Molecular dynamics simulations of a poly(p-phenylene) oligomer

We have studied the conformation and coefficient of thermal expansion in the poly(p-phenylene) oligomer p-sexiphenyl (C₃₆H₂₆) by molecular dynamics simulations. Studies of the backbone phenyl–phenyl torsion angle in a simulated p-sexiphenyl crystal at room temperature indicate the presence of torsional librations of approximately ±20°. Further analysis of the phenyl–phenyl backbone torsion angle in less closely packed regions of the simulated crystal (crystal ends) indicate the presence of 180° phenyl ring flips, in agreement with solid-state deuterium NMR data on poly(p-phenylene oligomers). The linear coefficient of thermal expansion was also calculated and found to be negative, in qualitative agreement with experimental data on rigid-rod compounds. © 1993 John Wiley & Sons, Inc.     

Simulation of Molecular Weight Distributions Obtained by Pulsed Laser Polymerization (PLP): New Analytical Expressions Including Intramolecular Chain Transfer to the Polymer

A new approach for the simulation of PLP (pulsed laser polymerization) is presented. This approach allows one to obtain new analytical solutions for different polymerization schemes, including either chain transfer to the monomer or intramolecular chain transfer to the polymer. The first results of the simulation of PLP experiments on n‐butyl acrylate at 20 °C and ambient pressure are presented.

MWDs simulated for PLP of n‐butyl acrylate, in bulk at 20 °C and ambient pressure using three models: the model with intramolecular chain transfer to the polymer (solid line), the model with chain transfer to monomer (dashed line), and the classical model (dotted line).     

Gas chromatographic method for simulated distillation up to a boiling point of 750°C using temperature-programmed injection and high temperature fused silica wide-bore columns

It is demonstrated that linear injection characteristics are obtained for a wide boiling point range sample using a temperature-programmed injector in combination with wide-bore fused silica columns. The applicability of the described combination for high temperature simulated distillation is described. The method, using external standardization, gives accurate and repeatable results for different types of samples in the boiling range between 50 and 750°C. The lifetime of the fused silica wide-bore columns was found to be acceptable, viz. over 80 temperature-programmed cycles between ambient and 430°C. Some comments are made on the accuracy of boiling points for normal alkanes.     

Low Temperature Plasma Assisted Catalytic Reduction of NO<Subscript><Emphasis Type="Italic">x</Emphasis></Subscript> in Simulated Marine Diesel Exhaust

Plasma Assisted Catalytic Reduction (PACR) of NO _x has been investigated at laboratory scale for gas stream compositions representative of marine diesel exhausts. PACR NO _x reduction in excess of 90% was measured at 350°C, a plasma specific energy of 60 J/l and two NO _x concentrations (1,200 and 1,800 ppm). PACR NO _x reduction of over 50% was measured for simulated marine engine conditions at 250°C, 60 J/l and 1,200 ppm NO _x . The performance under these conditions could be increased, achieving a peak of ∼74% NO _x reduction, although at a relatively high plasma power. Water, present in diesel exhaust, was shown to inhibit the poisoning effects of fuel sulphur using SO₂ as a representative exhaust component. The PACR system performance demonstrated tolerance to simulated fuel sulphur levels of up to 1% for the duration of the tests. PACR performance was also shown to be sensitive to the amount of hydrocarbon reductant used.     

Computer simulation to investigate absorption of energies of arrayed disk‐like nanoiron particles under magnetic fields

In this research, we focus on the studying of absorbed energies of materials under an external magnetic field frequency of 0.5 GHz. This wave corresponds to microwave irradiation. The absorbent materials were arrayed disk‐like iron particles with dimension on the nanometer scale and magnetic responses of the particles were simulated by solving the Landau–Lifshitz–Gilbert equation. The external fields were applied from various directions and energies of absorption of the system were calculated. The maximum absorbed energies were found when the field was 135° ± 30° along the X‐axis or the Y‐axis. The current simulation demonstrated that the direction of applied field results in different absorption energies of the system.     

Crystal Structure of the [(C5H4BMe2)2Fe]‐4,4′‐bipyridine Polymer from High Resolution X‐Ray Powder Diffraction

The crystal structure of [(C₅H₄BMe₂)₂Fe]‐4,4′‐bipyridine [ 2 · bipy]_n has been determined by the method of simulated annealing from high resolution X‐ray powder diffraction at room temperature. The compound is of interest, because it proves that highly ordered organometallic macromolecules can be formed in the solid state via the self‐assembly of N–B‐donor‐acceptor bonds. [ 2 · bipy]_n crystallizes in the triclinic space group, P 1, Z = 2, with unit cell parameters of a = 8.3366(2) Å, b = 11.4378(3) Å, c = 12.6740(5) Å, α = 112.065(2)°, β = 108.979(1)°, γ = 90.551(2)°, and V = 1047.06(6) ų. For the structure solution of [ 2 · bipy]_n 11 degrees of freedom (3 translational, 3 orientational, 5 torsion angles) were determined within several hours, demonstrating that the crystal packing and the molecular conformation of medium sized (< 50 non‐hydrogen atoms) coordination compounds can nowadays be solved routinely from high resolution powder diffraction data.     

Molecular dynamics study of ferrocene topology under various temperatures

We present the first quantum mechanical Atom-Centered Density-Matrix Propagation molecular dynamic (MD) study to investigate ferrocene (Fc) conformation in gas phase. The MD simulations were performed at several temperatures (7, 18, 80, 120, 180, 293, and 500 K) for a period of 10 ps. It is found that, at very low temperatures (≤18 K), ferrocene prefers eclipsed-like conformation. At higher temperatures (>18 K), the cyclopentadienyl rings (Cp) of ferrocene exhibit apparent fluxional rotations, leading to configurations with the rotational angle δ distributing within a range of 0° (eclipsed) to 18° (approximately half of 36° for the staggered conformation), accompanied by the cyclopentadienyl ring tilt up to approximately 12° at 500 K. The simulated mean inferred (IR) spectrum of ferrocene at 7 K is clearly dominant by a doublet-splitting band of eclipsed-like Fc features in the region of 400 to 600 cm⁻¹, in agreement with previous IR studies. The animation obtained from the MD simulations indicates that, at room temperature, the Fe-C distances in ferrocene are in fact not strictly congruent but 2:2:1-fold.     

New insight into dynamic mechanical relaxation in N-butyl-N-(2-nitroxy-ethyl) nitramine plasticized nitrocellulose through molecular dynamic simulations

We performed dynamic mechanical analysis (DMA) on nitrocellulose (NC) plasticized by an insensitive plasticizer N-butyl-N-(2-nitroxy-ethyl)nitramine (Bu-NENA). NC/Bu-NENA blend shows two mechanical relaxation processes in the temperature ranges of???50 to???40 °C and 30?~?40 °C, and their variations with deformation frequencies were studied. To explore further the effect of temperature on relaxation, the binary mixture model of NC/Bu-NENA was constructed, and molecular dynamic simulations were conducted. The simulated mean square displacements (MSD) show abrupt increase in the temperature range of???50 to???40 °C and 30?~?40 °C, which are consistent with those of the two relaxation processes observed in the DMA curves. Moreover, the free volume (V_free) and torsion energy obtained from molecular dynamic simulations exhibit distinct increase at the temperature above 30 °C and???50 °C respectively, reflecting the sudden enhancements on the mobility of polymer chain elements and the rotation of molecular bonds. Furthermore, the radial distribution function (RDF) associated with the intermolecular interactions reveals that the intensities of both hydrogen bond and van der Waals forces decrease with the increase of temperature, which is responsible for the decrease of storage modulus at high temperature. These computational and experimental studies reveal guidance to strengthening the NC base propellants in broad temperature range.

     

Electron diffraction and computer modeling of poly(naphthalic anhydride) crystal structure

Single crystals of poly(naphthalic anhydride) (PNA) have been grown using our confined thin film melt polymerization technique. Lamellae, 70–100 Å thick, are found for the crystals polymerized at 180°C with thinner lamellae for a 200°C polymerization temperature. In addition, irregular lath-shaped crystals are found for both polymerization temperatures, apparently formed by a solid-state polymerization process within the original needle-like monomer crystals. The crystal structure of PNA has been studied by electron diffraction (ED) and computer modeling based on seven different zonal ED patterns. It is found that, in most cases, two or three different zonal patterns are superimposed with a common plane, suggesting variable chain tilting even in individual lamellae. Shearing of the material shortly after the initiation of polymerization, permitted obtaining an additional [010] zone ED pattern. A monoclinic unit cell with one chain, two repeat units is proposed based on measurements of 21 independent reflections; the space group is Pc11; a = 6.26 Å, b = 4.33 Å, c = 18.60 Å, and α = 122.5°. The computer-simulated (Cerius²) molecular conformation and chain packing are described with the corresponding simulated electron diffraction patterns being in good agreement with the observed ones. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35 : 1575–1588, 1997     

A Thermodynamic Study of Bromo-Lanthanum (III) Complexes from EMF Measurements

The stability constants (for the formation) of LaBr²⁺ and LaBr₂⁺ ions were obtained potentiometrically at various ionic strengths at 20°, 25°, 30°, and 35°. The molal free energy was given by ΔG°=-2,444.04+2.67T log T+1.39T. The thermodynamic quantities for the formation of LaBr²⁺ were evaluated as ΔH_f° = ?207.9, ΔG_f° = ?199.1 kcal mole^?1 and S° = ?29.5 cal. deg^?1 mole^?1 at 25°.     

Adsorption of Eu(III) from aqueous solution using mesoporous molecular sieve

The adsorption behavior of Eu(III) from aqueous solution to mesoporous molecular sieves (Al-MCM-41) is investigated as a function of contact time, solid content, ionic strength, pH, foreign ions and temperature by using batch technique. The experimental results show that Eu(III) adsorption is strongly dependent on pH values, but independent of ionic strength and foreign cations under our experimental conditions. The kinetic process is described by a pseudo-second-order rate model very well. The adsorption isotherms are simulated by Langmuir model very well. The thermodynamic parameters (∆G°, ∆S°, ∆H°) are calculated from the temperature dependent adsorption isotherms at 293, 313 and 333 K, respectively, and the results suggest that the adsorption of Eu(III) on Al-MCM-41 is a spontaneous and endothermic process. Desorption studies indicate that the adsorbed Eu(III) is very difficult to be desorbed from the solid surface. Al-MCM-41 is a suitable material for the preconcentration and solidification of Eu(III) from large volumes of aqueous solutions.     

The effect of annealing temperatures on surface properties,hydroxyapatite growth and cell behaviors of TiO2 nanotubes

Well‐ordered TiO₂ nanotubes were prepared by the electrochemical anodization of titanium in an ethylene glycol electrolyte containing 1 wt% NH₄F and 10 wt% H₂O at 20 V for 20 min, followed by annealing. The surface morphology and crystal structure of the samples were examined as a function of the annealing temperature by field emission scanning electron microscopy (FE‐SEM) and X‐ray diffraction (XRD), respectively. Crystallization of the nanotubes to the anatase phase occurred at 450 °C, while rutile formation was observed at 600 °C. Disintegration of the nanotubes was observed at 600 °C and the structure vanished completely at 750 °C. Electrochemical corrosion studies showed that the annealed nanotubes exhibited higher corrosion resistance than the as‐formed nanotubes. The growth of hydroxyapatite on the different TiO₂ nanotubes was also investigated by soaking them in simulated body fluid (SBF). The results indicated that the tubes annealed to a mixture of anatase and rutile was clearly more efficient than that in their amorphous or plain anatase state. The in vitro cell response in terms of cell morphology and proliferation was evaluated using osteoblast cells. The highest cell activity was observed on the TiO₂ nanotubes annealed at 600 °C. Copyright © 2010 John Wiley & Sons, Ltd.     

Simulated Microgravity Affects Growth of <Emphasis Type="Italic">Escherichia coli</Emphasis> and Recombinant β-<Emphasis Type="SmallCaps">d</Emphasis>-Glucuronidase Production

Effects of simulated microgravity (SMG) on bacteria have been studied in various aspects. However, few reports are available about production of recombinant protein expressed by bacteria in SMG. In this study growth of E. coli BL21 (DE3) cells transformed with pET-28a (+)-pgus in double-axis clinostat that could model low shear SMG environment and the recombinant β-d-glucuronidase (PGUS) expression have been investigated. Results showed that the cell dry weights in SMG were 16.47%, 38.06%, and 28.79% more than normal gravity (NG) control, and the efficiency of the recombinant PGUS expression in SMG were 18.33%, 19.36%, and 33.42% higher than that in NG at 19 °C, 28 °C, and 37 °C, respectively (P < 0.05).     

Synthesis of two novel cobalt complexes and their crystal structures

Two new cobalt complexes were successfully synthesized from the reaction of binaphthyl Schiff base 2 with Co(OAc)₂ in the presence of sodium methoxide at 80 °C for 24 h and Co(acac)₃ in toluene under reflux. Their unique crystal structures are unambiguously disclosed by X‐ray analysis. Complex 3 is triclinic, space group P1 , unit cell dimensions a = 10.742(2) Å, b = 11.153(2) Å, c = 12.715 Å, α = 79.865(3) °, β = 76.053 °, γ = 72.532(4) °, volume 1401.3(5) ų, Z = 2. Complex 4 is triclinic, space group P1 , unit cell dimensions a = 10.801(2) Å, b = 12.554(3) Å, c = 15.219(3) Å, α = 105.672(4) °, β = 103.048 °, γ = 104.594(4) °, volume 1824.8(7) ų, Z = 2, calculated density 1.428 Mg m⁻³. Copyright © 2003 John Wiley & Sons, Ltd.     

On the Crystal Structure of a Previously Unknown Anhydrous Zinc Hydroxide Sulfate

Anhydrous zinc hydroxide sulfates are promising precursors for the preparation of pigments and ZnO nanomaterials. The crystal structure of one such compound 5[Zn(OH)₂] · 2[ZnSO₄] was determined from high resolution laboratory X‐ray powder diffraction data by use of a combination of charge flipping, 18 simulated annealing, 26 and difference Fourier analysis. The material crystallizes in the space group P$\bar{1}$ with the lattice parameters of a = 5.4559(2) Å, b = 8.0528(3) Å, c = 8.9275(3) Å, α = 112.697(2)°, β = 85.219(3)°, γ = 95.441(3)°, and a volume of V = 359.76(2) ų. The basic crystal structure consists of brucite type Zn(OH)₂ layers where every sixth octahedral site is vacant. Tetrahedrally coordinated zinc ions are located above and below these vacancies and consecutive layers are bridged by sulfate molecules. The composition of this layered structure can be written as [Zn₅^VI□(OH)₄ · Zn₂^IV(OH)₆ · (SO₄)₂]. Its thermal decomposition was studied by X‐ray powder diffraction and thermal analysis.     

Thermodynamic Studies on the Complexation Reactions of Copper(II) Macrocyclic Tetramine Complexes with Monodentate Ligands: Part II. A Spectrophotometric Study on the Reactions of Meso-5, 7, 7, 12, 14, 14-Hexamethyl-1, 4, 8, 11-Tetraazacyclotetradecane-Copper(II) (Blue) with Halide Ions

The stability constants for the formation of [Cu(tet a)X]⁺(blue) from [Cu(tet a)]²⁺(blue) and X- (where X=Cl, Br, I) were determined by spectrophotometric method at 15°, 25° and 35°C. The corresponding ΔH° and ΔS° values were obtained from the variations of the stability constants between 15° and 35°C. For the same halide ion, the stability constant of [Cu(tet b)X]⁺ (blue) is larger than that of [Cu(tet a)X]⁺(blue).     

THE CRYSTAL AND MOLECULAR STRUCTURE OF THE POTENTIAL ANTIBACTERIAL AGENT 2-PYRIDYL-PHENYL SULPHONE

Abstract

Crystals of 2-pyridyl-phenyl sulphone are monoclinic, space group P2₁/c, with eight molecules in the unit cell of dimensions a = 11.781, b = 5.903, c = 29.748 Å and B = 94.13°. The dihedral angles between the best planes of the two aromatic rings are significantly different in two crystallographically independent molecules (88.4° and 71.9° for molecule A and molecule B, respectively), as well as those between the CSC plane and the pyridine ring (59.4° and 67.4°) and between the CSC plane and the phenyl ring (51.7° and 81.8°). The average bond distances of interest include C?S 1.77(1) and S?O 1.44(1) Å; among the bond angles there are CSO = 108.1(7), CSC = 105.0(6) and OSO = 118.7(6)°. The packing of the molecule in the crystal is determined by the van der Waals interactions and by two intermolecular H?O contacts of 2.43 and 2.49 Å. The observed conformation in the solid state agrees well with results of previous investigations, in the solution state, by means of dipole moment method and theoretical M.O. calculations, for the analogous di-2-pyridyl sulphone.     

NIPAAm-containing amphiphilic block copolymers with tailored LCST: Aggregation behavior,cytotoxicity and evaluation as carriers of indomethacin,tetracycline and doxorubicin

Nanocarriers based on amphiphilic block copolymers, with tailored temperature and pH responsiveness, were prepared. The hydrophilic blocks consist of temperature-sensitive [N-isopropylacrylamide (NIPAAm)] or NIPAAm plus pH-sensitive units [5-methacryloyloxy pentatonic acid (5MPA) or 4-methacryloyloxy benzoic acid (4MBA)], while the hydrophobic block is composed of n-hexyl acrylate (HA) or styrene (ST). Particle sizes were within the suitable range for the desired application (30–182?nm). Drug loading was achieved via an organic solvent-free method and a THF-buffer method leading to drug loadings of indomethacin, tetracycline and doxorubicin of up to 11, 11 and 60?wt%, respectively. In vitro release kinetics were performed under simulated physiological conditions (pH 7.4 and 37?°C; pH 6.0 and 40?°C) and show differences depending on the copolymer composition. The average kinetic data were well fitted to the mathematical model of Peppas. NIPAAm-containing copolymers were slight or non-cytotoxic for rat primary hepatocytes at concentrations less than 200?µg mL^?1. Some of the polymeric aggregates prepared may find application as pharmaceutical carriers.     

X-Ray and thermal studies of nylon 5,7

The unit cell and probable space group of Nylon 5,7 has been determined. The unit cell is monoclinic with the dimensions a = 0.483 nm, b = 0.935 nm, c = 1.662 nm, and γ = 58.9°. The space group is probably P_b which is noncentrosymmetric. Rolled, annealed samples show three-dimensional orientation. The melting point peak of a rapidly cooled sample is about 213°C when it is heated at 20°C/min. Slow cooling, ≤°1°C/min generates a higher melting species, T_m = 228°C. Crystallinities are in the normal nylon range, up to 50% for a slow cooled sample.     

A mutant of Escherichia coli K12 exhibiting varying ultraviolet sensitivities depending on the temperature of incubation after irradiation

Abstract— A mutant, URT-43, was isolated from E. coli C600 dar⁺. The mutant has a characteristic feature in that its sensitivity to ultraviolet (u.v.) light is greatly influenced by the temperature at which irradiated bacteria are incubated. On the basis of dose-reduction factor, URT-43 is approximately ten times more sensitive at 42° than at 30°C, even though unirradiated bacteria are not thenno-sensitive, The mutant could not repair u.v.-irradiated bacteriophage Λ_vir in the dark either at 30° or at 42°C, indicating that it is defective in host-cell reactivation. In contrast, the same bacteriophage was reactivated in preirradiated URT-43 if the host-bacteriophage complex was plated at 30° but there was no reactivation at 42°C. Therefore u.v.reactivation was positive at 30° but negative at 42°C. The induction of prophage by URT-43(Λ_h) was achieved by much lower doses of U.V. light than that required for the induction of lysogenic wild type bacteria. Experiments were performed in which irradiated URT-43 was first incubated for various periods in liquid media and plated both at 30° and 42°C. It was found that irradiated bacteria came to be resistant to subsequent plating at 42° only when they were preincubated in the liquid medium containing necessary amino acids and at 30°C. Since this phenomenon was completely inhibited by chloramphenicol, the process seemed to require de novo protein synthesis. An hypothesis was proposed that there are at least two independent dark-repair mechanisms in E. coli; one is responsible for host-cell reactivation and the other is responsible for U.V. reactivation.