Anionic Sulfonate Research Articles

Sustainable Nanofluids Constructed from Size-Controlled Lignin Nanoparticles: Application Prospects in Enhanced Oil Recovery.

Lignin, a widely available, cost-effective, and structurally stable natural polymer, has recently attracted significant attention due to its diverse potential applications. A promising approach is to prepare lignin nanoparticles (LNPs) as a substitute for conventional nanoparticles to fulfill a variety of functions. In this study, LNPs with controlled size, regular morphology, and excellent dispersibility were synthesized by using industrial alkali lignin. The antisolvent method was employed, utilizing an aqueous solution of the anionic surfactant sodium apolyolefin sulfonate (AOS) as the antisolvent. Subsequently, the prepared LNPs were used to formulate nanofluids in combination with AOS and nonionic surfactant coconut diethanolamide (CDEA). The incorporation of LNPs has significantly enhanced the interfacial activity of the resulting nanofluids, thereby improving their emulsion stabilization, spreading on quartz surfaces, and oil droplet removal capabilities, which establish a strong foundation for the AOS/CDEA/LNPs nanofluid to achieve high performance in enhanced oil recovery (EOR), which was validated through microscopic visual physical model experiments. The quartz crystal microbalance with the dissipation monitoring (QCM-D) technique was employed to investigate the adsorption of surfactants onto quartz surfaces. It was found that the incorporation of LNPs significantly reduces the adsorption loss of surfactants, presenting a potential solution to overcome the challenges associated with surfactant adsorption in chemically enhanced oil recovery (EOR) processes, such as high cost and unreliable efficiency. This study reveals the good performance of LNPs/surfactant nanofluids and provides a potential approach to the advancement of green, sustainable, and intelligent EOR technologies.

Multi-scale evaluation of surfactant effects on asphalt desorption behavior from oil sand surfaces

This study created a hydrophobic oil sand model to investigate the impact of surfactants on the desorption behavior of asphalt from solid surface. Cationic surfactant cetyl trimethyl ammonium bromide (CTAB) and anionic surfactant sodium dodecyl benzene sulfonate (SDBS) were used to soak the model to observe the effect of surfactants on asphalt desorption. The effect of surfactant pretreatment on the wettability of the substrate was evaluated by measuring the contact angle of ultrapure water on the substrate and observing the morphological changes of the solid surface by atomic force microscopy. The results show that the contact angle of the model treated with SDBS decreases to 10° after 3 days, which significantly improves the wettability of the substrate surface and promotes the desorption of asphalt. However, CTAB has no obvious effect on asphalt desorption. The standard deviation of the gray value of the sand surface image is significantly reduced to 38.693 after the SDBS treatment, which can be seen by binarizing the image. This suggests that the asphalt and solution are evenly distributed and that there is hardly any discernible boundary. Nevertheless, neither of the two surfactants can improve the water-based extraction efficiency of oil sands after soaking treatment. The asphalt yield is less than 5% after 30 days of pretreatment with CTAB solution, while only 45% asphalt yield is obtained after 30 days of pretreatment with SDBS solution. Despite these variations, the quality of asphalt foam remains relatively the same. This may be related to the failure of surfactants to improve the surface wettability of hydrophobic sand. Therefore, the surface wettability of the sand is considered to be a key factor affecting the asphalt desorption and final yield. This study can provide a scientific basis for oil sand recovery to a certain extent.

Hydrophobic and positively charged magnetic nanoparticles for enhanced oil recovery from concentrated emulsion wastewaters

With the development of petroleum industry, a large amount of oil-in-water (O/W) emulsion wastewaters were produced, resulting in serious environmental pollution and resource waste. Up till now, magnetic nanoparticles (MNPs) were frequently reported in emulsion wastewater treatment and mainly focused on the water purification, but little effort was devoted to the facile recovery of oil resource. In the present work, a class of hydrophobic and positively charged MNPs, namely dimethyloctadecyl [3-(trimethoxysilyl) propyl] ammonium chloride (DOTAC)-coated MNPs (M−DOTAC), was carefully synthesized by regulating DOTAC anchoring density on Fe3O4@SiO2, and then employed to treat the concentrated emulsion wastewaters stabilized by anionic sodium dodecyl benzene sulfonate (SDBS) or nonionic Tween-80. M−DOTAC with relatively high DOTAC density (M−DOTAC 1.8) exhibited higher positive charge density and hydrophobicity, and hence could significantly promote the oil droplet coalescence and mergence via the electrostatic attraction and hydrophobic adsorption bridging as well as the hydrophilic-lipophilic transition of interfacial adsorption layer. Accordingly, with addition of moderate dosage of M−DOTAC 1.8, the emulsion was broken and divided into three layers: (1) a continuous oil layer was formed in the upper layer which could be directly recycled; (2) the middle layer was composed of MNPs-tagged oil droplets/flocs; (3) the bottom layer was the clearer water phase. The optimal recovery rate of oil resource reached ∼ 60 % in SDBS stabilized system, and further increased to ∼ 98 % in Tween-80 stabilized system. However, the oil recovery rate was declined at an excessive dosage of M−DOTAC 1.8 due the formation of double emulsion. Besides, M−DOTAC 1.8 exhibited good reusability. These results indicated the fabricated M−DOTAC had great application prospect in treating emulsion wastewaters containing high oil content.

Steric hindrance and orientation polarization by a zwitterionic additive to stabilize zinc metal anodes

AbstractZinc metal stands out as a promising anode material due to its exceptional theoretical capacity, impressive energy density, and low redox potential. However, challenges such as zinc dendrite growth, anode corrosion, and side reactions in aqueous electrolytes significantly impede the practical application of zinc metal anodes. Herein, 3‐(1‐pyridinio)‐1‐propanesulfonate (PPS) is introduced as a zwitterionic additive to achieve long‐term and highly reversible Zn plating/stripping. Due to the orientation polarization with the force of electric field, PPS additive with π–π conjugated pyridinio cations and strong coordination ability of sulfonate anion tends to generate a dynamic adsorption layer and build a unique water–poor interface. PPS with steric hindrance effect and strong coordination ability can attract solvated Zn2+, thereby promoting the desolvation process. Moreover, by providing a large number of nucleation sites and inducing zinc ion flow, the preferred orientation of the (002) crystal plane can be achieved. Therefore, the interfacial electrochemical reduction kinetics is regulated and uniform zinc deposition is ensured. Owing to these advantages, the Zn//Zn symmetrical cell with PPS additive exhibits remarkable cycling stability exceeding 2340 h (1 mA cm−2 and 1 mA h cm−2). The Zn//V2O5 full cell also delivers stable cycling for up to 6000 cycles.

Preparation and evaluation of a pyridine sulfonate betaine-based zwitterionic stationary phase for hydrophilic interaction chromatography

A zwitterionic stationary phase comprising pyridinium cations and sulfonate anions was successfully developed through thiol-ene click chemistry. Using seven polar small molecules as probes, the zwitterionic stationary phase showed high separation selectivity and excellent column efficiency (35,200–54,800 plates/m) compared with two commercial columns. The influence of water proportion, salt concentration, and pH in the mobile phase, and column temperature, on the retention of six polar compounds was examined. The retention mechanism was explored by three hydrophilic retention models, Tanaka test and linear solvation energy relationship analysis. For the analysis of sample dairy products (milk powder, milk, and yogurt), the stationary phase was operated in hydrophilic interaction chromatography mode without the addition of buffer salts, facilitating rapid and efficient detection and quantification of melamine. The LOD and LOQ are 0.04 mg⋅g−1 and 0.13 mg⋅g−1, respectively, and the recovery rate is 90.3 − 102.8 %. The zwitterionic stationary phase has the advantages of simple preparation, good method reproducibility, good selectivity and high precision.

Metalo Hydrogen-Bonded Organic Frameworks Constructed by Coordinated Chains for Magnetic and Proton-Conductive Bifunctionality.

Metalo hydrogen-bonded organic frameworks (MHOFs) have received growing interest in designing crystalline functional materials. However, reports on bifunctional MHOFs showing magnetic and proton-conductive properties are extremely limited and their design is challenging. Herein, we investigated the magnetic and proton-conductive properties of two sulfonated CoHOF and MnHOF, {M(H2O)2(abs)2}n (M = Co2+ and Mn2+, Habs = 4-aminoazobenzene-4'-sulfonic anion), constructed by coordination chains. The supramolecular frameworks sustained by H bonds between -SO3- and coordinated water show directional ladder-type H bonds with hydrophilic nanochannels, leading to high proton conduction with exceptionally high conductivity around 10-2 S cm-1 at 100 °C under 97% relative humidity. In particular, the maximum σ value of CoHOF, 2.11 × 10-2 S cm-1, recorded the highest value among the reported proton-conducting materials showing slow magnetic relaxation. Meanwhile, the molecular structure of organosulfonate enables the magnetic isolation of high-spin Co2+ and Mn2+ centers in the frameworks. Magnetic measurements indicated that the MHOFs show field-induced single-ion magnet (SIM) properties, making these compounds rare magnetic-proton-conductive MHOFs. The work provides not only two unique MHOFs with SIM behavior and high proton conduction performance but also avenues for designing stable bifunctional MHOFs via a coordination chain approach.

Effect of adsorption of different types of surfactants on conglomerate reservoir minerals on chemical oil recovery efficiency

Using surfactants to extract oil, the anionic surfactant Karamay petroleum sulfonate (KPS), the zwitterionic surfactant octadecyl betaine (BS-18) and the nonionic surfactant coconut oil fatty acid diethanolamide (6501) were selected for adsorption experiments with minerals contained in the conglomerate reservoir with different mineral compositions to study the adsorption law of different types of surfactants. Zeolite and montmorillonite, which have the highest specific surface area and zeta potential among the minerals in the conglomerate reservoir, have the most obvious adsorption effect on surfactants, resulting in a large amount of adsorption of KPS and BS-18. The three types of surfactants were then used to conduct physical simulation oil recovery experiments with conglomerate core samples, and the results showed that 6501 had better overall performance, the best adsorption resistance, and a higher degree of recovery in oil recovery experiments, which provided a basis for the selection of surfactants in the process of chemical drive in conglomerate reservoirs.

Narrow Range of Coagulation of Ion Associates of Poly(styrene sulfonate) with Alcian Blue Dye.

The ionic association of Alcian Blue dye with poly(styrene sulfonate) in aqueous solutions was studied for analytical purposes. The quadruple-charged cationic dye, Alcian Blue, was found to form colloidal ionic associates with poly(styrene sulfonate) anions. When the amounts of opposite charges are nearly equal, the resulting ionic associates lose solubility and coagulate rapidly. This effect occurs within a narrow range of the ratio of poly(styrene sulfonate) to Alcian Blue. At the point of charge equivalence, the zeta potential of the resulting particles is zero, which facilitates flocculation. The resulting flocs enlarge to approximately 0.05-0.5 mm and precipitate rapidly. FTIR spectroscopy confirms that the precipitate contains both poly(styrene sulfonate) and Alcian Blue dye. Sedimentation kinetics was studied in detail using scanning turbidimetry. Due to the high molar absorbance of the Alcian Blue dye at 600 nm, the point of equimolar charge ratio was precisely determined by spectrophotometry. The complete precipitation of ionic associates occurs when the amount of poly(styrene sulfonate) ranges from 1.4 to 1.55 mmol per 1 g of Alcian Blue dye. Such a narrow coagulation range allows for the use of the studied effect for quantitative analysis. Both Alcian Blue dye and poly(styrene sulfonate) can be quantified if one of their concentrations is known.

Effects of surfactants on the wettability of sodium propionate aqueous deacidification agent

Abstract To address the challenges of difficulty and low penetration speed of aqueous deacidification agents in paper, we aimed to enhance the wetting performance of these agents by incorporating a surfactant. We selected four surfactants for our study: anionic sodium dodecyl benzene sulfonate (SDBS), cationic cetyltrimethylammonium bromide (CTAB), nonionic polysorbate-80 (TW80), and polyether-modified trisiloxane (TRSE). The wetting properties of these surfactants on sodium propionate aqueous deacidification agent, the alkali stability of the solution, and the effects of moist heat aging on paper durability were explored. The results demonstrated that TRSE exhibited superior performance compared to the other three surfactants, effectively reducing the surface tension of sodium propionate solution to 21.02 mN/m. In alkaline conditions with a pH range of 8.00–10.00, the surface tension of SDBS, CTAB, and TW80 solutions remained stable for 30 days. Similarly, under weakly alkaline conditions with a pH value below 9, the surface tension of TRSE solutions exhibited stability. It should be noted that SDBS accelerated the decline of paper tensile index and whiteness during the heat and humidity aging process; at the same time, CTAB, TW80, and TRSE had no noticeable adverse effects on paper aging resistance.

Functional derivatives of chitosan, soluble in neutral medium as drugs and genetic material carrier: preparation and properties

Method of chitosan modification, providing controlled addition of the quaternized block has been proposed. The structure of the products obtained were studied by FT-IR and NMR spectroscopy; their solubility and acid-base properties was characterized by turbodimetry and potentiometry, respectively. Presence about 50% of quaternized amino groups was shown to be necessary to obtain soluble products. The difference in pH-sensitivity of modified derivatives with different types of quaternized block attachment was revealed by studying their interaction with a model polystyrene sulfonate anion. The possibility of preparing complexes based on the obtained derivatives with DNA — polyplexes, stable under conditions close to physiological ones has been demonstrated. It was shown the presence of primary amino groups on the polycation chains leads to a decrease in the polyplexe size. The data obtained can form the basis for development of drug and genetic material delivery system. The 2-stage method of chitosan modification providing controlled addition of the quaternized block has been proposed. The structure of the products obtained were studied by FT-IR and NMR spectroscopy; their solubility and acid-base properties was characterized by turbodimetry and potentiometry, respectively. The presence about 50% of quaternized amino groups was shown to be necessary to obtain soluble products. The difference in pH-sensitivity of modified derivatives with different types of quaternized block attachment was revealed by studying their interaction with a model polystyrene sulfonate anion. The possibility of preparing complexes based on the obtained derivatives with DNA, polyplexes stable under conditions close to physiological ones has been demonstrated. It is shown that the presence of primary amino groups on the polycation chains leads to a decrease in the polyplexe size. The data obtained can form the basis for development of drug and genetic material delivery systems.

Understanding the influence of sodium chloride concentration on ion diffusion in charged polymers

Previous observations made on sulfonated polysulfones equilibrated with solutions of increasing salinity, where salt diffusion coefficients increase concurrently with reductions in water content driven by osmotic de-swelling, are currently unexplained. To further explain the molecular underpinnings of these observations, we characterized the influence of external salt solution concentration on the average salt and ion diffusion properties of two sulfonated polymers: a model cross-linked material (XLAMPS) and a series of sulfonated polysulfones (HQ:BP – XX). Analysis of the average salt and co- and counter-ion diffusion coefficients in these polymers suggest that the increase in charge screening (of electrostatic interactions between anionic sulfonate groups and co-ions) that occurs with increasing salinity affects the salt diffusion coefficients of sulfonated polysulfone in a manner that is different from what would be expected based on changes in water content alone and from what was observed for XLAMPS. Free volume theory describes the influence of these electrostatic effects on salt diffusion using a parameter related to the characteristic free volume element size necessary for diffusion. The results and analysis suggest that charge screening reduces the characteristic free volume element size necessary for diffusion in sulfonated polysulfone, which provides an explanation for the observed increase in average salt diffusion coefficients with increased salinity.

Integrated Interfacial Modulation Strategy: Trace Sodium Hydroxyethyl Sulfonate Additive for Extended-Life Zn Anode Based on Anion Adsorption and Electrostatic Shield.

Aqueous zinc-ion batteries (AZIBs) are poised to play a pivotal part in meeting the growing demands for energy storage and powering portable electronics for their superior security, affordability, and environmentally friendly characteristics. However, the detrimental side reactions occurring at the zinc anode and the dendrite caused by uneven zinc plating/stripping have greatly compromised the cycling life of AZIBs, thereby impeding their practical prospects. In this study, the interfacial comodulation strategy was employed by combining the "electrostatic shielding" effect of cations with the characteristic adsorption of anions. Two molar ZnSO4 served as the matrix, and sodium hydroxyethyl sulfonate (SHES) was selected as a low-cost, nontoxic additive. Experimental results confirm that SHES and zinc anode exhibit robust interactions that lead to the formation of an electrostatic shield and a dynamic adsorption layer at the interface, thereby suppressing hydrogen evolution and corrosion. The combined "electrostatic shielding" effect of sodium ions and the robust characteristic adsorption of hydroxyethyl sulfonate anions serve to guide the directed three-dimensional (3D) diffusion of Zn2+, facilitating rapid, stable, and uniform deposition of zinc. Due to these effects, incorporating 0.2 M SHES as an additive extends the cycle life beyond 3600 h and enables a highly reversible process of deposition and stripping in symmetric cells. Additionally, the Zn-Cu half-cell exhibits reliable cycling for over 1400 cycles, achieving an average Coulombic efficiency of 99.6%. Moreover, the introduction of this additive substantially enhances the performance of Zn-MnO2 and Zn-NH4V4O10 full cells. This study demonstrates the practical feasibility of achieving anodes with high reversibility in AZIBs through the implementation of a strategy that involves anion adsorption at the interface, which holds paramount significance for the practical application of AZIBs.

Adhesive Zwitterionic Poly(ionic liquid) with Unprecedented Organic Solvent Resistance.

The resistance of adhesives to organic solvents is of paramount importance in diverse industries. Unfortunately, many currently available adhesives exhibit either weak intermolecular chain interactions, resulting in insufficient resistance to organic solvents, or possess a permanent covalent crosslinked network, impeding recyclability. This study introduces an innovative approach to address this challenge by formulating zwitterionic poly(ionic liquid) (ZPIL) derivatives with robust dipole-dipole interactions, incorporating sulfonic anions and imidazolium cations. Due to its unique dynamic and electrostatic self-crosslinking structure, the ZPIL exhibits significant adhesion to various substrates and demonstrates excellent recyclability even after multiple adhesion tests. Significantly, ZPIL exhibits exceptional adhesion stability across diverse nonpolar and polar organic solvents, including ionic liquids, distinguishing itself from nonionic polymers and conventional poly(ionic liquid)s. Its adhesive performance remains minimally affected even after prolonged exposure to soaking conditions. The study presents a promising solution for the design of highly organic solvent-resistant materials for plastics, coatings, and adhesives.

Comparative study of nanoemulsion and micelle formed by surfactants containing benzene ring for spontaneous imbibition displacement

Nanoemulsion has a wide range of applications in oilfield chemistry due to its unique nanoscale size, excellent kinetic stability and high specific surface area. In this paper, a novel nanoemulsion oil flooding system was prepared using anionic surfactant sodium dodecyl benzene sulfonate (SDBS), the nonionic surfactant alkylphenol ethoxylates (OP-10), kerosene, n-butanol and deionized water. The particle size, Zeta potential, interfacial tension (IFT) and wettability properties were evaluated in the laboratory. The displacement performance of nanoemulsion was evaluated by the spontaneous imbibition experiment. Meanwhile, it compared with the same concentration of SDBS + OP-10 + n-butanol (SOB) system. The results showed that the particle size of the nanoemulsion was 70 ∼ 100 nm. When the concentration of nanoemulsion was 0.10 %, the oil–water IFT could reach 0.091 mN/m. The spontaneous imbibition oil recovery of the nanoemulsion (0.10 wt%) could reach 33.20 %, which was 23.02 % higher than that of SOB system. We also research the spontaneous imbibition displacement mechanism of nanoemulsion and micelle in low-permeability reservoirs. This paper will help to select the best oil displacement agent for the design of enhanced oil recovery (EOR) projects and promote the application of oil displacement agent in oilfield.

An artificial liquid–liquid phase separation-driven silk fibroin-based adhesive for rapid hemostasis and wound sealing

The powerful adhesion systems of marine organisms have inspired the development of artificial protein-based bioadhesives. However, achieving robust wet adhesion using artificial bioadhesives remains technically challenging because the key element of liquid–liquid phase separation (LLPS)-driven complex coacervation in natural adhesion systems is often ignored. In this study, mimicking the complex coacervation phenomenon of marine organisms, an artificial protein-based adhesive hydrogel (SFG hydrogel) was developed by adopting the LLPS-mediated coacervation of the natural protein silk fibroin (SF) and the anionic surfactant sodium dodecylbenzene sulfonate (SDBS). The assembled SF/SDBS complex coacervate enabled precise spatial positioning and easy self-adjustable deposition on irregular substrate surfaces, allowing for tight contact. Spontaneous liquid-to-solid maturation promoted the phase transition of the SF/SDBS complex coacervate to form the SFG hydrogel in situ, enhancing its bulk cohesiveness and interfacial adhesion. The formed SFG hydrogel exhibited intrinsic advantages as a new type of artificial protein-based adhesive, including good biocompatibility, robust wet adhesion, rapid blood-clotting capacity, and easy operation. In vitro and in vivo experiments demonstrated that the SFG hydrogel not only achieved instant and effective hemostatic sealing of tissue injuries but also promoted wound healing and tissue regeneration, thus advancing its clinical applications. Statement of significanceMarine mussels utilize the liquid–liquid phase separation (LLPS) strategy to induce the supramolecular assembly of mussel foot proteins, which plays a critical role in strong underwater adhesion of mussel foot proteins. Herein, an artificial protein-based adhesive hydrogel (named SFG hydrogel) was reported by adopting the LLPS-mediated coacervation of natural protein silk fibroin (SF) and anionic surfactant sodium dodecylbenzene sulfonate (SDBS). The assembled SFG hydrogel enabled the precise spatial positioning and easy self-adjustable deposition on substrate surfaces with irregularities, allowing tight interfacial adhesion and cohesiveness. The SFG hydrogel not only achieved instant and effective hemostatic sealing of tissue injuries but also promoted wound healing and tissue regeneration, exhibiting intrinsic advantages as a new type of artificial protein-based bioadhesives.

Green Surfactant Assisted-Solidified Floating Organic Drop Micro-Extraction (SA-SFODME) for the Preconcentration of Trace Lead with Determination by Flame Atomic Absorption Spectrometry (FAAS)

Determination of trace lead from environmental samples was carried out by solidified floating organic drop microextraction for preconcentration before analysis by flame atomic absorption spectrometry. The determination of lead from environmental samples, even at trace levels, was possible with an ordinary flame atomic absorption spectrometer (FAAS). The lead formed a hydrophobic complex with the anionic surfactant sodium dodecyl benzene sulfonate (SDBS), and this hydrophobic complex was extracted into the 1-dodecanol drop. Parameters affecting analytical performance have been studied. The optimum pH value was 3.5. The optimum sample volume, SDBS concentration, and extraction solvent volume were 75 mL, 50 mM in dodecanol, and 75 µL, respectively. The optimum extraction time was determined as 30 min, the optimum extraction temperature was 45 °C, the optimum mixing speed was 650 rpm and the ideal extraction phase volume was 0.50 mL. Methanol has been shown to be effective when used as a diluent. Using the optimum conditions, the enhancement factor was 106, and the limit of detection (3s) and precision were 3.3 ng/mL and 2.3% (n = 9,15 ng/mL), respectively. The limit of quantification (LOQ) (10s) was 10 ng/mL and the linear working range was 15-100 ng/mL. The accuracy was evaluated by certified reference material analysis. The optimized method was applied to the determination of Pb(II) from environmental water samples. This method follows the principles of green analytical chemistry.

Achieving High-Performance Lithium-Sulfur Batteries by Modulating Li+ Desolvation Barrier with Liquid Crystal Polymers.

Lithium-sulfur (Li-S) batteries offer high theoretical capacity but are hindered by poor rate capability and cycling stability due to sluggish Li2S precipitation kinetics. Here a sulfonate-group-rich liquid crystal polymer (poly-2,2'-disulfonyl-4,4'-benzidine terephthalamide, PBDT) is designed and fabricated to accelerate Li2S precipitation by promoting the desolvation of Li+ from electrolyte. PBDT-modified separators are employed to assemble Li-S batteries, which deliver a remarkable rate capacity (761 mAh g-1 at 4 C) and cycling stability (500 cycles with an average decay rate of 0.088% per cycle at 0.5 C). A PBDT-based pouch cell even delivers an exceptional capacity of ≈1400 mAh g-1 and an areal capacity of ≈11 mAh cm-2 under lean-electrolyte and high-sulfur-loading condition, demonstrating promise for practical applications. Results of Raman spectra, molecular dynamic (MD) and density functional theory (DFT) calculations reveal that the abundant anionic sulfonate groups of PBDT aid in Li+ desolvation by attenuating Li+-solvent interactions and lowering the desolvation energy barrier. Plus, the polysulfide adsorption/catalysis is also excluded via electrostatic repulsion. This work elucidates the critical impact of Li+ desolvation on Li-S batteries and provides a new design direction for advanced Li-S batteries.

Crystal structures, Hirshfeld surface analysis, thermogravimetric, and spectroscopic properties of three Zn(Ⅱ) complexes bridged by 4,4′-bipy with organic sulfonate anions as counterions

Three Zn(Ⅱ) sulfonate compounds: {[Zn3(Ac)4(4,4′-bipy)4]·2(3-pySO3)·H2O}n (1), {[Zn(4,4′-bipy)(H2O)4]·2(Me-phSO3)}n (2), and {[Zn(4,4′-bipy)(H2O)4]·2(NH2-phSO3)}n (3), were synthesized through solvent diffusion method at room temperature (3-pySO3H = Pyridine-3-Sulfonic acid; Me-phSO3H = P-Toluene Sulfonic acid; NH2-phSO3H = Sulfanilic acid). Single-crystal X-ray diffractions reveal that the crystal structure of compound 1 contains a 2D cationic layer with pseudo-square grid motifs formed by trinuclear Zn(II) units which connected by 4,4′-bipy ligands. Water molecule forms hydrogen bonds with free 3-PySO3− anions which are located in the voids of the cationic grids. Compounds 2 and 3 show isostructural 1D [Zn(4,4′-bipy)(H2O)4]2+ chains with sulfonate anions connected to the chain via hydrogen bonding. The weak interactions in the structures of the three compounds have been assessed using Hirshfeld surface analyses and 2D fingerprint plots. The Hirshfeld surface shows that the most important contributions for the crystal packing are from H···H and H··O/O··H interactions, which indicate dominant van der Waals interactions. In addition, the compounds were investigated by powder X-ray diffraction (PXRD), elemental analyses, UV–vis, FT-IR, solid-state fluorescence spectroscopy, and thermal analyses (TG-DSC).

Oil spill dispersant formulation from Palmitoyl-DEA and methyl ester sulfonate

Surfactants are chemical compounds that can interact with solvents to reduce surface tension. Palmitoyl-Diethanolamide surfactant (Palmitoyl-DEA) and methyl ester sulfonate (MES) can be applied in dispersing oil in seawater as Oil Spill Dispersant (OSD). An OSD formulation derived from a mixture of two surfactant solutions, namely Palmitoyl-DEA and MES, was found. Diethanolamide non-ionic surfactant solution and anionic methyl ester sulfonate surfactant solution in various concentrations were mixed according to their respective ratios at 50℃ for 60 minutes. The OSD product obtained was then analyzed for density, surface tension, and emulsion stability. OSD products at a concentration of 4% MES and 2% DEA with a 2:1 ratio obtained the best analytical results. The OSD product has excellent density, surface tension, and emulsion stability (> 80%). Furthermore, testing of OSD products was carried out for oil pollution in seawater. The results of simulation tests using OSD products for handling petroleum pollution in seawater (15 mL/L) show an excellent ability to disperse oil (> 90%). The oil and OSD dispersed in seawater showed a more significant increase in COD and BOD values.

Synthesis, Crystal Growth, Structural Characterization, Supramolecular Chemistry, and Theoretical Calculations of Methylenium Salts of Benzenesulfonates

AbstractThe current investigation describes the synthesis of four novel methylene blue (MB) salts of benzene sulfonate derivatives, featuring bulky anionic groups. The process involves treating chloride salt of MB with sodium salts of 4‐aminobenzene sulfonate, 4‐styrenebenzene sulfonate, 3,7‐naphthalene disulfonate, and anthraquinone‐1,5‐naphthalene disulfonate to substitute the chloride ion with benzoate sulfonate anion in MB‐chloride. The synthesis includes quaternizing MB‐chloride with the corresponding benzene sulfonate in minimal aqueous solvent to promote precipitation. The resultant precipitates were subsequently dissolved in an appropriate solvent to enable the crystallization of the ultimate product. The dissolution occurs either at ambient temperature or with heat. The crystals of the resultant salts were characterized using various analytical techniques like UV‐visible, and FT‐IR spectroscopy, TGA, single crystal X‐ray diffraction and powder X‐ray diffraction analysis. The UV‐visible spectroscopic results, frontier molecular orbital, density of states, molecular electrostatic potentials, and HOMO‐LUMO energy gaps were estimated by DFT. Structural analysis revealed that supramolecular structure of compounds achieved stabilization through electrostatic interactions, a diverse range of both conventional and non‐conventional hydrogen bonds, π–π stacking interactions, and other short‐range interactions. The investigation delves into intricate details and offers a thorough discussion of the fundamental principles that contribute to the formation and stabilization of supramolecular structures.