Presence Of Cetyltrimethylammonium Bromide Research Articles

Fructose-mediated single-step synthesis of copper nanofluids with enhanced stability and thermal conductivity for advanced heat transfer applications

A precisely controlled solution-phase approach was employed to synthesize copper nanofluid through the reduction of copper sulfate by fructose in the presence of cetyltrimethylammonium bromide, utilizing a mixture of water and ethylene glycol in 1:1 ratio as the base fluid. We delved into the nanofluid’s thermal conductivity and rheological properties, with a keen interest on particle size and reaction rates that exhibited significant sensitivity to variations in reaction parameters. The homogeneous dispersion of nanoparticles in the base fluid resulted in an augmentation of thermal conductivity to 2.31 Wm−1K−1 for particle loading fraction of 0.19%, with a never before achieved stability of 9 months. This method has proven to be not only straightforward and dependable but also efficient for the rapid synthesis of highly stable Newtonian nanofluids, underscoring the nanofluid’s potential for highly powerful cooling applications.

Synergistic adsorption and UV degradation of perfluorooctanoic acid by amine-functionalized A-center sphalerite

Perfluorinated alkylated substances (PFAS), as a category of persistent organic pollutants, have garnered extensive concern due to their resilience against environmental degradation. Herein, we developed an amine-functionalized sphalerite (ZnS) with adjustable surface amine functional groups and Zn defects (ZnS-X%[N]) by in situ coprecipitation and simple hydrothermal method in the presence of cetyltrimethylammonium bromide (CTAB). This material demonstrated efficient PFAS adsorption and subsequent photo-induced degradation under UV irradiation. The characterization results by TEM, BET, FTIR, XPS and EPR revealed that CTAB primarily influences ZnS by modulating surface amine functionalities, zinc defect density, and enhancing its photoreductive capacity. Adsorption and kinetic degradation experiments further showed that a medium CTAB concentration in ZnS-40%[N] achieves highest PFAS adsorption capacity (Cmax: 0.201 mol kg-1), and the corresponding decomposition rate was the fastest (kde: 1.53; kdf: 1.19). This efficacy is attributed to the ZnS-40%[N]'s ideal adsorptive sites and surface shallow defects. Moreover, theoretical simulation also supports the above experimental inference. Overall, ZnS-X%[N] exhibits a synergistic effect on PFAS adsorption and degradation, showcasing its potential for environmental adaptability and practical application.

Ag0, Re0, and Ag@Re heterogeneous persulfate activators for reactive radical based oxidation of water contaminant

Silver-rhenium bi-metallic nanoparticles (Ag-Re) were prepared by the combination of colloidal sols of silver and rhenium at room temperature. The silver and rhenium sols were synthesized by using the chemical reduction of silver nitrate and ammonium perrhenate with sodium borohydride in presence of cetyltrimethylammonium bromide (CTAB). The morphology (shape, size, elemental composition, oxidation states, and crystalline nature) and textural properties (pore size, pore volume, and surface area) of Ag0-Re0 were determined with EDX, SEM, TEM, XPS, XRD, and nitrogen adsorption-desorption isotherm. The Ag0-Re0 was used as heterogeneous persulfate (S2O82−) activator to generate reactive radical species (SO4−• and HO•) for the degradation of xylenol orange (XO) at 434 nm. The Ag-Re exhibits higher XO degradation efficiency than that of mono-metallic Ag0 and Re0 nanoparticles, respectively. The degradation efficiency strongly depends on the concentrations of S2O82−, XO, pH, temperature, and amount of Ag0-Re0. The role of SO4−• and HO• were established by using ethanol, and tertiary butanol as radical scavengers. The activation energy was found to be 85.2, 63.5, and 32.6 kJ/mol, respectively, to the degradation of XO by activated S2O82− with Re0, Ag0, and Ag0-Re0.

Novel nickel-immobilized-SiO2-TiO2 fine particles in the presence of cetyltrimethylammonium bromide as a catalyst for ultrasound-assisted-Kumada cross-coupling reaction

Kumada cross-coupling reaction is useful for producing biphenyls, where nickel and copper have been widely investigated as catalysts but mainly homogeneous ones. In this study, we investigated ultrasound-assisted-Kumada cross-coupling reaction over the heterogeneous catalysts in which Ni2+, Cu2+, or both was immobilized on aminopropylsilane-functionalized-SiO2-TiO2 prepared in the presence of cetyltrimethylammonium bromide (CTAB). The presence of CTAB effectively prevented the particle growth and therefore SiO2–TiO2 fine particles with high surface area (502 m2 g−1) were formed. The Ni2+-immobilized catalyst showed high catalytic activity for the ultrasound-assisted-Kumada cross-coupling reaction of a wide variety of substrates and was reusable three times. Performing the reaction under ultrasound irradiation was very effective in significantly accelerating the reaction rate compared with the conventional mechanical method. In contrast to Ni2+, Cu2+ was deposited on the support as crystalline Cu(OH)2 and the resulting catalysts with Cu2+ and Ni2+-Cu2+ were less active and less stable under the reaction conditions.

CTAB Surfactant Promotes Rapid, Efficient, and Simultaneous Removal of Cationic and Anionic Dyes through Adsorption on Glycerol/Citrate Polyester

The discharge of dye waste by industries has caused environmental impacts on water properties, aquatic species, and human life. The production of eco-friendly materials for dye removal from wastewater has gained increasing interest, particularly through adsorption, as it is an efficient method for removing pollutants. However, the selectivity and limited adsorption capacity of materials for simultaneously adsorbing cationic and anionic dyes make it challenging to address the prevailing dye effluent issue. In this work, a poly(glycerol citrate) polyester was prepared without a solvent, using microwave heating, and was combined with cetyltrimethylammonium bromide (CTAB) to modulate the simultaneous adsorption of cationic (Rhodamine B, RB) and anionic dyes (acid blue 113, AB and acid red 27, AR). The formation of the polyester was successfully confirmed by ATR-FTIR and the thermal properties were evaluated by TGA and DCS. In the presence of CTAB 5 mM, the material removes almost 100% of the dyes, reaching the kinetics equilibrium in 30 min following the Pseudo-second order model. Additionally, dye adsorption on the polyester in the presence of CTAB was described by the Freundlich isotherm model, indicating a heterogeneous polyester surface that promotes a multi-layer adsorption driven by electrostatic interaction and hydrogen bonds. The material showed an adsorption capacity of 73.7 ± 3.2, 82.1 ± 4.4, and 21.2 ± 0.6 mg/g for RB, AB, and AR, respectively. Our results provide evidence that the poly(glycerol citrate)/CTAB has a higher potential for application in wastewater treatment to remove both anionic and cationic dyes.

Environmental analysis of nitrobenzene using newly synthesized anisotropic gold nanostructures: Reaction kinetics and electrocatalytic activity

In this article, we established to produce anisotropic, colloidally stable gold nanostructures (AuNS) by rapidly mixing aqueous solutions of gold(III) chloride trihydrate (HAuCl4) and citric acid (CA) as dual reducing and capping agents at room temperature without the aid of a templating agent. Furthermore, the impact of various anions and shape-directing agents on the morphology and reaction kinetics of citric acid-capped gold nanostructures (CA-AuNS) was investigated. Additionally, the electrocatalytic activity of AuNS towards nitrobenzene (NB) was examined using a CA-AuNS modified glassy carbon (GC) electrode. The rate of reaction for the formation of CA-AuNS increased rapidly with higher concentrations of CA, indicating a strong dependence on the reductant’s concentration. This process followed first-order kinetics, suggesting that the reaction rate is directly proportional to the citric acid concentration. Consequently, optimizing CA levels can effectively control the synthesis rate and yield of CA-AuNS. The presence of nitrite ions led to rapid aggregation of gold nanostructures (AuNS) and a quick reaction time. Chloride ions increased the size of the AuNS. As bromide ion concentration increased, the reaction time slowed significantly, resulting in spherical gold nanoparticles. Both acetate ions and polyvinylpyrrolidone (PVP) inhibited the growth of AuNS. High-resolution transmission electron microscopy (HR-TEM) images showed the formation of various shapes, including spherical, hexagonal, pentagonal, and boat-like structures. In the presence of cetyltrimethylammonium bromide (CTAB), both complex formation between CTAB and HAuCl4 and the formation of spherical gold nanoparticles occurred. Upon addition of silver nitrate (AgNO3) to the colloidal solution, the color shifted to pale violet, and the morphology transitioned from anisotropic to irregular. However, when ascorbic acid (AA) was utilized, it proved ideal for maintaining the morphology of gold nanostructures (AuNS). The analysis of X-ray diffraction spectroscopy (XRD), cyclic voltammetry (CV), electrochemical impedance spectroscopy (EIS), and Fourier transform infrared spectroscopy (FT-IR) further confirmed the synthesized CA-AuNS. The FT-IR spectra of CA before and after the formation of AuNS indicated the participation of carboxylic acid (–COOH) and hydroxyl (–OH) groups in the reduction process of Au3+ metal ions. The GC/CA-AuNS electrode exhibits a larger electroactive surface area due to the coating of AuNS onto the electrode surface, enhancing the electrode’s electrical conductivity by providing additional active sites for electron transfer. In addition, the electrocatalytic activity of NB was investigated in this study. The GC/CA-AuNS electrode had better electrocatalytic activity than the unmodified GC electrode. As a result, with a LOD of 28.2 nM (S/N = 3), this electrode was chosen for sensitive NB determination.

Amino‐Montmorillonite Crystalline Clay as Electrode Modifier for Electrochemical Detection of Ciprofloxacin in Presence of Cetyltrimethylammonium Bromide

AbstractThis research focused on harnessing amino‐functionalized montmorillonite (Mt) clay, achieved through the grafting of [3(2‐aminoethyl)amino]propyltrimethoxysilane (AEP‐TMS), as carbon paste electrode (CPE) modifier for the electroanalysis of ciprofloxacin (CF). The characterization of both Mt and the amino‐functionalized (Mt‐NH2) materials was carried out using various techniques including Fourier‐transform infrared spectroscopy (FTIR), scanning electron microscopy (SEM), and X‐ray diffraction (XRD). Afterwards, various CPEs modified using Mt and Mt‐NH2 were prepared and characterized employing SEM‐energy dispersive X‐ray (EDX), electrochemical impedance spectroscopy (EIS) and cyclic voltammetry (CV). By EIS, Mt‐NH2‐CPE exhibited significantly faster electron transfer with lower charge‐transfer resistance (438.5 Ω) compared to Mt‐CPE (3572.1 Ω) and to the bare CPE (2066.1 Ω). Additionally, CV experiments performed by using redox probes demonstrated the excellent accumulation capability of [Fe(CN)6]3− ions on Mt‐NH2‐CPE surface. The Mt‐NH2‐CPE was subsequently applied using square wave voltammetry to determine CF in the presence of cetyltrimethylammonium bromide (CTAB), yielding an impressive linear range from 30 to 240 μM (R=0.999) and a low detection limit of 0.07 μM (23.2 μg L−1). The method exhibited stable and reproducible responses (RSD=3.25 %; n= 6) under optimized conditions. Following interference studies, the optimized method was effectively applied to quantify CF concentrations in pharmaceutical and water samples.

Kinetics of permanganate–sulfuric acid redox reaction with cetyltrimethylammonium bromide

AbstractThe permanganate–H2SO4 redox reaction, useful in oxidative treatments under aqueous conditions, was studied spectrophotometrically in the absence and presence of cetyltrimethylammonium bromide (CTAB). The decolorization reactions were influenced by the [MnO4−], [H2SO4], and temperature. Permanganate reduction follows first‐, and complex–order kinetics with permanganate, and H2SO4 concentrations, respectively. The reduction of permanganate (Mn(VII)) proceeds through a complex formation between MnO4− and H2SO4. The characteristic absorption peaks for MnO42− (λmax = 439 and 606 nm), MnO43− (λmax = 667 nm), and MnO2 (λmax = 400–418 nm) were not appeared during the redox reaction. The KMnO4 degradation efficiency remains unaffected with sodium pyrophosphate and sodium fluoride. The results of this study demonstrated the formation of Mn(II) as the stable product in acidic reaction media. The degradation efficiency increases drastically from 15 to 100% with 2.0 × 10−4 to 16.0 × 10−4 mol/L CTAB concentration under sub‐, and post‐micellar reaction conditions, respectively. The thermodynamic parameters (activation energy = 98.8 and 43.2 kJ/mol), activation of enthalpy (96.3, and 39.0 kJ/mol), activation of entropy (16.2 and −149.5 J/K/mol), free energy of activation (93.1 and 83.5 kJ/mol) were calculated without and with CTAB, respectively. Hence, CTAB can be exploited for its multifunctional applications, and specifically for the catalytic role in the permanganate‐assisted redox reactions in future.

Polyaniline-Based Flexible Sensor for pH Monitoring in Oxidizing Environments

Measuring pH in oxidizing solutions is a crucial issue in areas such as aquaculture, water treatment, industrial chemistry, and environmental analysis. For this purpose, a low-cost potentiometric flexible sensor using a polymer film as a pH-sensitive material has been developed in this study. The sensor consists in a polyaniline film electrodeposited from a sulfuric acid solution on a gold electrode previously deposited on a flexible polyimide substrate. The resulting polyaniline-based pH sensors showed an interesting performance detection in aqueous solution, leading to sensitive (73.4 mV per unit pH) and reproducible (standard deviation of 1.75) responses over the entire pH range from 3 to 8. On the contrary, they were inoperative in the presence of oxidizing hypochlorite ions. Thus, other polyaniline films were electrodeposited in the presence of cetyltrimethylammonium bromide or Tritonx100 surfactant in an attempt to improve the sensing performance of the pH sensors in oxidizing solutions. The pH sensors based on polyaniline and Tritonx100 surfactant were then found to be sensitive (62.3 mV per unit pH) and reproducible (standard deviation of 1.52) in aqueous solutions containing hypochlorite ions. All polyaniline films were also characterized by profilometry and electronic microscopy to correlate the physicochemical features with the performance of the sensors.

Modification of Sugar Cane Bagasse with CTAB and ZnO for Methyl Orange and Methylene Blue Removal.

Sugar cane bagasse (SB) was modified with cetyltrimethylammonium bromide (CTAB), followed by impregnation with zinc oxide (ZnO) to create a synergistic adsorption and photocatalytic system for methyl orange (MO) and methylene blue (MB) removal. The presence of CTAB and ZnO was confirmed by X-ray diffraction, Fourier transform infrared, and energy dispersive X-ray (for Zn and O). Modification of SB with CTAB (CSB) generated more positive sites on the surface of SB, which enhanced MO removal compared with that of pristine SB. ZnO impregnation induces a decrease in MO removal due to the ZnO presence on the CSB surface, which might reduce the positive sites on the CSB. In addition, the positive sites on CSB can interact with Zn2+ and O2- to form ZnO and lead to a decrease in MO removal. In contrast, the presence of ZnO facilitated good removal of MB compared to CSB, indicating that the photocatalytic process plays a greater role in removing MB. However, the addition of H2O2 can improve MO and MB removal under irradiation due to the formation of external •OH. The photocatalytic performance of MO and MB was also observed to be favored under acidic and alkaline conditions, respectively.

Transformative Dynamics: Self-Assembly of Iron Oxide Hydroxide Nanorods into Iron Oxide Microcubes for Enhanced Perfluoroalkyl Substance Remediation.

We report the controlled synthesis of iron oxide microcubes (IOMCs) through the self-assembly arrays of ferric oxide hydroxide nanorods (NRs). The formation of IOMCs involves a complex interplay of nucleation, self-assembly, and growth mechanisms influenced by time, thermal treatment, and surfactant dynamics. The self-assembly of vertically aligned NRs into IOMCs is controlled by dynamic magnetism properties and capping agents like cetyltrimethylammonium bromide (CTAB), whose concentration and temperature modulation dictate growth kinetics and structural uniformity. These controlled structural growths were obtained via a hydrothermal process at 120 °C at various intervals of 8, 16, 24, and 32 h in the presence of CTAB as the capping agent. In this hydrothermal method, the formation of vertically oriented NR arrays was observed without the presence of ligands, binders, harsh drying techniques, and solvent evaporation. The formation of the self-assembly of NRs to IOMCs is obtained with an increase in saturated magnetization to attain the most stable state. The synthesized IOMCs have a uniform size, quasi-shape, and excellent dispersion. Due to its excellent magnetic and catalytic properties, IOMCs were employed to remove the various emerging pollutants known as per- and polyfluorinated substances (PFAS). Various microscopic and spectroscopic techniques were employed for the characterization and interaction studies of IOMCs with various PFAS. The interaction between IOMCs and perfluoroalkyl substances (PFAS) was investigated, revealing strong adsorption tendencies facilitated by electrostatic interactions, as evidenced by UV-vis and FT-IR spectroscopic studies. Furthermore, the higher magnetic and positive surface charge of IOMCs is responsible for an effective remediation eliminating any secondary pollution with ease of recovery after the sorption interaction studies, thereby making it practically worthwhile.

Design a Friendly Nanoscale Chemical Sensor Based on Gold Nanoclusters for Detecting Thiocyanate Ions in Food Industry Applications.

The surfactant cetyltrimethylammonium bromide (CTAB) induces the aggregation of gold nanoclusters (GNCs), leading to the development of a proposed fluorometric technique for detecting thiocyanate (SCN-) ions based on an anti-aggregation mechanism. This approach is straightforward to execute, highly sensitive, and selective. A significant quenching effect occurs in fluorescence upon using the aggregation agent CTAB in GNCs synthesis, resulting in a transition from intense red fluorescence to dim red. The decrease in fluorescence intensity of GNCs in the presence of CTAB is caused by the mechanism of fluorescence quenching mediated by aggregation. As the levels of SCN- rise, the fluorescence of CTAB-GNCs increases; this may be detected using spectrofluorometry or by visually inspecting under UV irradiation. The recovery of red fluorescence of CTAB-GNCs in the presence of SCN- enables the precise and discerning identification of SCN- within the concentration range of 2.86-140 nM. The minimum detectable concentration of the SCN- ions was 1 nM. The selectivity of CTAB-GNCs towards SCN- ions was investigated compared to other ions, and it was demonstrated that CTAB-GNCs exhibit exceptional selectivity. Furthermore, we believe that CTAB-GNCs have novel possibilities as favorable sensor candidates for various industrial applications. Our detection technique was validated by analyzing SCN- ions in milk samples, which yielded promising results.

Critical Assessment of Micellar Surface Charge-Dependent Disaggregation and Reaggregation of a Bis-Indole Self-Aggregate: What Should Be Our Case-Dependent Choice?

"Aggregation-caused quenching" is a deep-seated mechanism and has been widely used by the researchers as the possible basis for new sensor development. Contrast to aggregation, its turn around process, disaggregation, has gained much less consideration so far. Unfortunately, study of the further scope for reaggregation of the disaggregated probe assembly in the same solution, as and when required, is still under the rare category. The central theme of the current study is focused on this aspect. For this purpose, the effects of headgroup charge (cationic, anionic, and nonionic) and polarity of the micelles on the degree of disaggregation and subsequent emission amelioration of a synthesized bis-indole derivative, 3,3'-bisindolyl(phenyl)methane (BIPM), are studied using steady-state and time-resolved spectroscopic techniques. The relative emission yield of BIPM (φf = 0.01) is significantly enhanced in the presence of cetyltrimethylammonium bromide (φf = 0.21) and polyoxyethylene (20) sorbitan monolaurate (φf = 0.24), whereas comparatively less emission enhancement is recorded within the sodium dodecyl sulfate system (φf = 0.07). In contrast, addition of an external biophilic agent, uric acid, causes requenching of the enhanced emission because of the reaggregation of the disaggregated probes. Detailed microscopic and calorimetric studies are also adopted to investigate the disaggregation-reaggregation mechanism of BIPM associations. The study will provide prior insights about the use of suitable micellar systems for the required degree of disaggregation as well as for the modulation of emission efficiency by controlled tuning of the disaggregation-reaggregation equilibrium for similar probe associations in pure aqueous medium avoiding any chemical transformation.

Synthesis and Study of Superhigh-Concentrated Organosols of Silver Nanoparticles

Abstract Due to their unique properties, organosols of silver nanoparticles are widely used in optical and semiconductor devices, to produce electrically and thermally conductive films, as catalysts, antibacterial materials, etc. This work proposes a simple and highly productive method for the preparation of silver organosols, which have a metal concentration as high as 1800 g/L and contain spherical nanoparticles with low polydispersity and a median size of 9.1 nm. The method consists in the initial preparation of silver nanoparticle hydrosols with a concentration of higher than 30 g/L followed by the transfer of the NPs into an organic phase of o-xylene. A set of physical research methods has been employed to study the regularities of the extraction of silver nanoparticles with o-xylene in the presence of cetyltrimethylammonium bromide (CTAB) and ethanol and to determine the optimal process conditions, under which the extraction degree is as high as 62.5%. It has been found that bromine anions contained in CTAB molecules cause the aggregation of some amount of silver nanoparticles with the formation of silver metal sediment in the aqueous phase. According to X-ray photoelectron spectroscopy data, the sediment contains bromide ions (up to 4 at %) on the particle surface. Organosols synthesized under optimal conditions are stable for more than 7 months and withstand repeated cycles of drying and redispersing. Silver organosols have been used to obtain metal films with an electrical conductivity of about 68 500 S/cm, which increases to 412 000 and 509 500 S/cm (87.8% of the electrical conductivity of bulk silver) after thermal treatment at 150 and 250°C, respectively.

Seed-Mediated Electrodeposition of Silver Nanowires and Nanorods.

Here, we compare the amount and morphology of silver (Ag) nanostructures electrodeposited at varied potentials and times in the presence of cetyltrimethylammonium bromide (CTAB) onto glass/indium tin oxide (glass/ITO) electrodes functionalized with mercaptopropyltrimethoxysilane (MPTMS) and coated or not coated with 4 nm average diameter Au nanoparticle (Au NP) seeds. There is a significantly larger amount of Ag deposited on the seeded electrode surface compared to that in the nonseeded electrode at potentials of -150 to -300 mV (vs Ag/AgCl) since the Au NP seeds act as catalysts for Ag deposition. At more negative overpotentials of -400 to -500 mV, the amount of Ag deposited on both electrodes is similar because the deposition kinetics are fast enough on glass/ITO that the Au seed catalyst does not make as big of a difference. Ag nanorods (NRs) and nanowires (NWs) form on the seeded surfaces, especially at more positive potentials, where deposition primarily occurs on the Au seed catalysts. Deposition of Ag onto the Au seeds appears as a separate peak in the voltammetry. This procedure mimics the seed-mediated growth of Ag NRs observed in solution in the presence of CTAB using ascorbic acid as a reducing agent. The yield, length, and aspect ratio of the Ag NRs/NWs depend on the deposition time and potential with the average length ranging from 300 nm to 3 μm for times of 30-120 min and potentials of -150 to -200 mV. The electrochemical seed-mediated growth of Ag NRs/NWs across electrode gaps could find use for resistive and surface-enhanced Raman-based sensing and molecular electronic applications.

Improved electrochemical sensor using functionalized silica nanoparticles (SiO2-APTES) for high selectivity detection of lead ions

Mesoporous silica nanoparticles, functionalized by APTES, were used to modify glassy carbon electrodes (GCE) and their performance was assessed for the accurate quantification of trace Pb2+ ions under electrochemical methods. Mesoporous (3-aminopropyl) triethoxysilane modified-silica particles (SiO2-APTES), of about 200 nm, were synthesized by the modified Stӧber method in presence of cetyltrimethylammonium bromide. Silica particles were characterized by X-Ray diffraction analysis, scanning electron microscopy, infrared spectrum analysis, and electrochemical techniques such as cyclic voltammetry and electrochemical impedance spectroscopy (EIS). Furthermore, their mesoporous characteristics were investigated by the analysis of N2 adsorption/desorption isotherms. The functional groups on the silica particle surface showed remarkable selectivity towards Pb2+. Various experimental parameters, including incubation time, pH of the buffered solution, and quantity of SiO2-APTES deposited on the electrode were systematically investigated to identify optimal operating conditions for the system. After optimization, the sensors covered a working dynamic range from 8.8 × 10−8 M to 1.2 × 10−6 M achieving a noteworthy limit of detection of 2.6 × 10−8 M. Interference studies have demonstrated that GCE/SiO2-APTES electrodes exhibit high sensitivity and specificity for Pb2+ detection, making them a promising tool for rapid and portable detection of this heavy metal. Finally, the feasibility of these electrodes for Pb2+ ions detection was evaluated in real samples such as seawater (obtained from Monastir, Tunisia) and tap water by using the standard addition method. The high accuracy and reliability of the SiO2-APTES modified GCE was demonstrated by the excellent recovery studies, which ranged from 88 to 104% for all spiked samples. The overall finding supports the practical applicability of this sensor for a real-world context and confirms its potential for environmental monitoring.

Exploring the Specific Role of Iron Center in the Catalytic Activity of Human Serum Transferrin: CTAB-Induced Conformational Changes and Sequestration by Mixed Micelles.

Conformational changes play a seminal role in modulating the activity of proteins. This concept becomes all the more relevant in the context of metalloproteins, owing to the formation of specific conformation(s) induced by internal perturbations (like a change in pH, ligand binding, or receptor binding), which may carry out the binding and release of the metal ion/ions from the metal binding center of the protein. Herein, we investigated the conformational changes of an iron-binding protein, monoferric human serum transferrin (Fe-hTF), using several spectroscopic approaches. We could reversibly tune the cetyltrimethylammonium bromide (CTAB)-induced conformation of the protein, exploiting the concept of mixed micelles formed by three sequestrating agents: (3-[(3-cholamidopropyl)dimethylammonio]-1-propanesulfonate) hydrate (CHAPS) and two bile salts, namely, sodium cholate (NaC) and sodium deoxycholate (NaDC). The formation of mixed micelles between CTAB and these reagents (CHAPS/NaC/NaDC) results in the sequestration of CTAB molecules from the protein environment and aids the protein in reattaining its native-like structure. However, the guanidinium hydrochloride-induced denatured Fe-hTF did not acquire its native-like structure using these sequestrating agents, which substantiates the exclusive role of mixed micelles in the present study. Apart from this, we found that the conformation of transferrin (adopted in the presence of CTAB) displays pronounced esterase-like activity toward the para-nitrophenyl acetate (PNPA) substrate as compared to native transferrin. We also outlined the impact of the iron center and amino acids surrounding the iron center on the effective catalytic activity in the CTAB medium. We estimated ∼3 times higher specific catalytic efficiency for the iron-depleted Apo-hTF compared to the fully iron-saturated Fe2-hTF in the presence of CTAB.

A Zero-Valent Sulfur Transporter Helps Podophyllotoxin Uptake into Bacterial Cells in the Presence of CTAB.

Podophyllotoxin (PTOX) is naturally produced by the plant Podophyllum species. Some of its derivatives are anticancer drugs, which are produced mainly by using chemical semi-synthesis methods. Recombinant bacteria have great potential in large-scale production of the derivatives of PTOX. In addition to introducing the correct enzymes, the transportation of PTOX into the cells is an important factor, which limits its modification in the bacteria. Here, we improved the cellular uptake of PTOX into Escherichia coli with the help of the zero-valent sulfur transporter YedE1E2 in the presence of cetyltrimethylammonium bromide (CTAB). CTAB promoted the uptake of PTOX, but induced the production of reactive oxygen species. A protein complex (YedE1E2) of YedE1 and YedE2 enabled E. coli cells to resist CTAB by reducing reactive oxygen species, and YedE1E2 was a hypothetical transporter. Further investigation showed that YedE1E2 facilitated the uptake of extracellular zero-valent sulfur across the cytoplasmic membrane and the formation of glutathione persulfide (GSSH) inside the cells. The increased GSSH minimized oxidative stress. Our results indicate that YedE1E2 is a zero-valent sulfur transporter and it also facilitates CTAB-assisted uptake of PTOX by recombinant bacteria.

Porous organic polymer containing Tröger’s base skeleton and crown ether for cycloaddition of CO2 and efficient iodine vapor adsorption

A wide range of templating reagents containing crown ether-based Tröger's base structure and coordinating of various co-catalysts were synthesized by polymerization, and characterized using various analytic techniques. Their catalytic performance for CO2 conversion and adsorption properties for iodine vapor were examined. Delightfully, after CETB-X recognized with HBr, all exhibited excellent catalytic activity in the presence of cetyltrimethylammonium bromide. The best-performing catalyst could convert CO2 into cyclic carbonate with a yield of 93.1% under optimal reaction conditions. Furthermore, CETB-C16Br/C16N+Br- possessed excellent stability and substrate suitability with six times without any significant loss of catalytic activity. A preliminary kinetic study was investigated using CETB-C16Br/C16N+Br- and the activation energy has been calculated to be 41.51 kJ/mol. All of these polymers also exhibited iodine adsorption capacities above 3.0 g/g, with the most powerful adsorption reaching 4.68 g/g. Through kinetic simulations, the adsorption process was simulated as a pseudo-first-order kinetic model.

Hierarchically porous silica particles: One-pot synthesis, tunable hydrophilic/hydrophobic properties, prospects for selective oil adsorption

Submicron spherical silica particles were synthesized via base hydrolysis of tetraethoxysilane (TEOS) and phenyltriethoxysilane (PTEOS) in a presence of cetyltrimethylammonium bromide. It was shown that the replacement of a part of TEOS with PTEOS in the reaction mixture led to formation of particles containing hierarchical micro-mesoporous structure with specific surface area of up to ∼ 1170 m2 g−1. The amount of PTEOS leads to the increase of water contact angle of the particles from 10° to 155° which causes a gradual change in their surface properties from hydrophilic to superhydrophobic. The static adsorption capacity of the particles was measured for water, toluene and methyl isobutyl ketone and was found to be affected by both the amount of OH- or C6H5-groups on the surface and the characteristics of porosity. In particular, the adsorption capacity for non-polar volatile organics increases with the increase of the hydrophobicity of particles. It was found that synthesized superhydrophobic silica particles efficiently and quickly absorb oil from water surface and then can be easily removed mechanically.