organo-hydrogels based on p(AG-g-TO) comply with the Case II transport. In the light of the results obtained, their easy formability, their appropriate mechanical and physical properties make Organo-hydrogels suitable candidates for drug delivery systems.
... Eine Hypothese stellt die Annahme einer Solvathülle um die Hydroxylgruppe des HEMAs dar. [195] ...
... Organogels are cross-linked macromolecules that are an important class of soft materials; they can immobilize a large amount of organic liquids within the three-dimensional network structure by forming a network either of cross-linked or entangled chains for chemical and physical gels, respectively [24][25][26]. There exist a variety of different areas in which organogels can be used, such as controlled drug delivery systems [27], fragrances, surfactant industry, fire starters [28], hand sanitizers, and oil absorbents [29]. ...
Organogels with high and fast absorption properties, as well as reusability functions, were successfully prepared through the condensation reactions of different molecular weights of poly(propylene glycol)s (PPG)s and tris[3-(trimethoxysilyl) propyl] isocyanurate (ICS). The characterization of these organogels was determined by solid-state ¹³C and ²⁹Si cross polarization magic angle spinning (CPMAS) nuclear magnetic resonance (NMR) and Fourier transform infrared spectroscopy (FTIR). Thermal gravimetric analysis (TGA) was used to describe the thermal behavior of the prepared organogels. Obtained organogels are reusable and can absorb a large amount of oils, such as dichloromethane (DCM), tetrahydrofuran (THF), methyl tertiary butyl ether (MTBE), toluene, benzene, acetone, and gasoline. The capacity of the synthesized organogels did not change in either pure organic liquids or in organic liquid/water mixtures; these can be used at least ten times without loss of capacity.
