Chelating Effect of Siderophore Desferrioxamine-B on Uranyl Biomineralization Mediated by Shewanella putrefaciens.

In contaminated water and soil, little is known about the role and mechanism of the biometabolic molecule siderophore desferrioxamine-B (DFO) in the biogeochemical cycle of uranium due to complicated coordination and reaction networks. Here, a joint experimental and quantum chemical investigation is carried out to probe the biomineralization of uranyl (UO22+, referred to as U(VI) hereafter) induced by Shewanella putrefaciens (abbreviated as S. putrefaciens) in the presence of DFO and Fe3+ ion. The results show that the production of mineralized solids {hydrogen-uranium mica [H2(UO2)2(PO4)2·8H2O]} via S. putrefaciens binding with UO22+ is inhibited by DFO, which can both chelate preferentially UO22+ to form a U(VI)-DFO complex in solution and seize it from U(VI)-biominerals upon solvation. However, with Fe3+ ion introduced, the strong specificity of DFO binding with Fe3+ causes re-emergence of biomineralization of UO22+ {bassetite [Fe(UO2)2(PO4)2·8(H2O)]} by S. putrefaciens, owing to competitive complexation between Fe3+ and UO22+ for DFO. As DFO possesses three hydroxamic functional groups, it forms hexadentate coordination with Fe3+ and UO22+ ions via these functional groups. The stability of the Fe3+-DFO complex is much higher than that of U(VI)-DFO, resulting in some DFO-released UO22+ to be remobilized by S. putrefaciens. Our finding not only adds to the understanding of the fate of toxic U(VI)-containing substances in the environment and biogeochemical cycles in the future but also suggests the promising potential of utilizing functionalized DFO ligands for uranium processing.

Alkaloid-Based Isoxazolylureas: Synthesis and Effect in Combination with Anticancer Drugs on C6 Rat Glioma Model Cells.

Alkaloid-based urea derivatives were produced with high yield through the reaction of anabasine and cytisine with isoxazolylphenylcarbamates in boiling benzene. Their antitumor activity, in combination with the commonly used five anticancer drugs, namely cyclophosphane, fluorouracil, etoposide, cisplatin, ribomustine with different mechanisms of action, was investigated. Based on the quantum chemical calculations data and molecular docking, hypotheses have been put forward to explain their mutual influence when affecting C6 rat glioma model cells.

Alginate/chitosan hydrogels as perspective transport systems for cefotaxime.

This work reports synthesis of pH-responsive alginate/chitosan hydrogel spheres with the average diameter of 2.0 ± 0.05 mm, which contain cefotaxime that is an antibiotic of the cefalosporine group. The spheres provided the cefotaxime encapsulation efficiency of 95 ± 1%. An in vitro release of cefotaxime from the spheres in the media that simulate human biological fluids in peroral delivery conditions was found to be a pH-dependent process. The analysis of cefotaxime release kinetics by the Korsmeyer-Peppas model revealed a non-Fickian mechanism of its diffusion, which may be related to intermolecular interactions occurring between the antibiotic and chitosan. Conductometry, UV spectroscopy, and IR spectroscopy were used to study complexation of chitosan with cefotaxime in aqueous media with varied pH, characterize the composition of the complexes, and calculate their stability constants. The composition of the cefotaxime-chitosan complexes was found to correspond to the 1.0:4.0 and 1.0:2.0 molar ratios of the components at pH 2.0 and 5.6, respectively. Quantum chemical modeling was used to evaluate energy characteristics of chitosan-cefotaxime complexation considering the influence of a solvent.

Molecular and Electronic Structures of Neutral Polynitrogens: Review on the Theory and Experiment in 21st Century.

The data on the existence and physicochemical characteristics of uncharged single element chemical compounds formed by nitrogen atoms and containing more than two nuclides of this element (from N4 to N120, oligomeric and polymeric polynitrogens) have been systematized and generalized. It has been noticed that these data have a predominantly predictive character and were obtained mainly using quantum chemical calculations of various levels (HF, DFT, MP, CCSD etc.). The possibility of the practical application of these single element compounds has been considered. The review mainly covers articles published in the last 25 years. The bibliography contains 128 references.

Structure, Z' = 2 Crystal Packing Features of 3-(2-Chlorobenzylidene)-5-(p-tolyl)furan-2(3H)-one.

3-(2-Chlorobenzylidene)-5-(p-tolyl)furan-2(3H)-one (1), C18H13ClO2, crystallizes with Z = 8 and Z' = 2, and the structure at 100 K has orthorhombic (Pna21) symmetry. Each kind of molecule takes part in π-π stacking interactions to form infinite chains parallel to the c axis. We believe that the existence of two forms can be explained by the probable rotation around a single C-C bond. The quantum chemical modeling reveals that these molecules are almost equivalent energetically, and they can be described as the two most stable conformers (rotamers) with a minor rotational barrier of about 0.67 kcal/mol.

Structure and State of Water in Branched N-Vinylpyrrolidone Copolymers as Carriers of a Hydrophilic Biologically Active Compound.

Hydrated copolymers of N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate as a promising platform for biologically active compounds (BAC) were investigated by different physical chemical methods (dynamic light scattering, infrared spectroscopy, thermal gravimetric analysis, and differential scanning calorimetry) and the quantum chemical modeling of water coordination by the copolymers in a solution. According to the quantum chemical simulation, one to two water molecules can coordinate on one O-atom of the lactam ring of VP units in the copolymer. Besides the usual terminal coordination, the water molecule can form bridges to bind two adjacent C=O groups of the lactam rings of VP units. In addition to the first hydration shell, the formation of a second one is also possible due to the chain addition of water molecules, and its structure depends on a mutual orientation of C=O groups. We showed that N,N-dimethylbiguanidine hydrochloride (metformin) as a frontline drug for the treatment of type 2 diabetes mellitus can be associated in aqueous solutions with free and hydrated C=O groups of the lactam rings of VP units in studied copolymers. Based on the characteristics of the H-bonds, we believe that the level of the copolymer hydration does not affect the behavior and biological activity of this drug, but the binding of metformin with the amphiphilic copolymer will delight in the penetration of a hydrophilic drug across a cell membrane to increase its bioavailability.

Quantum Chemical Modeling of Pressure-Induced Spin Crossover in Octahedral Metal-Ligand Complexes.

Spin state switching on external stimuli is a phenomenon with wide applicability, ranging from molecular electronics to gas activation in nanoporous frameworks. Here, we model the spin crossover as a function of the hydrostatic pressure in octahedrally coordinated transition metal centers by applying a field of effective nuclear forces that compress the molecule towards its centroid. For spin crossover in first-row transition metals coordinated by hydrogen, nitrogen, and carbon monoxide, we find the pressure required for spin transition to be a function of the ligand position in the spectrochemical sequence. While pressures on the order of 1 GPa are required to flip spins in homogeneously ligated octahedral sites, we demonstrate a fivefold decrease in spin transition pressure for the archetypal strong field ligand carbon monoxide in octahedrally coordinated Fe2+ in [Fe(II)(NH3 )5 CO]2+ .

Nitrogen-Containing Analog of Dibenzoylmethanate of Boron Difluoride: Luminescence, Structure, Quantum Chemical Modeling, and Delay Fluorescence.

Boron difluoride of 3-amino-1,3-diphenyl-2-propene-1-onate (1) has been synthesized and its crystal structure has been determined. The comparative studies of 1 and its oxygen analog 1,3-diphenyl-1,3-dionate (dibenzoylmethanate) of boron difluoride (2) have been performed using the methods of stationary and time-resolved spectroscopy and quantum chemical modeling. It was established that at the transition from solutions to crystals, a bathochromic shift of the spectra and a significant increase of luminescence intensity of 1 take place. The luminescent properties of solutions of 1 and 2 are similar. The peculiarities of crystal packings of 1 and 2 are responsible for differences in crystals luminescent properties. For crystals of 2, one observes the luminescence of J-aggregates and excimers, while for 1, in which a dimer is an elementary structural fragment, only the excimer luminescence is registered. A delayed excimer fluorescence of the P-type was observed for crystals of 1 and 2 at room temperature. The intensity of the delayed fluorescence of 1 is 300-fold higher than that of 2. Graphical Abstract Luminescence of J-aggregates and the formation of excimers in crystals of 1 and 2.

Enhanced furfural extraction using neoteric hydrophobic solvents for sustainable biomass recovery and bioenergy applications.

The recovery of furfural from hemicellulosic biowastes is important for developing sustainable and renewable energy alternatives to fossil fuels. However, current methods are inefficient and environmentally questionable. To address this issue, this study introduces neoteric hydrophobic solvents, specifically deep eutectic solvents (DESs) and ionic liquids (ILs). Of the 32 solvents tested, thymol:decanoic acid 1:1 (Thy:DecA) DES and trihexyltetradecyl phosphonium bis(trifluoro methylsulfonyl) imide [P14,6,6,6][NTf2] IL were the most effective, with extraction efficiencies of 94.1% and 97.1%, respectively. These solvents outperformed the reference solvent toluene, with an efficiency of 81.2%, while also showing favorable characteristics in multiple investigated criterions. For the first time, excellent performance stability was demonstrated under various operational conditions and reusability over multiple extraction and regeneration cycles. Furthermore, to provide insights into the molecular mechanisms of extraction, computational quantum chemistry modeling was employed, which showed a strong agreement with the experimental results. The development of these new neoteric solvents for furfural recovery from biowaste offers a highly effective, sustainable, and eco-friendly alternative to traditional solvents, representing a significant breakthrough in the field of renewable bioenergy production and sustainable materials recovery.

XANES/EXAFS and quantum chemical study of the speciation of arsenic in the condensate formed in landfill gas processing: Evidence of the dominance of As-S species.

The XANES/EXAFS data and quantum chemical simulations presented in this study demonstrate several features of the chemistry of arsenic compounds found in the condensates and solids generated in landfill gas (LFG) processing carried out for renewable natural gas (RNG) production. The XANES data show the decrease in the position of the absorption edge of As atoms, similar to that characteristic for sulfur-containing As solutes and solids. The EXAFS data show that the As-O and As-S distances in these matrixes are similar to those in thioarsenates. Quantum-chemical calculations demonstrated the close agreement between the experimental and modeled As-S and As-O distances determined for a range of methylated and thiolated arsenic solutes. These calculations also showed that the increase of the number of the As-S bonds in the coordination shell of arsenic is accompanied by a consistent decrease of the charges of As atoms. This decrease is correlated with the number of the As-S bonds, in agreement with the trend observed in the XANES data. These results provide insight into the intrinsic chemistry and reactivity of As species present in LFG matrixes; they may be helpful for the development of treatment methods to control arsenic in these systems.

Speciation of Hexavalent Chromium in Aqueous Solutions Using a Magnetic Silica-Coated Amino-Modified Glycidyl Methacrylate Polymer Nanocomposite.

A new magnetic amino-functionalized polymeric sorbent based on glycidyl methacrylate was synthesized and used in the separation of chromium Cr(VI) oxyanions sorption from aqueous solutions in a static batch system. The kinetic and isothermal parameters of the sorption process were determined. The experimental data were best fitted by a pseudo-second-order model with R2 = 0.994 and χ2 = 0.004. The sorption process of Cr(VI) removal by amino-functionalized sorbent was controlled by both intraparticle diffusion and liquid film diffusion. The equilibrium results showed that the sorption process is best described by the Freundlich model, followed closely by the Sips isotherm model, with a maximum sorption capacity of 64 mg/g. Quantum chemical modeling revealed that the sorption sites on the sorbent surface are fragments with diethylenetriamine and aminopropyl silane groups that coated the magnetic nanoparticles. The calculations showed that Cr(VI) oxyanions (Cr2O72-, CrO42- and HCrO4-) bind to both sorption sites, with diethylenetriamine centers slightly favored. The X-ray photoelectron spectroscopy (XPS) spectra demonstrate that the chromium bound to the sorbent in the form of Cr(III), indicating that the Cr(VI) can be converted on the surface of the sorbent to a less harmful form Cr(III) due to the sorbent's chemical composition.

Electronic Structure of NdFeCoB Oxide Magnetic Particles Studied by DFT Calculations and XPS.

Neodymium-iron-boron magnetic oxide powders synthesized by sol-gel Pechini method were studied by using X-ray photoelectron spectroscopy (XPS) and quantum chemical modeling. The powder structure was examined by using X-ray diffraction (XRD) and modeled by using density functional theory (DFT) approximation. The electronic structures of the core and valent regions were determined experimentally by using X-ray photoelectron spectroscopy and modeled by using quantum chemical methods. This study provides important insights into the electronic structure and chemical bonding of atoms of NdFeCoB oxide particles with the partial substitution of Fe by Co atoms.

New Network Polymer Electrolytes Based on Ionic Liquid and SiO2 Nanoparticles for Energy Storage Systems.

Elementary processes of electro mass transfer in the nanocomposite polymer electrolyte system by pulse field gradient, spin echo NMR spectroscopy and the high-resolution NMR method together with electrochemical impedance spectroscopy are examined. The new nanocomposite polymer gel electrolytes consisted of polyethylene glycol diacrylate (PEGDA), salt LiBF4 and 1-ethyl-3-methylimidazolium tetrafluoroborate (EMIBF4) and SiO2 nanoparticles. Kinetics of the PEGDA matrix formation was studied by isothermal calorimetry. The flexible polymer-ionic liquid films were studied by IRFT spectroscopy, differential scanning calorimetry and temperature gravimetric analysis. The total conductivity in these systems was about 10-4 S cm-1 (-40 °C), 10-3 S cm-1 (25 °C) and 10-2 S cm-1 (100 °C). The method of quantum-chemical modeling of the interaction of SiO2 nanoparticles with ions showed the advantage of the mixed adsorption process, in which a negatively charged surface layer is formed from Li+ BF4- ions on silicon dioxide particles and then from ions of the ionic liquid EMI+ BF4-. These electrolytes are promising for use both in lithium power sources and in supercapacitors. The paper shows preliminary tests of a lithium cell with an organic electrode based on a pentaazapentacene derivative for 110 charge-discharge cycles.

Structure, Thermal Properties and Proton Conductivity of the Sulfonated Polyphenylquinoxalines.

This paper briefly reviews the results of scientific research on the proton conductivity of sulfonated polyphenylquinoxalines. Synthesis, structure (IR spectroscopy, SEM, quantum-chemical modeling, molecular weight distribution), moisture capacity, thermal properties, and proton conductivity of sulfonated polyphenylquinoxalines (sulfur content 2.6, 4.2, 5.5, and 7%) were studied. The relative stable configurations of sulfonated polyphenylquinoxalines with different positions of benzene rings and sulfogroups with the help of quantum chemical modeling were modeled. Sulfonation of the starting polyphenylquinoxalines was confirmed by IR spectroscopy and elemental analysis. The SEM method was used to study the surface of sulfonated polyphenylquinoxalines, and sulfonation regions were found. It was shown that sulfonated polyphenylquinoxalines contain water and are stable up to 250 °C; on further heating, the decomposition of the sulfogroups occurs. The conductivity of the obtained polymer electrolytes was studied by impedance spectroscopy, and long-term tests were carried out. It is shown that the proton conductivity at an ambient humidity of 98 rel. % reaches values 10-6-10-3 S/cm depending on the degree of sulfonation. It was shown that even after long-term storage in air (7 years), samples of sulfonated polyphenylquinoxalines with a high sulfur content of 7% at 98% air humidity have a conductivity of 8 × 10-4 S/cm.

New Nanosized Systems Doxorubicin-Amphiphilic Copolymers of N-Vinylpyrrolidone and (Di)methacrylates with Antitumor Activity.

Nanosized systems of DOX with antitumor activity on the base of micelle-like particles of amphiphilic thermosensitive copolymers of N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM), and N-vinylpyrrolidone and methacrylic acid (MAA) with TEGDM were explored. They were investigated in aqueous solutions by electron absorption spectroscopy, dynamic light scattering and cyclic voltammetry. Experimental data and quantum-chemical modeling indicated the formation of a hydrogen bond between oxygen-containing groups of monomer units of the copolymers and H-atoms of OH and NH2 groups of DOX; the energies and H-bond lengths in the considered structures were calculated. A simulation of TDDFT spectra of DOX and its complexes with the VP and TEGDM units was carried out. Electrochemical studies in PBS have demonstrated that the oxidation of encapsulated DOX appeared to be easier than that of the free one, and its reduction was somewhat more difficult. The cytotoxicity of VP-TEGDM copolymer compositions containing 1, 5 and 15 wt% DOX was studied in vitro on HeLa cells, and the values of IC50 doses were determined at 24 and 72 h of exposure. The copolymer compositions containing 5 and 15 wt% DOX accumulated actively in cell nuclei and did not cause visual changes in cell morphology.

Effect of the Solvate Environment of Lithium Cations on the Resistance of the Polymer Electrolyte/Electrode Interface in a Solid-State Lithium Battery.

The effect of the composition of liquid electrolytes in the bulk and at the interface with the LiFePO4 cathode on the operation of a solid-state lithium battery with a nanocomposite polymer gel electrolyte based on polyethylene glycol diacrylate and SiO2 was studied. The self-diffusion coefficients on the 7Li, 1H, and 19F nuclei in electrolytes based on LiBF4 and LiTFSI salts in solvents (gamma-butyrolactone, dioxolane, dimethoxyethane) were measured by nuclear magnetic resonance (NMR) with a magnetic field gradient. Four compositions of the complex electrolyte system were studied by high-resolution NMR. The experimentally obtained 1H chemical shifts are compared with those theoretically calculated by quantum chemical modeling. This made it possible to suggest the solvate shell compositions that facilitate the rapid transfer of the Li+ cation at the nanocomposite electrolyte/LiFePO4 interface and ensure the stable operation of a solid-state lithium battery.

Modeling the Energy Landscape of Side Reactions in the Cytochrome bc1 Complex.

Much of the metabolic molecular machinery responsible for energy transduction processes in living organisms revolves around a series of electron and proton transfer processes. The highly redox active enzymes can, however, also pose a risk of unwanted side reactions leading to reactive oxygen species, which are harmful to cells and are a factor in aging and age-related diseases. Using extensive quantum and classical computational modeling, we here show evidence of a particular superoxide production mechanism through stray reactions between molecular oxygen and a semiquinone reaction intermediate bound in the mitochondrial complex III of the electron transport chain, also known as the cytochrome b c 1 complex. Free energy calculations indicate a favorable electron transfer from semiquinone occurring at low rates under normal circumstances. Furthermore, simulations of the product state reveal that superoxide formed at the Q o -site exclusively leaves the b c 1 complex at the positive side of the membrane and escapes into the intermembrane space of mitochondria, providing a critical clue in further studies of the harmful effects of mitochondrial superoxide production.

Mesoporous Networks of N-Vinylpyrrolidone with (di)Methacrylates as Precursors of Ecological Molecular Imprinted Polymers.

Mesoporous polymer networks were prepared via the cross-linking radical copolymerization of non-toxic hydrophilic N-vinylpyrrolidone (VP) with triethylene glycol dimethacrylate (TEGDM) and poly(ethylene glycol) methyl ester methacrylate (PEGMMA) in bulk, using appropriate soluble and thermodynamically compatible macromolecular additives with a branched structure as porogens. The branched copolymers of various monomer compositions were obtained by radical copolymerization in toluene, controlled by 1-decanethiol, and these materials were characterized by a wide set of physical chemical methods. The specific surface areas and surface morphology of the polymer networks were determined by nitrogen low-temperature adsorption or Rose Bengal (RB) sorption, depending on the copolymer compositions and scanning electron microscopy. The electrochemical properties of RB before and after its encapsulation into a branched VP copolymer were studied on a glassy carbon electrode and the interaction between these substances was observed. Quantum chemical modeling of RB-VP or RB-copolymer complexes has been carried out and sufficiently strong hydrogen bonds were found in these systems. The experimental and modeling data demonstrate the high potency of such mesoporous polymer networks as precursors of molecularly imprinted polymers for the recognition of fluorescent dyes as nanomarkers for biomedical practice.

Aggregate Formation of Boron-Containing Molecules in Thermal Vacuum Deposited Films.

The spectral properties of new boron-containing dyes were studied. One-component (pure dyes) and composite "Alq3+dye" thin films were fabricated using the thermal vacuum deposition method. The positions of the transmission spectra maxima in a one-component film are different for different film thicknesses. The best correlation of the maxima positions of the dye transmission spectra in solid and liquid solutions was observed for thicknesses of films close to a few (up to 10) monolayers. On the other hand, the absorption spectra maxima positions of one-component dye films (upper 10 nm) and composite films with high concentration, did not match the corresponding positions of absorption spectra maxima recorded in solutions. Comparison of the absorption spectra in one-component dye films and in solutions indicates the presence of both monomers and their aggregates in one-component films (contrary to solutions where such processes of aggregation do not take place, even at very high concentrations). Simultaneously with aggregation manifestation in the absorption spectra, the intensity of fluorescence of one-component dye films dramatically decreases. A quantum chemical simulation of the possible relative arrangement of two dye molecules indicates that the most possible of the simplest types of aggregates are physical dimers. Films of practical importance (due to efficient energy transfer from host to guest molecules when all singlet excitons are captured) possess a high quantum yield of fluorescence when reaching an impurity concentration of a few percent (aggregation does not take place yet).

Theoretical modeling of sorption of metal ions on amino-functionalized macroporous copolymer in aqueous solution.

With regard to the harmful effects of heavy metals on human health and the environment, the demand for synthesis and investigation of macromolecules with large capacity of harmful substances sorption is ever greater. Quantum-chemical methods may be applied in structural modeling, prediction, and characterization of such molecules and reactions. Sorption of metal ions (Cu2+, Cd2+, Co2+, and Ni2+) to triethylenetetramine-functionalized copolymer poly(GMA-co-EGDMA)-teta was successfully modeled by quantum chemical calculations, at the B3LYP//6-311++G**/lanl2dz level. Optimized structures of metal complexes were used for calculation of real binding energy of metal ion within the complex (ΔEr). Solvent and hydrolyzation effects were essential for obtaining the objective values. Solvent effect was included in ΔEr by using the total solvation energy for reaction of formation of tetaOH complex (ΔEs1, the first approach) or by using dehydration energy of free metal ion (ΔEs2, the second approach). Experimental results were confirmed in our theoretical analyses (using the second approach). Graphical abstract Theoretical modeling of divalent metal ions sorption on triethylenetetramine-functionalized copolymer poly(GMA-co-EGDMA)-teta.