A multifunctional supramolecular hydrogel: preparation, properties and molecular assembly.

A novel supramolecular hydrogel was designed and constructed by molecular self-assembly of a cationic gemini surfactant, 1,3-bis(N,N-dimethyl-N-cetylammonium)-2-propylacrylate dibromide (AGC16), and an anionic aromatic compound, trisodium 1,3,6-naphthalenetrisulfonate (NTS). Owing to its unique structure, the hydrogel (abbreviated as AGC16/NTS) has the potential to be used as a multifunctional drug delivery system. The structure and properties of AGC16/NTS were characterized by rheological measurements, differential scanning calorimetry, variable-temperature 1H nuclear magnetic resonance, ultraviolet-visible spectroscopy, variable-temperature fluorescence emission spectroscopy, cryogenic scanning electron microscopy, transmission electron microscopy and X-ray diffraction methods. The rheological and DSC analysis results revealed that the gel AGC16/NTS was formed below 57 °C. It was found from UV-vis, fluorescence and 1H NMR spectroscopy characterization that aromatic π-π stacking and hydrophobic forces were indispensable to the formation of AGC16/NTS. The Cryo-SEM and TEM observation results indicated that gelators AGC16 and NTS self-assembled into one-dimensional fibers which further tightly intertwined to form a three-dimensional network structure. Based on the spectroscopic data and X-ray diffraction measurement results, a self-assembly model was proposed, helping to further understand the molecular self-assembly mechanism of AGC16/NTS. It was also found that the electrostatic force, hydrophobic force and π-π interaction were the three main driving forces for the gelation. The multiple non-covalent interactions between AGC16 and NTS endowed the hydrogel with excellent performance when the hydrogel was used as a carrier for drug delivery, due to multiple micro-domains within the same gel system. We further investigated the encapsulation and releasing properties of the hydrogel, using the hydrophobic model drug curcumin (Cur) and the model drug naproxen sodium (Npx) with aromatic ring structure. The fluorescence spectroscopy analysis confirmed that Npx was carried through aromatic π-π stacking and the 1H NMR measurement result revealed that Cur was encapsulated within the hydrophobic cavities of AGC16/NTS through hydrophobic interaction. Moreover, the drug release study results showed a sustained release of drugs from the hydrogel, indicating good application prospects in exploring new multifunctional drug delivery systems.

Bisphenols in Aquatic Products from South China: Implications for Human Exposure.

In this study, 245 representative samples of aquatic products were selected from local markets in Shenzhen by stochastic sampling. The samples comprised eight species and fell into three aquatic product categories: fish, crustaceans, and bivalves. A total of eight BPs were determined by liquid chromatography coupled with mass spectrometry, namely, bisphenol A (BPA), bisphenol AF (BPAF), bisphenol AP (BPAP), bisphenol B (BPB), bisphenol S (BPS), bisphenol P (BPP), bisphenol Z (BPZ), and bisphenol F (BPF). All BPs were detected in aquatic products, except for BPAF, indicating pervasive contamination by BPs in aquatic products. BPS demonstrated the highest detection rate both before and after enzymatic hydrolysis, whereas BPAP exhibited the lowest detection rate before enzymatic hydrolysis and BPB displayed the lowest detection rate after enzymatic hydrolysis. The concentration difference before and after enzymatic hydrolysis proved to be statistically significant. Moreover, 49-96% of BPs in aquatic products were found in the combined state, underscoring the essentiality of conducting detections on aquatic product samples following enzymatic hydrolysis. While the health risks associated with ingesting BPs residues through aquatic product consumption were found to be minimal for residents at risk of exposure, the results suggest the necessity for more stringent regulations governing the consumption of aquatic products.

Comprehensive Utilization of Formation Water Scale to Prepare Controllable Size CaCO3 Nanoparticles: A New Method to Improve Oil Recovery.

Formation water scale blocks pipelines and results in oil/gas production decreasing and energy consumption increasing. Many methods have been developed to inhibit scale formation. However, these previous methods are limited by their complications and low efficiency. A new method is proposed in this paper that uses the scale in formation water as a nanomaterial to improve oil recovery via controlling particle size. A series of ligands were synthesized and characterized. Micrometer-CaCO3 was formed and accumulated to form scale of a large size under uncontrolled conditions. The tetradentate ligands (L4) exhibited an excellent capturing yield of Ca2+ (87%). The particle size was very small, but they accumulated to form large particles (approximately 1300 nm) in the presence of Na2CO3. The size of the CaCO3 could be further controlled by poly(aspartic acid) to form sizes of about 700 nm. The flooding test showed that this material effectively improved oil recovery from 55.2% without nano CaCO3 to 61.5% with nano CaCO3. This paves a new pathway for the utilization of Ca2+ in formation water.

Novel Polymer Material for Efficiently Removing Methylene Blue, Cu(II) and Emulsified Oil Droplets from Water Simultaneously.

The pollution of water resources has become a worldwide concern. The primary pollutants including insoluble oil, toxic dyes, and heavy metal ions. Herein, we report a polymer adsorbent, named SPCT, to remove the above three contaminants from water simultaneously. The preparation process of SPCT contains two steps. Firstly, a hydrogel composed of sulfonated phenolic resin (SMP) and polyethyleneimine (PEI) was synthesized using glutaraldehyde (GA) as the crosslinking agent, and the product was named SPG. Then SPCT was prepared by the reaction between SPG and citric acid (CA) at 170 ∘ C. SPCT exhibited an excellent performance for the removal of methylene blue (MB) and Cu(II) from aqueous solution. For a solution with a pollutant concentration of 50 mg L-1, a removal efficiency of above 90% could be obtained with a SPCT dosage of 0.2 g L-1 for MB, or a SPCT dosage of 0.5 g L-1 for Cu(II), respectively. SPCT also presented an interesting wettability. In air, it was both superhydrophilic and superoleophilic, and it was superoleophobic underwater. Therefore, SPCT could successfully separate oil-in-water emulsion with high separation efficiency and resistance to oil fouling. Additionally, SPCT was easily regenerated by using dilute HCl solution as an eluent. The outstanding performance of SPCT and the efficient, cost-effective preparation process highlight its potential for practical applications.

Self-assembled pH-responsive supramolecular hydrogel for hydrophobic drug delivery.

In this study, a novel supramolecular hydrogel system, abbreviated as AGC16/NTS, prepared by molecular self-assembly of cationic gemini surfactant 1,3-bis(N,N-dimethyl-N-cetylammonium)-2-propylacrylatedibromide (AGC16) and anionic aromatic compound trisodium 1,3,6-naphthalenetrisulfonate (NTS), was used to encapsulate hydrophobic model drug curcumin (Cur), constructing a pH-responsive drug delivery system. Cur was effectively encapsulated into the hydrophobic domains of AGC16/NTS through hydrophobic interaction, which was confirmed by 1H NMR measurement. The effects of Cur on the mechanical strength, phase transition behaviour and morphology of AGC16/NTS were characterized by rheology and cryogenic scanning electron microscopy (cryo-SEM) methods. The pH-responsive release of Cur from AGC16/NTS was obtained and the release amount of Cur ascended with pH value decreasing from 7.4 to 3.0. The hydrodynamic sizes of the released Cur-aggregates determined by dynamic light scattering (DLS) were used to analyse the release process of Cur at different pH. The cell viability assay and cell imaging experiment demonstrated that Cur-loaded hydrogel has much higher cytotoxicity and better cell uptake compared to free Cur. Overall, the AGC16/NTS hydrogel is a prospective material for use in encapsulation and controlled-release of hydrophobic drug molecules.

Aqueous hybrids of amino-functionalized nanosilica and acrylamide-based polymer for enhanced oil recovery.

Amino-functionalized nanosilica (ANS) was prepared using nanosilica (NS) and 3-aminopropyltriethoxysilane (APTES) aiming to reinforce the interaction between nanoparticles and polymer molecules. The copolymer of acrylamide, 2-acrylamido-2-methyl-1-propane sulfonic acid (PM), and four ANS samples with different NS to APTES ratios were synthesized. A series of nanoparticle/polymer hybrid systems were fabricated by introducing NS or ANS suspension into PM aqueous solution. The rheological properties and surface activities of these hybrid systems were studied in comparison with PM. The results indicate that the salt-tolerance and heat-resistance properties of PM solution were improved by the introduction of ANS particles. Moreover, the structures of ANS samples have a significant effect on the effectiveness of the nanoparticles due to the fact that the amine group density on the ANS surface can affect the strength of intermolecular interaction between nanoparticles and polymer molecules. Additionally, the better ability of the ANS sample with proper amine group density showed in reducing the oil/water interfacial tension over NS and other ANS samples made it a more promising chemical for enhancing oil recovery. The results from core flooding tests show that the PM/ANS system has the greatest oil recovery factor (16.30%), while the values for PM/NS and PM are 10.84% and 6.00%, respectively.

Rapid and Effective Removal of Cu2+ from Aqueous Solution Using Novel Chitosan and Laponite-Based Nanocomposite as Adsorbent.

In this paper, a novel method for preparing nanoparticle-polymer hybrid adsorbent was established. Laponite was dispersed in distilled water to form Laponite nanoparticles. These nanoparticles were pre-adsorbed by 2-acrylamido-2-methylpropane-sulfonic acid (AMPS) to improve their dispersion stability in chitosan solution. The nanoparticle-polymer hybrid adsorbent was prepared by copolymerization of chitosan, acrylamide, acrylic acid, AMPS, and Laponite nanoparticles. Four adsorbents were obtained and characterized by Fourier transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and Brunauer-Emmett-Teller adsorption (BET). Additionally, the uptake capacities of Cu2+ using different samples were studied. Compared to the adsorbent without chitosan and Laponite components, the maximum uptake of the hybrid adsorbent increased from 0.58 to 1.28 mmol·g-1 and the adsorption equilibrium time of it decreased from more than 75 min to less than 35 min, which indicated that the addition of chitosan and Laponite could greatly increase the adsorption rate and capacity of polymer adsorbent. The effects of different experimental parameters-such as initial pH, temperature, and equilibrium Cu2+ concentration-on the adsorption capacities were studied. Desorption study indicated that this hybrid adsorbent was easy to be regenerated.