Molecular dynamics simulations of polyphosphazenes: poly[bis(chloro)phosphazene][NPCl2]n

Suitable parameter sets for the CHARMm force field were derived for the structural units in polychlorophosphazene [P=N, P N, P Cl] using the Dinur Hagler energy second derivative procedure based on quantum mechanical SCI calculations using the 6–31G^* basis set. To validate the reliability of the parameter set, structural results obtained with CHARMm for the adopted model compounds (OP₂NCl₅ and OP₃N₂Cl₅) were compared with those derived fromab initio quantum mechanics using the 6–31G^* basis set. Application of molecular dynamics (MD) simulations in combinatioin with the available X-ray diffraction data provided structural and conformational information on the polymer. The calculation made using the periodic boundary conditions (PBC) agree well with the polychlorophosphazene ordered in a monoclinic unit cell (a=5.98,b=12.99,c=4.92 A; =111.7). This model was stabilized mainly by the image atoms contribution to the electrostatic energy term and had aquasi-planar conformation of the backbone chain (glide symmetry). The MD calculations also provided evidence that the difference between single and double PN bonds is less marked than that measured experimentally. This result is, however, in agreement with more recent and accurate X-ray studies on poly(methylphosphazene). Validation of the polymer model provided a complete picture, otherwise experimentally inaccessible, of the internal fluctuations of the polymeric chains.Presented at the 1st Italian Workshop on Cyclo- and Poly(phosphazene) Materials, February 15–16, 1996, at the CNR Research Area in Padova, Italy.     

Bis-Schiff bases of isatin as new and environmentally benign corrosion inhibitor for mild steel

Inhibition effect of three bis-Schiff bases of isatin namely (2-methoxybenzylidene) hydrazono) indolin-2-one (HZ-1), (2-hydroxybenzylidene) hydrazono) indolin-2-one (HZ-2) and (4-nitrobenzylidene) hydrazono) indolin-2-one (HZ-3) was studied on mild steel corrosion in 1.0 M HCl by gravimetric measurements, electrochemical impedance spectroscopy (EIS), potentiodynamic polarization and quantum chemical study. The values of activation energy (E_a), equilibrium constant (K_ads), free energy of adsorption ΔG°_ads, activation enthalpy ΔH^* and activation entropy ΔS^*were discussed. The adsorption of inhibitors on metal followed Langmuir's adsorption isotherm. SEM and EDX observations confirmed the existence of protective inhibitor film on metal surface. Quantum chemical study supports the comparative inhibition effect of HZs.     

Propagation rate coefficient of acrylic acid: theoretical investigation of the solvent effect

The free-radical polymerization propagation rate coefficient (k_p) of acrylic acid (AA) was calculated using transition state theory and ab initio quantum chemistry in order to shed light on the very strong solvent effects observed experimentally. Calculations were performed using a gas-phase reaction simulation, and the contribution of solvent then taken into account using the Polarizable Continuum Model for two solvents—water and toluene. The frequency factor (A) for AA propagation was insensitive to both varying the level of quantum theory applied as well as introducing a solvent field into the calculations. The activation energy (E_a) decreased substantially (∼10 kJ mol⁻¹) upon introduction of the water solvent field relative to the gas phase; however, the toluene solvent field had little impact on E_a. From analyzing transition state (TS) bond lengths and angles, as well as electronic density, this variation in E_a was attributed to greater resonance stabilization of the TS in the polar solvent, as well as more substantial mixing of reactant molecular orbitals, assisting in the transfer of electrons from the alkene to the radical. This provides a partial explanation to the marked variation in aqueous-phase k_p of water-soluble monomers seen experimentally with changes in monomer and electrolyte concentrations, which alters the hydrogen bonding patterns in solution.     

An efficient method for a numerical description of virgin olive oil color with only two absorbance measurements

Four polynomial expressions are obtained that provide a good approximation and an easy, rapid calculation of the chromatic coordinates and the chroma—L ^*, a ^*, b ^*, and C—for the illuminant C and the standard observer, for a virgin or extra virgin olive oil; absorbance is measured at only 480 and 670 nm. These are as follows: L ^*=0.556458(A₄₈₀)²−2.51145A₄₈₀+0.55504(A₆₇₀)²−8.53016A₆₇₀+98.4089; a ^*=0.177372(A₄₈₀)²+2.1363A₄₈₀+1.43254(A₆₇₀)²−0.789231A₆₇₀−13.9246; b ^*=−16.0277(A₄₈₀)²+79.8932A₄₈₀−5.06558(A₆₇₀)²+3.36169A₆₇₀+31.9405; C=−15.8439(A₄₈₀)²+78.9312A₄₈₀−5.26784(A₆₇₀)²+3.56917A₆₇₀+33.3927. These give acceptable results, making the method a practical alternative to the extremely laborious Commission Internationale d’Eclairage (CIE) L ^* a ^* b ^* system, by which 391 absorbance values must be measured individually, nanometer by nanometer, before applying more complex equations. The validity of the proposed method has been confirmed by comparison, using a set of 20 sample oils different from the set of 25 oils used to generate the order of the equations. The variations between the values provided by the proposed and standard methods, respectively, had a mean of 0.00 for each of the chromatic variables—L ^* , a ^* , b ^* , and C; SD were moderate (0.71, 0.52, 1.22, and 1.22, respectively); the root mean square and the R ²-terms also confirmed the validity of the method.     

The first example of half-sandwich cobalt(III) complex with hydrotris(pyrazolyl)borate ligand

This paper presents the synthesis, crystal structure and spectroscopic properties of a novel half-sandwich mononuclear cobalt(III) complex with hydrotris(3,5-dimethylpyrazolyl)borate ligand and thiocyanate [Tp^*Co(Hpz^*)(NCS)₂]·H₂O·CH₃OH (Tp^*: hydrotris(3,5-dimethyl- pyrazolyl)borate, Hpz^*: 3,5-dimethylpyrazole). The structure was determined by X-ray diffraction. The complex crystallizes in the monoclinic system, space group C_c, a=18.591(6) Å, b=10.536(3) Å, c=17.568(5) Å, β=11.284(5)°, Z=4, R₁=0.0501, wR₂=0.1179. The cobalt(III) ion in the complex is six-coordinated with nitrogen atoms, three from Tp^*, two from pyrazole and two from two thiocyanates, to form octahedral environment. The hydrogen atoms of O(2) of water molecule are connected by hydrogen bonds with S atoms of two adjacent complex molecules to form 1-D chains. The hydrogen atom of N(8) of complex molecule is connected by hydrogen bond with methanol. The spectroscopic results are consistent with the crystallographic study.     

Influence of the lift force closures on the numerical simulation of bubble plumes in a rectangular bubble column

Numerical Eulerian-Eulerian simulations of the unsteady gas-liquid flow in a centrally aerated two-dimensional bubble column were carried out in order to understand the effect of different formulations of the lift force coefficient (C_L) on the computational results. Three different values of the superficial gas velocity (U_G=2.4, 12.0 and 21.3 mm s⁻¹) that ensure the existence of different flow regimes were experimentally and computationally studied. The validation of the simulated results was based on visual observations and measurements of the global gas hold-up (ε_G) and the plume oscillation period (POP). The results presented reveal that, at U_G=12.0 and 21.3 mm s⁻¹, using C_L<0 results in under- and over-estimation of the ε_G and POP, respectively. On the other hand, taking C_L>0 does not affect the POP while it leads to increasingly higher ε_G values, which are different from those experimentally reported. At U_G=2.4 mm s⁻¹, the effect of the lift force is not so evident, although it slightly improves the prediction of experimental values. Particularly interesting is the case of C_L>0.4 at U_G=21.3 mm s⁻¹, producing a non-symmetric bubble plume oscillation. Since using Tomiyama's lift coefficient correlation does not improve the results, including the lift force into the simulation of bubble plumes is not recommended.     

Synthesis,Structure, Molecular Orbital and Valence Bond Calculations for Tetrazole Azide,CHN7

The synthesis, NMR spectroscopic characterization and structure determination of highly explosive tetrazole azide, a very nitrogen‐rich material (88.3% N) is reported. Tetrazole azide was prepared in high yield from the diazotation reaction of aminotetrazole, followed by treatment of the formed diazonium salt with sodium azide. Synthesis in diethylether/methanol and recrystallization from diethylether afforded colorless cubes: CHN₇ ( 1 ): monoclinic, P1 2₁/n₁, a=1346.6(5), b=499.6(2), c=1360.9(5) pm, β=105.14(1)⁰, V=0.884(2) nm³, Z=8, ϱ=1.670 g cm⁻³. The observed structural parameters (X‐ray) are in good accordance with the results from molecular orbital (MO) calculations. The computed electrostatic potential (B3LYP) suggests a pronounced shock and friction sensitivity which was confirmed experimentally. Quantitative valence bond (VB) calculations were performed for the most important 21 VB structures in order to obtain the structural weights and to obtain an assessment for the importance of the various individual VB structures considered.     

Germacrene D Cyclization: An Ab Initio Investigation

Essential oils that contain large concentrations of germacrene D are typically accompanied by cadinane sesquiterpenoids. The acid-catalyzed cyclization of germacrene D to give cadinane and selinane sesquiterpenes has been computationally investigated using both density functional (B3LYP/6-31G^*) and post Hartree-Fock (MP2/6-31G^{* *}) ab initio methods. The calculated energies are in general agreement with experimentally observed product distributions, both from acid-catalyzed cyclizations as well as distribution of the compounds in essential oils.     

Mössbauer spectroscopic and chromaticity analysis on colorative mechanism of celadon glaze

The dependence of the color of a celadon glaze on the chemical composition and the electronic state of Fe was investigated by Mössbauer spectroscopic and chromaticity analysis. The amount of Fe₂O₃ was found to be the main factor influencing L* and b* values, whereas the amount of TiO₂ was found to affect all the parameters (L*, a*, b*). The effect of MnO on the color was significant only by interaction terms. The amount of P₂O₅ was found to be the main factor of the b* value. According to the Mössbauer analysis results, as the amount of divalent iron ions increases, the a* and b* values decreased; on the other hand, the L* value increased. As the amount of titanium increased, Fe²⁺ was found to be destabilized relative to Fe³⁺ due to the structural instability of Fe-O-Ti network.     

Kinetics measurements on a stationary disk electrode in a uniformly rotating fluid (SDERF). II. The electron transfer reaction in the Fe(CN)4−6/Fe(CN)3−6-system

The operation of the SDERF-cell in the study of the electron transfer kinetics of the Fe(CN)^4?₆/Fe(CN)^3?₆-system in 1 M KCl and 1 M KNO₃-solutions at a stationary Pt-disk electrode is reported. The experimental current—overpotential curves are recorded by linear sweep voltammetry and analysed by two different methods using the theoretical relationship derived for a stationary disk electrode placed in a free rotating fluid. Both methods give the same value for the experimental rate constant k*. The effects of the temperature (0° to 40°C) and of the ratio of the rotor radius (r_r) to the electrode radius (r_e)(r_r/r_e = 0.50 to 0.81) have been studied. The activation energy for the redox process in 1 M KCl and 1 M KNO₃ are: E_a = 3.4 ± 0.6 kcal/mol and E_a = 3.7 ± 0.7 kcal/mol respectively, while the k*-values at 25°C are: k* = (5.67 ± 0.41) × 10^?3 cm.s^?1 and k* = (4.53 ± 0.29) × 10^?3 cm.s^?1 respectively. The difference from the standard rate constant k₀ ? 0.100 cm.s^?1 is explained by the effect of the cell-geometry characterized by the G-factor, so that k° = Gk*, where G ? 19 for our cell.     

Corrosion inhibitors : Part II: Quantum chemical studies on the corrosion inhibitions of steel in acidic medium by some triazole, oxadiazole and thiadiazole derivatives

The corrosion inhibition efficiencies of some triazole, oxadiazole and thiadiazole derivatives for steel in presence of acidic medium have been studied by using AM1, PM3, MINDO/3 and MNDO semi-empirical SCF molecular orbital methods. Geometric structures, total negative charge on the molecule (TNC), highest occupied molecular energy level (E_HOMO), lowest unoccupied molecular energy level (E_LUMO), core-core repulsion (CCR), dipole moment (μ) and linear solvation energy terms, molecular volume (V_i) and dipolar-polarization (π^*), were correlated to corrosion inhibition efficiency. Four equations were proposed to calculate corrosion inhibition efficiency. The agreement with the experimental data was found to be satisfactory; the standard deviations between the calculated and experimental results ranged between ±0.03 and ±4.18. The inhibition efficiency was closely related to orbital energies (E_HOMO and E_LUMO) and μ. The correlation between quantum parameters and experimental inhibition efficiency has been validated by single point calculations for the semi-empirical AM1 structures using B3LYP/6-31G^** as a higher level of theory. The proposed equations were applied to predict the corrosion inhibition efficiency of some related structures to select molecules of possible activity from a presumable library of compounds.     

The synthesis and crystal structure of [M{H2B(tz*)2}2(H2O)] (M=Cu,Zn and tz*=3,5-dimethyl-1,2,4-triazole)

New ligand [KH₂B(tz^*)₂] (tz*=3,5-dimethyl-1,2,4-triazolyl) has been synthesized and the reactions of two different metal salts (copper and zinc) with the new ligand in agar gave two similar crystalline polymorphic forms: [Cu{H₂B(tz^*)₂}₂(H₂O)] (1) and [Zn{H₂B(tz^*)₂}₂(H₂O)] (2). A single crystal X-ray study revealed that the compound 1 was the monoclinic system with space group C2/c and a=8.462(3) Å, b=14.039(6) Å, c=19.991(8) Å, β=94.622(7)°, Z=4, R₁=0.0451, wR₂=0.1110. And the compound 2 was the monoclinic system with space group C2/c and a=8.4214(4) Å, b=13.8765(7) Å, c=20.2969(6) Å, β=95.615(2)°, Z=4, R₁=0.0667, wR₂=0.1375. The metal(II) ion in the complex is five-coordinated with four nitrogen atoms which come from triazolyl and one oxygen atom which come from water molecular. In both compounds, the hydrogen atoms of water molecule are connected by hydrogen bonding with N atoms of two adjacent complex molecules to form 2-D planes. The spectroscopic results are consistent with the crystallographic study.     

Structural and electronic properties of poly(3-thiophen-3-yl-acrylic acid)

This work presents a combined theoretical and experimental study of poly(3-thiophene-3-yl acrylic acid), a new polythiophene derivative soluble in polar solvents. Quantum chemical calculations on small oligomers were performed to propose a structural model for this polymer. Specifically, the minimum energy conformations and the rotational profiles of the different isomeric derivatives constructed for a model system formed by two monomeric units were calculated. The resulting model, which shows head-to-tail polymer linkages and the acrylic acid side group arranged in trans-conformation, were used to predict the π-π^∗ lowest transition energy of an infinite polymer chain. On the other hand, the polymer was prepared by chemical oxidative coupling using anhydrous ferric chloride and subsequent alkaline hydrolysis. The synthetized material, which is soluble in aqueous base and acetone solutions, was characterized by FTIR, ¹H NMR and UV-vis experiments. Both the structural information and electronic properties derived from such experiments are fully consistent with the theoretical model obtained using quantum mechanical calculations.     

Ring-opening polymerization of ϵ-caprolactone initiated by rare earth complex catalysts

The polymerization of caprolactone (ϵ-CL) was initiated by yttrium triisopropoxide {Y(OPⁱ_r)₃}, bimetallic isopropoxide of yttrium and aluminum {Y[Al(OPⁱ_s)₄]₃}, yttrium and tin(II) {Y[Sn(OPⁱ_r)₃]₃}, and tin(II) and yttrium {Sn[Y(OPⁱ_r)₄]₂}, respectively. The polymerization was carried out through coordinative insertion of a monomer into the free metal-oxygen bond. The molecular weight and yield of poly(ϵ-caprolactone) (PCL) were affected drastically by the mol % of the initiator to the monomer (C_o/M_o). The results showed that Y(OPⁱ_r)₃ and Sn[Y(OPⁱ_r)₄]₂ were more effective than were {Y[Al(OPⁱ_r)₄]₃} and {Y[Sn(OPⁱ_r)₃]₃} for the polymerization of ϵ-CL. When polymerization was conducted at 5°C using Y(OPⁱ_r)₃ as the initiator or at 10°C using Sn[Y(OPⁱ_r)₄]₄ as the initiator, polymers with a molecular weight of 45.9 × 10³ or 54.0 × 10³ and high yield resulted in 30 or 5 min, respectively. The polymer was characterized by FTIR, H-NMR, and GPC. © 1997 John Wiley & Sons, Inc. J Appl Polym Sci 64: 1295–1299, 1997     

Supersaturation of oxygen in acidic solution in the vicinity of an oxygen-evolving platinum anode

The concentration of O₂ in 1 M H₂SO₄ solution in the vicinity of the O₂-evolving smooth Pt anode was measured as a function of anodic cdi_a using the galvanostatic potential—transient method.The solution near the O₂-evolving anode was supersaturated with O₂. When the anodic current was interrupted, supersaturated concentration C^* decreased at a rate proportional to C^*  C₀, where C₀ is the solubility of O₂ in the electrolyte at 1 atm. The rate constant of the decay of the supersaturation under the open circuit condition was measured to be 0.069 sec^?1 at 25°C.At i_a < 40 mA/cm² there was a linear relation between log(C^*  C₀) and log i_a. At i_a > 200 mA/cm², however, the supersaturation exhibited a limiting value of 9.0 × 10^?2 mol/l.     

A model for initial-stage sintering thermodynamics of an alumina powder

A model was proposed to calculate several thermodynamic parameters for the initial-stage sintering of an alumina powder obtained after calcinations at 900 °C for 2 h of a precursor. The precursor was synthesized by an alumina sulphate-excess urea reaction in boiling aqueous solution. The cylindrical compacts of the powder with a diameter of 14 mm were prepared under 32 MPa by uniaxial pressing using oleic acid (12% by mass) as binder. The compacts were fired at various temperatures between 900 and 1400 °C for 2 h. The diameter (D) of the compacts before and after firing was measured by a micrometer. The D value after firing was taken as a sintering equilibrium parameter. An arbitrary sintering equilibrium constant (K_a) was calculated for each firing temperature by assuming K_a = (D_i − D) / (D − D_f), where D_i is the largest value before sintering and D_f is the smallest value after firing at 1400 °C. Also, an arbitrary change in Gibbs energy (ΔG _a°) was calculated for each temperature using the K_a value. The graphs of ln K_avs. 1 / T and ΔG _a° vs. T were plotted, and the real change in enthalpy (ΔH°) and the real change in entropy (ΔS°) were calculated from the slopes of the obtained straight lines, respectively. Inversely, real ΔG° and K values were calculated using the real ΔH° and ΔS° values in the ΔG° = − RT ln K = ΔH° − TΔS° relation. The best fitting ΔH° and ΔS° values satisfying this relation were found to be 157,301 J mol^− 1 and 107.6 J K^− 1 mol^− 1, respectively.     

Change in the structure of poly(tetramethylene succinate) under tensile stress monitored with solid state C NMR

A new solid-state NMR experimental equipment was developed to monitor the structural change of polymer and protein fibers under active uniaxial deformation. The equipment was applied to monitoring change in the structure of a biodegradable aliphatic polyester fiber, poly(tetramethylene succinate) (PTMS; [-O(CH₂)₄OCO-(CH₂)₂CO-]_n), as a function of tensile stress. The crystal transition from α to β forms for PTMS was induced by stress and monitored by the change of the methylene region in the ¹³C NMR spectra. The ¹³C chemical shielding constant for the model compound of poly(tetramethylene succinate) was calculated using the GIAO-CHF (gauge invariant atomic orbitals-coupled Hartree-Fock) with ab initio 6-311G^∗∗ basis set. This calculation acceptably explains the experimental results.     

A misunderstood member of the nagelschmidtite family unveiled: structure of Ca5Na2(PO4)4 from X-ray powder diffraction data

During the development of procedures to synthesize carbonate hydroxyapatite with properties resembling those of biological material, a new phase was found to form after high temperature treatments in the presence of sodium. The compound was isolated and analytically characterized, leading to its identification as Ca₅Na₂(PO₄)₄: an analogous Ca–Na phosphate was previously described, but with rather poor diffraction data and uncertain stoichiometry. Accurate XRD powder patterns revealed a hexagonal cell, space group P6₃mc (186), a=10.64 Å, c=21.71 Å, Z=6, ρ=2.93 g/cm³, with the a axis double and the c axis triple those of the subcell typical of α-phases in the well-known system A₂XO₄ (or ABXO₄). The complete structural determination was carried out and the relevant aspects and properties discussed.     

Photophysical processes and interactions between poly(ethylene terephthalate) and 1-amino-2-(2-methoxyethoxy)-4-hydroxy-9,10-anthraquinone

The effect of 1-amino-2-(2-methoxyethoxy)-4-hydroxy-9,10-anthraquinone (C. I. Disperse Red 59) on the phototendering of poly(ethylene terephthalate) (PET) was assessed. The photophysical processes occurring in the polymer, the dye, and the dyed polymer were determined. The energy and nature of the dye and polymer electronic excited states were assigned on the basis of absorption and luminescence properties. Irradiation failed to produce dye-sensitized phototendering of PET; however, the titanium dioxide delusterant in commercial PET did function as a sensitizer in the presence of moist air. The phototendering of blank-dyed PET yarn was found to obey (pseudo-) zero-order kinetics k = 1.69 × 10^?19 per cent breaking strength loss/quantum absorbed/cm². The dye exhibited fluorescence from a lowest, ～51.5 kcal/mole, singlet charge-transfer (C-T) excited state but did not phosphoresce. The PET possessed a complex fluorescence spectrum attributed to similar ¹(n,π^*)₁ excited states, ～78.1 kcal/mole, while its phosphorescence derives from a proposed ³(π,π^*) state, ～69.8 kcal/mole, populated by intersystem crossing from a ¹(π,π^*) state, ～92.3 kcal/mole. The dyed polymer exhibited a PET-sensitized delayed fluorescence from the dyestuff involving triplet–singlet transfer by a dipole–dipole (Coulumbic) long-range resonance excitation mechanism. The transfer process was characterized by an experimentally determined critical transfer distance, R₀, of approximately 40 Å.     

Influence of zirconocene structure and propene intent on melt rheology of polyethene and ethene/propene copolymers

Summary Ethene was homo- and copolymerized in the presence of methylaluminoxane (MAO)-activated zirconocenes comprising (Me₅CP)₂ZrCl₂ (Cp^*) and racemic dimethylsilylene-bis[-2-methyl-indenyl]-bridged zirconocene dichloride where the ligand framework was varied by benzannelation (MBI), 4-phenyl (MPI), and 4- naphthyl (MNI) substitution. Zero shear viscosity and shear thinning of the ethene homopolymers increased as a function of the catalyst system with MNI • MPI > MBI >> Cp^* and were correlated with the presence of long chain branches formed via reinsertion of vinyl-terminated polymer chains. The ranking was confirmed using the reduced vanGurp Palmen plot (δ vs. ?G^*?/G_N ⁰) being less sensitive on molecular weight for polyolefin materials. Poly(ethene-co-propene)s (EP) containing 17 and 30 wt.-% propene were long chain branched as reflected by pronounced viscosity build- up at low angular frequency and increased shear thinning at higher angular frequency, whereas with propene comonomer content exceeding 46 wt.-% EP was essentially linear. Received: 9 October 2000/Revised version: 12 January 2001/Accepted: 1 March 2001