Critical Concentration Values Research Articles

Phase separation, aggregation, and complexation of triton-X100 and bovine serum albumin mixture: A combined cloud point and UV–visible spectroscopic approaches

Phase separation and aggregation behaviour of triton X-100 (TX-100) and bovine serum albumin (BSA) mixture were investigated using cloud point and UV–visible spectroscopic techniques. The effects of various hydrotropes (HYTs) - namely, sodium salicylate (SS), sodium benzoate (SB), glycerol (Glyc), and 4-aminobenzoic acid (4-ABA) - on the cloud point (CP) of TX-100 + BSA were determined. The obtained CP values for the mixed system in the presence of HYTs followed the order:CPH2O+4−ABA<CPH2O+Glyc<CPH2O+SB<CPH2O+SS. The measured critical micellization concentration (CMC) values of the TX-100 + BSA mixture were found to be significantly altered with varying amounts of BSA. The calculated free energy of clouding and micellization indicated the non-spontaneous nature of the phase transition and the spontaneous association of the TX-100 + BSA mixture. The non-spontaneity of phase separation decreased with increasing concentrations of HYTs. The enumerated values of ∆Hco and ∆Sco were consistently recorded as negative and positive magnitudes, respectively, in all aqueous HYTs media. The clouding process occurred due to a combination of hydrophobic and electrostatic interactions. The binding constant of the mixed system was determined employing the UV–vis spectroscopic method using the Benesi-Hildebrand equation.

Excimer Fluorescence of Acriflavine Dye in Glycerol and Ethylene Glycol.

This research investigates the excimerisation of acriflavine dye in ethylene glycol and glycerol solvents. Acriflavine, a member of the acridine dye family, exhibits unique fluorescence properties with applications in various fields, including cellular nucleus observation, nucleic acid analysis, and dye laser active media etc. The study explores the impact of solvent and concentration on acriflavine's emission properties, with a focus on excimer formation, which can influence its suitability as a dye laser active medium. UV-Visible absorption spectroscopy reveals concentration-dependent absorption profiles, with distinctive monomer bands. Steady-state fluorescence studies demonstrate the emergence of red-shifted excimer fluorescence bands as concentrations increase in both solvents. Temperature-dependent fluorescence studies reveal the dynamics of excimer formation, suggesting dynamic diffusion as the excimerisation mechanism. Time-resolved fluorescence spectroscopy confirms the singlet character of both monomer and excimer states, providing insights into the excimerisation process. Critical concentration values are determined, representing the equilibrium between monomeric and excimeric forms. The study also explores pH-induced spectral shifts, highlighting the influence of acidity on fluorescence properties. Overall, this research deepens our understanding of acriflavine's excimerisation in ethylene glycol and glycerol, offering insights that can enhance its diverse applications, especially in laser technologies.

Virtual clinical QT exposure-response studies – A translational computational approach

Background and purposeA recent paradigm shift in proarrhythmic risk assessment suggests that the integration of clinical, non-clinical, and computational evidence can be used to reach a comprehensive understanding of the proarrhythmic potential of drug candidates. While current computational methodologies focus on predicting the incidence of proarrhythmic events after drug administration, the objective of this study is to predict concentration-response relationships of QTc as a clinical endpoint. Experimental approachFull heart computational models reproducing human cardiac populations were created to predict the concentration-response relationship of changes in the QT interval as recommended for clinical trials. The concentration-response relationship of the QT-interval prolongation obtained from the computational cardiac population was compared against the relationship from clinical trial data for a set of well-characterized compounds: moxifloxacin, dofetilide, verapamil, and ondansetron. Key resultsComputationally derived concentration–response relationships of QT interval changes for three of the four drugs had slopes within the confidence interval of clinical trials (dofetilide, moxifloxacin and verapamil) when compared to placebo-corrected concentration-ΔQT and concentration-ΔQT regressions. Moxifloxacin showed a higher intercept, outside the confidence interval of the clinical data, demonstrating that in this example, the standard linear regression does not appropriately capture the concentration-response results at very low concentrations. The concentrations corresponding to a mean QTc prolongation of 10 ms were consistently lower in the computational model than in clinical data. The critical concentration varied within an approximate ratio of 0.5 (moxifloxacin and ondansetron) and 1 times (dofetilide, verapamil) the critical concentration observed in human clinical trials. Notably, no other in silico methodology can approximate the human critical concentration values for a QT interval prolongation of 10 ms. Conclusion and implicationsComputational concentration-response modelling of a virtual population of high-resolution, 3-dimensional cardiac models can provide comparable information to clinical data and could be used to complement pre-clinical and clinical safety packages. It provides access to an unlimited exposure range to support trial design and can improve the understanding of pre-clinical-clinical translation.

Effect of Salt Stress on Morphological Characteristics and Secondary Metabolites of Some Forage Pea Cultivars

Forage pea (Pisum sativum L.) is an annual legume forage crop grown in various regions of Türkiye. It is high in protein, carbohydrate, and digestible matter and contains minerals such as phosphorus, calcium, and vitamins A and D. Salinity stress is an important problem in the cultivation of forage peas. Salinity reduces the osmotic potential of soil solutes, making it difficult for the roots to absorb the water. This study aimed to determine some parameters of two registered forage pea cultivars at different concentrations of two salt types. The effects of these salts on the morphological characteristics and biochemical components of two different registered cultivars of pea, cv. Ateş and cv. Töre were investigated in the present study. The trials were conducted in pots and Na2SO4 and CaCl2 were applied at concentrations of 0, 50, 100 and 150 mM. As a result of the trials, the morphological characteristics like fresh and dry weights and lengths of roots and shoots were investigated along with the biochemical properties like total antioxidant activity and total phenolic content. The study was performed in 2 replicates to determine the effect of different salt types and concentrations. The critical salt concentration values for the change in shoot and root fresh weight among morphological traits were determined as 100 and 150 mM for secondary metabolites. While the cv. Töre forage pea showed the highest salt resistance in shoot and root fresh weights in the presence of Na2SO4 the cv. Ateş forage pea showed the lowest salt resistance in the presence of CaCl2. In terms of shoot and root dry weights, the cv. Töre forage pea showed the least resistance at 50 mM Na2SO4 concentration. As for plant length, the cv. Ateş forage pea cultivar showed the least resistance in shoot length at 150 mM CaCl2 concentration, while it showed the highest resistance in root length at this value. The highest total antioxidant activity for the cv. Ateş forage pea and the highest total phenolic content for the cv. Töre forage pea were determined at 150 mM CaCl2 concentration. The lowest total phenolic content value was estimated in the cv. Töre forage pea cultivar at 150 mM Na2SO4 salt concentration.

Molecular interactions of cationic/anionic surfactants in presence of anionic antibiotic drug cloxacillin sodium at different temperatures: Micellization and thermodynamic studies

The physicochemical properties and interactions of surfactant–drug aggregates are regarded as essential features to achieve optimum therapeutic action of the drug. In this article, the effect of various concentrations of anionic antibiotic drug cloxacillin sodium (ClxNa) on the micellization of cationic surfactants such as cetyltrimethylammonium bromide (CTAB), tetradecyltrimethylammonium bromide (TTAB) and anionic surfactant sodium dodecyl sulphate (SDS) have been investigated using electrical conductance measurement at different temperatures (288.15 K, 293.15 K, 298.15 K, 303.15 K, 308.15 K, and 313.15 K). The results suggest an increase in critical micelles concentration (CMC) values for cationic surfactants (CTAB/TTAB) with a rise in drug concentration (0 mM up to 10 mM) whereas anionic surfactant SDS shows a decrease in CMC at higher drug concentrations (from 2.5 mM up to 10 mM) at all the studied temperatures. The degree of counterion dissociation (α) values for TTAB aggregates show a slight increase with [ClxNa], except at a few lower temperature ranges whereas such a regular trend was not obtained for CTAB and SDS aggregates. Temperature-dependent CMC values show a nonlinear nature with a rise in temperatures and follow a U-shaped curve for all studied pure surfactant and surfactant–ClxNa systems. Micellization for all surfactant-drug systems is found to be spontaneous. Investigation of other temperature-dependent thermodynamic parameters such as change in standard enthalpy (ΔHm0), and entropy (ΔSm0) of micellization suggest that surfactant–drug interactions are both endothermic (ΔHm0 < 0, particularly at lower temperatures) and exothermic (ΔHm0 < 0, at higher temperatures), whereas micellization is largely entropically driven (ΔSm0 > ΔHm0).

Talc concentration effect on shelf life of acetaminophen tablets

Excipients in pharmaceutical formulations are inactive ingredient from the biological point of view, but they have a key role in the preparation, and they can alter the stability of the active principle. In this work, we prepared acetaminophen tablets with different amounts of talc as excipient and the thermal stability was deeply investigated by thermogravimetric studies. Isoconversional analysis by Kissinger–Akahira–Sunose method and “Master plot” analysis have been successfully employed to describe the kinetics of degradation under inert atmosphere, and the shelf lives have been calculated as a function of the talc content. The shelf-life values as well as the activation energy, which is the dominant factor, evidenced that the inorganic filler enhances the drug degradation to a certain extend and that the composition dependence has a peculiar trend reflecting the particle cluster formation at a critical concentration value. An effort of physico-chemical explanation for this behaviour is put forward by a simple geometrical model from the microparticle-size analysis to predict the critical talc concentration.

A physiologically-based pharmacokinetic model for tuberculosis drug disposition at extrapulmonary sites.

Tuberculosis (TB) is a leading cause of mortality attributed to an infectious agent. TB primarily targets the lungs, but in about 16% cases can affect other organs as well, giving rise to extrapulmonary TB (EPTB). However, an optimal regimen for EPTB treatment is not defined. Although the recommended treatment for most forms of EPTB is the same as pulmonary TB, the pharmacokinetics of EPTB therapy are not as well studied. To address this gap, we formulate a whole-body physiologically-based pharmacokinetic (PBPK) model for EPTB that for the first time includes the ability to simulate drug concentrations in the pleura and lymph node, the most commonly affected sites of EPTB. Using this model, we estimate the time-dependent concentrations, at potential EPTB infection sites, of the following four first-line anti-TB drugs: rifampicin, ethambutol, isoniazid, and pyrazinamide. We use reported plasma concentration kinetics data to estimate model parameters for each drug and validate our model using reported concentration data not used for model formulation or parameter estimation. Model predictions match the validation data, and reported pharmacokinetic parameters (maximum plasma concentration, time to reach maximum concentration) for the drugs. The model also predicts ethambutol, isoniazid, and pyrazinamide concentrations in the pleura that match reported experimental values from an independent study. For each drug, the predicted drug concentrations at EPTB sites are compared with their critical concentration. Simulations suggest that although rifampicin and isoniazid concentrations are greater than critical concentration values at most EPTB sites, the concentrations of ethambutol and pyrazinamide are lower than their critical concentrations at most EPTB sites.

Zwitter-ionic amphiphilic calixresorcinarenes: Micellization in the bulk solution and non-surface activity

Here the amphiphilic calix[4]resorcinarenes, which form self-associates in an aqueous solution but do not exhibit surface activity, are described. Aqueous solutions of calix[4]resorcinarenes with different zwitter-ionic groups on the upper rim: carboxybetaine (C5-CB, C11-CB, C12OPh-CB), sulfobetaine (C5-SB, C11-SB), hydroxysulfobetaine (C5-hSB, C11-hSB), - and different hydrophobic substituents on the lower rim (pentyl, undecyl, dodecyloxyphenyl) were studied by fluorimetry, Fourier transform pulsed-gradient spin-echo (FT-PGSE) NMR spectroscopy, UV–vis spectroscopy, dynamic light scattering (DLS), and tensiometry. It was found that all macrocycles spontaneously form self-associates in an aqueous solution, but only sulfobetaine and hydroxysulfobetaine calixresorcinarenes with pentyl substituents on the lower rim are surface active. The critical association concentration (CAC) values, which were obtained by different methods, as well as values of averaged hydrodynamic diameter, averaged self-association numbers, solubilizing power, and other parameters of self-association are presented and discussed.

Experimental analysis of the impact of ionic concentration and type on shale’s stability: dilute vs. concentrated salt solutions

ABSTRACT Wellbore instability in shale formations is one of the most bothersome problems leading to significant changes in shale’s petrophysical, mechanical, and chemical properties, and could cost billions of dollars annually. Drilling fluid’s ionic composition is one of the factors affecting wellbore stability. This paper investigates the impact of chemical osmosis, ionic diffusion, and diffusion osmosis on the stability of shale, identify the critical salt concentration, and examine the impact of ionic type and concentration on shale’s stability. Experimental methods include utilisation of two different shale cores (I and II), in which each core is cut into several samples, to conduct linear expansion and gravimetric measurement tests using different salt solutions (KCl, NaCl, and CaCl2) of various salt concentrations. Results show that the critical salt concentrations of shale I and II is 8 w/w%. Chemical osmosis is found to be a reliable method for water extraction out of shale if the critical salt concentration value is not surpassed. Beyond this value, ionic diffusion and diffusion osmosis in shale I and II were adversely affecting shale’s stability through swelling. The swelling and gravimetric ions and water uptake tests showed that shale is a leaky semi-permeable membrane, and that chemical osmosis could be jeopardised by ionic transport into shale. In this study, the cation type (Na+, K+, Ca+2) that makes up the salt was varied. The impact of cation type on the stability of shale was clear as the anion type was fixed. Since both cations and anions tend to diffuse into shale in the presence of a concentration gradient, it is proposed for future work to study the combined impact of cation and anion types on shale’s stability by varying the anion and cation types.

Reciprocal effects of NOM and solution electrolyte ions on aggregation of ferrihydrite nanoparticles

The effects of natural organic matter (NOM) types and electrolyte ions are crucial to the aggregation of ferrihydrite nanoparticles (Fh NPs) in the environment. Dynamic light scattering (DLS) was employed for the aggregation kinetics of Fh NPs (10 mg/L as Fe) in the present study. The critical coagulation concentration (CCC) values of Fh NPs aggregation in NaCl were obtained in the presence of 15 mg C/L NOM as SRHA (857.4 mM) > PPHA (752.3 mM) > SRFA > (420.1 mM) > ESHA (141.0 mM) > NOM-free (125.3 mM), indicating Fh NPs aggregation was inhibited as the above order. Comparatively in CaCl2, the CCC values were measured in ESHA (0.9 mM), PPHA (2.7 mM), SRFA (3.6 mM), SRHA (5.9 mM), NOM-free (76.6 mM), implying NPs aggregation was enhanced following the order of ESHA > PPHA > SRFA > SRHA. To investigate the dominant mechanisms, the aggregation of Fh NPs was comprehensively studied under the effects of NOM types, concentrations (0–15 mg C/L) and electrolyte ions (NaCl/CaCl2 beyond CCC). In NaCl/CaCl2, the low concentration of NOM (<7.5 mg C/L) could accelerate NPs aggregation mainly due to patch-charge attraction. When NOM concentration was high (> 7.5 mg C/L), the inhibition effect on NPs aggregation occurred in NaCl due to steric repulsion, whereas the enhancement effect in CaCl2 of aggregation was dominated by the bridging effect. The results indicated that the effects of NOM types, concentration and electrolyte ions should be carefully considered for the environmental behavior of NPs.

Equilibrium and dynamic surface properties of cationic/anionic surfactant mixtures based on alcohol ether sulfate

The equilibrium and dynamic surface properties of anionic surfactant alcohol ether sulfate with different EO distribution(C-AE2S and N-AE2S) and cationic surfactant tetradecyltrimethylammonium bromide (TTAB) mixtures under different molar ratios were investigated. Their surface activities, adsorption, and spreading performances were investigated by static/dynamic surface tension measurements, molecular dynamics simulation, and dynamic contact angle techniques at 298 K. The static surface tension analysis reveals that the critical micellization concentration (cmc) values and the surface tension at cmc (γ cmc) of the binary systems are much lower than that of the individual component. Compared with C-AE2S/TTAB, N-AE2S/TTAB systems have higher cmc and lower γ cmc. It was found from the molecular dynamics simulation that negative charges of C-AE2S were drastically neutralized by the positively-charged TTAB at the interface in the system of C-AE2S/TTAB. The dynamic surface tension results indicate that the adsorption process of aqueous solutions for both C-AE2S/TTAB and N-AE2S/TTAB are mixed diffusion-kinetic adsorption mechanisms. From the dynamic contact angle measurements, it could be obtained that the mixtures exhibit better spreading behavior than that of the individual component and N-AE2S/TTAB systems have lower contact angles than that of C-AE2S/TTAB at the same mixing ratios.

Physicochemical studies of novel sugar fatty acid esters based on (R)-3-hydroxylated acids derived from bacterial polyhydroxyalkanoates and their potential environmental impact.

Sugar fatty acids esters are popular compounds widely used in both the nutritional, cosmetic and pharmaceutical industries due to their amphiphilic structure and consequent ability to reduce the surface tension of solutions. Furthermore, an important aspect in the implementation of any additives and formulations is their environmental impact. The properties of the esters depend on the type of sugar used and the hydrophobic component. In this work, selected physicochemical properties of new sugar esters based on lactose, glucose and galactose and hydroxy acids derived from bacterial polyhydroxyalkanoates are shown for the first time. Values for critical aggregation concentration, surface activity and pH make it possible that these esters could compete with other commercially used esters of similar chemical structure. The investigated compounds showed moderate emulsion stabilization abilities presented on the example of water-oil systems containing squalene and body oil. Their potential environmental impact appears to be low, as the esters are not toxic to Caenorhabditis elegans even at concentrations much higher than the critical aggregation concentration.

Reliability of chemical osmosis as a practical method to extract water out of shale and promote shale’s mechanical stability

Wellbore instability in shale formations is one of the most bothersome problems leading to significant changes in shale’s petrophysical, mechanical, and chemical properties, and could cost billions of dollars annually. Drilling fluid’s ionic composition is one of the factors affecting wellbore stability. This paper investigates the impact of chemical osmosis, ionic diffusion, and diffusion osmosis on the stability of shale, identify the critical salt concentration, and examine the impact of ionic type and concentration on shale stability. Experimental methods include utilization of shale I and II through linear expansion and gravimetric measurement tests using different salts. Results show that the critical salt concentration in shale I and II is 8 w/w%. Chemical osmosis is found to be a reliable method for water extraction out of shale if critical concentration value is not surpassed. Beyond this value, the ionic diffusion and diffusion osmosis in shale I and II were adversely affecting shale’s mechanical and chemical stability. The swelling and gravimetric ions and water uptake tests showed that shale is a leaky semi-permeable membrane, and that chemical osmosis could be jeopardized by ionic transport into shale. However, the water transport impact on changes in the thickness of diffuse double layer of clay needs to be investigated. The impact of temperature on water and ions transportation into shale needs to be examined to reflect in-situ conditions. In this study, the cation type that makes up the salt was varied while the anion type was fixed. Since both cations and anions tend to diffuse into shale in the presence of a concentration gradient, it is recommended to vary the anion type to study the combined impact of cation and anion type on shale stability.

Carboxybetaine and Carboxybetaine Ester Derivatives of Tetra(dodecyloxyphenyl)-calix[4]resorcinarene: Synthesis, Self-Assembly and In Vitro Toxicity

Amphiphilic calix[4]resorcinarenes are a class of macrocyclic compounds with broad potential utility including nanomedicine. Here the synthesis of new carboxybetaine and carboxybetaine ester calix[4]resorcinarene bearing 4-(dodecyloxy)phenyl groups on the lower rim is presented. The compounds were characterized by 1H-NMR, 13C-NMR, 2D NMR, IR, ESI and elemental analysis. The critical association concentration values are 1.00 × 10−5 and 1.18 × 10−5 mol·L−1 for carboxybetain and ester, respectively. The hemolytic activity of the macrocycles and their cytotoxicity against normal (WI-38, Chang liver) and tumor cells (M-HeLa) are also estimated.

Influence of fulvic acid sub-fractions on aggregation kinetics of graphene oxide in aqueous environments

Fulvic acid (FA) can affect the dispersion of graphene oxide (GO) in aquatic environments, however, the possible mechanisms remain unclear. Dynamic light scattering techniques combined with a multiple regression model were applied to explore the influence of FA sub-fractions (FApH3 − FApH13) on the aggregation kinetics of GO in aqueous environments. The ratios of critical coagulation concentration (CCC) values were CCCNa: CCCMg: CCCLa: CCCCe = 1:2–5.15:3–7.31:3–7.35, which were consistent with the Derjaguin−Landau−Verwey−Overbeek (DLVO) theory and Schulze−Hardy rules. The GO remained stable at pH 3–10 and aggregated at pH < 3 or pH > 10, and its critical coagulation pH values were 1.44 and 12.25 with 10 mM NaCl as background. The CCC values of GO in the presence of FApH3 − FApH13 were greater than those in the absence of FA sub-fractions. The ratios of CCC values of GO (r) increased in the presence of FA sub-fractions in the order of FApH13 > FApH9 > FApH7 > FApH5 > FApH3 and ranged from 1.01 to 2.15 for certain metal ions including Na+, Mg2+, La3+, and Ce3+. The CCC values of GO were significantly related to C, H, O, N, S, H/C, O/C, carboxylic C, and carbonyl C of FA sub-fractions (P < 0.05), respectively, and could be predicted using the multiple linear regression eq. CCC = Z-n (98.959– 60.911 ∗ O/C + 4.799 ∗ O-alkyl C – 0.845 ∗ aromatic C – 6.237 ∗ carbonyl C). The predicted CCC values for GO were within 90 % prediction intervals, and the average error of the CCC values was 3.3 % and R2 = 0.986. This investigation is expected to provide a scientific basis for the transport and ecotoxicity of GO in environments.

Fire suppression using trifluoroiodomethane (CF3I)-carbon dioxide (CO2) mixtures

With the regulatory prohibition for using Halon 1301 (CF3Br) in fire suppression systems onboard newly certified aircraft, significant research efforts have been undertaken to develop suitable halon replacements with comparable suppression performance that are also eco-friendly with low Ozone Depletion Potential (ODP) and Global Warming Potential (GWP). This paper determined the fire suppression effectiveness for mixtures of trifluoroiodomethane (CF3I) with carbon dioxide (CO2) under development as a drop-in halon replacement for onboard aircraft fire suppression systems. Through both experimental measurements and flame simulations using detailed chemical kinetics, we demonstrated that the extinguishment performance of CF3I-CO2 blends can be superior to that of the individual components alone. The extinction concentrations were determined for different CF3I-to-CO2 ratios introduced into ambient air using a heptane cup burner. The extinction concentrations for pure CF3I in air (3.36 ± 0.13% vol.) and CO2 in air (20.74 ± 0.64% vol.) are in close agreement with previously reported values, and first-time extinction concentration data for CF3I-CO2 blends are reported. To elucidate important reaction pathways, detailed chemical mechanisms have been compiled for modeling methane-, propane- and heptane-air flame inhibition at ambient conditions. These mechanisms were constructed from published sub-mechanisms for C7 and C1-C3 hydrocarbons and hydrofluorocarbons with additional oxidation chemistry developed for trifluoroiodomethane. The latter sub-mechanism contains 14 species and 91 reactions. Using the CANTERA software package, critical concentration values of CF3I-CO2 mixtures in air for extinguishing methane, propane, and n-heptane counterflow flames were determined and compared against experimental non-premixed flame extinction data.

Estimation of the surface potential of clay mineral taking Na+/K+-specific ion effects into account

Surface potential is a key electrochemical property of colloids in the study of particle interactions. However, the specific ion effects are not involved in the existing measuring methods. In this study, approaches for the estimation of the surface potential of montmorillonite with or without consideration of the specific ion effects were explored through the montmorillonite particle aggregation in the presence of Li+, Na+, and K+ ions. The montmorillonite aggregation process exhibited remarkable specific ion effects, and the critical coagulation concentration (CCC) values show the following: Li+ (271.8 mm) &amp;gt; Na+ (130.8 mm) &amp;gt; K+ (85.04 mm). Based on the mathematic relationship between electrostatic repulsion and the van der Waals attractive interaction at the CCC, the fluctuation coefficient ß was obtained. The value of β could quantify the strength of the specific ion effects of different cations. Then, the fluctuation coefficient β was introduced into the classical method for calculating the surface potential, considering the specific ion effects. The quantificational sequence of the ionic specificity of K+ and Na+ was as follows: βK = 1.433 &amp;gt; βNa = 1.187. Simultaneously, the surface potential considering specific ion effects can be obtained by introducing this coefficient. Our findings provide ideas for getting reliable surface potentials of charged particles in different electrolyte environments.

Polarisation‐induced covalent interactions between H+ and surface O atoms promote clay aggregation

AbstractAccumulation of H+ can cause soil acidification, affect soil particle interactions, and alter soil processes. In this study, aggregation kinetics of montmorillonite colloids induced by monovalent ions of Li+ and H+ were determined by dynamic light scattering. The experimental results indicated that the critical coagulation concentration (CCC) value of Li+ was 4.5 times that of H+, indicating that H+ can strongly promote montmorillonite colloids aggregation. Joint analysis of the adsorption force type and energy of Li+ and H+ as well as the infrared spectroscopy of Li+ and H+ montmorillonite indicated that there was only electrostatic adsorption for Li+, while there was not only electrostatic adsorption but also a new type of covalent adsorption for H+: polarisation‐induced covalent adsorption. The total adsorption energy of H+ is thus much higher than that of Li+ on montmorillonite surfaces. Moreover, the polarisation‐induced covalent adsorption energy of H+ increased linearly with increasing electric field strength, which is consistent with the quantum mechanical analysis of the asymmetric orbital hybridisation of surface O atoms on montmorillonite. On this basis, the polarisation‐induced covalent adsorption energy of H+ was employed to predict the CCC value of H+ induced montmorillonite aggregation, and it was 7.40 mmol L−1. The high agreement with experimental results (7.26 mmol L−1) proved that the polarisation‐induced covalent interactions between H+ and surface O atoms promotes montmorillonite aggregation. This polarisation induced covalent effect between H+ and surface O atoms might further affect the formation and stability of soil aggregates and the pore status of soil structure, especially as soil acidification is currently becoming a global issue. The discovery from this study will improve our understanding of the effects of soil acidification on soil properties and processes.Highlights H+ greatly promoted clay aggregation. Polarization‐induced covalent between H+ and surface O presented at clay surface. Polarization‐induced covalent bonding energy increase with increasing electric field. Electrostatic and covalent bonding forces jointly determined clay aggregation.

Mechanism and Control of Rockburst Induced by Draining Spatial Islands and Squaring

A small-pillar gob-side roadway showed rockburst appearance during the mining of a gob-side working face located in the Shaanxi-Inner Mongolia mining area. This study examines the 2202 gob-side working face of a coal mine in Inner Mongolia as a case study. A stress evolution model was built for the static-stress spatial islands formed by drainage regions and goafs based on the spatial relationships between drainage regions and goafs. The average microseismic frequency and energy of the high-stress zone of spatial islands were at least 1.37 times of those of other zones, validating the presence of spatial islands. The dynamic and static load effects of working face squaring were obtained based on the evolution of the stope roof as well as changes in microseismic data. Microseismically active zones were advanced to 200 m–300 m on working faces. The rockbursts induced by high static loads and dynamic and static loads formed by spatial islands and squaring were calculated. According to calculation results, the critical stress concentration value under high static loads was 3.27; the critical static stress concentration value under dynamic and static loads was 1.81. The superposition of drainage boundary stress, goaf lateral stress, and lead stress might reach the critical stress concentration under dynamic load disturbances, causing rockbursts. A stress adjustment scheme was established, including overall hydraulic fracturing of the external roof of the drainage region, reduction of stoping speed, and pressure relief of large-diameter boreholes. The stress adjustment scheme was implemented on-site and supplemented by monitoring and early warning methods to safely advance by the first squaring region.

Сalixresorcine cavitands bearing lipophilic cationic fragments in the construction of mitochondrial-targeting supramolecular nanoparticles

The development of mitochondrial-targeting therapeutic nanoparticles is one of the crucial tasks of nanotechnology and nanomedicine. Here the study of supramolecular macrocycles decorated by lipophilic cationic mitochondrial-targeting fragments in the formation of supramolecular nanoparticles with the potential mitochondria-dependent apoptosis ability is described. Four cavitands based on tetrapentyl- and tetraundecylcalix[4]resorcines were functionalized with pyridinium (С5-Pyr and C11-Pyr, respectively) and triethylammonium groups (С5-NEt3 and C11-NEt3, respectively). Cavitands demonstrate amphiphilic character with critical association concentration values of 1.21, 1.20, 0.27 and 0.13 mM for С5-Pyr, С5-NEt3, C11-Pyr, and C11-NEt3, respectively (DMSO/Н2О 5/95 v/v, conductometry), and form small self-associates (D2O, DMSO-d6/D2О 5/95 v/v, FT-PGSE NMR method). The supramolecular modification of cavitands self-associates by the formation of polymer complexes with biocompatible polymer alginate sodium (AlgNa) was carried out. It was found that the size and stability of polymer complexes depends on the cavitand choice; the average hydrodynamic diameter of particles is 142 nm for С5-Pyr + AlgNa, 122 nm for С5-NEt3 + AlgNa and C11-NEt3 + AlgNa, and 615 nm for C11-Pyr + AlgNa complexes (DLS method). The formation of polymer complexes mainly is the result of electrostatic interaction and leads to the binding of cavitands by alginate in the form of self-associates (electrophoretic light scattering method, IR, fluorimetry). It was shown that pentylcavitands С5-Pyr and С5-NEt3 show higher hemotoxicity and cytotoxicity against normal (Chang liver cells) and tumor cells (M-HeLa cells) than undecylcavitands C11-Pyr and С11-NEt3. It was found that cavitand С5-NEt3 reduces the mitochondrial membrane potential and leads to the increase of ROS in M-HeLa cells (Flow cytometry analysis). However С5-NEt3 + AlgNa complex loses the ability to reduce the membrane potential of mitochondria, the possible reason of which is discussed.