Compositions and structures of nanoparticles of pentagonal axial symmetry <Emphasis Type="Italic">D</Emphasis><Subscript>5<Emphasis Type="Italic">d</Emphasis></Subscript>: Nanotubes

The method of determination of the structure and the number of atoms in the shells of nanoparticles as a function of the arrangement of atoms at the symmetry elements of a symmetry group has been developed. The formulas for the calculation of the number of particles with symmetry group D _5d are reported. The number of particles in these shells is determined by three structurally invariant numbers and the “quantum number” of the group order n. The classification of all possible nanostructures with symmetry group D _5d is given: C _θ+10z , z = 0, 1, 2, …, where the basic shells are C _θ = C ₂, C ₁₀, C ₁₂. The sum rule has been obtained for the coordination numbers of shell sites located at symmetry axes. Pentagonal axial nanoparticles are shown to be the initial shells for obtaining (5,5) and (10,10) armchair nanotubes or (5,0) and (10,0) zigzag nanotubes. The general formula of these nanotubes closed with icosahedral and dodecahedral caps is N _20+10p , N _60+10p (p = 1, 2, …). The graphical constructions of all classes of nanoparticles and nanotubes of the pentagonal axial type are reported.     

Multicomponent reactions in the synthesis of dihydropyrimidine-containing podands having tuberculostatic activity

Dihydropyrimidinethione podands, as well as podands containing 2-thienyl substituents have been synthesized via the multicomponent Biginelli reaction. Tuberculostatic activity of the novel podands was shown to depend on the polyether unit length. In particular, activity of dihydropyrimidinethione podands against laboratory strains of Mycobacterium tuberculosis, H₃₇Rv, M. avium, M. terrae, and the clinical strain of multi-drug resistant M. tuberculosis (MDR), increases with a shortening of the polyether unit length.     

Optical Band Gap Energies in Quasi-Metal Carbon Nanotubes

The structure of carbon nanotubes is described by two positive integers (n₁, n₂). The π-electron model of the nanotube band structure predicts that when the difference n₁–n₂ is multiple of three, the energy gap between the valence and conduction bands vanishes so that such tubes should exhibit quasi-metal properties. The band structure of 50 chiral and achiral (n₁, n₂) nanotubes with 4 ≤ n₁ ≤ 18 and n₂ = n₁–3q has been calculated by the linearized augmented cylindrical wave method. Nanotubes have been identified for which the optical band gaps are in the terahertz range (1–40 meV) and which can be used for design of emitters, detectors, multipliers, antennas, transistors, and other nanoelements operating in the high-frequency range.     

Towards the optimization of carbon nanotube properties via <Emphasis Type="Italic">in situ</Emphasis> and <Emphasis Type="Italic">ex situ</Emphasis> studies of the growth mechanism

The synthesis conditions of multi-walled carbon nanotubes (MWCNTs) indirectly determine their application potential through the decisive role in the characteristics of individual tubes: diameter distribution, structure and defectiveness of graphene walls, the amount of metal impurities and amorphous carbon. In the present work, we have studied the influence of the catalyst composition and synthesis conditions on the diameter distribution and the structure of nanotube walls. We have observed the influence of the particle size for MWCNT synthesis (i.e. size effect) on catalytic activity by ex situ and in situ techniques: in situ X-ray diffraction on synchrotron radiation (SRXRD), gas chromatography, and ex situ transmission electron microscopy. The data obtained by in situ SRXRD are in agreement with the results collected using laboratory tubular fix-bed catalytic reactor allowing thereby extending the applicability of the approach. For the first time we have shown the increase of the fraction of graphene walls in the total MWCNT diameter with time.     

Polymer matrices with molecular memory as affine adsorbents for the determination of myoglobin as a cardiac marker of acute myocardial infarction by voltammetry

A possibility of myoglobin determination using screen-printed graphite electrodes modified with a poly(o-phenylenediamine)-based molecularly imprinted polymer (MIP) obtained by the electropolymerization of o-phenylenediamine monomer molecules on the surface of a screen-printed graphite electrode in the presence of myoglobin template molecules is considered. It is shown that the conjugation of MIP with multiwall carbon nanotubes (MWCNT) results in an increase in the sensitivity of the MIP-biosensor in the electrochemical determination of myoglobin by the direct registration of the reduction peak of hemoprotein Fe³⁺ by square wave voltammetry on screen-printed graphite electrodes modified with MWCNT/MIP and MIP. Equilibrium dissociation constants K _d for the interaction of myoglobin with MWCNT/MIP- and MIP-electrodes, which equaled (9.8 ± 2.6) × 10^–11 and (2.4 ± 0.5) × 10^–8 M, respectively, are calculated. It is shown that the sensitivity of the electrochemical MWCNT/MIP-biosensor for myoglobin determination (1.5 × 10^–2 A/nmol of myoglobin) is higher than that of the MIP-biosensor (2.0 × 10^–4 A/nmol of myoglobin).     

Compositions and structures of nanoparticles of trigonal symmetry <Emphasis Type="Italic">D</Emphasis><Subscript>3<Emphasis Type="Italic">d</Emphasis></Subscript>: Nanotubes

A method has been developed for the determination of the structure and number of atoms in the shells of nanoparticles as a function of the arrangement of atoms at the symmetry elements of a symmetry group. The formulas for calculation of the number of particles of symmetry D _3d have been reported. It has been shown that the number of atoms in trigonal shells is determined by three structurally invariant numbers and the quantum number of the group order n. All possible nanostructures of symmetry D _3d have been classified: C_{θ + 6z} , z = 0, 1, 2, ..., where the basic shells are C_θ = C₆, C₈, and C₁₄. A sum rule has been obtained for the coordination numbers of the shell sites located on symmetry axes. Trigonal nanoparticles are parent ones for obtaining (3,0), (6,0), and (9,0) nanotubes of trigonal type. The general formulas of these nanotubes with icosahedral, dodecahedral, and cubic caps are N_{8 + 12p} , N_{20 + 24p} , and N_{60 + 36p} (p = 1, 2, ...), respectively. The graphical constructions of all classes of trigonal nanoparticles and nanotubes are reported.     

Thermal and dielectric characterization of multi-walled carbon nanotubes−thermoplastic polyurethanes composites

Multi-walled carbon nanotubes–thermoplastic polyurethanes composites were characterized by means of differential scanning calorimetry and dielectric relaxation spectroscopy. The composite is characterized by two glass transition temperatures T _g . The T _g associated with the soft segment decreases by increasing of carbon nanotubes content, while carbon nanotubes content has practically no effect on the value of the T _g associated with the hard segments. It was observed that rising the temperature and carbon nanotubes content resulted in the increased of both the dielectric permittivity and the loss factor. The presence of carbon nanotubes produces an enhancement of charge carriers trapping, increasing the electrical conductivity. The electrical conductivity of the composite was found to exhibit an insulator to conductor transition at a carbon nanotubes critical content, i.e., the percolation threshold, near 6 wt %.     

Hydrogen physisorption energies for bumpy,saturated, nitrogen-doped single-walled carbon nanotubes

Finite saturated regular carbon nanotubes (CNTs) are predicted to exhibit higher capacity as hydrogen storage media compared to unsaturated regular CNTs. In the present study, molecular hydrogen physisorption energies (MHPEs) for finite saturated and unsaturated bumpy defected CNTs were calculated by density functional theory (DFT-D3) methods at the B3LYP/6-31G(d) theory level, with rigorous inclusion of van der Waals interactions. The calculated MHPEs for both regular and bumpy defected armchair, chiral and zigzag CNTs with similar diameters and lengths, with and without nitrogen doping, were compared in terms of Eph/H₂, defined as the MHPE per hydrogen molecule adsorbed inside the nanotube. For all studied systems, Eph/H₂ increased with the number of physisorbed hydrogen molecules. Nitrogen doping of regular and bumpy CNTs resulted in an increase in the Eph/H₂ values, with the exception of bumpy chiral nanotubes. The results of this study demonstrate that bumpy defects are important nanotube structural features whose effects depend on nanotube chirality. For instance, bumpy defects were beneficial for undoped and doped zigzag nanotubes, resulting in a decrease in Eph/H₂ values for regular structures from 0.5 and 0.74 to 0.26 and 0.42 eV, respectively. By contrast, for doped armchair regular structures with an Eph/H₂ value of 0.38 eV, bumpy defects increased Eph/H₂ to 0.45 eV. These Eph/H₂ values for bumpy doped armchair and the zigzag nanotubes are all within the range of 0.1–0.5 eV/H₂ reported as ideal for reversible hydrogen storage under environmental conditions.     

Voltammetric sensors based on gel composites containing carbon nanotubes and an ionic liquid

Possibilities of using electrode coatings based on a gel of carboxylated multiwall carbon nanotubes (MWCNTs) in an ionic liquid (1-butyl-3-methylimidazolium hexafluorophosphate, [BMIm]PF₆) for the creation of a voltammetric sensor with electrocatalytic properties with respect to the pharmacological group of catecholamines—levodopa, methyldopa, and carbidopa—are considered. Using cyclic voltammetry, it was found that a glassy carbon electrode coated with a thin layer of an MWCNT–[BMIm]PF₆ gel or an MWCNT–[BMIm]PF₆–Nafion gel-composite induced a decrease in overvoltage (~60 mV), improved the reversibility of the redox reaction, and increased oxidation currents of the studied substances in comparison with an unmodified glassy carbon electrode. The concentration dependence of the analytical signal was linear in the ranges of 1–250, 2–350, and 5–400 mM for carbidopa, levodopa, and methyldopa, respectively. In the determination of the specified substances in diluted urine samples and tableted drugs, the accuracy index was 98–102% and the relative standard deviation, 0.3–5% (n = 5, P = 0.95).     

Micromechanism of Cu and Fe alloying process on the martensitic phase transformation of NiTi-based alloys: First-principles calculation

Using first-principles pseudo-potential plane wave method, the formation enthalpy ΔH, binding energy ΔE, elastic constants, and electronic structure were calculated and analyzed carefully for NiTiX (X = Cu, Fe) shape memory alloy. The results show that the Cu or Fe element prefers to occupy the Ni site in the NiTi matrix phase respectively. Compared with the NiTi matrix phase, the ΔH, ΔE, c ₄₄ and c′ of NiTi (Cu) are similar to each other. However, the structural stability of the NiTi phase is improved obviously by the Fe alloying process. Simultaneously, the shear modulus c ₄₄ and c′ of NiTi (Fe) are larger than those of the NiTi matrix phase. Furthermore, Milliken population results indicate that Q _Cu–Ti is smaller than Q _Ni–Ti after the Cu alloying process, but Q _Fe–Ti is larger than Q _Ni–Ti. The electron density difference shows that some covalent bonding exists between Fe and Ti elements. Based on the upward analysis, the difference in the phase stability and elastic constants of NiTiX (X = Cu, Fe) is the substantial mechanism for the different M _s of NiTiX (X = Cu, Fe) although Cu or Fe substitutes for the same atom Ni elements in the NiTi matrix phase.     

Non-Isothermal Crystallization Behavior of β-Nucleated Isotactic Polypropylene/Multi-Walled Carbon Nanotube Composites with Different Melt Structures

In this study, the melt structure status of isotactic polypropylene/multi-walled carbon nanotubes composites (iPP/MWCNTs) nucleated with β-NA was tuned by changing the fusion temperature T _f . The non-isothermal crystallization behavior and subsequent melting behavior of the sample were studied in detail. The results showed that under different cooling rates (2, 5, 10, 20 and 40 deg/min), the crystallization temperature increased gradually with the decrease of T _f , meanwhile, when T _f was in the temperature range of 166–174°C where ordered structures survived in the melt (named Region II), the crystallization activation energy was significantly lower compared with the case T _f > 174°C or T _f < 166°C. On the subsequent melting curves, the occurrence of the melt structure can be observed at all the cooling rates studied; the location of the Region II was constant, which did not show dependency on the cooling rates; low cooling rate and relative low T _f within 166–174°C encouraged the formation of more β-phase triggered by melt structure.     

Synthesis of urethane—acrylic multi-block copolymers via electrochemically mediated ATRP

The electrochemically mediated atom transfer radical polymerisation (eATRP) of n-butyl acrylate was investigated under a variety of catalyst concentrations. Poly(n-butyl acrylate)-block-polyurethane-block-poly(n-butyl acrylate) copolymers were prepared via electrochemically mediated atom transfer radical polymerisation (eATRP) using only 7 × 10^?6 mole % of Cu^II complex. The successful chain extension and formation of penta-block copolymers confirmed the living nature of the poly(alkyl acrylates) prepared by eATRP. In this work, the tri-block and penta-block urethane-acrylate copolymers were synthesised for the first time by using tertiary bromine-terminated polyurethane macro-initiators as transitional products reacting with n-butyl acrylate, and subsequently with tert-butyl acrylate in the presence of the Cu^IIBr₂/TPMA catalyst complex. The results of ¹H NMR spectral studies support the formation of tri-block poly(n-butyl acrylate)-block-polyurethane-block-poly(n-butyl acrylate) copolymers, and penta-block poly(tert-butyl acrylate)-block-poly(n-butyl acrylate)-block-polyurethane-block-poly(n-butyl acrylate)-block-poly(tert-butyl acrylate) copolymers.     

Molecular dynamics simulations of the characteristics of sodium carboxymethyl cellulose with different degrees of substitution in a salt solution

Sodium carboxymethyl cellulose (SCMC) with different degrees of substitution (DS) possesses structural characteristics and physicochemical properties that are important in broad areas of industrial applications. This reported work investigated the structural characteristics, including the effective length (L _ef), the radius of gyration (R _g), and the hydrodynamic radius (R _H), and the physicochemical properties, including intrinsic viscosity ([η]) and salt tolerance, of SCMC with a DS more than 1.0 in NaCl solution using molecular dynamics (MD) simulations. In the MD simulations, the DS of SCMC varied from 1.2 to 2.8, and the NaCl concentration varied from 0 to 1.4 mol/L. MD simulation results showed that with the increment of NaCl concentration, the L _ef (or R _g or R _H) of SCMC decreased; with the increment of the DS, the L _ef of SCMC increased. Also, the variation tendency of [η] in the NaCl solution was consistent with its L _ef (or R _g or R _H). It was noted that the salt tolerance (represented by D) of SCMC increased as the DS increased. In addition, the sharp variation of the D value of SCMC occurred in the range of DS of 1.6 to 2.0, which agreed with the reported experimental results. Radial distribution function analyses showed that the Na⁺ cations had a stronger interaction with the carboxyl groups in SCMC with lower DS when it was present in a salt solution of higher concentration, which also reasonably explained the variation of L _ef, R _g, R _H, [η], and D of SCMC in NaCl solution.     

Preparation of polypyrrole/multi-walled carbon nanotube hybrids by electropolymerization combined with a coating method for counter electrodes in dye-sensitized solar cells

In this work, multi-wall carbon nanotubes coated with polypyrrole (PPy/MWCNT) have been used as counter electrode (CE) materials for dye-sensitized solar cells (DSSCs). PPy was deposited onto fluorine-doped tin-oxide-coated glass by electrochemical polymerization of pyrrole. Three surfactants were used in the preparation of the hybrids: cationic cetyltrimethylammonium bromide, anionic sodium dodecylbenzenesulfonate (DBSNa), and non-ionic polyoxyethylene sorbitan monolaurate (Tween20). The morphologies of the PPy and PPy/MWCNT hybrids were investigated using scanning electron spectroscopy. Chemical composition of the prepared CEs was determined by X-ray photoelectron spectroscopy and Fourier-transformed infrared spectroscopy. The catalytic activity of the PPy and PPy/MWCNT layers was evaluated using cyclic voltammetry, and the photovoltaic properties of DSSCs with PPy and PPy/MWCNT CEs were characterized using I–V measurements. PPy/MWCNT samples that were prepared by electrochemical polymerization showed the best results when the anionic surfactant DBSNa was used during polymerization. The photoelectric conversion efficiency of PPy/MWCNT prepared by electrochemical polymerization was 2.9%, which was 59% of that of Pt CE (4.9%).     

The influence of chemical structure on thermal properties and surface morphology of polyurethane materials

The surface morphology and thermal properties of polyurethanes can be correlated to their chemical composition. The hydrophilicity, surface morphology, and thermal properties of polyurethanes (differed in soft segments and in linear/cross-linked structure) were investigated. The influence of poly([R,S]-3-hydroxybutyrate) presence in soft segments and blending of polyurethane with polylactide on surface topography were also estimated. The linear polyurethanes (partially crystalline) had the granular surface, whereas the surface of cross-linked polyurethanes (almost amorphous) was smooth. Round aggregates of polylactide un-uniformly distributed in matrix of polyurethane were clearly visible. It was concluded that some modification of soft segment (by mixing of poly([R,S]-3-hydroxybutyrate) with different polydiols and polytriol) and blending of polyurethanes with small amount of polylactide influence on crystallinity and surface topography of obtained polyurethanes.     

Synthesis and structure of bis(1,2-diaminoethane) copper(II) bis(<Emphasis Type="Italic">o</Emphasis>-hydroxybenzoate) monohydrate and <Emphasis Type="Italic">trans</Emphasis>-diaquabis(1,2-diaminoethane)copper(II) bis(<Emphasis Type="Italic">o</Emphasis>-aminobenzoate)

X-ray structural analysis has been performed for two complex compounds: Cu(en)₂(o-HB)₂H₂O (I) (a = 16.873(4) Å, b = 8.713(2) Å, c = 14.803(3) Å, β = 91.15(2)°, V = 2175.8(8) ų, C2/c, Z = 4, R(F) = 0.0263, 1516 reflections with I > 3σ (I)) and [Cu(en)₂(OH₂)₂]²⁺(o-AB^?)₂ (II) (a = 7.488(5) Å, b = 22.122(8) Å, c = 7.856(5) Å, β = 118.77(2)°, V = 1140.7(11) ų, P2₁/n, Z = 2, R(F) = 0.0432, 1684 reflections with I > 3σ(I)) synthesized under identical conditions (en is ethylenediamine, o-HB is o-hydroxybenzoate, and o-AB is o-aminobenzoate). Although the compounds were assumed to have similar structures and the Cu-Lig bond lengths and the cis and trans angles are acceptable for an octahedral structure, the geometric parameters of o-HB suggest that the copper atom has a plane square environment.     

Covalent Functionalization of Single-Walled Carbon Nanotubes Through the Fluorination Stage for Integration into an Epoxy Composite

The upper limit of the elastic modulus has been estimated for a polymer–carbon nanotube–epoxy matrix nanocomposite. This limit can be achieved if the nanotubes are integrated into the matrix, i.e., they form a continuous reinforcing network inside the matrix, and if the nanotubes are single-walled or double-walled carbon nanotubes. A technique for carbon nanotube functionalization via fluorination and fluorine substitution and a technique for calculating the degree of nanotube functionalization based on reaction yield measurements are proposed. For fluorine substitution by epoxy-diane resin and diaminodiphenylmethane, the degree of functionalization is С–(FG)_x, x ~ 0.011–0.013 and the FG-molecular fragment containing the epoxy (amino) group corresponding to functionalization of ~5% of the surface С atoms of nanotubes. The control reaction showed that the epoxy groups preserve the chemical activity, while part of the amino groups are deactivated. The grafted epoxy(amino) groups ensure nanotube surface lyophilicity in epoxy composites and integrate the nanotubes into the epoxy matrix owing to the chemical bonds.     

A density-functional theory of hydrogen adsorption on indium nitride nanotubes

First-principles calculations based on density functional theory (DFT) are used to study the chemisorption properties of one, two, and four hydrogen atoms on the zigzag and armchair single-walled InN nanotubes (InNNTs).The results indicate that the H atom is strongly bounded to the exterior wall of (4, 4) InNNTs compared with the (7, 0) InNNTs, while the chemisorption energies corresponding to the most stable configuration of H₂ dissociation and a single H atom are found to be–3.85 and–3.26 eV, respectively. Furthermore, the effect of the hydrogen storage on the geometries and electronic properties of related InN nanotubes were also discussed. The computed density of states (DOS) indicates that the energy gap of the zigzag and armchair InN nanotubes on hydrogen adsorptions are significantly decreased which can increase the electrical conductance of the tubes. Therefore, InN nanotubes due to the high binding energy can be used for hydrogen storage.     

Mechanochemical synthesis of colloidal silver bromide particles in the NaBr–AgNO<Subscript>3</Subscript>–NaNO<Subscript>3</Subscript> system

X-ray diffraction and thermal analyses, electron microscopy, and dynamic light scattering have been employed to study silver bromide nanoparticles obtained by the mechanochemical exchange reaction NaBr + AgNO₃ + zNaNO₃ = (z + 1)NaNO₃ + AgBr in sodium nitrate matrix (diluent and side reaction product) at z = z₁ = 8.06 and z = z₂ = 4.31. AgBr nanoparticles have been obtained in the free form by dissolving the matrix in water, and their activity in the photodegradation of methylene blue dye has been studied.