Polymers and oligomers derived from pyrrole and N-hydroxymethylpyrrole: A theoretical analysis of the structural and electronic properties

This work reports a theoretical investigation about the structural and electronic properties of polymers constituted by pyrrole and N-hydroxymethylpyrrole in both neutral and p-doped states. Ab initio quantum mechanical calculations were performed on neutral and positively charged oligomers to evaluate the bond length alternation pattern in the π-system, the molecular conformation, the π-π* transition energies and the ionization potential. Results, which have been extrapolated to infinite polymer chains, allow analyze the influence of N-hydroxyalkylation of polypyrrole on these properties.     

Photophysics of Structurally Modified Flavin Derivatives in the Blue‐Light Photoreceptor YtvA: A Combined Experimental and Theoretical Study

The light‐induced processes of two flavin mononucleotide derivatives (1‐ and 5‐deaza flavin mononucleotide, 1DFMN and 5DFMN), incorporated into the LOV domain of YtvA protein from Bacillus subtilis, were studied by a combination of experimental and computational methods. Quantum mechanics/molecular mechanics (QM/MM) calculations were carried out in which the QM part was treated by density functional theory (DFT) using the B3LYP functional for geometry optimizations and the DFT/MRCI method for spectroscopic properties, whereas the MM part was described by the CHARMM force field. 1DFMN is incorporated into the protein binding site, yielding a red‐shifted absorption band (λ_max=530 nm compared to YtvA wild‐type λ_max=445 nm), but does not undergo any LOV‐typical photoreactions such as triplet and photoadduct formation. QM/MM computations confirmed the absence of a channel for triplet formation and located a radiation‐free channel (through an S₁/S₀ conical intersection) along a hydrogen transfer path that might allow for fast deactivation. By contrast, 5DFMN‐YtvA‐LOV shows a blue‐shifted absorption (λ_max=410 nm) and undergoes similar photochemical processes to FMN in the wild‐type protein, both with regard to the photophysics and the formation of a photoadduct with a flavin‐cysteinyl covalent bond. The QM/MM calculations predict a mechanism that involves hydrogen transfer in the T₁ state, followed by intersystem crossing and adduct formation in the S₀ state for the forward reaction. Experimentally, in contrast to wild‐type YtvA, dark‐state recovery in 5DFMN‐YtvA‐LOV is not thermally driven but can only be accomplished after absorption of a second photon by the photoadduct, again via the triplet state. The QM/MM calculations suggest a photochemical mechanism for dark‐state recovery that is accessible only for the adduct with a C4a? S bond but not for alternative adducts with a C5? S bond.     

Structural properties,electronic structures and optical properties of WB2 with different structures: A theoretical investigation

The structural, electronic and optical properties of six WB₂ diborides with hP3, hP6, hP12, oP6, hR9 and hR18 structures were systematically investigated using the first-principles calculation based on density functional theory. The optimized atomic coordinates and lattice parameters agree well with the corresponding experimental and theoretical results. All WB₂ are energetically stable, and hP6-WB₂ has the best phase stability and hP3-WB₂ shows the worst phase stability. The results of density of states and the charge density differences indicate that WB₂ have the strong W–B and B–B covalent bonds. The hardness was obtained from the Mulliken population. The predicted values of absorption coefficient α(ω) and reflectivity R(ω) reveal that the laser with a longer wavelength is recommended during the synthesis of WB₂ coatings on the substrate surface using the Nd-YAG laser. Finally, the anisotropy in optical properties for WB₂ was discussed via the polycrystalline and directional static dielectric constants ε₁(0) and static refractive indexes n(0).     

Electronic structures and molecular properties of FLBDOB and its derivatives: A combined experimental and theoretical study

Theoretical studies on a new unsymmetrical electrolyte salt, lithium [3-fluoro-1,2-benzenediolato(2-)-o,o′ oxalato]borate (FLBDOB), and its derivatives, lithium bis[3-fluoro-1,2-benzenediolato(2-)-o,o]borate (FLBBB), and lithium bis(oxalate)borate (LBOB) are carried out using density functional theory (DFT) method and B3LYP theory level. Bidentate structures involving two oxygen atoms are preferred. Based on these conformations, a linear correlation is observed between the highest occupied molecular orbital (HOMO) energies and the limiting oxidation potentials measured by linear sweep voltammetry, which supports experimental results that strongly electron-withdrawing substituent anions are more resistant against oxidation. The correlations are also observed between ionic conductivity and binding energy, solubility and theoretical set of parameters of anion, thermal stability and the hardness (η). Wave function analyses are performed by natural bond orbital (NBO) method to further investigate the cation-anion interactions.     

Poly(ester amide)s derived from tartaric and succinic acids: Changes in structure and properties upon hydrolytic degradation

The changes in structure and properties taking place in a set of tartaric acid‐based polyamides and poly(ester amide)s upon hydrolytic degradation were examined. Poly(hexamethylene 2,3‐di‐O‐methyl‐L ‐tartaramide)s, either pure or containing minor amounts of succinate ester groups (≤10%), were exposed to humidity or incubated in buffered water at pH 7.4 and 37°C, and their thermal and mechanical properties were evaluated as a function of time. Both moisture uptake and hydrolysis induced a noticeable decay in the tensile properties of polymers. These effects were greatly enhanced by the presence of ester groups, whereas no large differences were noticed for changes in the enantiomeric composition. Variations in the glass transition temperatures and melting points appeared to be slight, whereas crystallinity clearly increased with incubation time. The latter effect was most apparent in poly(ester amide)s with a nearly racemic composition, in which a crystal‐to‐crystal transition was observed to take place upon degradation. © 2000 John Wiley & Sons, Inc. J Appl Polym Sci 78: 486–494, 2000     

On the correlation of some theoretical and experimental parameters in polycondensation cross-linked networks

The use of the equation f = km/αE, correlating number of degrees of freedom m of polymer segments between cross-linking nodes in polycondensation networks to the energy of interaction polymer segment/polymer segment, both within the same polymer and at different polymers interfaces, through measures of deflection in bending by dynamic thermomechanical analysis, yields a number of consequences of interest in the field of polycondensation-hardened networks and of their process of hardening. From this equation, regression equations correlating only two parameters are obtained, which render easier the determination of the parameters that are more difficult or lengthy to obtain by experimental means. The process of networking, hence of the reaction of polycondensation between the gel point and complete hardening of the network, can be followed by the determination of the average number of degrees of freedom m of the polymer segments between cross-linking nodes obtained through these equations. Even the equation of Carrothers can be adapted through the use of the average number of degrees of freedom of polymer segments between cross-linking nodes to describe the course of the polycondensation after the gel point and up to complete stable networking. The dependence from the temperature of m can be connected to both the rate constant of advancement of the network and to the correlation of the value of m of the system to its glass transition temperature. Peculiarities in gel point forecasting by Flory's and Carrothers' theories, which depend on the well-known existence of reactions of cyclization during polycondensation and by a thermodynamic temperature dependence not previously recognized, indicate that the gel point predicted by each theory fails to consider the existence of one and one only of these effects for each theory. On this theoretical basis, the combination of the two theories into a single, simple equation, which can still be used with ease at the applied level, leads to much better precision of forecasting of the gel point than any of the two theories from which the equation is derived and than any of the more complex theories in this field. © 1996 John Wiley & Sons, Inc. J Appl Polym Sci 63: 603–617, 1997     

Acid-base properties of copper oxides and fluorides by means of band calculations: Relevance to metal-polymer adhesion

Classification of acids and bases in the Lewis sense implies electronic participation and it is extendable to non-protonic solvent interactions as well as solventless reactions. In many microelectronic applications, interfacial interactions between a polymer and a metal occur and contribute to the resulting adhesion of the bond. In the practical sense, metal surfaces are either oxidized or can be chemically altered by process conditions; therefore, the interaction is through a modified surface. The present study shows how tight binding calculations of the extended Hückel type can be used to estimate the relative acid strengths of copper, its oxides and fluorides. The trends obtained from bulk and surface layers in each case were related to the Fermi level of the crystal and the number of empty states derived from the copper 3d orbitals. Our results show the relative acid strengths follow the trend: CuF₂ > CuO > CuF ~ Cu₂O > Cu The methods used here can be directly applicable to classify the relative acid strengths of other metal-based substrates.     

In silico theoretical molecular modeling for Alzheimer's disease: the nicotine-curcumin paradigm in neuroprotection and neurotherapy

The aggregation of the amyloid-β-peptide (AβP) into well-ordered fibrils has been considered as the key pathological marker of Alzheimer's disease. Molecular attributes related to the specific binding interactions, covalently and non-covalently, of a library of compounds targeting of conformational scaffolds were computed employing static lattice atomistic simulations and array constructions. A combinatorial approach using isobolographic analysis was stochastically modeled employing Artificial Neural Networks and a Design of Experiments approach, namely an orthogonal Face-Centered Central Composite Design for small molecules, such as curcumin and glycosylated nornicotine exhibiting concentration-dependent behavior on modulating AβP aggregation and oligomerization. This work provides a mathematical and in silico approach that constitutes a new frontier in providing neuroscientists with a template for in vitro and in vivo experimentation. In future this could potentially allow neuroscientists to adopt this in silico approach for the development of novel therapeutic interventions in the neuroprotection and neurotherapy of Alzheimer's disease. In addition, the neuroprotective entities identified in this study may also be valuable in this regard.     

Application of FTIR spectroscopy to determine transport properties and water-polymer interactions in polypropylene (PP)/poly(ethylene-co-vinyl alcohol) (EVOH) blend films: Effect of poly(ethylene-co-vinyl alcohol) content and water activity

This paper reports the use of FTIR spectroscopy along with gravimetric analysis to simultaneously study water sorption, transport properties and water-polymer interactions in PP/EVOH films at 25 °C, as a function of EVOH content and water vapour activity. The results indicate the existence of two different mechanisms, below (dual-mode) and above a critical concentration value close to the clustering limit activity. Several spectroscopically distinguishable “types” of sorbed water molecules with different diffusion rates have been detected, and their evolution as a function of the penetrant concentration followed. The main changes in the water structure take place from the clustering limit activity onwards. Significant differences both in the state of water and diffusion sequence of free/bound water have been found between 90/10 PP/EVOH films and blends with EVOH content ≥20%, suggesting not only composite-dependence but also morphology-dependence.     

1-(2-Hydroxyethyl)-2-imidazolidinone as corrosion inhibitor of mild steel in 0.5 M HCl solution: thermodynamic,electrochemical and theoretical studies

The inhibition effect of 1-(2-Hydroxyethyl)-2-imidazolidinone (2-HEI) on mild steel (MS) corrosion in 0.5?M HCl solution was investigated at different inhibitor concentration and temperature by electrochemical experiments, such as linear polarization resistance (LPR), electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and quantum chemical calculations. The inhibitor adsorption process on mild steel in 0.5?M HCl system was studied at different temperatures (20?°C–50?°C). Furthermore, the surface morphology of MS was also investigated with SEM in the absence and the presence of inhibitor. The adsorption of 1-(2-Hydroxyethyl)-2-imidazolidinone on MS surface is an exothermic process and this process obeys the Langmuir adsorption isotherm. The Quantum chemical findings are good agreed with the empirical data.     

Proline residues in transmembrane helices of channel and transport proteins: a molecular modelling study

Proline residues are commonly found in putative transbilayerhelices of many integral membrane proteins which act as transporters,channels and receptors. Intramembranous prolines are often conservedbetween homologous proteins. It has been suggested that suchintrahelical prolines provide liganding sites for cations viaexposure of the backbone carbonyl oxygen atoms of residues i-3and i-4 (relative to the proline). Molecular modelling studieshave been carried out to evaluate this proposal. Bundles ofparallel proline-kinked helices are considered as simplifiedmodels of ion channels. The energetics of K⁺ ion-helix bundleinteractions are explored. It is shown that carbonyl oxygensexposed by the proline-induced kink and at the C-terminus ofthe helices may provide cation-liganding sites. ‘Hybrid’bundles of antiparallel helices, only some of which containproline residues, are considered as models of transport proteins.Again, praline-exposed carbonyi oxygens are shown to be capableof liganding cations. The roles of -helix dipoles and of thegeometry of helix packing are considered in relation to cation-bundleinteractions. Implications with respect to modelling of ionchannel and transport proteins are discussed     

Investigation of optical properties: Eu with Al codoping in aluminum silicate glasses and glass‐ceramics

Eu‐doped transparent oxyfluoride aluminosilicate glass was prepared by controlling with Al codoping of melt‐quenched glass fabricated under air atmosphere. In the presence of Al input, the photoluminescence emission spectra under 393 nm excitation shows a blue shift by adjusting the ratio of Eu³⁺ and Eu²⁺. After heat treatment of glass, the ratio of Eu³⁺ and Eu²⁺ of luminescence emission were changed by controlling treatment temperature. The PL intensity of Eu³⁺ and Eu²⁺ ions in the glass‐ceramics (GC) was much stronger than in the precursor glass (PG). The possible mechanism responsible for color tuneability of the ratio of Eu³⁺ and Eu²⁺ doped was discussed.     

Microwave irradiation-induced alterations in physicochemical properties and methane adsorption capability of coals: An experimental study using carbon molecular sieve

In order to comprehend the applicability of microwave irradiation for recovering coalbed methane, it is necessary to evaluate the microwave irradiation-induced alterations in coals with varying levels of metamorphism. In this work, the carbon molecular sieve combined with KMn O4oxidation was selected to fabricate carbon molecular sieve with diverse oxidation degrees, which can serve as model substances toward coals. Afterwards, the microwave irradiation dependences of pores, functional groups, and highpressure methane adsorption characteristics of model substances were studied. The results indicated that microwave irradiation causes rearrangement of oxygen-containing functional groups, which could block the micropores with a size of 0.40-0.60 nm in carbon molecular sieve; meanwhile, naphthalene and phenanthrene generated by macro-molecular structure pyrolysis due to microwave irradiation could block the micropores with a size of 0.70-0.90 nm. These alterations in micropore structure weaken the saturated methane adsorption capacity of oxidized carbon molecular sieve by 2.91%-23.28%, suggesting that microwave irradiation could promote methane desorption. Moreover, the increased mesopores found for oxidized carbon molecular sieve after microwave irradiation could benefit CH₄ diffusion. In summary, the oxidized carbon molecular sieve can act as model substances toward coals with different ranks. Additionally, microwave irradiation is a promising technology to enhance coalbed methane recovery.     

The modelling technology of protective silicone coatings in terms of selected physical properties: Hydrophobicity,scrub resistance and water vapour diffusion

This paper deals with an analysis of the simultaneous influence of the factors of the silicone coating manufacturing process, such as the contents of the organic and silicone resins used in the paint formulations, on selected physical parameters determining the quality of the coatings: hydrophobicity, resistance to wet scrubbing and the ability to diffuse water vapour through the coatings. This analysis was performed using statistical models based on multiple regression analysis. The proposed statistical models proved to be useful for the optimization of the recipe configurations for silicone coatings. Combining the analysis results enabled the selection of the optimal ranges of values for the analysed factors, from a physical as well as an economic point of view.     

Thermal behaviour, redox properties, and catalytic performance of alkali-promoted V2O5 catalysts in the selective oxidation of p-methoxytoluene: a comparative study

Alkali-promoted V₂O₅ catalysts M–V₂O₅ (M=Li, K, Cs) were synthesised by impregnation of V₂O₅ with alkali sulphate solution. Pure V₂O₅ was used for comparison. X-ray diffraction, spectroscopic (FTIR), and thermoanalytical methods (STA/MS) have been used to characterise the phase composition, the adsorption properties, and the reducibility of the catalysts. The catalytic performance was proved using the oxidation of p-methoxytoluene (PMT) to p-methoxybenzaldehyde (PMBA) as test reaction. The surface acidity is lowered, but the reducibility is enhanced with increasing size and basic properties of the alkali cation. This leads to an increased adduct (PMT) adsorption and decreased product (PMBA) adsorption in the order V₂O₅2O₅K–V₂O₅2O₅. Consequently, the catalytic performance is improved in the same way. The formation of bronze phases at relative low temperatures in the case of K– and Cs–V₂O₅ stabilise V⁴⁺ oxidation state and improve the redox properties and consequently the catalytic results. The admixture of the non-reactive pyridine enhances the aldehyde selectivity by further lowering of the surface acidity. Additionally, pyridinium cations generated during catalytic reaction and incorporated into the formed alkali bronze phases stabilise these structures.     

The role of Co ion substitution in SnFe2O4 spinel ferrite nanoparticles: Study of structural,vibrational, magnetic and optical properties

In order to accurately investigate the effect of cobalt substitutions in tin ferrite (SnFe₂O₄) properties, we prepared Co_xSn_1-xFe₂O₄ nanoparticles for different Co concentrations, x?=?0.0, 0.25, 0.50, 0.75, and 1.00 using a simple co-precipitation method. X-ray diffraction (XRD), Fourier transformed infrared spectroscopy (FTIR), vibrating sample magnetometer (VSM), field emission scanning electron microscopy (FESEM), Energy-dispersive X-ray spectroscopy (EDX) and diffuse reflectance spectra (DRS) are used to study of structural, magnetic, morphology, and optical properties. The XRD and FTIR results confirmed the formation of cubic spinel structure. The lattice parameter and unit cell volume of tin ferrite nanoparticles were found to increase by entering and increasing Co⁺² content in 0.25, and then significantly decrease for higher contents. In accordance with the XRD results, a slight shift in main band υ₁ (${\mathit{Fe}}_{\mathrm{tetra}}^{+3}?O)$ to lower wavenumber and then to higher wavenumber were observed in the IR spectra of Co content x?<?0.25 and x?>?0.25, respectively. In turn to, saturation magnetization, remanent magnetization and anisotropy constant of SnFe₂O₄ nanoparticles were gradually increased for x?=?0.50 and then decreased for x?>?0.50.     

Sn-ZSM-12, a new,large pore MTW type tin-silicate molecular sieve: synthesis,characterization and catalytic properties in oxidation reactions

A new large pore tin-silicate analogue of zeolite ZSM-12 (MTW topology) with Si/Sn molar ratio >70 has been synthesized hydrothermally using a new template, hexamethylene bis(benzyl dimethyl ammonium hydroxide). This material exhibits an expansion in unit cell volume (XRD), an IR band at 970 cm^–1 and a charge transfer band at 205 nm in the UV-Vis region indicating the presence of Si-O-Sn units with Sn⁴⁺ centers in T_d configuration. Sn-ZSM-12 catalyzes the oxidation of phenol,m-cresol andm-xylene using dilute H₂O₂ as an oxidizing agent.     

Characterisation and modelling of the transport properties in lithium battery gel electrolytes: Part I. The binary electrolyte PC/LiClO4

A recent development trend for rechargeable lithium batteries is the use of ternary gel electrolytes. The main advantage of the gels is the mechanical rigidity, which improves as the polymer content is increased. However, the transport properties deteriorate with increasing polymer amount. This dualistic optimisation problem has caused an increased interest in understanding the transport processes in gels, however no full characterisation or modelling study could be found in the literature. In this paper, which is the first part of a study of the transport in the ternary gel system PMMA/PC/LiClO₄, the liquid electrolyte PC/LiClO₄ is characterised and modelled for concentrations between 0.1 and 2 M according to a previously employed methodology, based on electrochemical measurements. A model using concentration dependent interaction parameters proved to describe the results in the whole concentration region well. The cationic transport number and salt diffusivity were determined to be approximately 0.3 and 1e−10 m²/s, respectively. The mean ionic activity factor variations prove to be substantial. Furthermore, it was demonstrated that the inter-ionic friction was important to consider at concentrations above 1 M. The fundamental friction parameters determined in this part will be used in the following part of the study to describe the friction between ions and solvent.     

Monitoring the Bi/Fe ratio at different pH values in BiFeO3 nanoparticles derived by normal and reverse chemical co-precipitation: A comparative study on the purity,microstructure and magnetic properties

Co-precipitation method was utilized for multiferroic ${\mathrm{BiFeO}}_3$(BFO) nanoparticles synthesis. The influence of different pH values on BFO powders properties was investigated. Thermogravimetric-differential thermal analysis (TG-DTA) technique indicated that optimal calcination and Curie temperatures are 550 °C and 818.7 °C. The precursor samples atomic absorption spectroscopy (AAS) results illustrate Bi and Fe atoms non-homogeneous distribution in normal co-precipitated samples. The phase formation and existence of transient phases like Bi₂₅FeO₃₉ and Bi₂Fe₄O₉ were studied by X-ray diffractometry (XRD). Nanopowders morphological features were characterized using field emission scanning electron microscopy (FESEM). Presence of absorption bands at 400–3600 cm^?1 was investigated by Fourier transformed infrared (FTIR) spectroscopy; and magnetic properties of synthesized powders were measured using vibration sample magnetometery (VSM). Results revealed that BFO powders have an R3c crystal structure. FESEM micrographs showed powders with pseudo-cubic shape and average particles size of 41.3 nm and 70.4 nm for normally and reversely synthesized powders. Magnetic hysteresis loops demonstrated a weak ferromagnetic behavior of the samples at room temperature. Due to the fact that the as-prepared powders particles size was lower than that of the spiral spin cycloid (62 nm) and that the nanoparticles surface-to-volume ratio was high and, in turn, led to more uncompensated spins, the weak ferromagnetic behavior was observed. Besides, the pH value decrement improved magnetization from 0.11 emu/g for pH = 10.5–0.2 emu/g for pH = 8.5.