Complexation Constants Research Articles

Experimental, equilibrium modelling, and column design for the reactive separation of biomass‐derived 2‐furoic acid

AbstractElectrochemical conversion of biomass to value‐added chemicals has gained impetus in recent years. Herein, we present a methodology for recovering biomass‐derived 2‐furoic acid from the dilute aqueous stream by reactive extraction. The reactive extraction was performed using a chemical extractant, trioctylamine (TOA), with diluents (octanol, chloroform, and diethyl ether). Equilibrium parameters influencing the recovery of 2‐furoic acid were evaluated. Using TOA in various diluents, the 2‐furoic acid was recovered with 85%–99% efficiency. A 1:1 complex of the 2‐furoic acid—TOA was formed in the organic phase, and the experimental equilibrium complexation constant was compared with that obtained from the relative basicity and Langmuir models. The equilibrium parameters were used for column design to estimate the solvent to feed ratio (S/F) and the number of theoretical stages (NTS). The NTS required is 12 to attain 99% recovery of 2‐furoic acid in counter‐current extraction. The present study sheds light on the reactive extraction process adopted for process intensification with electrochemical conversion, paving the way for the commercialization of valuable products obtained from biomass.

Estrogen receptor targeting with genistein radiolabeled Technetium-99m as radiotracer of breast cancer: Its optimization, characterization, and predicting stability constants by DFT calculation

ObjectiveGenistein is an isoflavone molecule with a high affinity for estrogen receptors (ER), which could lead to the mechanism of selective estrogen receptor modulators (SERMs) in breast cancer. Genistein labeling with technetium-99m can be a new promising strategy for diagnostic breast cancer. In this research, we evaluate the physicochemical characteristics of the [99mTc]Tc-genistein complex and describe the optimal labeling method parameters. We also calculated density functional theory to study the stability constants to support complex formation analysis (DFT). MethodsThe genistein was directly labeled with 99mTc, and its stability as well as its potential for usage as a radiotracer were all investigated. DFT calculations with thermodynamic cycles to determine chemical coordination models and calculate thermodynamic constants of complex more accurately. ResultsThe radiochemical purity of [99mTc]Tc-genistein showed a high yield of 93.25% ± 0.30% and had good physicochemical properties. The stability of the Tc(IV)-genistein complex was confirmed by DFT calculations at a value of 99.0822. ConclusionsAs a result, [99mTc]Tc-genistein could be a potential radiotracer kit for SPECT imaging of breast cancer.

Half-Sandwich Rhodium Complexes with Releasable N-Donor Monodentate Ligands: Solution Chemical Properties and the Possibility for Acidosis Activation.

Cancer chemotherapeutics usually have serious side effects. Targeting the special properties of cancer and activation of the anticancer drug in the tumor microenvironment in situ may decrease the intensity of the side effects and improve the efficacy of therapy. In this study, half-sandwich Rh complexes are introduced, which may be activated at the acidic, extracellular pH of the tumor tissue. The synthesis and aqueous stability of mixed-ligand complexes with a general formula of [Rh(η5-Cp*)(N,N/O)(N)]2+/+ are reported, where (N,N/O) indicates bidentate 8-quinolate, ethylenediamine and 1,10-phenanthroline and (N) represents the releasable monodentate ligand with a nitrogen donor atom. UV-visible spectrophotometry, 1H NMR, and pH-potentiometry were used to determine the protonation constants of the monodentate ligands, the proton dissociation constants of the coordinated water molecules in the aqua complexes, and the formation constants of the mixed-ligand complexes. The obtained data were compared to those of the analogous Ru(η6-p-cymene) complexes. The developed mixed-ligand complexes were tested in drug-sensitive and resistant colon cancer cell lines (Colo205 and Colo320, respectively) and in four bacterial strains (Gram-positive and Gram-negative, drug-sensitive, and resistant) at different pH values (5-8). The mixed-ligand complexes with 1-methylimidazole displayed sufficient stability at pH 7.4, and their activation was found in cancer cells with decreasing pH; moreover, the mixed-ligand complexes demonstrated antimicrobial activity in Gram-positive and Gram-negative bacteria, including the resistant MRSA strain. This study proved the viability of incorporating releasable monodentate ligands into mixed-ligand half-sandwich complexes, which is supported by the biological assays.

Conjugates of Chitosan with β-Cyclodextrins as Promising Carriers for the Delivery of Levofloxacin: Spectral and Microbiological Studies.

In this work, we synthesized chitosan 5 kDa conjugates with β-cyclodextrins with various substituents as promising mucoadhesive carriers for the delivery of fluoroquinolones using the example of levofloxacin. The obtained conjugates were comprehensively characterized by spectral methods (UV-Vis, ATR-FTIR, 1H NMR, SEM). The physico-chemical properties of the complex formations were studied by IR, UV, and fluorescence spectroscopy. The dissociation constants of complexes with levofloxacin were determined. Complexation with conjugates provided four times slower drug release in comparison with plain CD and more than 20 times in comparison with the free drug. The antibacterial activity of the complexes was tested on model microorganisms Gram-negative bacteria Escherichia coli ATCC 25922 and Gram-positive Bacillus subtilis ATCC 6633. The complex with the conjugate demonstrated the same initial levofloxacin antibacterial activity but provided significant benefits, e.g., prolonged release.

Solvent Phase Optimizations Improve Correlations with Experimental Stability Constants for Aqueous Lanthanide Complexes

ABSTRACT Stability constants provide insight into ion complexation in water. While computational studies have been shown to model the energy of the complexation successfully using a thermodynamic cycle approach, it does not extend to calculating the stability constants for 1:1 lanthanide to ligand complexes in solution. Using B3LYP and 6-31+G* Pople basis with small core effective core potential (ECP) on the lanthanum ion, and a solvent model based on the full solute electron density (SMD) solvation model we computed and compared with previously published stability constants of the ligands: acetate, acetohydroximate, acetylacetonate, methanoate, tropolonate, hydroxide, catecholate, malonate, oxalate, phthalate, and sulfate. The best R2 values for the thermodynamic cycle can only be determined by separating the mono and divalent ions to achieve an R2 value of 0.86 and 0.74 for mono and divalent ions, respectively. We show that by optimizing the lanthanide-ligand structures in implicit solvent, we achieve an improved correlation between experimental and computed stability constants of R2 value of 0.89 for the combined mono and divalent ions.

Structural Investigation of Beta-Cyclodextrin Complexes with Cannabidiol and Delta-9-Tetrahydrocannabinol in 1:1 and 2:1 Host-Guest Stoichiometry: Molecular Docking and Density Functional Calculations.

The complexation of β-cyclodextrin (β-CD) with cannabidiol (CBD) and Δ9-tetrahydrocannabinol (THC) was investigated using molecular docking and M062X/6-31G(d,p) calculations. The calculations suggested two possible complex formations of 1:1 and 2:1 host-guest molecular ratio of β-CD with CBD and THC. The preferred orientation of all complexes in this study exhibited the hydrogen bonding between hydroxy-substituted benzene ring of CBD and THC with the β-CD's secondary hydroxy groups at the wide rim. The calculated complexation energies indicate that formation of the 2:1 complexes (-83.53 to -135.36 kcal/mol) was more energetically favorable and chemically stable than the 1:1 complexes (-30.00 to -34.92 kcal/mol). However, the deformation energies of the host and the guest components in the 2:1 complexes (37.47-96.91 kcal/mol) are much higher than those in the 1:1 complexes (3.49-8.69 kcal/mol), which means the formation processes of the 2:1 complexes are more difficult due to the rigidity of the dimeric β-CDs. Therefore, the inclusion complexes of β-CD with CBD and THC are more likely to be in 1:1 host-guest ratio than in 2:1 molecular ratio. The results of this study supported the experimental results that the complexation constant of 1:1 β-CD/CBD (Ks = 300 M-1) is greater than that of 2:1 β-CDs/CBD (Kss = 0.833 M-1). Altogether, this study introduced the fitting parameters that could indicate the stability of the molecular fits in complex formation of each stoichiometry host-guest ratio, which are important for the assessment of the inclusion mechanisms as well as the relationships of reactants and products in chemical reactions.

Capturing the free energy of transition state stabilization: insights from the inhibition of mandelate racemase.

Mandelate racemase (MR) catalyses the Mg2+-dependent interconversion of (R)- and (S)-mandelate. To effect catalysis, MR stabilizes the altered substrate in the transition state (TS) by approximately 26 kcal mol-1 (-ΔGtx), such that the upper limit of the virtual dissociation constant of the enzyme-TS complex is 2 × 10-19 M. Designing TS analogue inhibitors that capture a significant amount of ΔGtx for binding presents a challenge since there are a limited number of protein binding determinants that interact with the substrate and the structural simplicity of mandelate constrains the number of possible isostructural variations. Indeed, current intermediate/TS analogue inhibitors of MR capture less than or equal to 30% of ΔGtx because they fail to fully capitalize on electrostatic interactions with the metal ion, and the strength and number of all available electrostatic and H-bond interactions with binding determinants present at the TS. Surprisingly, phenylboronic acid (PBA), 2-formyl-PBA, and para-chloro-PBA capture 31-38% of ΔGtx. The boronic acid group interacts with the Mg2+ ion and multiple binding determinants that effect TS stabilization. Inhibitors capable of forming multiple interactions can exploit the cooperative interactions that contribute to optimum binding of the TS. Hence, maximizing interactions with multiple binding determinants is integral to effective TS analogue inhibitor design. This article is part of the theme issue 'Reactivity and mechanism in chemical and synthetic biology'.

Promoters of genes encoding β-amylase, albumin and globulin in food plants have weaker affinity for TATA-binding protein as compared to non-food plants: in silico analysis.

It is generally accepted that during the domestication of food plants, selection was focused on their productivity, the ease of their technological processing into food, and resistance to pathogens and environmental stressors. Besides, the palatability of plant foods and their health benefits could also be subjected to selection by humans in the past. Nonetheless, it is unclear whether in antiquity, aside from positive selection for beneficial properties of plants, humans simultaneously selected against such detrimental properties as allergenicity. This topic is becoming increasingly relevant as the allergization of the population grows, being a major challenge for modern medicine. That is why intensive research by breeders is already underway for creating hypoallergenic forms of food plants. Accordingly, in this paper, albumin, globulin, and β-amylase of common wheat Triticum aestivum L. (1753) are analyzed, which have been identified earlier as targets for attacks by human class E immunoglobulins. At the genomic level, we wanted to find signs of past negative selection against the allergenicity of these three proteins (albumin, globulin, and β-amylase) during the domestication of ancestral forms of modern food plants. We focused the search on the TATA-binding protein (TBP)-binding site because it is located within a narrow region (between positions -70 and -20 relative to the corresponding transcription start sites), is the most conserved, necessary for primary transcription initiation, and is the best-studied regulatory genomic signal in eukaryotes. Our previous studies presented our publicly available Web service Plant_SNP_TATA_Z-tester, which makes it possible to estimate the equilibrium dissociation constant (KD) of TBP complexes with plant proximal promoters (as output data) using 90 bp of their DNA sequences (as input data). In this work, by means of this bioinformatics tool, 363 gene promoter DNA sequences representing 43 plant species were analyzed. It was found that compared with non-food plants, food plants are characterized by significantly weaker affinity of TBP for proximal promoters of their genes homologous to the genes of common-wheat globulin, albumin, and β-amylase (food allergens) (p < 0.01, Fisher's Z-test). This evidence suggests that in the past humans carried out selective breeding to reduce the expression of food plant genes encoding these allergenic proteins.

SPECTROSCOPIC STUDY OF COMPLEX FORMATION OF COPPER(II) WITH (S)-β-[3-ISOBUTYL-4-(2-METALLYL)-5-THIOXO-1,2,4-TRIAZOL-1-YL]-α-ALANINE IN AQUEOUS SOLUTION

The complex formation of (S)-β-[3-isobutyl-4-(2-methallyl)-5-thioxo-1,2,4-triazol-1-yl]-α-alanine amino acid with copper(II) chloride in aqueous solution has been investigated by means of UV-Vis and IR spectroscopy at 25 °C. The molar ratio method was used to determine the composition of that complex. It has been established that a complex compound of the ML2 type is formed in aqueous solution. Based on the data of UV-Vis spectra, the stability constant of this complex was calculated. The stability constant of the ML2 type complex is equal to (4.23±0.27)·106 L2·mol-2. In addition, on the basis of IR spectroscopy data the formation of the complex was confirmed, and the centers of the ligand involved in the complex formation were identified. In the IR spectrum of the complex isolated from the solution and dried in air, a new weak absorption band appears, which is characteristic of the coordination of the copper(II) ion with the carboxylate ion. In addition, there is a shift of the stretching vibration band of the N-H amino group to the region of large values, which indicates the participation of the lone electron pair of the nitrogen of the amino group in the formation of coordination with the copper(II) ion. Moreover, an absorption band of coordination water in the structure of the complex is also observed. Based on the data obtained, the structure of the chelate complex has been proposed, in which the copper(II) cation is bound to the oxygen atom of the carboxylate anion by electrostatic interaction, and to the nitrogen atom of the amino group by a covalent bond by the donor-acceptor mechanism. And the octahedral coordination sphere of the copper(II) ion is complemented by two water molecules. For citation: Sargsyan H.R., Grigoryan G.S., Markarian Sh.A. Spectroscopic study of complex formation of copper(II) with (S)-β-[3-isobutyl-4-(2-metallyl)-5-thioxo-1,2,4-triazol-1-yl]-α-alanine in aqueous solution. ChemChemTech [Izv. Vyssh. Uchebn. Zaved. Khim. Khim. Tekhnol.]. 2023. V. 66. N 2. P. 62-69. DOI: 10.6060/ivkkt.20236602.6740.

Cadmium behavior in sulfur-bearing aqueous environments: insight from CdS solubility measurements at 25-80°C

The present experimental study explores the effects of temperature and sulfur in Cd aqueous geochemistry under reduced conditions. Greenockite CdS solubility is measured in H2O-H2S-HClO4-NaHS solutions at 25-80°C as a function of pH and sulfur concentration. Based on solubility product measurements in highly acid solutions, the standard thermodynamic properties of greenockite (CdS) are revised, and the recommended value of ∆fG0298.15 for greenockite CdS(s) is -151.5±0.3 kJ mol-1. The stability of greenockite (CdS) is higher than predicted by calculations using previous literature data. At 80°C, the stability constants for Cd-HS complexes are measured for the first time, the values are 10–5.65±1.00 for CdS(s) + H+ = CdHS+, 10–6.00±0.40 for CdS(s) + H2S0(aq) = Cd(HS)20(aq), 10–3.87±0.10 for CdS(s) + H2S0(aq) + HS- = Cd(HS)3-, and 10–3.53±0.20 for CdS(s) + H2S0(aq) + 2HS- = Cd(HS)42-. Modeling of Cd behavior at 3-200°C shows that Cd-HS species are more important than previously believed. The fraction of Cd(HS)n2-n (n = 1-4) complexes increases with mH2S and decreases with T. Thus, in euxinic marine environments with mH2S ≥ 10-5, Cd speciation changes from Cd-Cl to Cd-HS. This speciation change is expected to affect Cd isotope fractionation and should be accounted for when applying Cd isotopic signature as a paleo tracer in marine sediments. The new thermodynamic data are indispensable for modeling Cd behavior in response to pH, T, and mH2S. As a function of these parameters, sulfur has the main control on Cd geochemistry being the main factor of Cd precipitation at low mH2S and favoring Cd mobilization at high mH2S.

Proton transfer kinetics of transition metal hydride complexes and implications for fuel-forming reactions.

Proton transfer reactions involving transition metal hydride complexes are prevalent in a number of catalytic fuel-forming reactions, where the proton transfer kinetics to or from the metal center can have significant impacts on the efficiency, selectivity, and stability associated with the catalytic cycle. This review correlates the often slow proton transfer rate constants of transition metal hydride complexes to their electronic and structural descriptors and provides perspective on how to exploit these parameters to control proton transfer kinetics to and from the metal center. A toolbox of techniques for experimental determination of proton transfer rate constants is discussed, and case studies where proton transfer rate constant determination informs fuel-forming reactions are highlighted. Opportunities for extending proton transfer kinetic measurements to additional systems are presented, and the importance of synergizing the thermodynamics and kinetics of proton transfer involving transition metal hydride complexes is emphasized.

Mononuclear discrete Ag(I) complexes of aryl substituted (E)-N-phenyl-1-(pyridin-3-yl)methanimine: In vitro biological activities and interactions with biomolecules

The synthesis of three pyridinyl imines (L1-L3) with electron-donating and electron-withdrawing functional groups, as well as their silver(I) complexes (1a-3a, 1b-3b and 1c-3c), resulted from our ongoing search for novel metallodrugs with potential pharmacological activity. Various analytical and spectroscopic analyses were used to characterize the Ag(I) complexes. The single crystal X-ray diffraction analysis of complexes 3a and 3b in the solid state confirmed their linear geometry around the Ag(I) center. In vitro antibacterial properties of the complexes evaluated using the minimum inhibitory concentration (MIC) method revealed that complexes containing either a Me- or an F-substituent exhibited greater activity. The ferric-reducing antioxidant power (FRAP) experiment revealed that complexes with hydroxyl substituents have high antioxidant potential. These complexes with IC50 values ranging from 0.86 to 2.47 mg mL-1 outperformed ascorbic acid, with an IC50 of 2.68 mg mL-1. The reported complexes bound to CT-DNA via intercalation mode with significant binding constants for complexes whose ligands bore the OH- substituent. Bovine serum albumin (BSA) binding affinity to the complexes ranges from moderate to high. The studied complexes with methyl substituents are promising anti-cervical cancer candidates.

Exploratory evaluation of iron and its speciation in surface waters of Admiralty Bay, King George Island, Antarctica.

The determination of dissolved iron concentrations and speciation was conducted for the first time in surface seawater coastline samples collected during the austral summer of 2020 in Admiralty Bay, King George Island, Antarctica. The technique of competitive ligand exchange/adsorptive cathodic stripping voltammetry with 2,3-dihydroxynaphthalene as the competing ligand was evaluated, showing a sensitivity between 14.25 and 21.05 nA nmol L-1 min-1, with an LOD of 14 pmol L-1 and a mean blank contribution of 0.248 nmol L-1. Physicochemical parameters such as pH (7.85 ± 0.2), salinity (32.7 ± 0.8) and dissolved oxygen (51.3 ± 26.6%) were compatible with those of the literature; however, the average temperature (4.2 ± 0.8 °C) was higher, possibly as a reflection of global warming. The dissolved iron mean value was 18.9 ± 6.1 nmol L-1, with a total ligand concentration of 23.6 ± 12.2 nmol L-1 and a conditional stability complex constant of 12.2 ± 0.2, indicating humic substances as possible ligands. On average, the calculated free iron concentrations were 0.7 ± 0.3 pmol L-1. Relatively high concentrations of iron indicate a possible local source of Fe, likely predominantly from upwelling sediments and secondarily from ice-melting waters, which does not limit the growth of the phytoplankton.

Determination of the parameters of thermodynamic stability constants of bromide complexes of rare earth metals for modeling the optimal regimes of hydrometallurgical extraction

Determination of the thermodynamic parameters of complex compounds of rare earth metals in aqueous solutions is of considerable interest for understanding the hydrometallurgical processes associated with the extraction and separation of yttrium and lanthanides from solutions of complex multicomponent composition. The composition of these solutions, as a rule, includes the following anions: SO4 2-, CO3 2-, PO4 3-, F-, which form strong complexes of the inner-sphere type, and anions, which form weak outer-sphere complexes, which primarily include complexes of the metal with halogens Cl-, Br-, I-. By the method of direct potentiometry with the use of a bromide-selective electrode while maintaining the ionic strength constant in the medium of sodium perchlorate, the stability constants (lgK) of the complexes of bromine with cerium, neodymium and samarium at the first stage were determined, the numerical values of which were 0,346; 0,257; 0,387, respectively. Based on the results obtained, the Gibbs energies of formation for the complexes under consideration are calculated. A method is proposed for extrapolating literature or experimental data, which makes it possible to calculate the values of thermodynamic stability constants for the entire series of lanthanides and yttrium. The fundamental possibility of using this method is shown by the example of calculating thermodynamic parameters for bromide complexes of rare-earth metals.

Single-Hydroxide Bridged Dimers of U and Np Actinyls: A Density Functional Study on Their Existence and Structure in Aqueous Solution

With quantum chemical calculations at the density functional theory level, we examined the structure and the stability of diactinyl monohydroxo complexes [(AnO2)2(OH)]3+/+ in aqueous solution for An = U(VI), Np(VI), and Np(V). In particular, this study contributes to understanding the hydrolysis of Np(VI) and Np(V), which is less well characterized than for U(VI). [(UO2)2(OH)]3+ is a known hydrolysis complex of U(VI) at low pH. Although not yet found in experiments, [(NpO2)2(OH)]3+ is suggested to exist due to the similarity between Np(VI) and U(VI) complexes, while [(NpO2)2(OH)]+ is a hypothetical species thus far. Our calculations suggest that the An(VI) complexes favor the parallel orientation of actinyls, whereas for the Np(V) complex a perpendicular arrangement is stabilized by hydrogen bonds between aqua ligands and the actinyl oxygen atoms. The Np(VI) complex [(NpO2)2(OH)]3+ features a structure and stability similar to its U(VI) analogue. From calculated formation constants for An(VI) diactinyl monohydroxo complexes, we find qualitative agreement with the experiment for U(VI). Both An(VI) complexes are only slightly less stable than the separate mononuclear constituents, the actinyl aqua and the monohydroxo complex. For the Np(V) species [(NpO2)2(OH)]+, we calculated a considerably lower complexation constant than for its An(VI) analogues, but it is more stable against decay into its constituents. Thus, this complex may exist at about the pH where Np(V) hydrolysis starts at not too low Np(V) concentrations.

Estradiol-Based Salicylaldehyde (Thio)Semicarbazones and Their Copper Complexes with Anticancer, Antibacterial and Antioxidant Activities

A series of novel estradiol-based salicylaldehyde (thio)semicarbazones ((T)SCs) bearing (O,N,S) and (O,N,O) donor sets and their Cu(II) complexes were developed and characterized in detail by 1H and ¹³C nuclear magnetic resonance spectroscopy, UV-visible and electron paramagnetic resonance spectroscopy, electrospray ionization mass spectrometry and elemental analysis. The structure of the Cu(II)-estradiol-semicarbazone complex was revealed by X-ray crystallography. Proton dissociation constants of the ligands and stability constants of the metal complexes were determined in 30% (v/v) DMSO/H2O. Estradiol-(T)SCs form mono-ligand complexes with Cu(II) ions and exhibit high stability with the exception of estradiol-SC. The Cu(II) complexes of estradiol-TSC and its N,N-dimethyl derivative displayed the highest cytotoxicity among the tested compounds in MCF-7, MCF-7 KCR, DU-145, and A549 cancer cells. The complexes do not damage DNA according to both in vitro cell-free and cellular assays. All the Cu(II)-TSC complexes revealed significant activity against the Gram-positive Staphylococcus aureus bacteria strain. Estradiol-TSCs showed efficient antioxidant activity, which was decreased by complexation with Cu(II) ions. The exchange of estrone moiety to estradiol did not result in significant changes to physico-chemical and biological properties.

Analysis of the interaction between chitosan with different molecular weights and casein based on optical interferometry

Chitosan can be used as a stabilizer in dairy products to help suspend and stabilize casein micelles, but the molecular weight (MW) effect of chitosan has not been much explored. This work aimed to construct interaction models with casein using chitosan with MW of 30 kDa, 150 kDa, 250 kDa and 300 kDa to reveal the effect of MW on the structure and stability of chitosan-casein complexes. These models were based on the ordered porous layer interferometry (OPLI) system that can generate time-resolved signals to monitor the chitosan-casein interaction process dynamically in real time. The zeta potential, size distribution, binding mechanism and binding constants of chitosan-casein complexes with different MW were also analyzed. It was found that the chitosan and casein at pH 5.5 with the strongest interaction. The zeta potential and size analysis of chitosan-casein complexes showed opposite trends with MW before and after the saturation concentration, and MW(150 kDa) chitosan produced the largest size change in the bridging flocculation stage. The order of binding constants for chitosan-casein interactions is MW(300 kDa) < MW(250 kDa) < MW(30 kDa) < MW(150 kDa). In addition to the attraction between chitosan and casein by electrostatic driving forces, the dependence of the hydrophobic interaction between chitosan molecules on MW all influenced the interaction with casein. The dynamic monitoring and accuracy of the OPLI technique open up more possibilities to obtain the interactions of chitosan/casein and other biopolymers in different condition variables.

Investigating the β-Mg17Al12 Alloy under Pressure Using First-Principles Methods: Structure, Elastic Properties, and Mechanical Properties

Calculations of first principles were employed to explore the elastic constants of the β-Mg17Al12 intermetallic complex under pressure, along with several related physical parameters, including the bulk modulus, the shear modulus, Young’s modulus, Poisson’s ratio, and the anisotropy index. The volume of the β-Mg17Al12 crystal in the ground state was V0 = 1180.353 Å3, and the lattice parameter was 10.57 Å. This is in agreement with the available results in the literature, which indicate that the calculations were correct. The three independent elastic constants, C11, C12, and C44, increased with increasing pressure. The bulk modulus B, shear modulus G, and Young’s modulus E increased with increasing pressure, indicating that the bulk deformation resistance, shear deformation resistance, and stiffness of the β-Mg17Al12 phase increased with increasing pressure. The phase had a B/G &gt; 1.75 and a Poisson’s ratio of ν &gt; 0.26 and increased with pressure, indicating that the β-Mg17Al12 crystals were ductile and that the ductility increased with pressure. The Cauchy pressure C12–C44 increased with increasing pressure. The anisotropy coefficients A(100) and A(110) deviated further from 1, and the anisotropy increased. The electronic structure calculations showed that the total density of the states (TDOS) was achieved mainly by the Mg-3p and Al-3p states, and the total density of states moved toward the higher energy regions under pressure, with enhanced interatomic bonding, leading to an increase in the elastic constants and ultimately to an increase in each physical property with increasing pressure.

Thermodynamics on the complexation of uranium (VI) with N-methylethylenediamine-N,N′,N'-triacetic acid in aqueous Solution: Potentiometry and microcalorimetry

Stability constants and enthalpies of N-methylethylenediamine-N,N′,N'-triacetic acid (MEDTA, denoted as H3L) complexes with uranyl were measured using potentiometry and microcalorimetry, I = 1.0 mol L−1 NaClO4 solution at 25 °C. Thermodynamic analyses revealed three U(VI)/MEDTA complexes: UO2(HL), UO2L−, and UO2(OH)L2−. The results showed that the complex formation of UO2L− (UO22+ ​+ ​L3− = UO2L−) is endothermic and driven solely by entropy. MEDTA in the UO2L− complex is a tetradentate and coordinates with U(VI) along the ethylenediamine backbone. Stability constant of mononuclear uranyl complex with MEDTA (UO2L−) is lower than UO22+/EDDA complex but higher than UO22+/HEDTA complex, indicating that dangling acetate arm of MEDTA or hydroxyethyl group of HEDTA would lower the stability.

Exploring the HSA/DNA/lung cancer cells binding behavior of p-Synephrine, a naturally occurring phenyl ethanol amine with anti-adipogenic activity: multi spectroscopic, molecular dynamic and cellular approaches

As a phenolic amine, p-Synephrine (SN) is known to exhibit lipolytic properties as well as enhancing energy expenditure, which can be an excellent alternative to ephedra as a dietary supplement. This study aimed to explore the subtle yet profound complex qualities and aspects of the interaction between SN, human serum albumin (HSA), and calf thymus DNA (ctDNA). To achieve a full comprehension on these fine-point distinctions, a nuanced and detail-oriented approach was implemented through a combination of different biophysical methods and molecular dynamics simulation techniques. The fluorescence spectroscopy revealed the binding of SN to HSA that led to the inducement of conformational changes. The quenching constants (KSV) of SN-HSA complex at 298, 303, and 308 K and were evaluated to be 2.95 × 104, 2.21 × 104 and 0.85 × 104 M−1, respectively. The thermodynamic parameters indicated the spontaneous formation of SN-HSA complex along with its regulation through H-bonding and van der Waals forces. The distance between SN and Trp residue of HSA was estimated at 3.91 nm by the Forster’s theory of non-radiative resonance energy transfer. According to CD spectroscopy, the binding of SN to HSA results in stabilization and promotes its functionality. Various spectroscopy methods and viscosity measurements proved the propensity of SN for binding to the grooves of ctDNA. Thermodynamic parameters indicate that the SN binds to DNA via a spontaneous and entropy-driven process that is mainly regulated by hydrophobic interactions. In conformity to the molecular modeling of HSA-SN complex, SN can be located in the active site of HSA and make a firm interaction, while the outcomes of ctDNA-SN interaction also indicated its tendency towards binding in DNA groove. In comparison to normal cells, SN caused a more pronounced reduction in lung cancer cell viability by increasing the expression of Bax and p53 at the mRNA and protein levels. Moreover, the incubation of H460 cells with the IC50 concentration of SN induced a notable decease in mRNA levels of PI3K, AKT, and mTOR, as well as protein levels of PI3Kγ-P110, P-AKT, and P-m TOR. These data indicate the potential of SN in binding with HSA, which reduces the proliferation of lung cancer cells mediated by apoptosis through the down regulation of PI3K/AKT/m TOR signaling pathway.