The temperature dependence of the Hildebrand solubility parameters of selected hydrocarbon polymers and hydrocarbon solvents: a molecular dynamics investigation.

CONTEXT: To determine the miscibility of liquids at high temperatures using the concept of Hildebrand solubility parameter δ , the current practice is to examine the difference in δ between two liquids at room temperature, assuming that δ is not sensitive to temperature. However, such an assumption may not be valid for certain polymer blends and solutions. Therefore, a knowledge of the δ values of the liquids of interest at high temperatures is desirable. The determination of δ at high temperatures, especially for high-molecular-weight polymers, is impossible, as polymers have vapor pressures of zero. To this end, molecular dynamics (MD) simulations provide a practical means for determining δ over a wide range of temperatures. In this work, we study the temperature dependence of δ of five hydrocarbon polymers: polyethylene (PE), isotactic and atactic polypropylene (i-PP and a-PP), polyisobutylene (PIB), and polyisoprene (PI) in five hydrocarbon solvents: n-pentane, n-hexane, n-dodecane, isobutene, and cyclohexane. The polymers are modeled as monodisperse chains with 100 repeat units. The average δ values of PE, i-PP, a-PP, PIB, and PI at 300 K are determined as 18.6, 14.9, 14.6, 14.3, and 16.4 MPa1/2, respectively, in a good agreement with experimental data. The δ values of these polymers at various temperatures are also determined. The temperature dependence of δ is fitted to two linear equations, one above and the other below the polymer's glass transition temperature Tg. The δ values are more sensitive to temperature at T ≥ Tg. The Tg values of the polymers, determined based upon their specific volumes and δ values agree with the experiment qualitatively. The determination of the temperature dependence of δ has a great potential for industrial applications, such as determining miscibility, developing polymeric organogelators as flocculants and oil spill treating agents, and identifying potential solvents and ideal processing temperatures. METHODS: The MD simulations are performed using the GROMACS 2022.3 package with optimized potential for liquid simulations-all atom (OPLS-AA) force field parameters. All polymers are built as extended chains using CHARMM-GUI Polymer Builder.

Density functional theory investigation of the contributions of π-π stacking and hydrogen bonding with water to the supramolecular aggregation interactions of model asphaltene heterocyclic compounds.

CONTEXT: A complex supramolecular process involving electrostatic and dispersion interactions and asphaltene aggregation is associated with detrimental petroleum deposition and scaling that pose challenges to petroleum recovery, transportation, and upgrading. The homodimers of seven heterocyclic model compounds, representative of moieties commonly found in asphaltene structures, were studied: pyridine, thiophene, furan, isoquinoline, pyrazine, thiazole, and 1,3-oxazole. The contributions of hydrogen bonding involving water bridges spanning between dimers and π-π stacking to the total interaction energy were calculated and analyzed. The distance between the planes of the aromatic rings is correlated with the π-π stacking interaction strength. All the dimerization reactions were exothermic, although not spontaneous. This was mostly modulated by the strength of the hydrogen bond of the water bridge and the π-π stacking interaction. Dimers bridged by two water molecules were more stable than those with additional water molecules or without any water molecule in the bridge. Energy decomposition analysis showed that the electrostatic and polarization components were the main stabilizing terms for the hydrogen bond interaction in the bridge, contributing at least 80% of the interaction energy in all dimers. The non-covalent interaction analysis confirmed the molecular sites that had the strongest (hydrogen bond) and weak (π-π stacking) attractive interactions. They were concentrated in the water bridge and in the plane between the aromatic rings, respectively. METHODS: The density functional ωB97X-D with a dispersion correction and the Def2-SVP basis set were employed to investigate supramolecular aggregates incorporating heterocycles dimers with 0, 1, 2, and 3 water molecules forming a stabilizing bridge connecting the monomers. The non-covalent interactions were analyzed using the NCIplot software and plotted as isosurface maps using Visual Molecular Dynamics.

Assessing the Novel Mixed Tutton Salts K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 for Thermochemical Heat Storage Applications: An Experimental-Theoretical Study.

In this paper, novel mixed Tutton salts with the chemical formulas K2Mn0.03Ni0.97(SO4)2(H2O)6 and K2Mn0.18Cu0.82(SO4)2(H2O)6 were synthesized and studied as compounds for thermochemical heat storage potential. The crystallographic structures of single crystals were determined by X-ray diffraction. Additionally, a comprehensive computational study, based on density functional theory (DFT) calculations and Hirshfeld surface analysis, was performed to calculate structural, electronic, and thermodynamic properties of the coordination complexes [MII(H2O)6]2+ (MII = Mn, Ni, and Cu), as well as to investigate intermolecular interactions and voids in the framework. The axial compressions relative to octahedral coordination geometry observed in the crystal structures were correlated and elucidated using DFT investigations regarding Jahn-Teller effects arising from complexes with different spin multiplicities. The spatial distributions of the frontier molecular orbital and spin densities, as well as energy gaps, provided further insights into the stability of these complexes. Thermogravimetry, differential thermal analysis, and differential scanning calorimetry techniques were also applied to identify the thermal stability and physicochemical properties of the mixed crystals. Values of dehydration enthalpy and storage energy density per volume were also estimated. The two mixed sulfate hydrates reported here have low dehydration temperatures and high energy densities. Both have promising thermal properties for residential heat storage systems, superior to the Tutton salts previously reported.

Evaluating crude oil distribution tendencies in a multi-phase aquatic system: Effects of oil type, water chemistry, and mineral sediment.

Planning for effective response to crude oil spills into water depends on evidence of oil behavior, including its tendency to become distributed throughout an aquatic system. An improved laboratory method is employed to quantitatively assess crude oil distribution among different layers that form after mixing within a multi-phase system of water and sediment. Mixtures of conventional crude oil or diluted bitumen with different water types in the presence or absence of mineral sediment are first mixed by a standard end-over-end rotary agitation protocol. After a settling period, each mixture's visibly distinct floating, surface oil (e.g., slick or emulsion), subsurface bulk water, and bottom layers are then separated. Finally, the masses of oil, water, and sediment constituting each layer are isolated, quantified, and compared. The novel results reveal how component properties affect oil distribution among layers to inform spill behavior models, risk assessments, and response plans, including applications of spill-treating agents.

Molecular dynamics investigation of the asphaltene-kaolinite interactions in water, toluene, and water-toluene mixtures.

Understanding the interactions of petroleum asphaltenes with mineral surfaces is important for diluted bitumen spill response and modeling. In this study, molecular dynamics and umbrella sampling simulations are performed using interfacially active and non-interfacially active asphaltene model compounds individually positioned near each of the surfaces of kaolinite in the presence of explicit solvent environments containing water, toluene, and mixtures of toluene and water in varying proportions. The interfacially active asphaltene bonds the strongest to the silicon oxide surface of kaolinite in pure water and the bonding weakens to nearly zero in toluene-water mixtures. The non-interfacially active asphaltenes bond to kaolinites silicon oxide surface in water about half as strongly as the interfacially active one in water and the bonding weakens in the presence of toluene. The number of non-hydrogen bonded contacts between the interfacially active asphaltene and the aluminum hydroxide surface of kaolinite increases as the proportion of toluene is increased and the contacts with water are decreased. In these conditions, the non-interfacially active asphaltenes do not form non-hydrogen bonded contacts with kaolinite. On the silicon oxide surface, the number of non-hydrogen bonded contacts of all asphaltenes with kaolinite tends to decrease as the proportion of toluene is increased and the contacts with water are decreased. The number of hydrogen bonds of the interfacially active asphaltene with water decreases as the proportion of toluene is increased. The radii of gyration indicate that the interfacially active asphaltene is extended in water and when adsorbed on kaolinite, and becomes compact as the proportion of toluene is increased. The simulation results highlight the competitive interfacial interactions in the complex scenario of diluted bitumen spills in the presence of water and clay minerals.

Comparison of O3, UV/O3, and UV/O3/PS processes for marine oily wastewater treatment: Degradation performance, toxicity evaluation, and flocs analysis.

Efficient on-site treatment technology is crucial for mitigating marine oily wastewater pollution. This work investigates the ozone (O3), ultraviolet (UV)/O3, UV/O3/persulfate (PS) processes for the treatment of marine oily wastewater, including degradation performance, acute toxicity evaluation, and oil flocs analysis in a benchtop circulating flow photoozonation reactor. Degradation performances have been studied by measuring the degradation rate of total oil concentrations, specific oil components (n-alkanes and polycyclic aromatic hydrocarbons (PAHs)), and total organic carbon (TOC). The results show that UV/O3/PS could significantly enhance the removal efficiency than the other two processes, with above 90% of removal efficiency in 30 min. Acute toxicity analysis further shows that the wastewater quality is significantly improved by four-fold of the EC50 of Vibrio fischeri, and the mortality of Artemia franciscana decreases from 100% to 0% after 48 h exposure. Further, the morphology and functional groups of flocs have been further characterized, showing that the floating flocs could be further degraded especially in UV/O3/PS process. Our study further raised discussions regarding the future on-site application of O3-based systems, based on the results generated from the treatment efficiency, toxicity, and flocs characterization. The regulation of the oxidation strength and optimization of the reaction systems could be a practical strategy for on-site marine oily wastewater treatment.

Crystal growth, crystal structure determination, and computational studies of a new mixed (NH4)2Mn1-xZnx(SO4)2(H2O)6 Tutton salt.

Tutton salts have been extensively explored in recent decades due to their attractive physical and chemical properties, which make them potential candidates for thermochemical heat storage systems and optical technologies. In this paper, a series of new mixed Tutton salts with the chemical formula (NH4)2Mn1-xZnx(SO4)2(H2O)6 is reported. Crystals are successfully grown by the solvent slow evaporation method and characterized by powder X-ray diffraction (PXRD) with Rietveld refinement. In particular, the crystal structure of the mixed (NH4)2Mn0.5Zn0.5(SO4)2(H2O)6 crystal is solved through PRXD data using the DICVOL06 algorithm for diffraction pattern indexing and the Le Bail method for lattice parameter and spatial group determination. The structure is refined using the Rietveld method implemented in TOPAS® and reported in the Cambridge Structural Database file number 2104098. Moreover, a computational study using Hirshfeld surface and crystal void analyses is conducted to identify and quantify the intermolecular interactions in the crystal structure as well as to determine the amount of free space in the unit cell. Furthermore, 2D-fingerprint plots are generated to evaluate the main intermolecular contacts that stabilize the crystal lattice. Density functional theory is employed to calculate the structural, thermodynamic, and electronic properties of the coordination [Zn(H2O)6]2+ and [Mn(H2O)6]2+ complexes present in the salts. Molecular orbitals, bond lengths, and the Jahn-Teller effect are also discussed. The findings suggest that in Mn-Zn salts several properties dependent on the electronic structure can be tuned up by modifying the chemical composition.

Synthesis, characterization, and thermal and computational investigations of the L-histidine bis(fluoride) crystal.

Nonlinear optical materials have been investigated recently due to their potential technological applications in information storage and communications. In this context, semi-organic crystals can effectively combine the desired nonlinear optical properties of amino acids with the promising mechanical and thermal properties of inorganic materials. In this work, we have synthesized and characterized a semi-organic crystal of the amino acid L-histidine and hydrofluoric acid and investigated the chemical interactions between the organic and inorganic moieties. The crystal of L-histidine bis(fluoride) has been produced by slow solvent evaporation and characterized by X-ray diffraction (XRD) crystallography and thermogravimetric and differential thermal analyses. The XRD conducted using the Rietveld method shows that the unit cell is orthorhombic with the P21212 space group and contains four L-histidine bis(fluoride) units. Both differential thermal analysis and temperature-dependent XRD show that the crystals are thermally stable up to 191°C and do not undergo phase transition. The computational Hirshfeld surface analysis of the crystal structure reveals the main intermolecular interactions. Density functional theory has been employed to calculate the ionic interaction energy and electrostatic potential maps and confirm the spontaneity of ionic association at 191°C. The combined experimental and computational results show that the thermal stability of the semi-organic L-histidine bis(fluoride) crystal makes it suitable for nonlinear optical applications in optical sensing and communication systems.

Computational Investigation of the Metal and Ligand Substitution Effects on the Structure and Electronic States of the Phosphoranimide Tetramer Complexes of Cu(I), Ni(I), Co(I), and Fe(I).

The structurally unique saddle-shaped paramagnetic tetrametallic clusters of Co(I) and Ni(I) with phosphoranimide ligands have been synthesized and proposed as catalyst precursors. The analogous Cu(I) nanocluster is planar and diamagnetic. These notable variations in geometry and ground electronic states indicate that the effect of metal and ligand substituents on the structure and electronic properties of these complexes requires investigation. We present a computational study of a series of these novel homoleptic complexes containing Co(I), Ni(I), and Cu(I) as well as Fe(I) coordinated to phosphoranimides with electron-donating and withdrawing substituents, conducted at the relativistic density functional theory level using ZORA-PBE/TZP. The optimized structures of the saddle-shaped Co(I) and Ni(I) and planar Cu(I) tetramers with linear N-M-N coordination are validated with respect to X-ray diffraction determinations. The ground-state analysis indicates that Cu(I) complexes are diamagnetic, whereas Ni(I) and Co(I) complexes are in high-spin states, in agreement with magnetic susceptibility measurements. The computational results show that Fe(I) complexes are saddle shaped and high spin. The Co(I) complex is stabilized by a metal macrocycle distortion from square to diamond, as elucidated from its Walsh diagram. The effects of metals and ligand substituents on the ground electronic state, metal center coordination environment, and energy of the complexes are investigated. The bulky tertiary butyl substituent causes the largest saddle-shape distortion of the tetramer marcocycle, which partially offsets its electron-donating effect. Macrocycle distortions with N-M-N site angles ranging from obtuse to alternating obtuse reflex are correlated with the increasing number of unpaired electrons. The phenyl-substituted complexes are expected to have the highest reactivity toward electrophiles. Understanding the interplay between structural and electronic parameters is intended to guide the development of synthetic cooperative systems for multielectron redox reactions, models of biological systems, and molecular magnets.

Advanced oxidation processes in microreactors for water and wastewater treatment: Development, challenges, and opportunities.

The miniaturization of reaction processes by microreactors offers many significant advantages over the use of larger, conventional reactors. Microreactors' interior structures exhibit comparatively higher surface area-to-volume ratios, which reduce reactant diffusion distances, enable faster and more efficient heat and mass transfer, and better control over process conditions. These advantages can be exploited to significantly enhance the performance of advanced oxidation processes (AOPs) commonly used for the removal of water pollutants. This comprehensive review of the rapidly emerging area of environmental microfluidics describes recent advances in the development and application of microreactors to AOPs for water and wastewater treatment. Consideration is given to the hydrodynamic properties, construction materials, fabrication techniques, designs, process features, and upscaling of microreactors used for AOPs. The use of microreactors for various AOP types, including photocatalytic, electrochemical, Fenton, ozonation, and plasma-phase processes, showcases how microfluidic technology enhances mass transfer, improves treatment efficiency, and decreases the consumption of energy and chemicals. Despite significant advancements of microreactor technology, organic pollutant degradation mechanisms that operate during microscale AOPs remain poorly understood. Moreover, limited throughput capacity of microreactor systems significantly restrains their industrial-scale applicability. Since large microreactor-inspired AOP systems are needed to meet the high-throughput requirements of the water treatment sector, scale-up strategies and recommendations are suggested as priority research opportunities. While microstructured reactor technology remains in an early stage of development, this work offers valuable insight for future research and development of AOPs in microreactors for environmental purposes.

Computational and infrared spectroscopic investigations of N-substituted carbazoles.

The carbazole moiety is a commonly identified structural motif in the high-molecular-weight components of petroleum, known as asphaltenes. Detailed characterization of carbazoles is important for understanding the structure of asphaltenes and addressing challenges in the areas of heavy oil recovery, transportation, upgrading, and oil spills, arising from asphaltene properties and composition. In this work we study carbazole and the four N-substituted carbazoles 9-methylcarbazole, 9-ethylcarbazole, 9-vinylcarbazole and 9-phenylcarbazole. Experimental far- and mid-infrared spectra of these five carbazoles are measured using transmission and photoacoustic techniques. The molecular structures of the monomers and the respective dimers, optimized at the ωB97X-D/6-311++G(d,p) level of the density functional theory (DFT), are subjected to harmonic vibrational frequency calculations. The effect of changing substituents on the N-H bond, π-π stacking distances, and angles between monomers within the dimers, in addition to intermolecular interactions, is investigated. Noncovalent interaction analysis is employed to highlight the areas of attractive and repulsive interactions in the dimers. Thermochemistry calculations show that the formation of dimers of all carbazoles is spontaneous at 298 K. Comparison of the calculated vibrational spectra of these compounds with experimental spectra indicates that the existence of both monomers and dimers must be invoked to account for the observed bands in the infrared spectra. Excellent correlations between the experimentally-determined and calculated harmonic vibrational energies are obtained, with an experimental-to-calculated scaling factor of 0.95-0.96. These findings highlight the coupled computational-experimental approach for the interpretation of vibrational spectra and are essential for improving the spectroscopic characterization of N-substituted carbazoles.

Direct mass spectrometric analysis of naphthenic acids and polycyclic aromatic hydrocarbons in waters impacted by diluted bitumen and conventional crude oil.

Crude oil spills have well-documented, deleterious impacts on the hydrosphere. In addition to macroscopic effects on wildlife and waterscapes, several classes of petroleum derived compounds, such as naphthenic acids (NAs) and polycyclic aromatic hydrocarbons (PAHs), may be released into the water and present aquatic contamination hazards. The concentrations of these contaminants may be affected by both oil type and water chemistry. We characterize the concentrations of NAs and PAHs in natural and constructed waters, spanning a range of pH and salinity, and directly compare the influence of diluted bitumen (DB) and conventional crude (CC) oil, using condensed-phase membrane introduction mass spectrometry (CP-MIMS) as a direct sampling, on-line technique. The concentration and isomer class profiles of classical NAs in the aqueous phase were assessed using electrospray ionization in negative-ion mode as [M-H]- whereas PAH concentrations were monitored using liquid electron ionization (LEI) in positive-ion mode as [M+•]. NA concentrations (0.03-25 ppm) were highly pH-dependent, and an order of magnitude greater in water samples contaminated with DB than CC. Conversely, concentrations of naphthalene (10-130 ppb) and alkyl-naphthalenes (10-90 ppb) were three to four-fold higher in water samples exposed to CC. We demonstrate that naturally occurring dissolved organic matter does not bias results from the membrane sampling approach employed, and that DB and CC contaminated waters can be differentiated using principal component analysis of the NA isomer class distribution in both constructed and natural waters. Finally, we describe the first demonstration of the concurrent analysis of trace NAs and PAHs in the same water sample by controlling perm-selectivity at the membrane and the ionization mode of the mass spectrometer. The techniques employed here for trace analysis of petroleum derived compounds in water can be applied to rapid screening and real-time monitoring of contamination and remediation processes.

COSMO-RS-Based Descriptors for the Machine Learning-Enabled Screening of Nucleotide Analogue Drugs against SARS-CoV-2.

Chemical similarity-based approaches employed to repurpose or develop new treatments for emerging diseases, such as COVID-19, correlates molecular structure-based descriptors of drugs with those of a physiological counterpart or clinical phenotype. We propose novel descriptors based on a COSMO-RS (short for conductor-like screening model for real solvents) σ-profiles for enhanced drug screening enabled by machine learning (ML). The descriptors' performance is hereby illustrated for nucleotide analogue drugs that inhibit the ribonucleic acid-dependent ribonucleic acid polymerase, key to viral transcription and genome replication. The COSMO-RS-based descriptors account for both chemical reactivity and structure, and are more effective for ML-based screening than fingerprints based on molecular structure and simple physical/chemical properties. The descriptors are evaluated using principal component analysis, an unsupervised ML technique. Our results correlate with the active monophosphate forms of the leading drug remdesivir and the prospective drug EIDD-2801 with nucleotides, followed by other promising drugs, and are superior to those from molecular structure-based descriptors and molecular docking. The COSMO-RS-based descriptors could help accelerate drug discovery for the treatment of emerging diseases.

Synthesis and Computational and Experimental Investigations of a para-Nicotinic Acid-Bridged Dirhenium(I) Dimer Complex.

The Re(I) dimer complex, [fac(CO)3(phen)Re1-N(py)COORe2(phen)fac(CO)3]+ (py = pyridine; phen = 1,10-phenanthroline), contains two different Re(I) centers 9.3 Å apart, one with a nitrogen donor and the other with an acetate donor from the bridging isonicotinate ligand. The complexes were characterized by 1H NMR, UV-vis, fluorescence, and IR spectroscopy, elemental analysis, and single-crystal X-ray diffraction. The absorption and emission properties of the dimer dominated by charge transfer transitions are analyzed with respect to those of the monomers, [fac(CO)3(phen)Re-N(pyCOOCH3)]+ and [fac(CO)3(phen)ReOOCCH3]. Spectral comparison of these three complexes results in the unexpected finding that the dimer emission (575 nm) occurs near that of the nicotinate-containing monomer (580 nm) rather than near the lower energy-emitting state (650 nm) of the acetate-containing monomer. Density functional theory (DFT) calculations elucidate this unusual emission behavior. The geometries of the dimer and two monomers are optimized in the singlet ground and lowest-energy triplet excited states (LLTS's) to interpret absorption and emission behaviors, respectively. The singlet excited states calculated using time-dependent DFT correlate well with the absorption spectra in the lowest-energy and other major electronic transitions. The energy gaps and low-lying singlet excited states of the dimer are close to those of the acetate-containing monomer. The lowest-energy Franck-Condon triplet excited state of the dimer arising from electronic transitions localized on the acetate moiety is unstable. The next higher Franck-Condon triplet excited state arises from long-range charge transfer transition, and its energy is close to that of the nicotinate-containing monomer. Optimization of the dimer LLTS yields a stable state based on a long-range charge transfer transition involving occupied orbitals partially localized on the bridging nicotinate moiety. The LLTS energies of the dimer and nicotinate-containing monomer are in very good agreement as are the emission energies of these complexes. The correlated spectroscopic and computational results corroborate to the understanding of charge transfer states and transitions toward the development of photosensitive compounds for photoelectrochemical solar energy conversion cells.

Development and application of an amylopectin-graft-poly(methyl acrylate) solidifier for rapid and efficient containment and recovery of heavy oil spills in aqueous environments.

Effective oil spill preparedness and response are crucial to ensure environmental protection and promote the responsible development of the petroleum industry. Hence, interest in developing new approaches and/or improving existing oil spill response measures has increased greatly in the past decade. Solidifiers are an attractive and underutilized option to mitigate the effects of oil spills, as they interact with oil to contain the spill, prevent it from spreading, and facilitate its removal from the environment. In this work, we have synthesized an inexpensive and easy-to-make natural-based sorbent, a subclass of solidifiers. Our amylopectin-graft-poly(methyl acrylate) (AP-g-PMA) sorbent is highly oleophilic and hydrophobic, and selectively solidifies diluted bitumen and conventional crude oil from biphasic mixtures of oil and water. The complete solidification of conventional crude oil and diluted bitumen by the AP-g-PMA sorbent occurs within 8 and 32 min, respectively, and even a low solidifier-to-oil ratio of 4% w/w is sufficient to enable complete recovery of diluted bitumen. This innovative natural-based polymeric sorbent may be applied as a key component of oil spill response procedures, especially for heavy oils. The AP-g-PMA sorbent combines the biodegradability and non-toxicity of the amylopectin with the hydrophobicity and oleophilicity of the synthetic polymer poly(methyl acrylate).

Distributions of diluted bitumen and conventional crude oil in a range of water types.

Concern about the impacts that accidental discharge of under-investigated, heavy petroleum products may have on aquatic environments has prompted a comparative examination of the behaviours of diluted bitumen (DB) and light conventional crude (CC) oil in different water types. Distributions of oil among the water column and floating water-in-oil (w/o) emulsion are evaluated by a novel, reproducible procedure involving mixing oil with water, then separating, extracting, and quantifying the total absolute oil content of the water column via gravimetric and gas-chromatographic (high-temperature simulated distillation) analyses. The CC contents of water columns tend to be significantly greater than those of DB under comparable conditions, while the fraction of oil remaining afloat at the water's surface is greater for DB than for CC. The elucidated phase distribution patterns have important implications pertaining to the recoverability of these oils in the event of their release into aquatic environments, which serves to inform best practices for oil spill response. For both DB and CC, oil contents within water columns are the highest in waters of low salinity and high pH. Water contents of buoyant w/DB emulsions are significantly greater than those of w/CC emulsions after 60 min at rest, and are the highest in waters of low salinity and low pH. The effect of crude oil on the pH of water is also studied, and DB is found to have a greater effect than CC on water samples of varying initial pH.

A DFT study of the interaction between [Cd(H2O)3]2+ and monodentate O-, N-, and S-donor ligands: bond interaction analysis.

A series of B3LYP/6-311+G(d,p) calculations of the affinity of monodentate ligands for [Cd(H2O)3]2+ are performed. Three types of ligands containing O (phosphine oxide, lactam, amide, carboxylic acid, ester, ketone, aldehyde, ether, halohydrin, enol, furan), N (thiocyanate, amine, ammonia, azide), and S (thioester, thioketone, thiol, thiophene, disulfide) interacting atoms are investigated. The results show that phosphine oxide has the largest affinity for the cadmium cation due to the polarization of the P=O bond. As the P atom has a large atomic radius, the O atom can polarize the electronic cloud enhancing its amount of electronic charge and favoring the interaction with Cd2+. The affinity order found is phosphine oxide > thioester > lactam > amide > carboxylic acid > ester > thioketone > ketone > thiocyanate > amine > ammonia > aldehyde > ether > thiol > thiophene > enol > halohydrin > disulfide > azide > furan ligands. These results were also corroborated by the functional M06-2X. The electronic effects (resonance and induction) of neighboring groups of the interacting atom modulate the strength of metal-ligand binding. For almost all the O-donor ligands the electrostatic component has the same magnitude as the covalent term, while for the N- and S-donor ligands the covalent term is predominant. The polarization term accounts for twice the exchange term as part of the covalent component. The dispersion term varies less than 2 kcal mol-1 for the complexes analyzed. The Pauli repulsion term is correlated with the metal ligand distance, increasing in the compounds with decreased metal-ligand bond length. The charge between the interacting atoms is also strongly correlated with both the interacting strength and the electrostatic interaction component. The natural bond orbital analysis highlights correlations of the bond order, and S and P contributions of the interacting metal-ligand orbital with the coordination strength. Graphical abstract The affinity of 20 monodentate ligands with different functional groups for the [Cd(H2O)3]2+ cation is calculated based on the interaction enthalpy and Gibbs free energy for the substitution of one water molecule from the fully hydrated cation. The affinity is correlated with geometric, electronic, and energetic parameters of the ligands and the complexes as well as with energy decomposition and natural bond order analyses results.

Application of solidifiers for oil spill containment: A review.

The need for new and/or improvement of existing oil spill remediation measures has increased substantially amidst growing public concern with the increased transportation of unconventional crudes, such as diluted bitumen products. Solidifiers may be a very good spill response measure to contain and mitigate the effects of oil discharge incidents, as these interact with the oil to limit hydrocarbon release into air and water, prevent it from adhering onto sediment and debris, and could allow for oil recovery and reuse. Solidifiers change the physical state of the spilled oil from liquid to a coherent mass by chemical interactions between the spilled oil and the solidifier. Currently, the use of solidifiers is limited to small spills near shorelines. To extend their use to large-scale spill containment operations, it is necessary to understand the mechanism of solidifier action and to establish consistent criteria for evaluation of their effectiveness. The research effort to date has been focused mainly on gelators and cross-linking agents, with particularly impressive advancements in the areas of phase-selective polymeric and small-molecule gelators. Substantial research efforts are needed to improve solidifier performance and integrate solidifiers as part of spill response procedures, particularly for acute oil spills involving unconventional petroleum products.

A density functional theory investigation of the interaction of the tetraaqua calcium cation with bidentate carbonyl ligands.

Calcium complexes with bidentate carbonyl ligands are important in biological systems, medicine and industry, where the concentration of Ca2+ is controlled using chelating ligands. The exchange of two water molecules of [Ca(H2O)6]2+ for one bidentate monosubstituted and homo disubstituted dicarbonyl ligand was investigated using the B3LYP/6-311++G(d,p) method. The ligand substituents NH2, OCH3, OH, CH3, H, F, Cl, CN and NO2 are functional groups with distinct electron-donating and -withdrawing effects that bond directly to the sp2 C atom of the carbonyl group. The geometry, charge and energy characteristics of the complexes were analyzed to help understand the effects of substituents, spacer length and chelation. Coordination strength was quantified in terms of the enthalpy and free energy of the exchange reaction. The most negative enthalpies were calculated for the coordination of bidentate ligands containing three to five methylene group spacers between carbonyls. The chelate effect contribution was analyzed based on the thermochemistry. The electronic character of the substituent modulates the strength of binding to the metal cation, as ligands containing electron-donor substituents coordinate stronger than those with electron-acceptor substituents. This is reflected in the geometric (bond length and chelating angle), electronic (atomic charges) and energetic (components of the total interacting energy) characteristics of the complexes. Energy decomposition analysis (EDA)-an approach for partitioning of the energy into its chemical origins-shows that the electrostatic component of the coordination is predominant, and yields relevant contribution of the covalent term, especially for the electron-withdrawing substituted ligands. The chelate effect of the bidentate ligands was noticeable when compared with substitution by two monodentate ligands. Graphical abstract The affinity of 18 bidentate carbonyl ligands toward the [Ca(H2O)4]2+ cation is evaluated in terms of energetic, geometric and electronic parameters of the isolated ligands and the substituted aqua complexes. The electronic effects-inductive and mesomeric-intrinsic to the molecular structure of each ligand are found to modulate the strength of the metal-ligand interaction. The effects of polysubstitution, chelation and the length of the alkyl spacers between the anchor points of the ligand are also analyzed.

Cellulose Aggregation under Hydrothermal Pretreatment Conditions.

Cellulose, the most abundant biopolymer on Earth, represents a resource for sustainable production of biofuels. Thermochemical treatments make lignocellulosic biomaterials more amenable to depolymerization by exposing cellulose microfibrils to enzymatic or chemical attacks. In such treatments, the solvent plays fundamental roles in biomass modification, but the molecular events underlying these changes are still poorly understood. Here, the 3D-RISM-KH molecular theory of solvation has been employed to analyze the role of water in cellulose aggregation under different thermodynamic conditions. The results show that, under ambient conditions, highly structured hydration shells around cellulose create repulsive forces that protect cellulose microfibrils from aggregating. Under hydrothermal pretreatment conditions, however, the hydration shells lose structure, and cellulose aggregation is favored. These effects are largely due to a decrease in cellulose-water interactions relative to those at ambient conditions, so that cellulose-cellulose attractive interactions become prevalent. Our results provide an explanation to the observed increase in the lateral size of cellulose crystallites when biomass is subject to pretreatments and deepen the current understanding of the mechanisms of biomass modification.