Influence of the length of the spacer group on the performance of the sulfate-based Gemini surfactants

PurposeA series of sulfate-based Gemini anionic surfactants were synthesized via etherification, ring opening and sulfation reactions using epichlorohydrin, fatty alcohol, ethylene glycol and chlorosulfonic acid as the main raw materials. Orthogonal experiments for 1,8-bisalkoxymethylene-3,6-dioxin-1,8-octane disulfate were performed on the sulfation reaction to determine the optimal reaction conditions.Design/methodology/approachA series of sulfate-based Gemini anionic surfactants were synthesized via etherification, ring opening and sulfation reactions using epichlorohydrin, fatty alcohol, ethylene glycol and chlorosulfonic acid as the main raw materials. Orthogonal experiments for 1,8-bisalkoxymethylene-3,6-dioxin-1,8-octane disulfate were performed on the sulfation reaction to determine the optimal reaction conditions. The structures of the intermediate and final products were characterized by FT-IR (Fourier transform infrared spectroscopy analysis), 1H-NMR (proton nuclear magnetic resonance spectroscopy) methods. The thermal performance of surfactants was analyzed using thermogravimetric analysis (TGA). The thermogravimetric results showed that the sulfate-based Gemini surfactants had good heat resistance (the thermal decomposition temperature of which was in the range of 140∼170?). The Krafft point, surface tension, foaming, Hydrophile–Lipophile Balance Number (HLB), emulsifying, wetting, and lime-soap dispersing performance were measured by visual observation, hanging drop method, aqueous surfactant solution method and Borghetti–Bergman method, respectively. The results have shown that all the sulfate-based Gemini surfactants had good water solubility and lime-soap dispersing ability. When spacer group was -(CH2)2-, with the increase of the carbon chain length from C12 to C14, the micellar concentration critical micelle concentration and surface tension (CMC) gradually increased from 8.25 × 10–4 mol/L to 8.75 × 10–4 mol/L and 27.5 mN/m to 30.9 mN/m, respectively. Also, the sulfate-based Gemini surfactants with the different length of the spacer group had a different effect on their performance on foaming properties and foam properties, HLB and emulsifying ability and wetting ability. FindingsIn view of the important role of the spacer group and the general use of anionic surfactants in oil fields, this article considers the preparation of a series of sulfate-based Gemini surfactants by changing the spacer group and the chain length of the hydrophobic group and evaluating their surface activity, and finally its Kraffi, on the foam properties, HLB value, emulsifying performance, lime soap dispersing ability etc.Originality/valueSulfate-based Gemini surfactants have broad application prospects in the fields of oil and gas exploitation, environmental protection, chemistry and daily chemical industry and so on.

Chitosan with Sulfonic Groups: A Catalyst for the Esterification of Caprylic Acid with Methanol

Esterification of caprylic acid with methanol was performed over chitosan with sulfonic acid groups, as a catalyst, at 60 °C. The sulfonic acid groups were introduced into chitosan (CH) by using chlorosulfonic acid. Catalysts were characterized by scanning electron microscopy (SEM), elemental analysis, thermogravimetric analysis (TGA), X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FTIR), and acid–base titration. Catalytic activity increased with the amount of sulfonic acid groups present on chitosan. The 4–CH–SO3H catalyst (chitosan with sulfonic acid groups—sample 4 prepared) showed the highest activity of all materials. The esterification of caprylic acid with methanol was optimized using a 4–CH–SO3H catalyst. Under optimized reaction conditions, it was found that, at 60 °C, with 0.2 g of catalyst loading and with a molar ratio methanol to caprylic acid equal 1:95, a caprylic acid conversion of about 83%, after 4 h could be obtained. Catalytic stability of the 4–CH–SO3H material was evaluated through consecutive batch runs. After the second batch, the catalytic activity stabilized.

Hierarchical Porous MIL-101(Cr) Solid Acid-Catalyzed Production of Value-Added Acetals from Biomass-Derived Furfural

Considering economic and environmental impacts, catalytic biomass conversion to valuable compounds has attracted more and more attention. Of particular interest is furfural, a versatile biorefinery platform molecule used as a feedstock for the production of fuels and fine chemicals. In this study, the Cr-based metal-organic frameworks (MOFs) MIL-101 were modified by chlorosulfonic acid, and MIL-101 was changed into a hierarchical MOF structure with smaller particles and lower particle crystallinity by CTAB, which significantly improved the acidic sites of the MOFs. The original and modified MIL-101(Cr) catalysts were characterized by XRD, N2 adsorption-desorption, SEM, TEM, and FT-IR. The effects of different catalysts, reaction temperature, catalyst amount, and alcohol type on the reaction were studied. Under the action of the MOFs catalyst, a new mild route for the condensation of furfural with various alkyl alcohols to the biofuel molecules (acetals) was proposed. The conversion route includes the conversion of furfural up to 91% yield of acetal could be obtained within 1 h solvent-free and in room-temperature reaction conditions. The sulfonic acid-functionalized MIL-101(Cr) is easy to recover and reuse, and can still maintain good catalytic activity after ten runs.

Sulfated Modification, Characterization and Potential Bioactivities of Polysaccharide From Ziziphus jujuba cv. Jinsixiaozao

In this study, jujube polysaccharide (JP) was extracted from Ziziphus jujuba cv. Jinsixiaozao and sulfated JP (SJP) was prepared. The optimum preparation conditions were as follows: reaction temperature 75°C, reaction time 1 h, ratio of chlorosulfonic acid-to-pyridine ( VCSA/ VPyr) 1. The degree of substitution of SJP was 0.664 ± 0.014. JP and SJP were typical heteropolysaccharides, which were composed of rhamnose, arabinose, xylose, mannose, glucose, and galactose, but the molar ratio of monosaccharides was different. Fourier transform infrared spectra showed that JP was sulfated successfully. Compared with JP, the molecular weight of SJP increased to 3.17 × 105 Da, its water solubility increased significantly, and its viscosity decreased significantly. When the microstructure of SJP was examined, it was found that the surface of the polysaccharides became loose and porous after sulfation. SJP had a higher hydroxyl radical scavenging activity than the unsulfated polysaccharide. Moreover, sulfation enhanced the antibacterial activity of the polysaccharides against Escherichia coli and Bacillus subtilis. Therefore, sulfation is an effective way to improve the biological activity of the polysaccharide, and SJP can be used as a potential antioxidant and antimicrobial agent in the field of food and medicine.

Synthesis of polyhydroquinolines and 2-amino-4H-chromenes and their alkylene bridging derivatives using Sulfonic acid functionalized heterogeneous nanocatalyst based on modified poly (styrene-alt-maleic anhydride)

: A highly efficient heterogeneous nanocatalyst based on modified poly (styrene-alt-maleic anhydride) (MPSAMA) in three steps was fabricated. Then, the MPSAMA surface was modified using chlorosulfonic acid (CAS) to achieve a sulfonated MPSAMA (SMPSAMA) with high acidity and efficiency. FT-IR spectroscopy, CHNS analysis, FESEM, and TGA were employed to characterize the prepared nanocatalyst. The catalytic activity of the SMPSAMA was examined for the formation of the polyhydroquinoline derivatives through Hantzsch condensation and the synthesis of 2-amino-4H-chromene derivatives. This new heterogeneous nanocatalyst has been efficiently used for the synthesis of bifunctional bis polyhydroquinoline, and new alkylene bridging bis 2-amino-5-oxo-5,6,7,8-tetrahydro-4H-benzo[b]pyran derivatives.

Chlorosulfonic Acid Stretched Carbon Nanotube Sheet for Flexible and Low-Voltage Heating Applications

The carbon nanotube (CNT) is celebrated for its electrothermal property, which indicates the capability of a material to transform electrical energy into heat due to the Joule effect. The CNT nanostructure itself, as a one-dimensional material, limits the electron conduction path, thereby creating a unique heating phenomenon. In this work, we explore the possible correlation between CNT alignment in sheets and heating performance. The alignment of carbon nanotubes is induced by immersion and stretching in chlorosulfonic acid (CSA) solution. The developed CSA-stretched CNT sheet demonstrated excellent heating performance with a fast response rate of 6.5 °C/s and reached 180 °C in less than 30 s under a low voltage of 2.5 V. The heating profile of the stretched CNT sheet remained stable after bending and twisting movements, making it a suitable heating material for wearable devices, heatable smart windows, and in de-icing or defogging applications. The specific strength and specific conductance of the CSA-stretched CNT sheet also increased five- and two-fold, respectively, in comparison to the pristine CNT sheet.

Sulfated modification and anti-HIV activity evaluation of Lycium barbarum polysaccharides

BACKGROUND: Lycium barbarum polysaccharides (LBPs) belong to a very important class of biological macromolecules from Lycium barbarum berries in nature, and have received much attention due to their various biological activities. Since sulfated polysaccharides have antiviral activity in vitro, there is no published research on the sulfated modification of LBPs. RESULTS: The objective of this study was to investigate the feasibility of sulfated modification of LBPs and their potential application in inhibiting HIV-1. The LBPs with different molecular weight were prepared by fractional precipitation from crude LBP through aqueous extraction, ethanol precipitation and deproteinization. The purified LBPs (G1, G2 and G3) were sulfated by chlorosulfonic acid pyridine method to give rise to the sulfated LBPs (G1S1-G1S4, G2S1-G2S4 and G3S1-G3S4) with different degrees of substitution. The anti-HIV-1activities were evaluated by TD50 of the cytotoxicity and IC50 of inhibitory activity using the CCK-8 and Magi test with Azidothymidine (AZT) as positive control. The results showed that LBPs and sulfated LBPs showed non-toxicity with the TD50 >100 μg/mL. Compared with the LBPs, the inhibition of anti-HIV-1 activity of sulfated LBPs was increased significantly with the IC50 value from 0.0924-0.1206 μg/mL to 0.0206-0.0722 μg/mL. The G1S4 (Mw=2.13×104 Da and DS=1.12) showed excellent anti-HIV-1 activity with the IC50 value near to that of AZT (0.0200μg/mL), which would make it possible to become a candidate compound with anti-HIV-1 activity.CONCLUSION: The outcome of the study indicated that sulfated modification of LBPs was feasible and sulfated LBPs had good potential as an anti-HIV drug.