Low Critical Gelation Concentrations Research Articles

Ultralight aerogels via supramolecular polymerization of a new chiral perfluoropyridine-based sulfonimidamide organogelator.

Chiral and enantiopure perfluorinated sulfonimidamides act as low-molecular weight gelators at low critical gelation concentration (<1 mg mL-1) via supramolecular polymerization in nonpolar organic solvents and more heterogenic mixtures, such as biodiesel and oil. Freeze-drying of the organogel leads to ultralight aerogel with extremely low density (1 mg mL-1). The gelation is driven by hydrogen bonding resulting in a helical molecular ordering and unique fibre assemblies as confirmed by scanning electron microscopy, CD spectroscopy, and computational modeling of the supramolecular structure.

Self-Assembly of a Series of Carbazole-Based Vinyl-benzoxazole Derivatives in Gel Phases.

A series of carbazole-based vinyl-benzoxazole derivatives have been synthesized in order to verify whether X-ray diffraction (XRD) simulation can give more information about intermolecular stacking in the gel phase. It was found that their gelation capabilities were strongly dependent on the length of the alkyl chain. The compounds with shorter alkyl chains have lower critical gelation concentrations (CGCs) in nonpolar alkane and alcohols with longer carbon chains. On the other hand, compounds with long alkyl chains presented small CGCs in polar methanol. Powder XRD structure solution gave more information about intermolecular stacking than the traditional way of analyzing diffraction peaks to derive approximate molecular stacking patterns. The results verified that gelators had a similar head-to-tail π-stacking between aromatic groups in gel phases although different slipping angles existed. Moreover, ordered stacking between the alkyl chains was also present.

Macadamia oil-based oleogels as cocoa butter alternatives: Physical properties, oxidative stability, lipolysis, and application

In this study, macadamia oil-based oleogels were prepared using monoglyceride stearate (MG) as a gelator with a low critical gelation concentration (3.0 wt%). The physical properties of the oleogels were evaluated by polarized light microscopy, Fourier transform infrared spectroscopy, differential scanning calorimetry, X-ray diffraction, texture and rheological analysis. And the lipid digestion and oxidative stability of the macadamia oil were determined by pH titration and accelerated oxidation test, respectively. The results showed that the hardness, oil binding capacity, and thermal stability of the oleogels increased with increasing MG concentration, which was attributed to the formation of a network of MG crystals held together by van der Waals interactions and hydrogen bonds. Rheological analysis indicated that all the oleogels exhibited a thermally reversible solid-to-liquid transition and viscoelastic behavior at ambient temperatures. Moreover, the formation of oleogels increased fatty acid release during in vitro lipid digestion and improved the oxidative stability of the macadamia oil. In addition, the potential application of these oleogels as replacements for saturated fats in foods was demonstrated by creating a chocolate product where the cocoa butter was replaced with macadamia oil-based oleogels with a high degree of unsaturation. These results can provide guidance for the preparation of macadamia oil-based oleogels, which may increase their application in foods.

Macrocycle Self-Assembly Hydrogel for High-Efficient Oil-Water Separation.

Supramolecular hydrogels involved macrocycles have been explored widely in recent years, but it remains challenging to develop hydrogel based on solitary macrocycle with super gelation capability. Here, the construction of lantern[33 ]arene-based hydrogel with low critical gelation concentration (0.05 wt%), which can be used for efficient oil-water separation, is reported. The lantern[33 ]arenes self-assemble into hydrogen-bonded organic nanoribbons, which intertwine into entangled fibers to form hydrogel. This hydrogel which exhibits reversible pH-responsiveness characteristics can be coated on stainless-steel mesh by in situ sol-gel transformation. The resultant mesh exhibits excellent oil-water separation efficiency (>99%) and flux (>6 × 104 L m-2 h-1 ). This lantern[33 ]arene-based hydrogel not only sheds additional light on the gelation mechanisms for supramolecular hydrogels, but also extends the application of macrocycle-based hydrogels as functional interfacial materials.

Room-temperature triphenylene-based discotic liquid crystal dimers: effects of amide linkage and central fluoromethylene spacer

ABSTRACT Two series of triphenylene-based dimers both having a central fluoromethylene spacer of four or six carbon atoms and ester or amide linkages were synthesised and their phase behaviour investigated. All the synthesised dimers are room-temperature discotic liquid crystals and exhibit hexagonal columnar mesophases that supercool into a stable anisotropic columnar glass. The length of the fluoromethylene spacer has a minor effect on the phase transition temperatures of these dimers. However, dimers 1a and 2a with a (CF2)4 spacer exhibit approximately 40°C higher clearing points and wider mesomorphic phase ranges compared with their hydrocarbon analogs 1c and 2c with a (CH2)4 spacer respectively. Compared to the corresponding ester-linked dimers 1a-c, three amide-linked dimers 2a-c exhibit 20°C higher clearing points upon cooling. The observation indicates not only that the introduction of the fluoromethylene spacer stabilised the mesophase in these discotic dimers, but also that the two interactions have synergistic effects on columnar packing in this system. Moreover, only amide-linked dimers exhibit good gelation property in a mixture of toluene and petrol ether, with a lower critical gelation concentration of 1.5 wt/vol%, thus indicating that gel formation occurred under the collaboration of hydrogen bonding and intrinsic π interactions in these dimers.

Aryl-Capped Lysine-Dehydroamino Acid Dipeptide Supergelators as Potential Drug Release Systems.

Employing amino acids and peptides as molecular building blocks provides unique opportunities for generating supramolecular hydrogels, owing to their inherent biological origin, bioactivity, biocompatibility, and biodegradability. However, they can suffer from proteolytic degradation. Short peptides (<8 amino acids) attached to an aromatic capping group are particularly attractive alternatives for minimalistic low molecular weight hydrogelators. Peptides with low critical gelation concentrations (CGCs) are especially desirable, as the low weight percentage required for gelation makes them more cost-effective and reduces toxicity. In this work, three dehydrodipeptides were studied for their self-assembly properties. The results showed that all three dehydrodipeptides can form self-standing hydrogels with very low critical gelation concentrations (0.05–0.20 wt%) using a pH trigger. Hydrogels of all three dehydrodipeptides were characterised by scanning tunnelling emission microscopy (STEM), rheology, fluorescence spectroscopy, and circular dichroism (CD) spectroscopy. Molecular modelling was performed to probe the structural patterns and interactions. The cytotoxicity of the new compounds was tested using human keratinocytes (HaCaT cell line). In general, the results suggest that all three compounds are non-cytotoxic, although one of the peptides shows a small impact on cell viability. In sustained release assays, the effect of the charge of the model drug compounds on the rate of cargo release from the hydrogel network was evaluated. The hydrogels provide a sustained release of methyl orange (anionic) and ciprofloxacin (neutral), while methylene blue (cationic) was retained by the network.

Synthesis of low-molecular-weight gel with tunable gel-sol transition temperature for thermo-sensitive drug controlled release

A phenylboronic acid (PBA)-based gelator was synthesized, and host-guest low-molecular-weight gel (LMWG) was fabricated by the inclusion complexes (ICs) of the gelator and β-cyclodextrin (β-CD). Translucent gel consisting of nanofiber or nanobelt (60–430 nm wide) was obtained with low critical gelation concentration (CGC) of 2.9 mg/mL (0.36 wt%). The gel-sol transition temperature (Tgel) of the IC gel could be regulated from 37.5 °C to 44.9 °C by different inclusion ratio of gelator and β-CD. And the rheological properties exhibited the rapid recovery of the sol, the gel was re-formed in 2.5 min at 37 °C, and fully restored the initial storage modulus (G’). This tunable gel-sol-gel transition has been applied in thermo-sensitive controlled release of naproxen for tumor fever. Naproxen (16.7 μg•mL−1•min−1) was released from the drug-loaded gel (Loading Efficiency = 8.3%) when heated at 38.5 °C, and the release process terminated when the sol reconverted into gel at 37 °C, and it was achieved again when the gel converted to sol at 38.5 °C. Both the blank and drug-loaded gel could gellated rapidly after subcutaneous injection. The stability of gel was greatly improved to 102 h by the salts' induce, and the gel-sol transition was also controlled by vary kinds of salts and salt concentration.

A novel multi-stimuli-responsive organogel sensor for detecting Cu2+ and Co2+ based on benzotriazole derivative

A novel low molecular organic gelator (BTA) based on the derivative of benzotriazole has been successfully synthesized and developed. Extremely stable organogel (BTAG) with the low critical gelation concentration could be formed in methanol by heating and cooling. Interestingly, the BTAG could act as a multi-stimuli-responsive sensor for detecting Cu2+ and Co2+ and presents selective fluorescent and colorimetric response for Cu2+ and Co2+. Moreover, the detection limits of the multi-stimuli-responsive sensor for Cu2+ and Co2+ ions are 0.962 × 10−6 M and 1.08 × 10−6 M, respectively. Notably, the BTAG could be induced to a rare organo-to-metallogel transformation at room temperature by Cu2+ or Co2+ without any external assistances. The results provide an effective strategy for sensing Cu2+ and Co2+ and also offer a new method for the enrichment of Cu2+ and Co2+ in the environment with the low molecular organogel.

Crucial Impact of Residue Chirality on the Gelation Process and Biodegradability of Thermoresponsive Polypeptide Hydrogels.

Thermosensitive polypeptide hydrogels have gained considerable attention in potential biomedical applications, of which the polymer structure may be tuned by residue chirality. In this study, polypeptide-based block copolymers with different chiralities were synthesized by ring-opening polymerization of γ-ethyl-l-glutamate N-carboxyanhydride and/or γ-ethyl-d-glutamate N-carboxyanhydride using amino-terminated monomethoxy poly(ethylene glycol) as a macroinitiator. All mPEG-polypeptide copolymers underwent sol-gel transition with an increase in temperature. The block copolymers with mixed enantiomeric residues of γ-ethyl-l-glutamate (ELG) and γ-ethyl-d-glutamate (EDG) in the polypeptide blocks exhibited lower critical gelation concentrations and lower critical gelation temperatures compared with those composed of pure ELG or EDG residues. We established that the difference in gelation properties between the copolymers was derived from the distinction of the secondary structures. We further demonstrated the influence of polypeptide chirality on the degradability and biocompatibility of hydrogels in vivo. Our findings provide insights into the design of hydrogels having tailored secondary conformation, gelation property, and biodegradability.

Modulation and Characterization of Wax-Based Olive Oil Organogels in View of Their Application in the Food Industry.

Olive oil has recognized health benefits but lacks structural resilience to act in a similar fashion as do the typically used triglycerides (TAGs) when applied in food manufacturing. Therefore, olive oil structuring is critical to widening its use as a healthier alternative in spreadable products. Foreseeing the development of an application for the food industry, three types of natural waxes were used as organogelators, generating olive oil organogels with distinct properties. Retail-simulated storage conditions were used to mimic real-life industrial and commercial use. Organogel systems were evaluated according to their oxidation stability and textural and rheological properties. Textural and rheological parameters increased in response to increasing gelator concentration, while oxidation values (below 1.5 meq O2·kg−1) remained within legal limits. Organogels displayed similar textural properties to those of commercially available spreadable products, while displaying a low critical gelation concentration. In short, it was shown that tailoring the physicochemical properties of organogels towards specific applications is possible. The produced organogels showed similar properties to the ones of commercially available spreadable products, revealing favourable oxidative profiles. Therefore, an industrial application can be easily foreseen, building on the natural characteristics of olive oil as a healthier alternative to current spreadable products.

A fast and versatile cross-linking strategy via o-phthalaldehyde condensation for mechanically strengthened and functional hydrogels.

Fast and catalyst-free cross-linking strategy is of great significance for construction of covalently cross-linked hydrogels. Here, we report the condensation reaction between o-phthalaldehyde (OPA) and N-nucleophiles (primary amine, hydrazide and aminooxy) for hydrogel formation for the first time. When four-arm poly(ethylene glycol) (4aPEG) capped with OPA was mixed with various N-nucleophile-terminated 4aPEG as building blocks, hydrogels were formed with superfast gelation rate, higher mechanical strength and markedly lower critical gelation concentrations, compared to benzaldehyde-based counterparts. Small molecule model reactions indicate the key to these cross-links is the fast formation of heterocycle phthalimidine product or isoindole (bis)hemiaminal intermediates, depending on the N-nucleophiles. The second-order rate constant for the formation of phthalimidine linkage (4.3 M−1 s−1) is over 3000 times and 200 times higher than those for acylhydrazone and oxime formation from benzaldehyde, respectively, and comparable to many cycloaddition click reactions. Based on the versatile OPA chemistry, various hydrogels can be readily prepared from naturally derived polysaccharides, proteins or synthetic polymers without complicated chemical modification. Moreover, biofunctionality is facilely imparted to the hydrogels by introducing amine-bearing peptides via the reaction between OPA and amino group.

Synthesis and self-assembly of 1,8-naphthalene-based hexacatenar mesogens

ABSTRACT A novel series of hexacatenars consisting of a central naphthalene core functionalised with 1,2,3-triazole dendritic wings at 1 and 8 positions were synthesised by Sonogashira coupling and Click reactions. POM, DSC and XRD investigations revealed that all hexacatenars could self-assemble into absolutely Colhex/p6 mm mesophase in the bulk state. Interestingly, these compounds could gel some organic solvents with low critical gelation concentration and the gel morphologies varied from 3D porous structures via nanofiber structures to 3D spherical aggregates with increasing polarity of solvents. These investigations provide a new strategy to generate supramolecular self-assembly materials.

Widely Adaptable Oil-in-Water Gel Emulsions Stabilized by an Amphiphilic Hydrogelator Derived from Dehydroabietic Acid.

A surfactant, R-6-AO, derived from dehydroabietic acid has been synthesized. It behaves as a highly efficient low-molecular-weight hydrogelator with an extremely low critical gelation concentration (CGC) of 0.18 wt % (4 mm). R-6-AO not only stabilizes oil-in-water (O/W) emulsions at concentrations above its critical micelle concentration (cmc) of 0.6 mm, but also forms gel emulsions at concentrations beyond the CGC with the oil volume fraction freely adjustable between 2 % and 95 %. Cryo-TEM images reveal that R-6-AO molecules self-assemble into left-handed helical fibers with cross-sectional diameters of about 10 nm in pure water, which can be turned to very stable hydrogels at concentrations above the CGC. The gel emulsions stabilized by R-6-AO can be prepared with different oils (n-dodecane, n-decane, n-octane, soybean oil, olive oil, tricaprylin) owing to the tricyclic diterpene hydrophobic structure in their molecules that enables them to adopt a unique arrangement in the fibers.

A monopyrrolotetrathiafulvalene based naphthalimide tailored organogelator with stimuli responsive properties and absorption for rhodamine B

A novel 1,8-naphthalimide functionalized monopyrrolotetrathiafulvalene (MPTTF) derivative had been established as a low molecular weight supramolecular gelator. Supramolecular organogels could be obtained in solvents with different polarity through the heating-cooling process. Further addition of 7,7,8,8-tetracyanoquino-dimethane (TCNQ) to the supramolecular gel systems via the electron donor-acceptor interaction between the MPTTF and TCNQ, especially in polar solvents, could fabricate charge-transfer (CT) complex gels at relatively lower critical gelation concentrations. Interestingly, the self-assembly mode of the CT complexes was closely related to the type of solvents. As expected, due to the dynamic and reversible nature of the non-covalent interactions, the resultant gels exhibited external stimuli-responsiveness to different parameters, including temperature, chemical redox reagent and acid-base. However, the redox stimulus response of the gels depended on the polarity of the solvents, and the reversible gel-sol transformation could be achieved in nonpolar solvent, such as benzene. Moreover, the prepared gels showed irreversible gel-sol transitions on successively triggering with trifluoroacetic acid and triethylamine unless washed with water. Importantly, the original and CT complex gels could effectively remove the cationic rhodamine B dye from water.

Benzohydrazide Derivatives: Gelation and Application in Oil Spill Recovery

The synthesis and gelation properties of a series of organogelators containing a benzohydrazide unit and two alkoxy chains(oBn) were reported herein. oBn(n=8, 10, 12) could form stable gels in commercial fuels(e.g., diesel), which were characterized by low critical gelation concentrations(CGCs) and good mechanical properties (G′>105 Pa). The gelation process was further studied by field-emission scanning electron microscopy(FE-SEM), Fourier transform infrared spectroscopy(FTIR) and X-ray diffraction(XRD), etc. It was demonstrated that in these organogels, molecules self-assembled into fibrils 3D-network, where hydrogen bonding, van der Waals force and π-π interaction were confirmed as the driving forces. As compounds oBn(n=8, 10, 12) show very good gelation properties in diesel, their applications in oil spill treatment have also been tested. It was found that oBn could achieve rapid (<30 s) and effective oil removal at room temperature, being good candidates for oil spill treatment in the future. Also, the removal efficiency could be as high as 95%.

Effect of Core Cross-linking on the Physical Properties of Poly(dimethylsiloxane)-Based Diblock Copolymer Worms Prepared in Silicone Oil

A trithiocarbonate-capped poly(dimethylsiloxane) (PDMS) precursor is chain-extended via reversible addition–fragmentation chain transfer dispersion polymerization of 2-(dimethylamino)ethyl methacrylate (DMA) in decamethylcyclopentasiloxane (D5) silicone oil at 90 °C. For a fixed mean degree of polymerization (DP) of 66 for the PDMS steric stabilizer block, targeting core-forming PDMA block DPs of between 105 and 190 enables the preparation of either well-defined worms or vesicles at a copolymer concentration of 25% w/w. The as-synthesized linear PDMS66–PDMA100 worms exhibit thermoresponsive behavior in D5, undergoing a worm-to-sphere transition on heating to 100 °C. Variable temperature 1H NMR spectroscopy indicates that this thermal transition is driven by reversible solvent plasticization of the PDMA cores. This change in copolymer morphology is characterized by transmission electron microscopy (TEM) studies, variable temperature dynamic light scattering and small-angle X-ray scattering experiments. Oscillatory rheology studies indicate that degelation occurs at 32 °C, but shear-induced polarized light imaging measurements suggest that full conversion of worms into spheres requires significantly higher temperatures (∼110 °C). 1,2-Bis(2-iodoethoxy)ethane (BIEE) is evaluated as a cross-linker for PDMS66–PDMAx diblock copolymer nano-objects in D5. This bifunctional reagent quaternizes the tertiary amine groups on the DMA residues within the worm cores, introducing cross-links via the Menshutkin reaction. TEM studies confirm that such covalently-stabilized worms no longer undergo a worm-to-sphere transition when heated to 100 °C. Kinetic studies performed on PDMS66–PDMA176 vesicles suggest that cross-linking requires approximately 13 h at 20 °C to ensure that these nano-objects remain intact when dispersed in chloroform, which is a good solvent for both blocks. Oscillatory rheology studies of a PDMS66–PDMA100 worm gel indicated that covalent stabilization using a BIEE/DMA molar ratio of 0.15 increased its dynamic elastic modulus (G′) by almost two orders of magnitude. Furthermore, such cross-linked worms exhibit a much lower critical gelation concentration (∼2% w/w) compared to that of the linear precursor worms (∼12% w/w).

Synthesis and self-assembly of aroylhydrazone based polycatenars: A structure-property correlation

Two series of aroylhydrazone based polycatenars which differ from each other in terms of the linking groups (semi flexible ester or flexible ether linkage) were synthesized. These hexacatenars were mesogenic and also showed gelation in organic solvents at very low concentration, which is assisted by the intermolecular hydrogen bonding. Both the series of hexacatenars were prepared by varying the peripheral chain length from n-hexyloxy to n-hexadecyloxy chain. In the case of ester based series on moving from n-decyloxy to n-dodecyloxy chain, a transition from columnar rectangular phase to columnar hexagonal phase was noticed. Such behavior was not seen in the case of ether-based hexacatenars, irrespective of the chain length. Representative hexacatenars from each series exhibited gelation at low concentration, but the critical gelation concentration of ester-based hexacatenar was almost half of that observed for ether-based hexacatenar. From these studies we can understand the importance of the linking group, which constitutes very small part of the molecule, but has a significant effect on the type of the self-assembly in bulk as well as in presence of solvents. The presence of semi-flexible ester group provides a bent conformation to the molecule, while the presence of flexible ether group provides a linear shape to the molecule, as evident from the molecular modeling studies. Further the presence of the ester group enhances the extent of intermolecular hydrogen bonding with the solvent that leads to a lower critical gelation concentration in comparison to the ether-based linking group. Such H-bonded liquid crystals have potential in the preparation of liquid crystalline physical gels and related applications.

New Poly[(R )-3-hydroxybutyrate-co -4-hydroxybutyrate] (P3HB4HB)-Based Thermogels

Poly[(R)-3-hydroxybutyrate] (P3HB) is a potential candidate for biomaterials due to its biocompatibility and biodegradability. However, P3HB needs to have tunable hydrophobicity, modification through chemical functionalization and the right hydrolytic stability to increase their potential for water-based biomedical applications such as using them as in situ forming gels for drug delivery. This work focuses on using a copolymer, poly[(R)-3-hydroxybutyrate-co-4-hydroxybutyrate] (P3HB4HB) in a thermogelling multiblock system with polypropylene glycol and polyethylene glycol to study the effect of the hydrophobic P3HB4HB on gelation properties, degradation, and drug release rates with reference to P3HB. Thermogels containing P3HB4HB segments show lower critical micellization concentration values in a range from 3 × 10−4 to 1.08 × 10−3 g mL−1 and lower critical gelation concentration values ranging from 2 to 6 wt% than that of gels containing P3HB. Furthermore, gels containing P3HB4HB degrade at a slower rate than the gels containing P3HB. Drug release studies of 5 µg mL−1 of doxorubicin show that gels containing P3HB4HB exhibit sustained release although the release rates are faster than gels containing P3HB. However, this can be modified by varying the concentration of the gels used. Process optimization of purifying the starting material is one important factor before the synthesis of these biomaterials.

Influence of topology on the gelation behavior of coordination polymers prepared via ROMP of macrocyclic olefins

ABSTRACTThis work reports on the consequences of concatenation of two twin macrocycles on the gelation behavior of coordination polymers obtained via ring‐opening metathesis polymerization (ROMP) initiated by 2nd generation Grubbs' catalyst. The influence of concatenation is evaluated by comparison with the behavior of a non‐interlocked model complex under the same reaction conditions. The suitability of the choice of the non‐interlocked model complex is discussed in terms of molecular structure and effective molarity (EM). It is found that concatenation has a primary role in the gelation process, resulting in lower critical gelation concentrations for the endotopic, interlocked complex compared with the exotopic, non‐interlocked one. © 2016 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2016, 55, 1237–1242

Aromatic ionene topology and counterion-tuned gelation of acidic aqueous solutions.

Unusual gelation of acidic solutions was achieved using polycations bearing quaternary ammonium moieties. These ionene polymers are based on a disubstituted phenylene dibenzamide core, which allows the construction of different topomers (i.e. ortho-1, meta-2 and para-3). The topology of the polymers was found to play a key role on their aggregation behaviour both in pure water and in a variety of aqueous acidic solutions leading to the formation of stable acidic gels. Specifically, ortho-1 showed superior gelation ability than the analogues meta-2 and para-3 in numerous solutions of different pH and ionic strengths. Lower critical gelation concentrations, higher gel-to-sol transition temperatures and faster gelation were usually observed for ortho-1 regardless the solvent system. Detailed computational molecular dynamic simulations revealed a major role of the counterion (Cl-) and specific polymerpolymer interactions. In particular, hydrogen bonds, N-Hπ interactions and intramolecular π-π stacking networks are distinctive in ortho-1. In addition, counterions located at internal hydration regions also affect to such polymerpolymer interactions, acting as binders and, therefore, providing additional stability.