A molecular‐thermodynamic approach to predict the micellization of binary surfactant mixtures containing amino sulfonate amphoteric surfactant and nonionic surfactant

A molecular‐thermodynamic approach was adopted to predict the value of mixed critical micelle concentration (cmc) for the binary surfactant mixtures constituted by an amino sulfonate amphoteric surfactant, sodium 3‐(N‐dodecyl ethylenediamino)‐2‐hydropropyl sulfonate (abbr. C12AS), and a nonionic surfactant, octylphenol polyethylene ether (OP‐n, where n denotes the average number of oxyethylene glycol ether). In this investigation, considering two positive charges on the hydrophilic group of C12AS, which is unlike to conventional zwitterionic surfactants having one positive charge (such as, alkylbetaine, etc.), three schemes were designed to obtain the geometric parameter describing the dipole structure of C12AS. According to the selected optimum scheme, four cases corresponding to the different conformations of both the headgroup and the hydrocarbon chain of surfactant were discussed. The results show that the predicted value of mixed cmc for the C12AS/OP‐n mixtures agrees well with the experiment value. The deviation of the predicted value from the experimental value can be explained by the effect of the hydrophilicity of OP‐n on the process of micellization. © 2017 American Institute of Chemical Engineers AIChE J, 2017     

Characterization of methyl‐substituted polyamides used for reverse osmosis membranes by positron annihilation lifetime spectroscopy and MD simulation

Three kinds of polyamides were synthesized from three diamines and 1,3,5‐benzenetricarbonyl trichloride (TMC). The diamines used were m‐phenylene diamine, N‐methyl‐m‐phenylenediamine, and N,N′‐dimethyl‐m‐phenylenediamine. The average free volume sizes of the polyamides were measured by positron annihilation lifetime spectroscopy (PALS), and the free volume fractions were evaluated by molecular dynamics (MD) simulations. The methyl substitution on amino groups of diamines brought about an increase in interstitial space of molecular chains of the polyamides. In addition, reverse osmosis (RO) membranes were prepared by interfacial polymerization from the three diamines and TMC. The increase in the degree of methyl‐substitution of diamines led to increased chlorine resistance and decreased salt rejections of the polyamide RO membranes. Thus, the methyl‐substitution of diamines significantly influenced membrane performance. The vacancy sizes and fractional volumes in polyamides evaluated by PALS measurement and MD simulation were well correlated with salt rejection of polyamide RO membranes. © 2009 Wiley Periodicals, Inc. J Appl Polym Sci, 2009     

A new insight to validation of local composition models in binary mixtures using molecular dynamic simulation

A computational method based on molecular dynamics (MD) simulation is developed to predict the interaction parameters in local composition (LC) models such as Wilson, nonrandom two‐liquid (NRTL), and universal quasichemical activity coefficient (UNIQUAC) applicable in vapor‐liquid equilibrium calculations so that LC models are validated. The five binary mixtures of water‐acetonitrile, water‐isopropanol, methanol‐chloroform, acetone‐cyclohexane, and meta xylene‐benzene were simulated. The MD simulations are performed using the condensed phase optimized molecular potential for atomistic simulation studies force field and all ranges of radial distribution function (RDF) are considered. In addition, the interaction parameters are determined by optimization through experimental data and are compared with the MD results. The interaction parameters are calculated through RDF where the effective radius is investigated by experimental data. The present results demonstrate that interaction parameters are composition dependent which are best fitted by a third‐order polynomial relation. Based on the deviation in the activity coefficients, the results of the UNIQUAC model are more accurate than Wilson and NRTL models. © 2015 American Institute of Chemical Engineers AIChE J, 62: 275–286, 2016     

A Combined Solid‐State NMR and MD Characterization of the Stability and Dynamics of the HET‐s(218‐289) Prion in its Amyloid Conformation

Dynamic and rigid : The prion HET‐s(218–289) consists, in its amyloid form as shown here, of highly ordered and rigid parts and a very dynamic loop, which could be of great importance for fibril formation. Indeed, MD simulations explain the experimental NMR results and describe the dynamics of the salt‐bridge network that stabilizes the amyloid fibril, a feature not easily accessible by experiment.

     

Conformational Analysis of a High‐Mannose‐Type Oligosaccharide Displaying Glucosyl Determinant Recognised by Molecular Chaperones Using NMR‐Validated Molecular Dynamics Simulation

Exploration of the conformational spaces of flexible oligosaccharides is essential to gain deeper insights into their functional mechanisms. Here we characterised dynamic conformation of a high‐mannose‐type dodecasaccharide with a terminal glucose residue, a critical determinant recognised by molecular chaperones. The dodecasaccharide was prepared by our developed chemoenzymatic technique, which uses ¹³C labelling and lanthanide tagging to detect conformation‐dependent paramagnetic effects by NMR spectroscopy. The NMR‐validated molecular dynamics simulation produced the dynamic conformational ensemble of the dodecasaccharide. This determined its spatial distribution as well as the glycosidic linkage conformation of the terminal glucose determinant. Moreover, comparison of our results with previously reported crystallographic data indicates that the chaperone binding to its target oligosaccharides involves an induced‐fit mechanism.     

Synthesis of a hole‐containing polypyrrole film modified by copper cementation

A simple procedure enables to obtain a hole‐containing PPy film on SAE 4140 steel in sodium bis(2‐ethylhexyl) sulfosuccinate (AOT) solutions. The film characterization was made by electrochemical and morphological studies. The effects of electropolymerization parameters on the obtained morphology are discussed. The formation of the coating is conditioned by the nature of the substrate and surfactant and the electrochemical technique employed. Electrochemical investigations demonstrate that the hole‐containing PPy film presents an increase in surface area. The polymer was modified by cementation of copper particles. The modified polymer offers a higher electrocatalytic activity for the HER than usual PPy. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016 , 133, 43650.     

Development of 3D polymer DFT and its application to molecular transport through a surfactant‐covered interface

We have developed a three‐dimensional polymer density functional theory (DFT) and applied it to predict the thermodynamic and structural information of molecular transport through a surfactant‐covered interface. The green recursive function method has been employed to consider the chain conformation effect. The reference ideal gas method has been developed, extending it from molecular DFT to polymer DFT, with a universal form to calculate thermodynamic properties such as the grand potential and free energy. We have demonstrated the accuracy of the theory by comparing it to available simulations. Furthermore, we have applied the theory to predict the free energy barrier and density profile of molecular transport through a surfactant‐covered interface. The free energy profile provides reasonable predictions of the transition velocity, while the density profile gives insight into the microstructural information of the transport process, which is consistent with the available molecular simulations. © 2017 American Institute of Chemical Engineers AIChE J, 63: 238–249, 2018     

A low‐disturbance nonequilibrium molecular dynamics algorithm applied to the determination of thermal conductivities

A new nonequilibrium molecular dynamics algorithm is proposed for the determination of thermal conductivity and other transport properties. The proposed algorithm aims at diminishing the energy drift problem observed in this type of method while conserving linear momentum and being compatible with constrained molecules. The features of the proposed algorithm are evaluated by determining thermal conductivities of water at 323 K, n‐octane at 300 K, and argon close to its triple point, and by comparing these results with those obtained using established methods. The analysis of systems presenting diverse molecular characteristics allowed us to assess the usefulness of the proposed algorithm. The energy drift and temperature variation were reduced in the range of 10–80%, depending on the parameters of the proposed algorithm and the characteristics of the system. The determined thermal conductivities showed good agreement when compared to experimental and simulation data. © 2015 American Institute of Chemical Engineers AIChE J, 61: 2881–2890, 2015     

The effect of soft bake on adhesion property between SU‐8 photoresist and Ni substrate by molecular dynamics simulation

SU‐8 photoresist is a negative, epoxy‐type, near UV photoresist and is commonly used in micro electro mechanical systems (MEMS) and other thick resist application fields. However, poor adhesion strength between SU‐8 photoresist and metal substrate makes it difficult to bind, even contributes to the lithography failure. This significantly restricts the improvement of image resolution and depth‐to‐width ratio. As soft bake temperature and time are important for the interfacial adhesion property, in this article, molecular dynamics (MD) simulation was performed to investigate the effects of these two parameters on adhesion property between SU‐8 photoresist and Ni substrate. According to the adsorption theory, the simulation results were analyzed and validated by experiments. It is shown that with increasing soft bake temperature the adhesional work firstly increases and then decreases, and with increasing soft bake time the adhesional work decreases. This study provides theory basis for the confirmation of soft bake parameters. © 2012 Wiley Periodicals, Inc. J. Appl. Polym. Sci., 2013     

Indolo[3,2‐c]quinoline G‐Quadruplex Stabilizers: a Structural Analysis of Binding to the Human Telomeric G‐Quadruplex

A library of 5‐methylindolo[3,2‐c]quinolones (IQc) with various substitution patterns of alkyldiamine side chains were evaluated for G‐quadruplex (G4) binding mode and efficiency. Fluorescence resonance energy transfer melting assays showed that IQcs with a positive charge in the heteroaromatic nucleus and two weakly basic side chains are potent and selective human telomeric (HT) and gene promoter G4 stabilizers. Spectroscopic studies with HT G4 as a model showed that an IQc stabilizing complex involves the binding of two IQc molecules (2,9‐bis{[3‐(diethylamino)propyl]amino}‐5‐methyl‐11H‐indolo[3,2‐c]quinolin‐5‐ium chloride, 3 d ) per G4 unit, in two non‐independent but equivalent binding sites. Molecular dynamics studies suggest that end‐stacking of 3 d induces a conformational rearrangement in the G4 structure, driving the binding of a second 3 d ligand to a G4 groove. Modeling studies also suggest that 3 d , with two three‐carbon side chains, has the appropriate geometry to participate in direct or water‐mediated hydrogen bonding to the phosphate backbone and/or G4 loops, assisted by the terminal nitrogen atoms of the side chains. Additionally, antiproliferative studies showed that IQc compounds 2 d (2‐{[3‐(diethylamino)propyl]amino}‐5‐methyl‐11H‐indolo[3,2‐c]quinolin‐5‐ium chloride) and 3 d are 7‐ to 12‐fold more selective for human malignant cell lines than for nonmalignant fibroblasts.     

Predicted Incorporation of Non‐native Substrates by a Polyketide Synthase Yields Bioactive Natural Product Derivatives

The polyether ionophore monensin is biosynthesized by a polyketide synthase that delivers a mixture of monensins A and B by the incorporation of ethyl‐ or methyl‐malonyl‐CoA at its fifth module. Here we present the first computational model of the fifth acyltransferase domain (AT5_mon) of this polyketide synthase, thus affording an investigation of the basis of the relaxed specificity in AT5_mon, insights into the activation for the nucleophilic attack on the substrate, and prediction of the incorporation of synthetic malonic acid building blocks by this enzyme. Our predictions are supported by experimental studies, including the isolation of a predicted derivative of the monensin precursor premonensin. The incorporation of non‐native building blocks was found to alter the ratio of premonensins A and B. The bioactivity of the natural product derivatives was investigated and revealed binding to prenyl‐binding protein. We thus show the potential of engineered biosynthetic polyketides as a source of ligands for biological macromolecules.     

Specificity of a UDP‐GalNAc Pyranose–Furanose Mutase: A Potential Therapeutic Target for Campylobacter jejuni Infections

Pyranose–furanose mutases are essential enzymes in the life cycle of a number of microorganisms, but are absent in mammalian systems, and hence represent novel targets for drug development. To date, all such mutases show preferential recognition of a single substrate (e.g., UDP‐Gal). We report here the detailed structural characterization of the first bifunctional pyranose–furanose mutase, which recognizes both UDP‐Gal and UDP‐GalNAc. The enzyme under investigation (cjUNGM) is involved in the biosynthesis of capsular polysaccharides (CPSs) in Campylobacter jejuni 11168. These CPSs are known virulence factors that are required for adhesion and invasion of human epithelial cells. Using a combination of UV/visible spectroscopy, X‐ray crystallography, saturation transfer difference NMR spectroscopy, molecular dynamics and CORCEMA‐ST calculations, we have characterized the binding of the enzyme to both UDP‐Galp and UDP‐GalpNAc, and compared these interactions with those of a homologous monofunctional mutase enzyme from E. coli (ecUGM). These studies reveal that two arginines in cjUNGM, Arg59 and Arg168, play critical roles in the catalytic mechanism of the enzyme and in controlling its specificity to ultimately lead to a GalfNAc‐containing CPS. In ecUGM, these arginines are replaced with histidine and lysine, respectively, and this results in an enzyme that is selective for UDP‐Gal. We propose that these changes in amino acids allow C. jejuni 11168 to produce suitable quantities of the sugar nucleotide substrate required for the assembly of a CPS containing GalfNAc, which is essential for viability.     

Modulation of CD14 and TLR4⋅MD‐2 Activities by a Synthetic Lipid A Mimetic

Monosaccharide lipid A mimetics based on a glucosamine core linked to two fatty acid chains and bearing one or two phosphate groups have been synthesized. Compounds 1 and 2 , each with one phosphate group, were practically inactive in inhibiting LPS‐induced TLR4 signaling and cytokine production in HEK‐blue cells and murine macrophages, but compound 3 , with two phosphate groups, was found to be active in efficiently inhibiting TLR4 signal in both cell types. The direct interaction between compound 3 and the MD‐2 coreceptor was investigated by NMR spectroscopy and molecular modeling/docking analysis. This compound also interacts directly with the CD14 receptor, stimulating its internalization by endocytosis. Experiments on macrophages show that the effect on CD14 reinforces the activity on MD‐2 ? TLR4 because compound 3 's activity is higher when CD14 is important for TLR4 signaling (i.e., at low LPS concentration). The dual targeting of MD‐2 and CD14, accompanied by good solubility in water and lack of toxicity, suggests the use of monosaccharide 3 as a lead compound for the development of drugs directed against TLR4related syndromes.     

A DMA study of the interfacial changes on injection‐molded iPP/mica composites modified by a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene

Present work concerns to the study of the dynamic mechanical and thermal responses of selected polypropylene (iPP)/mica composites with a modified interface from the matrix side by using a p‐phenylen‐bis‐maleamic acid grafted atactic polypropylene, coming from a byproduct of industrial polymerization reactors. Thus, the study is mainly focused on the 75/25 iPP/mica ratio since it was identified in previous works as providing the maximum inter mica particle distance to assure they should participate in the overall process of dissipation of the mechanical energy supplied to the composites. Hence, the present dynamic mechanical analysis discussion tries to correlate the damping responses of the injection‐molded composites with those previously obtained but over compression molded composites as the basis of further studies all along the compositional iPP/mica map. Therefore, the latter let us, on the one hand, to follow how the main values of the different dynamic mechanical analysis parameters vary because of the interfacial modifier presence, and on the other, to develop a robust correlation between them and the corresponding macroscopic mechanical parameters. © 2017 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2017 , 134, 45366.     

Capture of H2S from binary gas mixture by imidazolium‐based ionic liquids with nonfluorous anions: A theoretical study

Selective capture of H₂S from gas mixture is essential to reduce its undesirable high corrosiveness and toxicity. Ionic liquids have been proposed as a promising material, and there is a need to clarify the capture mechanisms and search for optimal combination of cation and anion for application. This work aims to elucidate the interactions between H₂S and nonfluorous imidazolium ionic liquids (NIILs) at a molecular level. The effects of hydroxyl group on the tail of alkyl chain, and combinations of imidazolium cations and nonfluorous anions on H₂S capture are explored using quantum chemistry calculations. Furthermore, molecular dynamics simulations are used to explore the microstructural features of NIIL–H₂S–CH₄ mixture systems. It is found that the hydroxyl groups in the cations is essential in governing the absorption properties of NIILs, including the interaction sites for hydrogen bonding, interaction geometries and energies, diffusion coefficients, and organization of H₂S and CH₄ around cations and anions. A molecular viewpoint to design appropriate ionic liquids for promoting their applications for H₂S capture is provided. © 2013 American Institute of Chemical Engineers AIChE J, 59: 3824–3833, 2013     

A Model for the Phosphorus Dynamics of VPO Catalysts during the Selective Oxidation of n‐Butane to Maleic Anhydride in a Tubular Reactor

A model for the phosphorus dynamics in vanadium‐phosphorus oxide (VPO) catalysts for the oxidation of n‐butane to maleic anhydride was developed. According to the model, reversible sorption processes determine the phosphorus content of the catalyst. Simulations reveal that several phenomena can be successfully described. If no phosphorus is added to the reactant feed, the catalytic activity increases until runaway occurs. With addition of a proper amount of phosphorus, the loss can be compensated while excessive phosphorus addition results in complete catalyst deactivation. Adjusting the model parameters to experimental data may result in a model that can be used to optimize the performance of maleic anhydride reactors.     

Phase‐separation process in a poly(methyl methacrylate)‐modified epoxy system: A novel approach to understanding the effect of the curing temperature on the final morphology

In this study, the physical and chemical changes of a poly(methyl methacrylate) (PMMA)‐modified epoxy system were examined to understand the effect of the curing conditions on its final morphology. The curing process of the PMMA–epoxy reactive system was complementarily analyzed by Fourier transform infrared spectroscopy in the near range (FT‐NIR) and fluorescence spectroscopy. The relationships among (1) the chemical conversion of the curing reaction, (2) the first moment of the fluorescence emission band (〈ν〉) arising from a chromophore chemically bonded to the epoxy reactive system, (3) the phase‐separation process, and (4) the dynamics of the epoxy thermoset during its curing process are discussed. From a chemical point of view, FT‐NIR did not reveal any significant change in the curing reaction with the presence of 2 wt % PMMA. However, in terms of physical changes, the analysis of the fluorescence response clearly showed variations in the curing reaction due to the presence of the thermoplastic polymer. Also, fluorescence allowed the estimation of the glass‐transition temperature of the system with curing when the reaction was diffusion‐controlled, whereas Fourier transform infrared spectroscopy was not sensible enough. In the second part of this study, scanning electron microscopy images of the PMMA‐modified epoxy system were analyzed to understand the effect of the temperature on the final morphology when the amount of thermoplastic was below the critical volume fraction. A linear dependence between the inverse of the mean area of the thermoplastic‐rich domains and the inverse of the absolute temperature was obtained. © 2010 Wiley Periodicals, Inc. J Appl Polym Sci, 2010     

One‐step oxidation of aniline by peroxotitanium acid to polyaniline–titanium dioxide: A highly stable electrode for a supercapacitor

In this study, to make a stable electrode material for a supercapacitor, we selected a polyaniline and titanium dioxide (TiO₂) hybrid material. Peroxotitanium acid was used to oxidize aniline in the presence of sulfuric acid to a poly(aniline sulfate) salt–titanium oxide composite in one step. IR, X‐ray diffraction, and energy dispersive X‐ray analysis (EDAX) analyses supported the formation of the composite. The poly(aniline sulfate) salt–titanium oxide composites (50 wt % each) showed an amorphous, flakelike morphology having a conductivity value of 8 × 10^?3 S/cm with an excellent yield and stability (300°C).This composite material in the cell configuration showed a specific capacitance of 320 F/g at a 0.33 A/g discharge current density. Thirty thousand charge–discharge (CD) cycles at a heavy CD current density of 3.3 A/g were carried out on the supercapacitor cell. The values of equivalent series resistance (ESR) (8–9 Ω) and efficiency (100–98%) were found to be independent of the cycle number with an excellent retention capacity of 83%. © 2014 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2015 , 132, 41711.