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Crude oil emulsions are prevalent in the petroleum industries due to different natural emulsifiers in crude oil. In addition, adding amphiphilic compounds for enhanced oil recovery at high temperatures and pressure under extreme shear stress conditions improved the stability of these emulsions. However, these emulsions are not desirable because they cause different operational problems. Herein, this work aims to synthesize and characterize two novel ionic liquids (ILs) and apply them to the dehydration of water-in-crude oil (W/O) emulsions. For that, tetraethylene glycol (TEG) was reacted with thionyl chloride (TC), yielding dialkyl halide (TEC). After that, TEC was reacted with 4-hexylaniline (HA) or 4-tetradecylaniline (TA) in the presence of sodium carbonate, obtaining the amines TC-HA and TC-TA, respectively. Finally, TC-HA and TC-TA were reacted with acetic acid, yielding the corresponding ionic liquids, THA-IL and TTA-IL. Chemical structure, surface tension (ST), interfacial tension (IFT), thermal stability, and micelle size were investigated using various techniques. The conventional bottle test was used to evaluate the performance of these ILs for dehydration W/O emulsion at different crude oil/brine ratios (ranging from 90/10 to 50/50). The results indicated that the dehydration performance (DP) increased with an increase in IL concentration. In addition, DP improved with increased water contents, reaching 100% for THA-IL and 80% for TTA-IL, respectively, at a crude oil/brine ratio of 50/50. Furthermore, TTA-IL showed higher DP and separated more clear water than THA-IL, which could be linked to its higher ability to reduce IFT due to a longer alkyl chain than THA-IL. The results showed that the synthesized ILs could serve as demulsifiers in the petroleum industry.

Oil spills in marine environments are a serious environmental concern and using low-cost materials for oil spill cleanup is an emerging subject. In recent years, surface-modified magnetite nanoparticles (MNPs) have shown promising properties for oil spill cleanup due to their high performance, low cost, magnetic properties, and reusability. This study aims to modify the surface of magnetite nanoparticles (MNPs) using two new polyamines and employ them for oil spill remediation. First, tetraethylene glycol (TEG) was converted to the corresponding alkyl halide (AH). Next, two polyamines were synthesized via the alkylation of diamines, 1,11-undecanediamine (UD) and 1,5-pentanediamine (PD), yielding the corresponding AH-UD and AH-PD polyamines. Finally, AH-UD and AH-PD were applied to MNPs’ surface modification, yielding the corresponding surface-modified MNPs, AU-MNPs, and AP-MNPs. The performance of AU-MNPs and AP-MNPs for oil spill uptake (OSU%) was investigated using various MNPs-to-oil ratios at different contact times. Furthermore, the reusability of AU-MNPs and AP-MNPs was also investigated over four cycles. The results indicated that the OSU values of AU-MNPs and AP-MNPs were affected by MNPs’ ratios and contact time, where their OSU increased as their ratios and contact time increased. In addition, AU-MNPs showed a higher OSU than AP-MNPs, which could be ascribed to the longer alkyl chain in the polyamine (AH-UA) used for their surface modification compared to AP-MNPs. Furthermore, AU-MNPs and AP-MNPs reusability results exhibited effective OSU in four cycles with a relative decline with an increasing number of cycles.

Recently, magnetite nanoparticles (MNPs) have gained great attention for oil spill cleanup due to their unique properties, e.g., high oil removal efficiency, high surface area, and response to an external magnetic field. The efficiency of MNPs for oil spill uptake can be enhanced by functionalizing their surface using different materials. Furthermore, the functionalization of MNP surface using these materials promotes their chemical stability. This study aims to functionalize the surface of magnetite nanoparticles (MNPs) using two newly synthesized hydrophobic ionic liquids (ILs) and apply them for oil spill cleanup. ILs were synthesized by the reaction of glycidyl-4-nonyl ether (GE) with fatty amines, either octadecylamine (OA) or dodecylamine (DA), to yield the corresponding amines, GEOA and GEDA, respectively. GEOA and GEDA were quaternized with acetic acid (AA) to produce the corresponding ILs, GEOA-IL and GEDA-IL. The produced ILs, GEOA-IL and GEDA-IL, were applied for the surface modification of magnetite nanoparticles (MNPs), producing surface-modified MNPs, GO-MNPs and GD-MNPs, respectively. GO-MNPs and GD-MNPs were characterized using Fourier transform infrared, X-ray diffraction, transmission electron microscopy, dynamic light scattering, contact angle, and vibrating sample magnetometer. Their oil removal efficiency (ORE) was investigated at different MNP : crude oil ratios ranging from 1 : 1–1 : 50. GO-MNPs and GD-MNPs showed high ORE even at low MNP ratios. Furthermore, GO-MNPs showed higher oil removal efficiency than GD-MNPs, which may be explained using GEOA-IL containing a longer alkyl chain for MNP surface modification in comparison to GEDA-IL. Furthermore, GO-MNPs and GD-MNPs displayed excellent reusability in five cycles, with a slight decrease in ORE with increasing cycles.

Due to the release of hazardous heavy metals from various industries, water pollution has become one of the biggest challenges for environmental scientists today. Mercury Hg(II) is regarded as one of the most toxic heavy metals due to its ability to cause cancer and other health issues. In this study, a tailor-made modern eco-friendly molecularly imprinted polymer (MIP)/nanoporous carbon (NC) nanocomposite was synthesized and examined for the uptake of Hg(II) using an aqueous solution. The fabrication of the MIP/NC nanocomposite occurred via bulk polymerization involving the complexation of the template, followed by polymerization and, finally, template removal. Thus, the formed nanocomposite underwent characterizations that included morphological, thermal degradation, functional, and surface area analyses. The MIP/NC nanocomposite, with a high specific surface area of 884.9 m2/g, was evaluated for its efficacy towards the adsorptive elimination of Hg(II) against the pH solution changes, the dosage of adsorbent, initial concentration, and interaction time. The analysis showed that a maximum Hg(II) adsorption effectiveness of 116 mg/g was attained at pH 4, while the Freundlich model fitted the equilibrium sorption result and was aligned with pseudo-second-order kinetics. Likewise, thermodynamic parameters like enthalpy, entropy, and Gibbs free energy indicated that the adsorption was consistent with spontaneous, favorable, and endothermic reactions. Furthermore, the adsorption efficiency of MIP/NC was also evaluated against a real sample of condensate from the oil and gas industry, showing an 87.4% recovery of Hg(II). Finally, the synthesized MIP/NC showed promise as a selective adsorbent of Hg(II) in polluted environments, suggesting that a variety of combined absorbents of different precursors is recommended to evaluate heavy metal and pharmaceutical removals.

In this study, we tested the biosorption capacity of trimethyl chitosan (TMC)-ZnO nanocomposite (NC) for the adsorptive removal of Escherichia coli (E. coli) in aqueous suspension. For the formation of ZnO NPs, we followed the green synthesis route involving Terminalia mantaly (TM) aqueous leaf extract as a reducing agent, and the formed ZnO particles were surface-coated with TMC biopolymer. On testing of the physicochemical characteristics, the TM@ZnO/TMC (NC) hydrogel showed a random spherical morphology with an average size of 31.8 ± 2.6 nm and a crystal size of 28.0 ± 7.7 nm. The zeta potential of the composite was measured to be 23.5 mV with a BET surface area of 3.01 m2 g−1. The spectral profiles of TM@ZnO/TMC NC hydrogel on interaction with Escherichia coli (E. coli) revealed some conformational changes to the functional groups assigned to the stretching vibrations of N-H, C-O-C, C-O ring, and C=O bonds. The adsorption kinetics of TM@ZnO/TMC NC hydrogel revealed the pseudo-second-order as the best fit mechanism for the E. coli biosorption. The surface homogeneity and monolayer adsorption of the TM@ZnO/TMC NC hydrogel reflects majorly the entire adsorption mechanism, observed to display the highest correlation for Jovanovic, Redlich–Peterson, and Langmuir’s isotherm models. Further, with the use of TM@ZnO/TMC NC hydrogel, we measured the highest adsorption capacity of E. coli to be 4.90 × 10 mg g−1, where an in-depth mechanistic pathway was proposed by making use of the FTIR analysis.

The present study deals with the adsorptive removal of Escherichia coli (E. coli) by making use of chitosan-silica/calcium carbonate (CS-SiO2/CaCO3) nanocomposites (NCs) where it was synthesized using the waste eggshells and rice husks occurred by natural sources. The bioadsorbent CS-SiO2/CaCO3 NCs were synthesized by incorporating eggshell-CaCO3 nanoparticles (NPs) and rice husk-SiO2 NPs in chitosan NPs solution. The adsorbents were characterized using HRTEM, BET, DLS, and TGA. The characterization of NCs revealed the formation of adsorbents in the range of 10–50 nm and some structural changes to the spectra of adsorbents before and after the adsorption of E. coli was revealed by the FTIR analysis. Moreover, the adsorption efficiency of E. coli over the adsorbents after 35 min of incubation was about 80% for CS-SiO2/CaCO3 NCs. Further, the kinetics of adsorption studies were observed to be well-fitted to the Langmuir isotherm model with an adsorption capacity of 3.18 × 101 (CFU E. coil per gram of CS-SiO2/CaCO3). From the analysis, the synthesized bioadsorbent demonstrated the potential for ameliorating the inherent risk of pathogens in water.

Pollution with oil spills, a major contributor to water contamination, has a remarkable effect on the economy, biodiversity, and environment. To protect marine species and environment, efforts should be undertaken for developing efficient ways to remove oil spills. The current work discusses the oil spill removal using magnetite nanoparticles (MNPs) functionalized with hydrophobic polyethyleneimine (HPEA). In this respect, nonylphenol pentaethylenehexamine (NTEPA) and nonylphenol triethylenetetramine (NDETA) were prepared by a simple one-step method and used as capping agents in the synthesis of hydrophobically modified magnetite nanoparticles designated as NDETA/Fe3O4 (magnetite as a core and NDETA as a shell) and NTEPA/Fe3O4 (magnetite as a core and NTEPA as a shell). The prepared MNPs were characterized using FTIR, XRD, TEM, DLS, TGA, and DSA to determine their physical and chemical properties. Additionally, MNPs were applied as oil spill collectors with high efficiencies that reached 93% and 90% for NDETA/Fe3O4 and NTEPA/Fe3O4, respectively, at low magnetite to oil ratios.

The present study develops on insulin-release studies from the chitosan-amide-modified stimuli-responsive polymers formed from various fatty acids including stearic acid, oleic acid, linoleic acid, and linolenic acid. This is the continuation of an earlier reported study that investigates the insulin-release profiles of chitosan-modified fatty acid amides (without stimuli responsive polymers). Following the synthesis and characterization of many different fatty acid amides with a varying amount of unsaturation, the insulin drug loading and release effects were compared among N-isopropylacrylamide (NIPAm), a thermo-responsive polymer, and 2-acrylamide-2-methylpropane sulfonic acid (AMPS), a pH-responsive polymer-modified hydrogel that is expected to enhance environmental response and the controllability of release. Finally, drug release effects were studied to investigate the drug release mechanisms with the help of five different pharmacokinetic models including the zero-order, first-order, Higuchi, Korsmeyers–Peppas, and Hixson models. The results indicate that the Higuchi and Hixson models are valid in terms of the operation of the NIPAm and AMPS matrices during the delivery of insulin.

Over the past few decades, there has been an increased trend for the use of natural compounds and their derivatives as alternatives to traditional chemicals and is due to their renewability, green character, and wide availability. This work aims to convert sodium alginate (S.ALG), a natural polysaccharide, into amides through its conversion to alginic acid (H.ALG). The formed H.ALG was esterified using methanol, followed by a reaction with octadecylamine (OA) and dodecylamine (DA) to produce corresponding amides, OA-ALG, and DA-ALG, respectively. The synthesized OA-ALG and DA-ALG were used as capping agents to further form hydrophobic magnetite nanoparticles (MNPs), OA-MNPs and DA-MNPs, respectively. The chemical structures, morphology, hydrophobicity, and magnetic properties of OA-MNPs and DA-MNPs were investigated using different instrumental techniques. Furthermore, the efficacy of as-synthesized MNPs as oil spill collectors were also evaluated using different ratios of MNPs:crude oil. From the analysis of results, the OA-MNPs and DA-MNPs exhibited high efficiency in the collection of oil spill even at low ratios of MNPs:crude oil.

A portable electrochemical aptamer-antibody based sandwich biosensor has been designed and successfully developed using an aptamer bioreceptor immobilized onto a screen-printed electrode surface for Mycobacterium tuberculosis (M. tuberculosis) detection in clinical sputum samples. In the sensing strategy, a CFP10-ESAT6 binding aptamer was immobilized onto a graphene/polyaniline (GP/PANI)-modified gold working electrode by covalent binding via glutaraldehyde linkage. Upon interaction with the CFP10-ESAT6 antigen target, the aptamer will capture the target where the nano-labelled Fe3O4/Au MNPs conjugated antibody is used to complete the sandwich format and enhance the signal produced from the aptamer–antigen interaction. Using this strategy, the detection of CFP10-ESAT6 antigen was conducted in the concentration range of 5 to 500 ng/mL. From the analysis, the detection limit was found to be 1.5 ng/mL, thereby demonstrating the efficiency of the aptamer as a bioreceptor. The specificity study was carried out using bovine serum albumin (BSA), MPT64, and human serum, and the result demonstrated good specificity that is 7% higher than the antibody–antigen interaction reported in a previous study. The fabricated aptasensor for M. tuberculosis analysis shows good reproducibility with an relative standard deviation (RSD) of 2.5%. Further analysis of M. tuberculosis in sputum samples have shown good correlation with the culture method with 100% specificity and sensitivity, thus making the aptasensor a promising candidate for M. tuberculosis detection considering its high specificity and sensitivity with clinical samples.

New magnetic imidazolium ionic liquid (IIL) was synthesized to improve the curing, mechanical, and thermal characteristics of the epoxy/polyamine system. In this respect, 2-(4-minophenyl)-1.3-bis(triethoxysilyl)-1H-imidazol-3-ium acetate as IIL was synthesized and characterized by different spectroscopy tools. The IIL was used as capping to prepare Fe3O4 nanoparticles (NPs) as new Fe3O4-IIL NPs. The thermal stability, morphology, crystal lattice structures, and magnetic properties were evaluated to confirm the formation of uniform, thermal, stable, and superparamagnetic Fe3O4-IIL NPs. The prepared Fe3O4-IIL NPs were mixed with an epoxy/polyamine system to improve the curing, thermal, and mechanical properties of epoxy through chemical reactions. The dynamic mechanical analyzer and differential scanning calorimeter were used to investigate the flexibility and storage modulus of the cured epoxy/polyamine system in the absence and presence of Fe3O4-IIL NPs. The atomic force microscope and scanning electron microscope were used to evaluate the dispersion and embedding of Fe3O4-IIL NPs into epoxy matrix. The thermal, mechanical, and surface morphologies data confirmed that the incorporation of Fe3O4-IIL NPs using 3 wt. % during the curing of an epoxy/polyamine system produces superior epoxy films without cracks, holes, and NPs agglomeration.

The alkaline hydrolysis of carboxylate (1-naphthylbutyrate) and carbonate esters (2-(methylsulfonyl)-ethyl-4-nitrophenylcarbonate) in the presence of different surfactants has been studied. The rate of hydrolysis of these esters was determined under pseudo first order condition in which the concentration of NaOH was kept in large excess over the [ester]. The cationic micelles of cetyltrimethylammonium bromide (CTABr) and cetyltrimethylammonium sulfate ((CTA)2SO4) enhanced the rate of hydrolysis of esters to a maximum value and thereafter, the increasing concentration of surfactant decreased the reaction rate. The anionic micelles of sodium dodecyl sulfate (SDS) inhibited the rate of the hydrolysis. The reaction proceeds through the attack of OH− ions on the carbonyl carbon forming tetrahedral intermediate. The tetrahedral intermediate is unstable and collapses immediately to yield respective acid and alcohol. The micelles influence the stability of tetrahedral intermediate, in turn, altering the rate of hydrolysis. The variation in the rate of hydrolysis by micelles was treated by considering the pseudophase ion-exchange model and Menger–Portnoy model. The added salts viz. NaBr, NaCl, and LiCl inhibited the rate of the reaction in the presence of cationic and anionic micelles. The kinetic parameters i.e. km and Ks were determined from the rate–[surfactant] profile.

In the present paper, kinetics of alkaline degradation of well known drug, indomethacin (2-[1-(4-chlorobenzoyl)-5-methoxy-2-methylindol-3-yl]acetic acid), was studied in presence of excess [NaOH]. The rate of hydrolysis of substrate was independent of the [indomethacin] though it increased linearly with increasing the hydroxide ion concentration with a positive slope, suggesting the following rate law: kobs = k1[OH−]. Cationic surfactants having non-reactive ions (cetyltrimethylammonium bromide, CTAB and cetyltrimethylammonium sulfate (CTA)2SO4) first increased the rate constants at lower concentrations and then decreased it at higher concentrations while in case of the surfactant with reactive counterions (cetyltrimethylammonium hydroxide, CTAOH) the rate increases sharply at lower concentrations of surfactant until it reaches to a plateau in contrast to the appearance of maxima in case of CTAB and (CTA)2SO4. Anionic surfactant, sodium dodecyl sulfate (SDS), inhibited the reaction rate at all concentrations used in the study. Pseudophase ion-exchange model was used for analyzing the effect of cationic micelles while the inhibition by SDS micelles was fitted using the Menger–Portnoy model. The effect of salts (NaCl, NaBr and (CH3)4NBr) was also seen on the hydrolysis of indomethacin and it was found that all salts inhibited the rate of reaction. The inhibition followed the trend NaCl < NaBr < (CH3)4NBr.

A facile method for synthesis of environmentally friendly magnetite nanomaterials (MNMs) was applied using hydrophobic biocomponents as capping and stabilizing agents. The biocomponents were extracted from Matricaria aurea (MAE) and Ochradenus baccatus (OBE) and used for the surface modification of MNMs to increase their dispersion efficiency on the collection of heavy crude oil spills. Synthesized MNM samples (MAE-MNMs and OBE-MNMs) were verified using thermogravimetric analysis; Fourier-transform infrared spectroscopy; transmission electron microscopy; dynamic light scattering, and vibrating-sample magnetometry. The application of these nanomaterials in the collection of oil spill showed that the MAE-MNMs and OBE-MNMs successfully collected 95% and 91% of the oil spill, respectively. These results support the potential use of these materials as eco-friendly composites for the successful collection of oil spills that might occur during offshore operations.

Advanced materials reliant on cross-linked magnetic poly (ionic liquids) (PILs) have been widely utilized in environmental applications for water purification. The present work demonstrates our preparation of a new magnetic cross-linked PIL based on quaternized 4-vinyl-pyridine-co-acrylamide (QVP/AAm). The chemical composition, thermal stability, magnetic properties, morphology, particle sizes, and zeta potential of the magnetic QVP/AAm composites were investigated. Fast adsorption and desorption kinetics, high adsorption capacity, rapid magnetic separation, and the absence of secondary pollution in the adsorption process make QVP/AAm-Fe3O4 a highly effective adsorbent for the elimination of anionic acidic Congo red contaminants from industrial wastewater.

Superhydrophobic nanomaterials are promising in the important pursuit to alleviate the environmental pollution caused by the petroleum crude oil industry, especially to clean-up oil spills. In this work, asphaltenes isolated from crude oil were modified to act as capping agents during the synthesis of hydrophobic silica nanoparticles (HSNPs). The chemical structure, surface morphology, particle size, and surfaces charge of HSNPs were investigated. The contact angles of water droplets on HSNP film surfaces were measured to investigate their wetting properties. Finally, superhydrophobic sand and polyurethane sponge were prepared by coating them with HSNPs and applied in the cleanup of oil spills of viscous heavy Arabian crude oil.

Inorganic nanoparticles based on magnetite were used to improve the mechanical, thermal, and magnetic properties of microporous cryogel polymer composites. Here we report the synthesis of microporous cryogel based on the crosslinked sodium vinyl sulfonate (Na-VS) and 2-acrylamido-2-methylpropane sulfonic acid sodium salt (Na-AMPS). The magnetite nanoparticles were incorporated into Na-VS/Na-AMPS cryogel networks either during its crosslinking polymerization or by the in-situ technique after its crosslinking. The morphology, particle sizes, thermal stability, and magnetite contents of Na-VS/Na-AMPS cryogel and its magnetite composite were investigated. The prepared Na-VS/Na-AMPS cryogel and its magnetite composite were used as adsorbents for methylene blue (MB) cationic dye using optimum conditions. The magnetite Na-VS/Na-AMPS cryogel composite prepared by in-situ technique achieved the best adsorption MB removal capacity for 7 cycles among the other adsorbents via chemical adsorption mechanism at room temperature.

Effect of two amphiphilic drugs (tricyclic antidepressant, nortriptyline hydrochloride (NORT), and nonsteroidal anti-inflammatory drug, sodium salt of ibuprofen (IBF)) on the cloud point of biopolymer hydroxypropylmethyl cellulose (HPMC) was studied. Effect of NaCl was also seen on the CP of HPMC-drug system. CP of HPMC increases uniformly on increasing the (drug). Both drugs, though one being anionic (IBF) and other cationic (NORT), affect the CP in almost the same manner but with different extent implying the role of hydrophobicity in the interaction between drug and polymer. Salt affects the CP of the drug in a dramatic way as low concentration of salt was only able to increase the value of the CP, though not affecting the pattern. However, in presence of high concentration of salts, minimum was observed on CP versus (drug) plots. Various thermodynamic parameters were evaluated and discussed on the basis of the observed results.

New method was used to prepare magnetite nanoparticle based on reduction of Fe(III) ions with potassium iodide to produce Fe3O4 nanoparticle. The prepared magnetite was stabilized with cross-linked polymer based on 2-acrylamido-2-methylpropane sulfonic acid (AMPS to prepare novel core-shell nanogel. In this respect, Fe3O4/poly(2-acrylamido-2-methylpropane sulfonic acid) (PAMPS) magnetic nanogels with controllable particle size produced via free aqueous polymerization at 65°C have been developed for the first time. The polymer was crosslinked in the presence of N,N-methylenebisacrylamide (MBA) as a crosslinker and potassium peroxydisulfate (KPS) as redox initiator system. The structure and morphology of the magnetic nanogel were characterized by Fourier transform infrared spectroscopy (FTIR) and transmission and scanning electron microscopy (TEM and SEM). The effectiveness of the synthesized compounds as corrosion inhibitors for carbon steel in 1 M HCl was investigated by various electrochemical techniques such as potentiodynamic polarization and electrochemical impedance spectroscopy (EIS). The results showed enhancement in inhibition efficiencies with increasing the inhibitor concentrations. The results showed that the nanogel particles act as mixed inhibitors. EIS data revealed that Rct increases with increasing inhibitor concentration.