Physicochemical and Adsorption Characterization of Char Derived from Resorcinol-Formaldehyde Resin Modified with Metal Oxide/Silica Nanocomposites.

A series of metal- and silica-containing carbon-based nanocomposites were synthesized by pyrolysis of a resorcinol-formaldehyde polymer modified with metal oxide/silica nanocomposites (MxOy/SiO2, where M = Mg, Mn, Ni, Cu and Zn) via the thermal oxidative destruction of metal acetates adsorbed on highly dispersed silica (A380). The concentration of metals was 3.0 mmol/g SiO2. The phase composition and morphological, structural and textural properties of the carbon materials were analyzed by X-ray diffraction, SEM, Raman spectroscopy and low-temperature N2 adsorption. Thermal decomposition under a nitrogen atmosphere and in air was analyzed using TG-FTIR and TG-DTG-DSC techniques to determine the influence of the filler on the decomposition process. The synthesized composites show mesoporous structures with high porosity and narrow pore size distributions. It could be shown that the textural properties and the final composition of the nanocomposites depend on the metal oxide fillers of the precursors. The data obtained show that nickel and copper promote the degree of graphitization and a structural order with the highest porosity and largest specific surface area of the hybrid composites. The good adsorption properties of the obtained materials were shown for the recovery of p-chlorophenol and p-nitrophenol from aqueous solutions.

Nanostructure and thermal characteristics of silica/human serum albumin systems based on a modified nanosilica entero-vulnerosorbent.

Entero-vulnerosorbents based on geometrically modified (GM) (mechanical treatment at different times, tMT = 1, 4, and 7 h) fumed nanosilica A300 (NS) and protein molecules (human serum albumin/GM-nanosilica systems) were characterized with a focus on their surface, morphology, topography, and thermal properties. Microscopic, spectroscopic, and analytical techniques, including atomic force microscopy (AFM), optical profilometry (OP), high-resolution transmission electron microscopy (HRTEM), energy dispersive X-ray spectroscopy (EDX), X-ray photoelectron spectroscopy (XPS), and elemental analysis (CHN), were used. The differentiation in the surface morphology, micro-nanoroughness, surface chemistry, thermal properties of the silica support, and protein/nanosilica systems were found. AFM, OP, and HRTEM microscopic methods showed that the albumin/silica composite surface is less rough, wavy, and asymmetrical; it is also smoother, flat, and homogeneous because of the formation of a continuous layer of a protein film on the support surface. CHN, XPS, and S/TEM-EDX analysis showed that HSA adsorbed on the unmodified and GM-treated silica carrier led to variations in the physical and chemical features of materials (elemental composition, element concentration, chemical states, chemical bonds between enzyme molecules, and silica surface). Thermal studies were carried out using a thermogravimetric technique linked with a quadrupole mass spectrometer (TG/DTG/DSC-QMS). The degradation of the HSA/nanosilica system is a two-stage process that takes place within the temperature range 160-450-900 °C.

Physicochemical, structural, and adsorption characteristics of DMSPS-co-DVB nanopolymers.

The aim of this work is the synthesis and characterization of the series of S,S'-thiodi-4,1-phenylene bis(thio-methacrylate)-co-divinylbenzene (DMSPS-co-DVB) nanomaterials. The series of new nanopolymers including three mixed systems with different ratios of DMSPS and DVB components, DMSPS-co-DVB = 1:1, DMSPS-co-DVB = 1:2, and DMSPS-co-DVB = 1:3, was synthesized in the polymerization reaction. The research task is to investigate the influence of the reaction mixture composition on morphological, textural, and structural properties of final nanosystems including size, shape, and agglomeration effect. The advanced biphasic nanomaterials enriched with thiol groups were successfully synthesized as potential sorbents for binding organic substances, heavy metals, or biomolecules. To determine the impact of the DMSPS monomer on the final properties of DMSPS-co-DVB nanocomposites, several techniques were applied to reveal the nano-dimensional structure (SAXS), texture (low-temperature nitrogen sorption), general morphology (SEM), acid-base properties (potentiometric titration), and surface chemistry and phase bonding effectiveness (FTIR/ATR spectroscopy). Finally, kinetic studies of aniline sorption on polymeric materials were performed.

Conformational degrees of freedom and stability of splay-bend ordering in the limit of a very strong planar anchoring.

We study the self-organization in a monolayer (a two-dimensional system) of flexible planar trimer particles. The molecules are made up of two mesogenic units linked by a spacer, all of which are modeled as hard needles of the same length. Each molecule can dynamically adopt two conformational states: an achiral bent-shaped (cis-) and a chiral zigzag (trans-) one. Using constant pressure Monte Carlo simulations and Onsager-type density functional theory (DFT), we show that the system consisting of these molecules exhibits a rich spectrum of liquid crystalline phases. The most interesting observation is the identification of stable smectic splay-bend (S_{SB}) and chiral smectic-A (S_{A}^{*}) phases. The S_{SB} phase is also stable in the limit, where only cis- conformers are allowed. The second phase that occupies a considerable portion of the phase diagram is S_{A}^{*} with chiral layers, where the chirality of the neighboring layers is of opposite sign. The study of the average fractions of the trans- and cis- conformers in various phases shows that while in the isotropic phase all fractions are equally populated, the S_{A}^{*} phase is dominated by chiral conformers (zigzag), but the achiral conformers win in the smectic splay-bend phase. To clarify the possibility of stabilization of the nematic splay-bend (N_{SB}) phase for trimers, the free energy of the N_{SB} and S_{SB} phases is calculated within DFT for the cis- conformers, for densities where simulations show stable S_{SB}. It turns out that the N_{SB} phase is unstable away from the phase transition to the nematic phase, and its free energy is always higher than that of S_{SB}, down to the transition to the nematic phase, although the difference in free energies becomes extremely small when approaching the transition.

Interaction of Bis-(sodium-sulfopropyl)-Disulfide and Polyethylene Glycol on the Copper Electrodeposited Layer by Time-of-Flight Secondary-Ion Mass Spectrometry.

The interactions of the functional additives SPS (bis-(sodium-sulfopropyl)-disulfide) and polyethylene glycol (PEG) in the presence of chloride ions were studied by time-of-flight secondary-ion mass spectrometry (TOF-SIMS) in combination with cyclic voltammetry measurements (CV). The PEG, thiolate, and chloride surface coverages were estimated and discussed in terms of their electrochemical suppressing/accelerating abilities. The conformational influence of both the gauche/trans thiolate molecules, as well as around C-C and C-O of PEG, on the electrochemical properties were discussed. The contribution of the hydrophobic interaction of -CH2-CH2- of PEG with chloride ions was only slightly reduced after the addition of SPS, while the contribution of Cu-PEG adducts diminished strongly. SPS and PEG demonstrated significant synergy by significant co-adsorption. It was shown that the suppressing abilities of PEG that rely on forming stable Cu-PEG adducts, identified in the form C2H4O2Cu+ and C3H6OCu+, were significantly reduced after the addition of SPS. The major role of thiolate molecules adsorbed on a copper surface in reducing the suppressing abilities of PEG rely on the efficient capture of Cu2+ ions, diminishing the available copper ions for the ethereal oxygen of PEG.

Mesocellular Silica Foams (MCFs) with Tunable Pore Size as a Support for Lysozyme Immobilization: Adsorption Equilibrium and Kinetics, Biocomposite Properties.

The effect of the porous structure of mesocellular silica foams (MCFs) on the lysozyme (LYS) adsorption capacity, as well as the rate, was studied to design the effective sorbent for potential applications as the carriers of biomolecules. The structural (N2 adsorption/desorption isotherms), textural (SEM, TEM), acid-base (potentiometric titration), adsorption properties, and thermal characteristics of the obtained lysozyme/silica composites were studied. The protein adsorption equilibrium and kinetics showed significant dependence on silica pore size. For instance, LYS adsorption uptake on MCF-6.4 support (pore diameter 6.4 nm) was about 0.29 g/g. The equilibrium loading amount of LYS on MCF-14.5 material (pore size 14.5 nm) increased to 0.55 g/g. However, when the pore diameter was larger than 14.5 nm, the LYS adsorption value systematically decreased with increasing pore size (e.g., for MCF-30.1 was only 0.27 g/g). The electrostatic attractive interactions between the positively charged lysozyme (at pH = 7.4) and the negatively charged silica played a significant role in the immobilization process. The differences in protein adsorption and surface morphology for the biocomposites of various pore sizes were found. The thermal behavior of the studied bio/systems was conducted by TG/DSC/FTIR/MS coupled method. It was found that the thermal degradation of lysozyme/silica composites was a double-stage process in the temperature range 165-420-830 °C.

Are hydrogen supramolecular structures being suppressed upon nanoscale confinement? The case of monohydroxy alcohols.

In this paper, the molecular dynamics, H-bonding pattern and wettability of the primary and secondary monohydroxyalcohols, 2-ethyl-1-hexanol (2E1H), 2-ethyl-1-butanol (2E1B) and 5-methyl-3-heptanol (5M3H) infiltrated into native and functionalized silica and alumina pores having pore diameters, d = 4 nm and d = 10 nm, have been studied with the use of Broadband Dielectric (BDS) and Fourier Transform InfraRed (FTIR) spectroscopies, as well as contact angle measurements. We found significant differences in the behavior of alcohols forming chain- (2E1H, 2E1B) or micelle-like (5M3H) supramolecular structures despite of their similarities in the wettability and interfacial energy. It turned out that nanoassociates as well as H-bonds are more or less affected by the confinement dependently on the chemical structure and alcohol order. Moreover, a peculiar behavior of the self-assemblies at the interface was noted in the latter material (5M3H). Finally, it was found that irrespectively to the sample, type of pores, functionalization, the temperature evolution of Debye relaxation times, τD, of the confined systems deviates from the bulk behavior always at similar τD due to vitrification of the interfacial layer. This finding is a clear indication that unexpectedly dynamics (mobility) of the supramolecular structures close to the hydrophilic and hydrophobic surfaces is similar in each system.

Mesoporous silica/protein biocomposites: Surface, topography, thermal properties.

The biocomposite systems based on mesoporous MCF silica support and protein molecules are characterized with regard to their surface, topographic, thermal properties. Mesoporous silica materials (MCF) covered by the adsorbed protein molecules (BSA and OVA) were examined and characterized by using various techniques including X-ray diffraction, the Fourier transform infrared spectroscopy with attenuated total reflectance, X-ray photoelectron spectroscopy and scanning electron microscopy with microanalysis. The results of study focused on a detailed analysis of microstructure (topography, texture), and chemistry (chemical bonds, functional groups, elemental composition) of protein/mesoporous silica biocomposite. Moreover, the thermal properties of prepared biomaterials were investigated by means of TG/DSC-FTIR-MS-coupled technique. These powerful methods provided detailed information for understanding protein adsorption on MCF. Significant differentiation in surface chemistry and topography of MCF material was observed after protein adsorption. Basing on the results of thermal analysis stronger changes of the surface properties and more stable interactions of biomolecules with MCF-d16 support were observed for larger BSA molecules compared to smaller ovalbumin ones.

Mean-field model of boomerang nematic liquid crystals with diminished coupling of molecular uniaxial and biaxial susceptibilities.

The mean-field theory approach has been applied to the boomerang type particles from P. I. C. Teixeira, A. Masters, and B. Mulder [Mol. Cryst. Liq. Cryst. 323, 167 (1998)MCLCE91058-725X10.1080/10587259808048440] but with diminished strength of the interaction coefficient responsible for the coupling between molecular uniaxial and biaxial susceptibilities. For the rodlike particles, when the apex boomerang angle is larger than 107.35^{∘}, the stable uniaxial rodlike phase occurs. For smaller angles, beyond the point where the transition is of the second order (the Landau point) and for diminished parameter of molecular biaxial-uniaxial coupling, a biaxial phase is observed with the transition undergoing directly from the isotropic phase. According to the order parameters the character of this transition is of the first order. Such behavior is in accordance with the Sonnet-Durand-Virga model of the biaxial phases. The change in the type of the phase transition order is also illustrated by the changes in the equations of state and the changes in second and third derivatives of the free energy. The possibilities to tailor interaction coefficients of real molecules to obtain such a phase transition scenario are discussed.

Nematic twist-bend phase in an external field.

The response of the nematic twist-bend ([Formula: see text]) phase to an applied field can provide important insight into the structure of this liquid and may bring us closer to understanding mechanisms generating mirror symmetry breaking in a fluid of achiral molecules. Here we investigate theoretically how an external uniform field can affect structural properties and the stability of [Formula: see text] Assuming that the driving force responsible for the formation of this phase is packing entropy, we show, within Landau-de Gennes theory, that [Formula: see text] can undergo a rich sequence of structural changes with the field. For the systems with positive anisotropy of permittivity, we first observe a decrease of the tilt angle of [Formula: see text] until it transforms through a field-induced phase transition to the ordinary prolate uniaxial nematic phase (N). Then, at very high fields, this nematic phase develops polarization perpendicular to the field ([Formula: see text]). For systems with negative anisotropy of permittivity, the results reveal new modulated structures. Even an infinitesimally small field transforms [Formula: see text] to its elliptical counterpart ([Formula: see text]), where the circular base of the cone of the main director becomes elliptic. With stronger fields, the ellipse degenerates to a line, giving rise to a nonchiral periodic structure, the nematic splay-bend ([Formula: see text]), where the two nematic directors are restricted to a plane. The three structures-[Formula: see text], [Formula: see text], and [Formula: see text]-with a modulated polar order are globally nonpolar. But further increase of the field induces phase transitions into globally polar structures with nonvanishing polarization along the field's direction. We found two such structures, one of which is a polar and chiral modification of [Formula: see text], where splay and bend deformations are accompanied by weak twist deformations ([Formula: see text]). Further increase of the field unwinds this structure into a polar nematic ([Formula: see text]) of polarization parallel to the field.

Computational aspects of the smectization process in liquid crystals: An example study of a perfectly aligned two-dimensional hard-boomerang system.

A replica method for calculation of smectic liquid crystal properties within the Onsager theory has been presented and applied to an exemplary case of two-dimensional perfectly aligned needlelike boomerangs. The method allows one to consider the complete influence of the interaction terms in contrast to the Fourier expansion method which uses mostly first or second order terms of expansion. The program based on the replica algorithm is able to calculate a single representative layer as an equivalent set of layers, depending on the size of the considered width of the sample integration interval. It predicts successfully smectic density distributions, energies, and layer thicknesses for different types of layer arrangement-of the antiferroelectric or of the smectic A order type. Specific features of the algorithm performance and influence of the numerical accuracy on the physical properties are presented. Future applications of the replica method to freely rotating molecules are discussed.

Kinetic-contact-driven gigantic energy transfer in a two-dimensional Lennard-Jones fluid confined to a rotating pore.

A two-dimensional Lennard-Jones system in a circular and rotating container has been studied by means of molecular dynamics technique. A nonequilibrium transition to the rotating stage has been detected in a delayed time since an instant switching of the frame rotation. This transition is attributed to the increase of the density at the wall because of the centrifugal force. At the same time the phase transition occurs, the inner system changes its configuration of the solid-state type into the liquid type. Impact of angular frequency and molecular roughness on the transport properties of the nonrotating and rotating systems is analyzed.

Comment on the diffusion properties presented in "Temporal and structural characteristics of a two-dimensional gas of hard needles".

The intensive properties of two-dimensional anisotropic systems like the average number of collisions, pressure or diffusivities, are, despite the fact that the thermodynamical types of phase transitions are attributed to the Kosterlitz-Thouless mechanism, determined by local properties. In the case of hard needles they are influenced by the local orientational transition governed by the steric excluded-volume interactions which, according to the Onsager theory, takes place at the reduced density ρ* = 4.7 . The density dependence of the diffusion coefficients from the affine transformation model and the Enskog theory with the help of the Onsager distribution function are compared to the outcome of the data presented by M.E. Foulaadvand and M. Yarifard in Eur. Phys. J. E 34, 41 (2011). The similarities and discrepancies are discussed.

Nonequilibrium restructuring in two-dimensional Lennard-Jones system induced by a simple square start configuration.

In the present paper, we report a molecular dynamics simulation of two-dimensional Lennard-Jones system with a simple square start configuration. Mean square displacement was computed showing interesting dependence on high pressure conditions in short time scale, corresponding to an abrupt restructurization. This paper is the first to report the qualitative and quantitative details of this phenomenon.

The Enskog-type theory of the velocity autocorrelations in the two-dimensional nematic of hard needles.

As it was shown from molecular dynamics of two-dimensional hard needles, the uniaxial velocity autocorrelation function (VACF) of this system exhibits a two time scale character. This corresponds to the symmetry of the particles. In this paper we provide a theory of the Enskog type that corroborates the idea that the VACF can be successfully described as a sum of two single decays. From the comparison between molecular dynamics and theoretical results, we show that the Enskog approach is a satisfactory kinetic theory, which functions as well in the nematic as in the isotropic phase. Different properties of VACFs have been investigated, in particular, the dependence on the orientational order, temperature, and particles' inertness.

Velocity correlations of two-dimensional hard needles from molecular dynamics.

We present velocity correlations of a two-dimensional system of perfectly smooth hard needles from molecular dynamics. In a nematic phase the autocorrelation velocity function (ACF) clearly separates into two domains with, first, a very quick decay and, then, a long-lasting exponential-like decay that pertains to several characteristic times of the fast decay. The latter one is strongly subjected to the order of the system. We demonstrate that the existence of two time scales corresponds to different relaxations of the transverse and longitudinal components of the ACF.