Self-assembled Gels Research Articles

Stiff-Stilbene-Linked Bis-Cholesterol: Synthesis and Investigation of Its Supramolecular Gelation and Photophysical Behaviors.

Here, we report the design, synthesis, and comprehensive characterization of the bis-cholesterol supramolecular gelator, which contains photochromic stiff-stilbene as a bridging unit. The cis-isomer of stiff-stilbene bridged bis-cholesterol (Z-D) was first synthesized with a systematic design, which can be further converted into its trans-isomer (E-D) with a high degree of efficiency (ca. 100%) upon exposure to 385 nm UV light. Unusual gelation behavior was observed for Z-D, which exhibited supergelator properties in mixed solvents of acetonitrile (ACN)/dichloromethane (DCM) (v/v = 1:1), DCM/MeOH (v/v = 1:2), ACN/CHCl3 (v/v = 2:1), and CHCl3/MeOH (v/v = 1:2), with minimum gelation concentrations (MGCs) as low as 0.2 w/v%. These gels formed rapidly at room temperature without the aid of any mechanical forces upon the addition of an antisolvent into the vial containing the gelator and its dissolving solvent. The formation of the self-assembled gel was primarily driven by hydrogen bonding, van der Waals forces, and dipole-dipole interactions, as confirmed by 1H NMR, Fourier transform infrared spectroscopy (FT-IR), and UV-vis spectroscopies. The gelator molecule Z-D entraps organic solvents and organizes itself into three-dimensional (3D) fibrillar networks in various single and mixed solvents, as confirmed by scanning electron microscopy (SEM) analysis. Upon irradiation with 385 nm light, the gel networks disintegrated into a precipitate suspension, resulting in the transformation of the fibrous structures into irregular spherical-like aggregates. This proves that the structural conformation changes in the gelator significantly influence the resulting self-assembled structures. Overall, the findings present in this study pave the way for the future development of novel light-responsive bis-cholesterol-based gelators, especially in their Z-isomeric form.

Formulation and Release of Active Pharmaceutical Ingredients Using a Supramolecular Self-Healing Two-Component Gel.

A two-component low-molecular-weight gelator (LMWG) formed from a modified amino acid and an aldehyde was formulated with active pharmaceutical ingredients (APIs). Basic APIs (propranolol, atropine) can be mixed with the LMWG prior to gel assembly while acidic APIs (naproxen, rosuvastatin) inhibit assembly by disrupting the LMWG imine bond and were loaded by diffusion after gel assembly. For diffusion-loaded gels, the API in the liquid-like phase was rapidly released, with the remainder, interacting with gel fibres, retained in the gel. Rosuvastatin release was particularly low with Saturation Transfer Difference (STD) NMR indicating interactions between the aromatic ring and the self-assembled gel network. Propranolol also interacted with the gel via its aromatic unit, and its release led to gel erosion. Using agarose as a polymer gelator additive reinforced the gel, restricting erosion. In contrast, atropine was readily released over a period of hours - it is primarily in the liquid-like phase with STD NMR indicating no interactions with the gel network. The atropine-loaded gel retained its thixotropic properties. Overall, APIs must be carefully chosen to optimise formulation/release. Of the APIs investigated, atropine has most potential for further development. Atropine has applications in treating myopia, and our results suggest potential ophthalmic applications of supramolecular gels.

Silver and Copper Nanoparticle-Loaded Self-Assembled Pseudo-Peptide Thiourea-Based Organic-Inorganic Hybrid Gel with Antibacterial and Superhydrophobic Properties for Antifouling Surfaces.

The escalating threat of antimicrobial resistance has become a global health crisis. Therefore, there is a rising momentum in developing biomaterials with self-sanitizing capabilities and inherent antibacterial properties. Despite their promising antimicrobial properties, metal nanoparticles (MNPs) have several disadvantages, including increased toxicity as the particle size decreases, leading to oxidative stress and DNA damage that need consideration. One solution is surface functionalization with biocompatible organic ligands, which can improve nanoparticle dispersibility, reduce aggregation, and enable targeted delivery to microbial cells. The existing research predominantly concentrates on the advancement of peptide-based hydrogels for coating materials to prevent bacterial infection, with limited exploration of developing surface coatings using organogels. Herein, we have synthesized organogel-based coatings doped with MNPs that can offer superior hydrophobicity, oleophobicity, and high stability that are not easily achievable with hydrogels. The self-assembled gels displayed distinct morphologies, as revealed by scanning electron microscopy and atomic force microscopy. The cross-linked matrix helps in the controlled and sustained release of MNPs at the site of bacterial infection. The synthesized self-assembled gel@MNPs exhibited excellent antibacterial properties against harmful bacteria such as Escherichia coli and Staphylococcus aureus and reduced bacterial viability up to 95% within 4 h. Cytotoxicity testing against metazoan cells demonstrated that the gels doped with MNPs were nontoxic (IC50 > 100 μM) to mammalian cells. Furthermore, in this study, we coated the organogel@MNPs on cotton fabric and tested it against Gram +ve and Gram -ve bacteria. Additionally, the developed cotton fabric exhibited superhydrophobic properties and developed a barrier that limits the interaction between bacteria and the surface, making it difficult for bacteria to adhere and colonize, which holds potential as a valuable resource for self-cleaning coatings.

Self-assembled gel microneedle formed by MS deep eutectic solvent as a transdermal delivery system for hyperpigmentation treatment

Hyperpigmentation (HP) is an unfavorable skin disease that typically caused by injury, inflammation, or photoaging and leads to numerous physical and psychological issues in patients. Recently, development and application of natural whitening substances, particularly compound curcumin (CUR), is one of the most prevalent treatments for HP. However, it is still a formidable challenge to improve the percutaneous delivery of CUR due to its inadequate solubility in water and excellent barrier function of skin. To overcome the limitations of conventional delivery and increase the percutaneous absorption of CUR, the efficient delivery of CUR is urgently required. Herein, we developed a new malic acid-sorbitol deep eutectic solvent (MS/DES) gel microneedle loaded with CUR as a transdermal delivery system for HP treatment. The MS/DES gel produces three-dimensional (3D) network structure by self-assembly of hydrogen bond interactions, which conferred the CUR-MS/DES-GMN with sufficient mechanical properties to successfully penetrate skin tissue while also helping to enhance the drug's release rate. The CUR-MS/DES-GMN exhibit high biocompatibility and mechanical property in vivo of mice. The zebrafish experiments also show that CUR-MS/DES gel has significant effect of anti-pigmentation. Therefore, the designed CUR-MS/DES-GMN system provides a novel strategy for HP treatment based on self-assembly of naturally molecules.

Comparison and analysis of mechanism of β-lactoglobulin self-assembled gel carriers formed by different gelation methods

Based on the findings of our previous studies, a comprehensive comparative investigation of the quality and formation mechanism of gels obtained from protein self-assemblies induced by different methods is necessary. Self-assembled heat-induced gels had higher gel mechanical strength, and hydrophobic interactions played a greater role. Whether or not heat treatment was used to induce gel formation may play a more important role than the effect of divalent cations on gel formation. Hydrogen bonds played an important role in all gels formed using different gelation methods. Furthermore, Self-assembled cold-induced gels were considered to can load bioactive substances with different hydrophilicity properties due to the high water-holding capacity and the smooth, dense microstructure. Therefore, β-lactoglobulin fibrous and worm-like self-assembled cold-induced gels as a delivery material for hydrophilic bioactive substances (epigallocatechin gallate, vitamin B2) and amphiphilic bioactive substance (naringenin), with good encapsulation efficiency (91.92 %, 97.08 %, 96.72 %, 96.52 %, 98.94 %, 97.41 %, respectively) and slow-release performance.

Peptide Gel Electrolytes for Stabilized Zn Metal Anodes.

The rechargeable aqueous Zn ion battery (AZIB) is considered a promising candidate for future energy storage applications due to its intrinsic safety features and low cost. However, Zn dendrites and side reactions (e.g., corrosion, hydrogen evolution reaction, and inactive side product (Zn hydroxide sulfate) formation) at the Zn metal anode have been serious obstacles to realizing a satisfactory AZIB performance. The application of gel electrolytes is a common strategy for suppressing these problems, but the normally used highly cross-linked polymer matrix (e.g., polyacrylamide (PAM)) brings additional difficulties for battery assembly and recycling. Herein, we have developed a gel electrolyte for Zn metal anode stabilization, where a peptide matrix, a highly biocompatible material, is used for gel construction. Various experiments and simulations elucidate the sulfate anion-assisted self-assembly gel formation and its effect in stabilizing Zn metal anodes. Unlike polymer gel electrolytes, the peptide gel electrolyte can reversibly transform between gel and liquid states, thus facilitating the gel-involved battery assembly and recycling. Furthermore, the peptide gel electrolyte provides fast Zn ion diffusion (comparable to conventional liquid electrolyte) while suppressing side reactions and dendrite growth, thus achieving highly stable Zn metal anodes as validated in various cell configurations. We believe that our concept of gel electrolyte design will inspire more future directions for Zn metal anode protection based on gel electrolyte design.

Transparent Organogels as a Medium for the Light-Induced Conversion from Spiropyran to Merocyanine.

Low-molecular-weight peptide gelators are a versatile class of compounds able to form gels under a variety of conditions, even via simple ultrasound sonication. In this paper, the ability of Boc-L-Phe-D-Oxd-L-Phe-OBn to gelate three organic solvents (toluene, tert-butyl methyl ether, and ethanol) was evaluated. The rheological behaviour of the materials was assessed via strain sweep analysis, while the fibrous network was analysed via optical microscopy on the wet gels. The gel obtained from toluene is a highly transparent material, and the one from ethanol appears translucent, while the one from tert-butyl methyl ether is opaque. These gels were used to study the reversible light-induced transformation from spyropiran (SP) to merocyanine (MC) and back, as a model system to check the effect of the gel medium onto the rection kinetic. We observed that the solvent used to form the organogels has a crucial effect on the reaction, as gels from aprotic solvents stabilize the SP form, while the ones from protic solvents stabilize the MC form. We thus obtained a solid support to stabilize the two photochromic species just by changing the solvent polarity. Moreover, we could demonstrate that the self-assembled gels do not interfere with the light-driven conversion process, either starting from SP or MC, thus representing a valid and economical photochromic material.

Development of Self-Assembled Biomimetic Nanoscale Collagen-like Peptide-Based Scaffolds for Tissue Engineering: An In Silico and Laboratory Study.

Development of biocomposite scaffolds has gained tremendous attention due to their potential for tissue regeneration. However, most scaffolds often contain animal-derived collagen that may elicit an immunological response, necessitating the development of new biomaterials. Herein, we developed a new collagen-like peptide,(Pro-Ala-His)10 (PAH)10, and explored its ability to be utilized as a functional biomaterial by incorporating it with a newly synthesized peptide-based self-assembled gel. The gel was prepared by conjugating a pectin derivative, galataric acid, with a pro-angiogenic peptide (LHYQDLLQLQY) and further functionalized with a cortistatin-derived peptide, (Phe-Trp-Lys-Thr)4 (FWKT)4, and the bio-ionic liquid choline acetate. The self-assembly of (PAH)10 and its interactions with the galactarate-peptide conjugates were examined using replica exchange molecular dynamics (REMD) simulations. Results revealed the formation of a multi-layered scaffold, with enhanced stability at higher temperatures. We then synthesized the scaffold and examined its physicochemical properties and its ability to integrate with aortic smooth muscle cells. The scaffold was further utilized as a bioink for bioprinting to form three-dimensional cell-scaffold matrices. Furthermore, the formation of actin filaments and elongated cell morphology was observed. These results indicate that the (PAH)10 hybrid scaffold provides a suitable environment for cell adhesion, proliferation and growth, making it a potentially valuable biomaterial for tissue engineering.

Morphological Evaluation of Supramolecular Soft Materials Obtained through Co-Assembly Processes.

Low-molecular-weight gelators (LMWGs) are compounds with an intrinsic tendency to self-assemble forming various supramolecular architectures via non-covalent interactions. Considering that the development of supramolecular assemblies through the synergy of molecules is not entirely understood at the molecular level, this study introduced a Fmoc-short peptide and four Fmoc-amino acids as building blocks for the self-assembly/co-assembly process. Hence, we investigated the formation of supramolecular gels starting from the molecular aggregation following two triggering approaches: solvent/co-solvent method and pH switch. The complex morphological analysis (POM, AFM, and STEM) offered an insight into the spontaneous formation of well-ordered nanoaggregates. Briefly, POM and AFM images demonstrated that self-assembled gels present various morphologies like dendrimer, spherulite, and vesicle, whereas all co-assembled supramolecular systems exhibit fibrillar morphologies as a result of the interaction between co-partners of each system. STEM study has confirmed that the molecules interact and join together, finally forming a fibrous network, an aspect seen in both self-assembled and co-assembled gels. XRD allowed the determination of the molecular arrangement. The study emphasized that the Fmoc motif protected the amino groups and facilitated gelation through additional π-π interactions.

Thermoelectric Properties of One-Pot Hydrothermally Synthesized Solution-Processable PEDOT:PSS/MWCNT Composite Materials.

The combination of organic and inorganic materials has been considered an effective solution for achieving ambient thermoelectric energy harvesting and has been developing rapidly. Here, PEDOT:PSS/MWCNT (PPM) composite hydrogels were synthesized using the self-assembled gelation process of poly(3,4-ethylenedioxythiophene)-poly(styrenesulfonate) (PEDOT:PSS) and the interaction between PEDOT:PSS and multi-walled carbon nanotubes (MWCNTs) without the addition of any surfactant. After immersion in dimethyl sulfoxide and freeze-drying, the hydrogel is easily dispersed in water and used as a direct ink writing (DIW) 3D printing ink. At room temperature, the PPM-20 printed film with 20 wt% MWCNT solids achieved a maximum power factor of 7.37 μW m-1 K-2 and maintained stable thermoelectric properties during repeated bending cycles. On this basis, a thermoelectric generator (TEG) consisting of five legs was printed, which could be produced to generate an open circuit voltage of 6.4 mV and a maximum output power of 40.48 nW at a temperature gradient of 50 K, confirming its great potential for application in high-performance flexible organic/inorganic thermoelectric materials.

A gel-forming α-MSH analog promotes lasting melanogenesis

The α-MSH peptide plays a significant role in the regulation of pigmentation via the melanocortin 1 receptor (MC1R). It increases the DNA repair capacity of melanocytes and reduces the incidence of skin cancers. As such, α-MSH analogs could have the utility for protecting against UV-induced skin DNA damage in susceptible patients. Recently, α-MSH analogs have been approved for the treatment of erythropoietic protoporphyria, hypoactive sexual desire, or pediatric obesity. However, the delivery of these drugs requires inconvenient implants or frequent injections. We recently found that select palmitoylated melanocortin analogs such as afamelanotide and adrenocorticotropin peptides self-assemble to form liquid gels in situ. To explore the utility of these novel analogs, we studied their pharmacological characteristics in vitro and in vivo. Acylated afamelanotide (DDE 313) and ACTH1-24 (DDE314) analogs form liquid gels at 6–20% and have a significantly increased viscosity at >2.5% compared to original analogs. Using the DDE313 analog as a prototype, we showed gel-formation reduces the passage of DDE313 through Centricon filters, and subcutaneous injection of analog gel in rats leads to the sustained presence of the peptide in circulation for >12 days. In addition, DDE313 darkened the skin of frogs for >4 weeks, whereas those injected with an equivalent dose of afamelanotide lost the tanning response within a few days. Because self-assembled gels allow sustained activation of melanocortin receptors, further studies of these analogs may allow the development of effective and convenient tanning therapies to prophylactically protect against UV-induced malignant transformation of skin cells in susceptible patients.

Gels of Semiconducting Polymers in Benign Solvents.

Gels of semiconducting polymers have many potential applications, including biomedical devices and sensors. Here, we report a self-assembled gel system consisting of isoindigo-based semiconducting polymers with galactose side chains in benign, alcohol-based solvents. Because of the carbohydrate side chains, the modified isoindigo polymers are soluble in alcohols. We obtained thermoreversible gels in 1-propanol using these polymers and di-Fmoc-l-lysine, a molecular gelator. The polymers and molecular gelators have been selected in such a way that they do not have significant physical interactions. The molecular gelator self-assembled to form a fibrous structure that confines the polymer chains in the interstitial spaces of the fibers. The polymer chains formed local aggregations and increased the shear moduli of the gels significantly. Bulky galactose side chains and the less planar nature of the polymer backbone hindered the formation of long-range assembled structures of the polymers. However, the dispersion of polymers throughout the gel samples resulted in a percolated structure in the dried gel films. The bulk electrical conductivity of dried gels confirmed the presence of such percolated structures. Our results demonstrated that carbohydrate-containing conjugated polymers can be combined with molecular gelators to obtain gels in eco-friendly solvents.

Self-Assembling Nanoarchitectonics of Twisted Nanofibers of Fluorescent Amphiphiles as Chemo-Resistive Sensor for Methanol Detection.

The inhalation, ingestion, and body absorption of noxious gases lead to severe tissue damage, ophthalmological issues, and neurodegenerative disorders; death may even occur when recognized too late. In particular, methanol gas present in traces can cause blindness, non-reversible organ failure, and even death. Even though ample materials are available for the detection of methanol in other alcoholic analogs at ppm level, their scope is very limited because of the use of either toxic or expensive raw materials or tedious fabrication procedures. In this paper, we report on a simple synthesis of fluorescent amphiphiles achieved using a starting material derived from renewable resources, this material being methyl ricinoleate in good yields. The newly synthesized bio-based amphiphiles were prone to form a gel in a broad range of solvents. The morphology of the gel and the molecular-level interaction involved in the self-assembly process were thoroughly investigated. Rheological studies were carried out to probe the stability, thermal processability, and thixotropic behavior. In order to evaluate the potential application of the self-assembled gel in the field of sensors, we performed sensor measurements. Interestingly, the twisted fibers derived from the molecular assembly could be able to display a stable and selective response towards methanol. We believe that the bottom-up assembled system holds great promise in the environmental, healthcare, medicine, and biological fields.

Study of Physicochemical and Gelation Properties of Fish Gelatin from Different Sources

Fish gelatin has been increasingly used as a safe alternative to cattle and pig gelatin due to its similar structure, avoiding the health and socio-cultural issues associated with the use of materials of mammalian origin. Fish gelatin can be produced from processed fish products to achieve a high yield at a low cost. Recent studies show that although fish gelatin comes from a wide range of sources, the protein content and amino acid composition of fish gelatin from different sources are different, and some fish gelatin is soft and unstable transglutaminase (TGase) can catalyze the γ-amide group of glutamine residues and the ε-amino group of lysine residues in proteins to form covalent bonds to form a stable protein network structure, improve the strength of the gel so that it can be applied in a more special environment. In this experiment, after screening the raw materials of cold-water fish gelatin M06 and M08, warm-water fish gelatin M03 and M04, a strong fish gelatin was successfully prepared by catalytic modification of cold-water fish gelatin by transglutaminase (TGase), and the excellent performance of TG enzyme-catalyzed modified gelatin was proved through the application effect of chicken salt soluble protein. In this experiment, the protein content of cold-water fish M08 was the highest, which was up to 99.9%, 1.09 times that of warm-water fish. The gelatin content of cold-water fish M08 was the highest of the four kinds of fish gelatin, with a wide proportion of components and rich amino acid composition. Cold-water fish M08 gelatin-derived gel had the highest strength of 253 ± 1 g/cm at 4 °C. It was found that fish gelatin with protein molecular weight distribution and rich amino acid composition had higher gel strength. M08 gelatin is cross-linked by transglutaminase (TGase), which increases the strength of enzyme gels by approximately 200% compared to self-assembled gels. Fish gelatin catalyzed by the TG enzyme improves the gel strength of raw material and makes it more applicable. M08 gelatin also showed good application performance at low temperatures in compound chicken salt-soluble protein gel, with a water retention rate of 95.84% and gel strength of 198.5 g/cm. This study expanded the application range of fish gelatin by TG enzyme and improved the application potential of fish gelatin.

Biologically inspired anthraquinone redox centers and biomass graphene for renewable colloidal gels toward ultrahigh-performance flexible micro-supercapacitors

Biomass carbon and small redox biomolecules are attractive materials for green, sustainable energy storage devices owing to their environmentally friendly, low-cost, scalable, and novel sources. However, most devices manufactured using these materials have low specific capacitance, poor cycle stability, short lifetime, complexity, and low precision of device fabrication. Herein, we report the directed self-assembly of mononuclear anthraquinone (MAQ) derivatives and porous lignin-based graphene oxide (PLGO) into a renewable colloidal gel through noncovalent interactions. These self-assembled gel electrode materials exhibited high capacitance (484.8 F g−1 at a current density of 1 A g−1) and could be further printed as flexible micro-supercapacitors (FMSCs) with arbitrary patterns and a relatively high resolution on specific substrates. The FMSCs exhibited excellent areal capacitance (43.6 mF cm−2), energy and power densities (6.1 μWh cm−2 and 50 μW cm−2, respectively), and cycle stability (> 10,000 cycles). Furthermore, the printed FMSCs and integrated FMSC arrays exhibited remarkable flexibility while maintaining a stable capacitance. The proposed approach can be applied to other quinone biomolecules and biomass-based carbon materials. This study provides a basis for fabricating green and sustainable energy storage device architectures with high capacitance, long-term cycling, high scalability, and high precision.

Effect of self-assembly gel crosslinking property and the wetting characteristics of coal under different acid solution

In view of the serious dust pollution in coal mines, the self-assembly gels that can uniformly distribute acid are investigated. The effect of acid type and concentration of the self-assembly gel on the viscosification and wettability in coal, as well as the internal mechanism for the changes are revealed. The results show that the formed micelles of the inorganic acid self-assembly gels are compact and thick, and the high potential enhances the interaction force inside the micelles. In the organic acid environment, it is not conducive to assemble the surfactant molecules, to be specific, the wormlike micelles are sparse and short, but has a better wettability and the minimum surface tension of 12.50 mN/M. In the inorganic acid environment, the wettability is poor, however, it shows a strong adsorption on the coal, and imposes the greatest influence on -OH group in coals. • The viscosification behavior of self-assembly gel in different acid solutions were found. • The wettability of self-assembly gel in different acid solutions were found. • The internal mechanism in viscosification and wetting were obtained.

Effectiveness and safety of a newly designed self-assembling gel in the treatment of endoscopic submucosal dissection-induced gastric ulcer: A multicenter randomized controlled trial.

Objectives: To evaluate the effectiveness and safety of a newly designed self-assembling gel in treating ESD-induced gastric ulcers in patients. Methods: This open-label, multicenter, randomized controlled trial enrolled patients who underwent ESD between September 2020 and May 2021. Patients were randomized (1:1) to receive the gel (applied to cover the entire ulcer bed under endoscopic guidance immediately after ESD; gel group) or not (control group). The primary outcome was the ulcer healing rate at 28days. And the secondary outcomes were the delayed bleeding, changes in the ulcer stage, and adverse events. Results: Finally, 125 patients (mean age, 63.7years; 70 [56.0%] males) were enrolled. The ulcer healing rate was higher in the gel group than in the control group at 28days (96.9 ± 4.1% vs. 94.7 ± 5.0%; p = 0.001). The ulcer reduction rate at 28days differed significantly (p < 0.001) between ulcers with majority gel coverage (99.8%), ulcers with minority gel coverage (96.2%), and ulcers with no gel coverage (98.0%). Delayed bleeding was found in 1/63 gel-treated patients (1.6%) versus 5/62 controls (8.1%). A1-stage ulcers were found in 16/63 patients in the gel group versus 44/62 patients in the control group (25.4% vs. 71.0%, p < 0.001) at 3-5days. Conclusion: The newly developed self-assembling gel was safe and effective in accelerating gastric ulcer healing in patients after ESD. Clinical Trial Registration: UMIN Clinical Trials Registry System (registration number, ChiCTR2100052935).

Single-Walled Carbon Nanotubes as Fluorescent Probes for Monitoring the Self-Assembly and Morphology of Peptide/Polymer Hybrid Hydrogels.

Hydrogels formed via supramolecular self-assembly of fluorenylmethyloxycarbonyl (Fmoc)-conjugated amino acids provide excellent scaffolds for 3D cell culture, tissue engineering, and tissue recovery matrices. Such hydrogels are usually characterized by rheology or electron microscopy, which are invasive and cannot provide real-time information. Here, we incorporate near-infrared fluorescent single-walled carbon nanotubes (SWCNTs) into Fmoc-diphenylalanine hydrogels as fluorescent probes, reporting in real-time on the morphology and time-dependent structural changes of the self-assembled hydrogels in the transparency window of biological tissue. We further demonstrate that the gelation process and structural changes upon the addition of cross-linking ions are transduced into spectral modulations of the SWCNT-fluorescence. Moreover, morphological differences of the hydrogels induced by polymer additives are manifested in unique features in fluorescence images of the incorporated SWCNTs. SWCNTs can thus serve as optical probes for noninvasive, long-term monitoring of the self-assembly gelation process and the fate of the resulting peptide hydrogel during long-term usage.

Biocompatible Self-Assembled Hydrogen-Bonded Gels Based on Natural Deep Eutectic Solvents and Hydroxypropyl Cellulose with Strong Antimicrobial Activity.

Natural deep eutectic solvents (NADES)-hydroxypropyl cellulose (HPC) self-assembled gels with potential for pharmaceutical applications are prepared. FT-IR, 1HNMR, DSC, TGA and rheology measurements revealed that hydrogen bond acceptor–hydrogen bond donor interactions, concentration of NADES and the water content influence significantly the physico-chemical characteristics of the studied gel systems. HPC-NADES gel compositions have thermal stabilities lower than HPC and higher than NADES components. Thermal transitions reveal multiple glass transitions characteristic of phase separated systems. Flow curves evidence shear thinning (pseudoplastic) behavior. The flow curve shear stress vs. shear rate were assessed by applying Bingham, Herschel–Bulkley, Vocadlo and Casson rheological models. The proposed correlations are in good agreement with experimental data. The studied gels evidence thermothickening behavior due to characteristic LCST (lower critical solution temperature) behavior of HPC in aqueous systems and a good biocompatibility with normal cells (human gingival fibroblasts). The order of antibacterial and antifungal activities (S.aureus, E.coli, P. aeruginosa and C. albicans) is as follows: citric acid >lactic acid > urea > glycerol, revealing the higher antibacterial and antifungal activities of acids.

Fluorescent Quinoline-Based Supramolecular Gel for Selective and Ratiometric Sensing Zinc Ion with Multi-Modes.

A gelator 1 containing functional quinoline and Schiff base groups that could form organogels in DMF, DMSO, acetone, ethanol and 1,4-dioxane was designed and synthesized. The self-assembly process of geator 1 was characterized by field emission scanning electron microscopy (FESEM), UV-vis absorption spectroscopy, fluorescence emission spectroscopy, Fourier transform infrared spectroscopy(FTIR), X-ray powder diffraction (XRD) and water contact angle. Under non-covalent interactions, gelator 1 self-assembled into microbelts and nanofiber structures with different surface wettability. Weak fluorescence was emitted from the solution and gel state of 1. Interestingly, gelator 1 exhibited good selectivity and sensitivity towards Zn2+ in solution and gel states along with its emission enhancement and change. The emission intensity at 423 nm of solution 1 in 1,4-dioxane was slightly enhanced, and a new emission peak appeared at 545 nm along with its intensity sequentially strengthened in the titration process. The obvious ratiometric detection process was presented with a limit of detection (LOD) of 5.51 μM. The detection mechanism was revealed by a theoretical calculation and NMR titration experiment, which was that Zn2+ induced the transition from trans- to cis- of molecule 1 and further coordinated with 1. This study will introduce a new method for the construction of functional self-assembly gel sensors for the detection of Zn2+.