Net Surface Charge Research Articles

Wide-pore fully porous mixed-mode octyl/pyridyl-bonded silica material with pH-dependent surface charge reversal for high-performance hydrophobic charge-induction chromatography of proteins

In an attempt to overcome silanophilic interactions like observed on popular reversed-phase butyl‑bonded silica stationary phases in protein HPLC, a mixed-mode stationary phase based on wide pore silica (3 µm, 300 Å) was prepared by co-immobilization of octyl and 2-pyridylethyl ligands. The surface modification was performed by a new approach using synthesized functional silatranes of the above ligands and prewetted silica. It allowed to generate a dense polymeric siloxane layer on the silica surface. Butyl-bonded silica and octyl/3-aminopropyl-bonded mixed-mode silica phases were prepared for comparison. The modified silicas were subsequently characterized by elemental analysis regarding ligand densities, by solid-state 29Si and 13C cross polarization/magic angle spinning nuclear magnetic resonance spectroscopy for confirming the surface-bonded structure, and by pH-dependent ζ-potential measurements via electrophoretic light scattering providing net surface charge information at distinct pH values. While the classical butyl‑bonded stationary phase revealed negative ζ-potential over the entire pH range investigated (pH 3.5–9.5) due to residual silanols and the mixed-mode octyl/3-aminopropyl-bonded silica positive ζ-potential over the entire pH range, pH-dependent charge reversal was observed at approximately pH 5.5 for the octyl/pyridyl-bonded stationary phase. Then, a test set of proteins differing in hydrophobicities and isoelectric points was employed to evaluate the retention characteristics of all three synthesized stationary phases over the pH range of 3 to 7.5 by acetonitrile-gradient elution reversed-phase HPLC. Under acidic conditions (pH 3) the mixed-mode phases octyl/pyridyl-silica and octyl/aminopropyl-silica showed reduced retention and improved peak shapes due to repulsive interactions preventing silanophilic interactions, while protein separations by their hydrophobicities were achieved (repulsive charge-assisted protein RPLC). Finally, the prepared novel mixed-mode octyl/pyridyl-bonded stationary phase was evaluated in hydrophobic charge induction chromatography mode for protein separation of the same test set. Instead of an organic modifier gradient, elution was enforced by a pH gradient from almost neutral to acidic pH at constant organic modifier content of 10 %. This chromatographic mode showed orthogonal retention characteristics and reversed elution order compared to above organic gradient RP-HPLC. In addition, significantly less organic solvent was used under these conditions, classifying it as a green protein LC technology.

Maximization of Micractinium sp., biomass and use of Dual-Purpose reduced graphene supported vanadium oxide nanoparticles for harvesting and subsequent biodiesel production

A sustainable media composition comprising of nanourea (NU), groundnut de-oiled cake (GDOC), and seaweed Extract (SE) was formulated using a mixture design for the cultivation of Micractinium sp. Maximum biomass yield and productivity of 5.52 ± 0.09 g/L and 0.72 ± 0.03 g/L d−1 were observed at 1.67 mM NU, 0.134 g/L GDOC and 0.250 mL L−1 SE, respectively. The highest lipid yield of 2.73 ± 0.24 g/L was also observed, respectively. The reduced graphene-supported vanadium oxide nanoparticles (RGO-VNPs) with a net surface charge of + 34.10 mV were developed, which acted as a % as well as a catalyst for transesterification. A maximum flocculation efficiency of 98 % was observed with 200 ppm of RGO-VNPs. The Fatty Acid Methyl Ester (FAME) yield of 96.81 ± 1.61 % was observed. Thus, the present study could provide a plausible solution for one-pot harvesting and synthesis of biodiesel utilizing microalgal lipids.

Developing analytical ion exchange chromatography methods for antibody drug conjugates containing the hydrolysis-prone succinimide-thioether conjugation chemistry

Charge variants are one of the most important quality attributes for protein therapeutics, including antibody drug conjugates (ADCs). ADCs are conjugation products between monoclonal antibodies (mAbs) and highly potent payloads. After attaching a payload, the charge profile of a mAb can be modified due to the change in net charge or surface charge. In this study, we present a unique challenge of charge assay development that arises from a desirable engineering of ADCs that incorporates the hydrolysis-prone succinimide-thioether conjugation chemistry. This engineered hydrolysis at conjugation sites is usually not complete during conjugation process and continuously progressing during mild stress. This hydrolysis also creates a carboxylic functional group, which manifests as acidic peaks in the ADC charge profiles. As a result, ion exchange chromatograms become sensitive measurements of this hydrolysis, which often masks the charge profile change due to other important post-translational modifications. In this study, two approaches were explored to address this unique challenge: to remove the hydrolysis heterogeneity by incubating ADCs under high pH conditions to drive complete hydrolysis; and to analyze charge variants at the subunit level after IdeS digestion. Acceptable charge profiles and quantitative integration results were successfully obtained by both approaches.

Impact of pH on the structure, interfacial and foaming properties of pea protein isolate: Investigation of the structure – Function relationship

This study explored the relationship between pea protein foaming properties and their structure and physicochemical properties under neutral and acidic pH. Results showed that pH modified the zeta potential, particle size and surface tension due to electrostatic changes. FT-MIR and fluorescence spectra revealed pH-induced conformational changes, exposing hydrophobic groups and increasing sulfhydryl content, promoting protein aggregation. At pH 3, the highest foaming capacity (1.273) and lowest foam expansion (6.967) were observed, associated with increased surface hydrophobicity and net charges, ideal for creating light foams with high liquid incorporation for acidic beverages or fruit-based mousses. Pea protein isolate generated stable foams with foam volume stability between 86.662 % and 94.255 %. Although neutral pH conditions showed the highest foam volume stability, their air bubbles increased in size and transitioned from spherical to polyhedral shape, suitable for visual-centric applications, like cappuccino foam and beer-head retention. Foams at pH 5 exhibited the smallest bubbles and maintained their spherical shape, enhancing drainage resistance, beneficial for whipped toppings. Strong correlations (Pearson correlation coefficient higher than 0.600) were noted between the structure, surface and foaming properties, providing crucial insights into optimizing pea protein functionality across various pH conditions, enabling the development of plant-based foamed products with tailored properties.

Methylglyoxal alters collagen fibril nanostiffness and surface potential

Collagen fibrils are fundamental to the mechanical strength and function of biological tissues. However, they are susceptible to changes from non-enzymatic glycation, resulting in the formation of advanced glycation end-products (AGEs) that are not reversible. AGEs accumulate with aging and disease and can adversely impact tissue mechanics and cell-ECM interactions. AGE-crosslinks have been related, on the one hand, to dysregulation of collagen fibril stiffness and damage and, on the other hand, to altered collagen net surface charge as well as impaired cell recognition sites. While prior studies using Kelvin probe force microscopy (KPFM) have shown the effect glycation has on collagen fibril surface potential (i.e., net charge), the combined effect on individual and isolated collagen fibril mechanics, hydration, and surface potential has not been documented. Here, we explore how methylglyoxal (MGO) treatment affects the mechanics and surface potential of individual and isolated collagen fibrils by utilizing atomic force microscopy (AFM) nanoindentation and KPFM. Our results reveal that MGO treatment significantly increases nanostiffness, alters surface potential, and modifies hydration characteristics at the collagen fibril level. These findings underscore the critical impact of AGEs on collagen fibril physicochemical properties, offering insights into pathophysiological mechanical and biochemical alterations with implications for cell mechanotransduction during aging and in diabetes. Statement of SignificanceCollagen fibrils are susceptible to glycation, the irreversible reaction of amino acids with sugars. Glycation affects the mechanical properties and surface chemistry of collagen fibrils with adverse alterations in biological tissue mechanics and cell-ECM interactions. Current research on glycation, at the level of individual collagen fibrils, is sparse and has focused either on collagen fibril mechanics, with contradicting evidence, or surface potential. Here, we utilized a multimodal approach combining Kelvin probe force (KPFM) and atomic force microscopy (AFM) to examine how methylglyoxal glycation induces structural, mechanical, and surface potential changes on the same individual and isolated collagen fibrils. This approach helps inform structure-function relationships at the level of individual collagen fibrils.

Unique myoglobin adaptation to endothermy and flight since the origin of birds.

Myoglobin (Mb) mediates oxygen diffusion and storage in muscle tissue and thus is important for the energy utilization and activity of animals. Birds generally have a high body temperature, and most species also possess the capability of powered flight. Both of these require high levels of aerobic metabolism. Within endothermic mammals, bats also independently evolved flight. Although the functional evolution of myoglobins in deep-diving amniote vertebrates has been well-studied, the functional evolution of myoglobin since the origins of both birds and bats is unclear. Here, with Mb-coding sequences from >200 extant amniote species, we reconstructed ancestral sequences to estimate the functional properties of myoglobin through amniote evolution. A dramatic change in net surface charge on myoglobin occurred during the origin of Aves, which might have been driven by positively selected amino acid substitutions that occurred on the lineage leading to all birds. However, in bats, no change in net surface charge occurred and instead, the Mb genes show evidence of strong purifying selection. The increased net surface charge on bird myoglobins implies an adaptation to flight-related endothermic and higher body temperatures, possibly by reducing harmful protein aggregations. Different from the findings of net surface charge, myoglobins of extant birds show lower stability compared with other amniotes, which probably accelerates the rate of oxygen utilization in muscles. In bats and other mammals, higher stability of Mb may be an alternative pathway for adaptation to endothermy, indicating divergent evolution of myoglobin in birds and bats.

Designing of SrFe2O4-decorated sulfur-MXene for super-fast adsorption of mercury

Needless to say, the severity of water pollution reached its peak, raising awareness to find a convenient strategy for improving this troublesome situation. Mercury (Hg2+) is listed as the 6th among the most jeopardous heavy metals. In this respect, MXene was double modified by; (i) Sulfur-doping to boost its affinity toward Hg2+, and then (ii) blending sulfur-doping MXene with the magnetic SrFe2O4 that could provide excellent recyclability and adsorption aptitude. Characterization analyses like XRD, XPS, and FTIR were applied to assure the well-fabrication of SrFe2O4/S-MXene and investigate its crystallinity, chemical composition, and function groups. The morphological structure of SrFe2O4/S-MXene was shown via SEM. Besides, the magnetization character and net surface charge were deduced by VSM and ZP measurements, respectively. Interestingly, it was observed superior adsorbability of SrFe2O4/S-MXene towards Hg2+ where qmax attained 838.99 mg/g during 15 min merely at pH 6 and 25 °C. Equilibrium isotherms elucidated the appropriateness of Freundlich and Langmuir to model the Hg2+ adsorption onto SrFe2O4/S-MXene. Additionally, kinetic analysis denoted that the adsorption data of Hg2+ obeyed the PSO. The adsorption mechanism of Hg2+ onto SrFe2O4/S-MXene was assumed to proceed by electrostatic interaction, surface complexation, and reduction reaction.

An induced mutation of ABC-transporter component VraF(K84E) contributes to vancomycin resistance and virulence in Staphylococcus aureus strain MW2

Staphylococcus aureus is a notorious pathogen responsible for various severe diseases. Due to the emergence of drug-resistant strains, the prevention and treatment of S. aureus infections have become increasingly challenging. Vancomycin is considered to be one of the last-resort drugs for treating most methicillin-resistant S. aureus (MRSA), so it is of great significance to further reveal the mechanism of vancomycin resistance. VraFG is one of the few important ABC (ATP-binding cassette) transporters in S. aureus that can form TCS (two-component systems)/ABC transporter modules. ABC transporters can couple the energy released from ATP hydrolysis to translocate solutes across the cell membrane. In this study, we obtained a strain with decreased vancomycin susceptibility after serial passaging and selection. Subsequently, whole-genome sequencing was performed on this laboratory-derived strain MWA2 and a novel single point mutation was discovered in vraF gene, leading to decreased sensitivity to vancomycin and daptomycin. Furthermore, the mutation reduces autolysis of S. aureus and downregulates the expression of lytM, isaA, and atlA. Additionally, we observed that the mutant has a less net negative surface charge than wild-type strain. We also noted an increase in the expression of the dlt operon and mprF gene, which are associated with cell surface charge and serve to hinder the binding of cationic peptides by promoting electrostatic repulsion. Moreover, this mutation has been shown to enhance hemolytic activity, expand subcutaneous abscesses, reflecting an increased virulence. This study confirms the impact of a point mutation of VraF on S. aureus antibiotic resistance and virulence, contributing to a broader understanding of ABC transporter function and providing new targets for treating S. aureus infections.

Octenyl succinylation of myofibrillar protein: Structural, physicochemical and emulsifying properties

In this study, different succinylation degree octenyl succinic anhydride modified myofibrillar protein (OSA-modified MP) were prepared through succinylation modification by adding various OSA (1%, 3%, 6%, 11%, 16%, 21% and 26% of the weight of MP) to MP. The structure, physicochemical properties and emulsifying properties of OSA-modified MP were investigated. Results showed that succinylation degree of the modified protein rose from 1.46% to 94.99%. Electrophoresis, fourier transform infrared spectroscopy, intrinsic tryptophan fluorescence emission spectroscopy and scanning electron microscopy demonstrated the structure of MP was changed. As the DS increased, the particle size decreased by the maximum values of 0.24 times, the surface net charge and solubility increased by the minimum values of 2.71 and 13.50 time, respectively. All these results caused emulsifying activity and emulsifying stability to increase by 2.32 and 1.46 times, respectively, indicated that succinylation greatly improved the emulsifying properties of MP. Compared to the native MP, OSA-modified MP was more beneficial to stabilize Pickering emulsion. Thus, succinylation improved the emulsifying properties of MP and effectively expanded the application range of MP in the food industry.

Green synthesis of zinc oxide nanoparticles from Sida acuta leaf extract for antibacterial and antioxidant applications, and catalytic degradation of dye through the use of convolutional neural network

This study synthesized zinc oxide nanoparticles (ZnO NPs) using a novel green approach, with Sida acuta leaf extract as a capping and reducing agent to initiate nucleation and structure formation. The innovation of this study lies in demonstrating the originality of utilizing zinc oxide nanoparticles for antibacterial action, antioxidant potential, and catalytic degradation of Congo red dye. This unique approach harnesses eco-friendly methods to initiate nucleation and structure formation. The synthesized nanoparticles' structure and conformation were characterized using UV–vis (λmax = 280 nm), X-ray, atomic force microscopy, SEM, HR-TEM and FTIR. The antibacterial activity of the Nps was tested against Pseudomonas sp, Klebsiella sp, Staphylococcus aureus, and E. coli, demonstrating efficacy. The nanoparticles exhibited unique properties, with a crystallite size of 20 nm (XRD), a surface roughness of 2.5 nm (AFM), and a specific surface area of 60 m2/g (SEM). A Convolutional Neural Network (CNN) was effectively employed to accurately classify and analyze microscopic images of green-synthesized zinc oxide nanoparticles. This research revealed their exceptional antioxidant potential, with an average DPPH scavenging rate of 80% at a concentration of 0.05 mg/mL. Additionally, zeta potential measurements indicated a stable net negative surface charge of approximately −12.2 mV. These quantitative findings highlight the promising applications of green-synthesized ZnO NPs in healthcare, materials science, and environmental remediation. The ZnO nanoparticles exhibited catalytic capabilities for dye degradation, and the degradation rate was determined using UV spectroscopy. Key findings of the study encompass the green synthesis of versatile zinc oxide nanoparticles, demonstrating potent antibacterial action, antioxidant capabilities, and catalytic dye degradation potential. These nanoparticles offer multifaceted solutions with minimal environmental impact, addressing challenges in various fields, from healthcare to environmental remediation.

Abstract 2096: Role Of Divalent Cations In The Enzymatic Activation Of Coagulation Factor XII By Lipopolysaccharides

Background: Lipopolysaccharide (LPS) is the primary pathogenic factor in Gram-negative sepsis. LPS is a polyanionic molecule that may act as a site of initiation of coagulation by activating factor (F)XII. While the physicochemical properties of LPS are known to be sensitive to interactions with divalent cations, it is unknown whether divalent cations modulate the activation of FXII by LPS. Aims: To determine whether divalent cations regulate the kinetics of FXII activation by select LPS chemotypes from E. coli . Methods: Aggregates of E. Coli LPS chemotypes O26:B6 and Rd2 were prepared in ultrapure water in the presence or absence of calcium (Ca 2+ ). The biophysical characterization of LPS chemotypes were determined by dynamic light scattering (DLS) and measurement of zeta potential (ZP). Chromogenic substrate assays were used to study the effects of LPS on FXII activation. Results: The LPS O26:B6 and Rd2 in the absence of Ca 2+ produced aggregates in form of micelles with hydrodynamic diameters of 190±10 and 200±7 nm and ZP of -25±0.8 and -60±2 mV, respectively. The presence of Ca 2+ produced aggregates in the form of vesicles with hydrodynamic diameters of 400±15 and 1300±60 nm and ZP of –11±2 and –3±0.5 mV, respectively. FXII was incubated in HEPES buffer with the distinct LPS morphologies in varying salt concentrations. We found maximal autoactivation of FXII by O26:B6 and Rd2 chemotypes at lower NaCl concentrations. The presence of Ca 2+ , however, selectively reduced the ability of O26:B6 to activate FXII. Strikingly, the neutralization of the surface net charge of the LPS chemotype Rd2 by Ca 2+ ions abrogated the amidolytic activity of Rd2. Conclusions: The presence of calcium ions induces changes in the physicochemical properties of LPS that result in distinct effects on FXII activation in vitro . We are currently studying whether this phenomena is conserved for other divalent cations including Zn, Mg, Cu, and Mn.

Size, polyglycerol grafting, and net surface charge of iron oxide nanoparticles determine their interaction and toxicity in Caenorhabditis elegans

The widespread application of engineered nanoparticles (NPs) in environmental remediation has raised public concerns about their toxicity to aquatic organisms. Although appropriate surface modification can mitigate the ecotoxicity of NPs, the lack of polymer coating to inhibit toxicity completely and the insufficient knowledge about charge effect hinder the development of safe nanomaterials. Herein, we explored the potential of polyglycerol (PG) functionalization in alleviating the environmental risks of NPs. Iron oxide NPs (ION) of 20, 100, and 200 nm sizes (IONS, IONM and IONL, respectively) were grafted with PG to afford ION-PG. We examined the interaction of ION and ION-PG with Caenorhabditis elegans (C. elegans) and found that PG suppressed non-specific interaction of ION with C. elegans to reduce their accumulation and to inhibit their translocation. Particularly, IONS-PG was completely excluded from worms of all developmental stages. By covalently introducing sulfate, carboxyl and amino groups onto IONS-PG, we further demonstrated that positively charged IONS-PG-NH3+ induced high intestinal accumulation, cuticle adhesion and distal translocation, whereas the negatively charged IONS-PG-OSO3– and IONS-PG-COO– were excreted out. Consequently, no apparent deleterious effects on brood size and life span were observed in worms treated by IONS-PG and IONS-PG bearing negatively charged groups. This study presents new surface functionalization approaches for developing ecofriendly nanomaterials.

Preparation of Edible Colorant Lake Using Calcium Carbonate and β-Carotene: Structural Characterization and Formation Mechanism Study.

This study prepared a novel β-carotene colorant lake using calcium carbonate (CaCO3) and investigated the lake formation process and its basic characteristics. Kinetic adsorption analysis confirmed that medium pH (9.3) and medium temperature (40 °C) were more suitable for lake preparation, while desorption occurred, possibly due to crystalline transformation of CaCO3. The isothermal analysis and model fitting results suggested that the β-carotene and CaCO3 particles combined via a monolayer adsorption process driven by physical force. Electrostatic attraction likely participated in the process due to the net negative surface charges of β-carotene dispersion and positively charged groups on the CaCO3 particle surfaces. Ethanol, ultrasonic treatment, and drying method significantly influenced the immobilization efficiency (IE) of β-carotene in the lake and light stability of the lake, without affecting its crystal form. The thermogravimetric analysis (TGA) and differential scanning calorimetry (DSC) curves confirmed absorption of β-carotene onto CaCO3. Fourier-transform infrared spectroscopy (FTIR) and X-ray photoelectron spectroscopy (XPS) analyses indicated no obvious chemical bonds between β-carotene and CaCO3. Energy-dispersive spectroscopy (EDS) confirmed the presence of β-carotene on surfaces but not in the interior of the CaCO3 particles. The adsorption of β-carotene by calcium carbonate was further confirmed to be a physical adsorption on surface.

Liposome Encapsulation of the Palmitoyl-KTTKS Peptide: Structural and Functional Characterization.

In this study, the amphiphilic N-palmitoyl-KTTKS peptide was integrated in the bilayer of egg-derived phosphatidylcholine (PC) vesicles using two different preparation methods, namely thin-film evaporation (TLE) and reverse-phase evaporation (REV). Both the REV and TLE methods allowed for the formation of homogeneous liposome dispersions (PdI < 0.20) with mean hydrodynamic diameters of <100 nm and <200 nm, respectively, a net negative surface charge and a percentage of structured phospholipids higher than 90%. The inclusion of the amphiphilic N-palmitoyl-KTTKS peptide within phospholipid-based vesicles could improve peptide stability and skin delivery. Therefore, the obtained liposomes were evaluated via experiments assessing the synthesis of collagen and the ECM in 3T3-NIH fibroblasts. The obtained results showed that, when delivered with PC liposomes, pal-KTTKS stimulated collagen production more than free pentapeptide and 1 mM ascorbic acid, used as a positive control.

Enhanced thermostability of xylanase XynA via computationally designed assembly of multiple N-terminal disulfide bridges

Xylanase is one of the critical enzymes for the degradation of xylan. The poor thermostability of xylanase hinders its industrial application. Disulfide bonds are important in stabilizing protein structure. In this study, the disulfide bonds of xylanase XynA were predicted by Disulfide by Design 2, Discovery Studio 2020 and sequence alignment. Mutants Mut1, Mut2 and Mut3 were generated and successfully expressed via assembling the disulfide bonds A1CT30C, T26CT44C, S28CS40C and T39CA49C. The half-life of Mut1, Mut2 and Mut3 was significantly increased at both 60 °C and 80 °C compared to XynA, respectively, and the Tm of mutants were increased by 7–9 °C. Additionally, the specific activity of Mut1 was 1.24-fold that of XynA. Computer simulation showed that increased interactions and decreased net surface charge may be responsible for the increased thermostability, while the improved specific activity may be attributed to the flexibility of the "thumb" and more open cleft. To our knowledge, this is the first report of the simultaneous insertion of three disulfide bonds into the N-terminus of xylanase to improve enzyme stability while maintaining good activity, suggesting that inserting disulfide bonds at the suitable site of xylanase can achieve a balance between its thermal stability and specific activity.

Effect of pH on the Structure, Functional Properties and Rheological Properties of Collagen from Greenfin Horse-Faced Filefish (Thamnaconus septentrionalis) Skin.

Collagen is an important biopolymer widely used in food, cosmetics and biomedical applications. Understanding the effect of pH on the structure and properties of collagen is beneficial for its further processing and exploitation. In this study, greenfin horse-faced filefish skin collagen (GHSC) was prepared and identified as a type I collagen. We systematically investigated the effect of pH on the structural, functional and rheological properties of GHSC. Scanning electron microscopy showed that the collagen morphology changed from an ordered stacked sheet structure to a rough silk-like structure as pH increased. Gaussian-fitted Fourier infrared spectroscopy results of the collagen revealed that it unfolded with increasing pH. Moreover, the ordered structure was reduced, and random coils became the dominant conformation. Its β-sheet and random coil contents increased from 18.43 ± 0.08 and 33.62 ± 0.17 to 19.72 ± 0.02 and 39.53 ± 1.03%, respectively, with increasing pH. α-helices and β-turns decreased from 35.00 ± 0.26 and 12.95 ± 0.01 to 29.39 ± 0.92 and 11.36 ± 0.10%, respectively. The increase in β-sheets and random coils allowed the pI-treated collagen to exhibit maximum water contact angle. The emulsification and foaming properties decreased and then increased with increasing pH in a V-shape. The increased net surface charge and β-sheets in collagen benefited its emulsification and foaming properties. The rheological results showed that the protoprotein exhibited shear-thinning properties in all pH ranges. The collagen solutions showed liquid-like behaviour in low-pH (2, 4) solutions and solid-like behaviour in high-pH (6, 7.83 and 10) solutions. Moreover, the frequency-dependent properties of the storage modulus (G') and loss modulus (G″) of the collagen solutions weakened with increasing pH. Collagen has considerable frequency-dependent properties of G' and G″ at low pH (2, 4). Thus, the importance of collagen raw material preparation for subsequent processing was emphasised, which may provide new insights into applying collagen-based materials in food, biomaterials and tissue engineering.

Визначення водневого показника в точці нульового поверхневого заряду для гумінової кислоти бурого вугілля

Humic acids are a complex mixture of high molecular weight aromatic oxycarboxylic acids that act as polyelectrolytes. Their structure includes aromatic nuclei, side chains, and functional groups, resulting in a variation of physicochemical properties such as solubility and stability. Carboxylic and phenolic groups impart acidic properties, while amino groups cause amphotericity, which is related to the isoelectric point (pI). The amphiphilic character contributes to the formation of micelle-like structures in neutral and acidic environments. Humic acids form supramolecular colloids connected by hydrogen bonds. It is known that the pH at the zero charge point of different humic acids varies from 0.5 to 9.3, reflecting their chemical diversity. In our experiments humic acids were obtained by alkaline extraction from lignite with a carbon content of 40.5% and an ash content of 40%. The zero charge point (the pH at which a molecule carries no net electrical charge or is electrically neutral in the statistical mean) was determined by two methods using a pH titration procedure. These methods showed quite close pH values (2.0 and 1.6) at which the surface of humic acid has a net zero surface charge. This allows us to have information about the protonation state and charge dynamics of humic acid under different pH conditions. The data obtained helps to determine the solubility of the acid depending on the pH of the medium, which is important at the stage of acid precipitation in the process of its production, because of the zero charge point value can affect the solubility of a molecule at a given pH. Keywords: lignite, humic acids, composition, extraction, zero surface charge, pH indicator, acid-base titration. Corresponding author Savchenko V.V., e-mail: korbinity@gmail.com

Fabrication of poly (quinine-co-itaconic acid) incorporated reduced graphene oxide nanocomposite and its application for electrochemical sensing and photocatalysis of hydroquinone.

In this work, we report the synthesis of poly (quinine-co-itaconic acid) incorporated graphene oxide composite that is electro-active and photo-active simultaneously. The poly (quinine-co-itaconic acid)@rGO composite was successfully utilized for electrochemical detection and photocatalytic degradation of hydroquinone (HQ). HQ is recognized as an environmental pollutant because of its high toxicity to human health even at low concentrations. The synthesized composite was characterized using different characterization techniques i.e. Fourier Transform Infrared Spectroscopy (FTIR), Energy Dispersive X-ray Spectroscopy (EDX), Scanning Electron Microscopy (SEM), X-ray Diffractometry (XRD), Brunauer-Emmett-Teller (BET) and zeta potential. The characterization studies revealed the net negative surface charge of -17.6 mV for poly (quinine-co-itaconic acid)@rGO composite that confirms its stability. Moreover, the XRD and FTIR studies confirmed the fabrication of poly (quinine-co-itaconic acid)@rGO composite. The electrochemical properties of synthesized composite were determined via cyclic voltammetry and electrochemical impedance spectroscopy which showed high conductivity and charge transfer kinetics. Under optimized condition, the sensor showed excellent response for hydroquinone i.e. potential window from -0.6 to 0.6 V at scan rate 50 mV s-1 and borate buffer of pH 8 as supporting electrolyte. The developed method was comprehensively validated and found linear between 0.1 to 40 μM of HQ, with limit of detection 0.03 μM and limit of quantification 0.1 μM, respectively. The real water and personal care products samples were used to check the applicability of developed sensor and good percent recovery was achieved. The synthesized poly (quinine-co-itaconic acid)@rGO composite was also utilized for photocatalytic degradation of HQ and the degradation efficiency was obtained as 99% with dosage of 0.5 g L-1 under optimized conditions such as solution pH 7, initial concentration of HQ 10 mg L-1, catalyst dosage of 5 mg and irradiation time of 40 min, respectively. The degradation efficiency of poly (quinine-co-itaconic acid)@rGO composite was also evaluated in real water samples from industry and river.

Insights into biofilm development on polyhydroxyalkanoate biofilm carrier for anoxic azo dye decolourization of acid orange 7

Polyhydroxyalkanoates (PHAs) are promising alternatives to non-degradable polymers in various applications. This study explored the use of biologically recovered PHA as a biofilm carrier in a moving bed biofilm reactor for acid orange 7 treatment. The PHA was comprised of 86 ± 1 mol% of 3-hydroxybutyrate and 14 ± 1 mol% of 3-hydroxyhexanoate and was melt-fused at 140 °C into pellets. The net positive surface charge of the PHA biocarrier facilitated attachment of negatively charged activated sludge, promoting biofilm formation. A 236-µm mature biofilm developed after 26 days. The high polysaccharides-to-protein ratio (>1) in the biofilm’s extracellular polymeric substances indicated a stable biofilm structure. Four main microbial strains in the biofilm were identified as Leclercia adecarboxylata, Leuconostoc citreum, Bacillus cereus, and Rhodotorula mucilaginosa, all of which exhibited decolourization abilities. In conclusion, PHA holds promise as an effective biocarrier for biofilm development, offering a sustainable alternative in wastewater treatment applications.

Microbial reduction of synthetic Biogenic Iron Oxides containing various amounts of Organic Carbon and Silica

Iron oxides formed in close association with bacteria are referred to as biogenic minerals (BIOS). Both the organic part of BIOS and the iron oxide particles affect the net surface charge of those iron-organic carbon aggregates and offer reactive sites that can immobilize many soluble contaminants (Warren and Haack 2001) making BIOS a contender in bioremediation technologies. However, before using BIOS in bioremediation, it is essential to understand the interactions of impurities such as organic matter and other minor components (including silica) (Dyer et al. 2010). This project involves the synthesis of Biogenic Iron Oxides (BIOS) using various silica contents and different soluble alginate concentrations (as an analogue for bacterial exopolysaccharides) close to natural environmental conditions. The mineralogical, chemical and physical composition of the synthesized samples was determined by X-Ray Diffraction (XRD), Scanning Electron Microscopy (SEM), Field Emission Scanning Electron Microscopy (FESEM), Fourier-transform Infrared Spectroscopy (FTIR), and with a Malvern Zetasizer Nano instrument. The various samples (mainly ferrihydrite) were then reduced in the presence of Shewanella putrefaciens CN32, a well-known iron reducing bacterium. All microbial reduction experiments (see Table 1) with different types of BIOS were performed under anoxic conditions. Results indicate that the ratio of organic matter and silica to Fe (III) in BIOS affects the reduction rate. It is proposed that alginate binds to iron oxide particles and protects them from reduction. However, samples in presence of high concentration of silica (i.e.,&amp;gt; 0.05) showed structural disorder which likely prevented nucleation of well ordered ferrihydrite, which in return increased their rate of reduction. In addition, higher reduction rates of ferrihydrite were reported at higher concentrations of silica in BIOS, even in the presence of alginate.