Conformational polymorphism in thiophenyl substituted quinones and the disappearing NMR spectrum

The stepwise addition of thiophenol to benzoquinone gives thiophenylbenzoquinone (1b), 2,5-and 2,6-di-(thiophenyl)benzoquinone (2,3),2,3,6-tri(thiophenyl)benzoquinone (4) and 2,3,5,6-tetra(thiophenyl)benzoquinone. (5). Compounds1–4 can be crystallized, and the¹³C NMR spectra are readily interpreted. Compound5 could not be crystallized easily, and the NMR showed more than twice as many lines as the number of carbon atoms. Slow evaporation in an NMR tube produced three distinct crystals. X-ray analysis of two crystals (5a and5c) showed the compounds to be conformational polymorphs. Direct synthesis of5 from tetrachlorobenzoquinone and thiophenol yielded only conformer5a, and the¹³C NMR spectrum showed only the 6 lines expected for four equivalent phenyl substituents on benzoquinone. Subjecting5a to a variety of solvents, reagents and temperatures did not regenerate the original¹³C NMR spectrum. The crystal structures, conformations, and polymorphs are discussed.     

Effect of supersaturation on the crystallization of phenylbutazone polymorphs

The article describes the effect of degree of supersaturation, σ, on the crystallization of specific polymorphs of phenylbutazone from its methanolic solution at 20 °C. At low initial supersaturation, σ ≤ 2.0, the fraction of the metastable α polymorph in the crystallized product exceeds that of the δ polymorph, while at σ ≥ 5.0, the fraction of the stable δ polymorph increases in the crystallized product. The results are explained by the effect of supersaturation on the relative rates of nucleation and crystal growth of the polymorphs. Furthermore, the mechanism of nucleation and crystal growth also change with supersaturation. Supersaturated methanolic solutions of phenylbutazone exhibit a critical temperature at which the nucleation rates of the polymorphs decrease drastically. This effect is partly explained by the decreased mobility of phenylbutazone molecules at lower temperatures. Nucleation is most rapid when the crystallization temperature is close to the transition temperature, T_t(α ⟷ δ), between the polymorphs, α and δ. The nucleation rate decreases as the temperature difference between T_t(α ⟷ δ) and the crystallization temperature increases. (© 2005 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

The precipitation of barium sulphate and chromate powders from aqueous solution with slow development of supersaturation. Crystal numbers and final crystal sizes

The precipitations of barium sulphate and chromate were studied by slow addition of anion to metal cation solution at 20°C, to give final equivalent metal salt solutions; the final solute concentrations (C_fin) were varied from 0.002 to 0.30 mol l⁻¹ while the rates (R) of addition of anion were varied from 10⁻⁴ to 10⁻² ion l⁻¹. At first, mainly heterogeneous nuclei formed continuously during induction periods; then, as the metal salt concentration in solution increased, homogeneous nucleation soon predominated. This second nucleation process probably attained its maximum rate when the metal salt concentration in solution reached its maximum value (C_max) and then probably terminated quite rapidly. Some further nuclei also formed during the growth process when crystal growth was prolonged. The final nucleus numbers (N), and thence the crystal numbers for slow precipitations from very dilute solutions were then rather higher than the number N ∞ (het) of heterogeneous nuclei in solution: nucleus numbers then increased with increasing mixing rate according to the relation, (where β = 0.7–0.9) (where β = 0.7–0.9). The final average crystal lengths of any precipitate were then 2 to 40 times the sizes noted for rapid precipitation from equivalent solutions of the same concentration: generally, final lengths varied with mixing rate according to the relation, .     

Crystal growth of PbTe and (Pb,Sn)Te by the bridgman method and by THM

Synthesis and growth of PbTe and (Pb, Sn)Te single crystals by the Bridgman method and by the Travelling Heater Method (THM) from Te-rich solutions are described. It is to be seen from comparative investigations that seeded THM growth reproducibly provides oriented single-crystalline ingots free of low-angle grain boundaries and with etch pit densities of 8–12 × 10⁴ cm⁻². All the materials were p-type with carrier concentrations from 1 to 2 × 10¹⁸ cm⁻³.     

The annealing of alkaline-earth metal polymetaphosphate powders (I). Crystallisation and sintering processes

Amorphous barium, strontium, calcium and magnesium polymetaphosphate powders (MP₂O₆)_n, n = 20 were prepared by dehydration of the corresponding polymetaphosphate hydrate precipitates. These powders were annealed by different continuous and isothermal heat treatments over the temperature range 450° to 700 °C, the glass transition temperatures T_g to above (T_g + 120) °C. The morphologies at different degrees of crystallisation were studied by scanning electron microscopy. For the main crystallisation process (ten to sixty-seventy percent crystallisation), the powder particles retained their original pea-pod form; then after seventy percent crystallisation, these crystallised particles sintered laterally to lozenge-shaped twin-hexagonal crystals of lengths 0.5 to 3 μm. Differential thermal analysis confirmed that a markedly exothermic crystallisation process (overall enthalpy changes from about 30 to 45 kJ mol⁻¹) was occurring within the powder particles. Crystallisation rates varied from < 0.005 min⁻¹ at temperatures near T_g to > 0.5 min⁻¹ at higher temperatures; the activation energies for this process varied from 360 to 560 kJ mol⁻¹. The completely annealed crystals were studied by scanning electron microscopy, X-ray diffraction and further differential thermal analysis to 1000 °C. The X-ray diffraction d value patterns, the fusion temperatures and the enthalpies of fusion were all in close agreement with the literature values for the corresponding beta alkaline-earth metal polymetaphosphates prepared by melt crystallisation.     

Magnetic and electric properties of the ternary alloys AB

The results of experimental studies of the electrophysical and magnetic properties of solid solutions based on the AB compounds with anion (Zn₃(P_xAs_1−x)₂ and cation (Zn_xCd_1−x)₃ P₂ substitution are reported. The Zn₃(As_xP_1−x)₂ solid solutions are characterized by p-type conductivity (∼ 10¹⁵  10¹⁷ cm⁻³), low Hall mobility and conductivity of ∼ 10⁻² — 10⁻³ ohm⁻¹ cm⁻¹. In the (Zn_xCd_1−x)₃P₂ solid solutions the samples rich in zinc are p-type, those rich in cadmium — n-type, the carrier concentration is ∼ 10¹⁶ — 10¹⁸ cm⁻³. From the measurements of the magnetic properties of the above mentioned alloys it is shown that in the investigated solid solutions a transition from the structure with direct optical transition to those with indirect optical transition occurs.     

Structures of two conformational polymorphs of the cholesterol-lowering drug probucol

Two polymorphic forms of the drug probucol, (4,4-[(1-Methylethylidene)-bis(thio)]bis-[2,6-bis (1, 1-dimethylethyl)phenol]), have been isolated and characterized by thermal analysis, X-ray powder diffraction and single crystal X-ray analyses. Form I, with onset melting point 125°C, is monoclinic, space groupP2₁ c witha=16.972(5),b=10.534(4),c=19.03(1)Å,=113.66(3)°,Z=4. Form II, with onset melting temperature 116°C, is monoclinic, space groupP2₁/_n witha=11.226(2),b=15.981(2),c=18.800(3)Å,=104.04(1)°,Z=4. The probucol molecule adopts different conformations in the two polymorphs. In Form II, the C-S-C-S-C chain is extended and the molecular symmetry approximates C_2v whereas in Form I, the two S-C-S-C torsion angles are approximately 80° and 165°. Molecular mechanics calculations show that the less symmetrical conformer of Form I is more stable than the conformer in Form II by approximately 26 kJ mol^–1. Crystal packing in both polymorphs is determined by van der Waals interactions only. X-ray powder diffraction indicates that Form II converts to Form I on grinding.     

Dilithium dialuminium trisilicate phase obtained using coal bottom ash

The Li₂Al₂Si₃O₁₀ glass-ceramics well crystallized and with a regular morphology was produced starting from a mixture of Li₂CO₃, TiO₂, Al₂O₃ and coal bottom ash, after reducing the magnetite phase content. Its measured thermal expansion coefficient in the temperatures range from 25 °C to 300 °C is α_(25–300) = −23.4 × 10⁻⁷ °C⁻¹. This value is ≈18% smaller than that for the commercial lithium glass-ceramics (−23.4 × 10⁻⁷ °C⁻¹ to 50 × 10⁻⁷ °C⁻¹).     

Zur Kenntnis des lithium-neodym-polyphosphates LiNd(PO3)4

LiNd(PO₃)₄ crystallized from a LiPO₃ flux exhibits (100) platelet or [001] prismatic habit, bot with pseudo-orthorhombic tracht. - Crystals are optically biaxial positive. Indices of refraction are nα = 1.6125; nβ = 1,6195 ± 0.0005 (λ = 589.3 nm); optic axial angle 2Vγ = 43°; maximum birefrigence δn = 12.7 · 10⁻³; birefrigence in (100) δn_a = 5.9 · 10⁻³.     

Crystal growth of FeCO3 in mixed monoethylene glycol and water solvent

The transportation of natural gas in long subsea pipelines is a challenge when it comes to hydrate prevention, corrosion and mineral scaling. When monoethylene glycol (MEG) is injected into carbon steel pipelines to prevent formation of gas hydrates, the solubility of the corrosion products is altered. Understanding the kinetics of FeCO₃ precipitation may make it possible to avoid deposition in the gas liquid separation process and improve solids removal in MEG recovery units. In this work, the growth kinetics of iron carbonate (siderite) has been studied in seeded batch experiments in MEG‐water solutions with 0 and 40 wt% MEG at 50 and 70 °C. Precautions were taken to keep anaerobic conditions and avoid oxidation of ferrous ions. The growth rate (G) was measured as function of supersaturation (S) and fitted to the equation: G = k_r(S‐1)^g. The growth order (g) was approximately 2 independent of the MEG concentration at the two temperatures. The growth rate constant (k_r) was in the range of 6 × 10⁻¹¹ to 1 × 10⁻¹⁰ m/s. Temperature increase from 50 to 70°C had no measurable effect on the growth rate while in the presence of 40 wt% MEG the growth rate constant decreased.     

Plastic Deformation of Cesium Iodide Single Crystals at High Temperatures

The plastic deformation of CsI crystals of three crystallographic orientations 〈100〉. 〈110〉. and 〈111〉 at temperatures from 423 to 773 K (0.5 to 0.86T_m) and strain rates from 2 × 10⁻³ to 10⁻⁵ s⁻¹ is studied. Four-stage stres-strain curves were found, three stages being more and more distinct with an increase in temperature up to 623 K above which stage III prevails. For all the temperatures, strain rates and oreintations studied the superplasticity features (jerky flow, deformation localization, active dynamical recovery etc.) were observed. The thermal activatoin analysis has shown that the rate of high temperature deformation of CsI is controlled by dislocation climb limited in its turn by mobility of cation vacancies (quasiviscous creep).     

Relationship between density,viscosity and structure of GeO2 melts at low and high pressures

A correlative study of the viscosity, density and structure of GeO₂ melts has been carried out at low and high pressures. It is observed that under isothermal (1425°C) conditions the viscosity decreases from 6.0 × 10³ poise at 1 bar to 1.2 × 10³ poise at 9.5 kbar. The maximum variation in the density of quenched GeO₂ glasses is from 3.62 ± 0.02 g cm^?3 for glass formed from a liquid quenched at 1 atm and 1425°C to 3.95 ± 0.04 g cm^?3 for glass formed from a liquid quenched at 18 kbar and 1700°C.The similarity of the Raman spectra of GeO₂ melt quenched at 1 atm (1425°C) and at 18 kbar (1700°C) implies that the scattering units in GeO₂ glasses quenched at low and high pressures are the same. The intensity of the Rayleigh tail, however, decreases in glasses quenched at successively higher pressures, the structure apparently becoming more ordered with increasing pressure. The Raman spectra of the GeO₂ polymorphs with quartz and rutile structures, crystallized at 1150°C and at 4 and 6 kbar, respectively, are distinct because of the difference in Ge coordination, resulting in a large difference in the frequency and intensity of the GeO symmetric stretching mode in the two polymorphs. A comparison of the Raman spectra of GeO₂ glasses with those of crystalline GeO₂ polymorphs shows that the local ordering in GeO₂ glass is similar to that of hexagonal GeO₂ in which Ge is tetrahedrally coordinated.The decrease in the viscosity of GeO₂ melt with increasing pressure cannot be attributed to a pressure-induced coordination change [1]. More likely, there is a systematic change in the nature of the GeO bond with increasing pressure. The increase in the degree of local ordering in GeO₂ melts quenched at high pressures does explain the progressive increase in melt density.     

A polymorphic polycycle—evidence for a sickle-shaped dodecenyl oxyallylic cation

A polycycle containing a cyclodecanone ring gives two polymorphs on crystallization from hexanes. Form 1 is space group P2₁/n with a = 17.145(2), b = 6.8979(9), c = 13.721(2) Å, and = 99.689(5)°. Form 2 is space group P2₁/c, with a = 19.046(2), b = 6.8211(4), c = 12.890(1), and = 105.302(4)°.     

Liquid-Phase Epitaxy of (Hg,Cd)Te on CdTe Substrates by a Vertical Dipping Technique

Hg_1−xCd_xTe layers on CdTe substrates were grown from Te-rich melt solutions by a vertical dipping technique using a special quasi-closed system with ground-glass sealing. Results are good reproducibilities of the electrical properties after annealing in Hg-rich atmosphere (p77 ≈ 2 · 10¹⁶ cm⁻³ μ77 ≈ 500 cm² V⁻¹ s⁻¹) and of the x-value, respectively. A horizontal position of the substrate downwards to the melt solution yields, in difference to a vertical one, to homogeneous layer thicknesses. Short meltback steps before growth leads to sharper profiles of composition.     

Effect of BaO on the crystallization kinetics of glasses along the Diopside-Ca-Tschermak join

We report on the effect of BaO on the crystallization kinetics of glasses in the diopside (CaMgSi₂O₆)-Ca-Tschermak (CaAl₂SiO₆) system. Partial substitution (i.e. 5%, 10% and 20%) of Ba²⁺ for Ca²⁺ was attempted in composition CaMg_0.8Al_0.4Si_1.8O₆, in three different glasses while partial substitution of B³⁺ for Al³⁺ was made in the fourth glass. Structural investigations on the glasses have been made by density measurements, molar volume and Infra-red spectroscopy (FTIR). Non-isothermal crystallization kinetic studies have been employed to study the mechanism of crystallization in all the four glasses. The Avrami parameter for the glass powders is ∼2, indicating the existence of intermediate mechanism of crystallization. Crystallization sequence in the glasses has been followed by X-ray diffraction (XRD) analysis, scanning electron microscopy (SEM) and FTIR. Augite crystallized out being the dominant phase in all the glass-ceramics, while different polymorphs of BaAl₂Si₂O8 were present as secondary or minor phases.     

Deformation mechanism and dislocation structure of high-purity molybdenum single crystals at low temperatures

High purity molybdenum single crystals were deformed in tension and compression along the symmetric double slip orientation [110] in the temperature range from 300 K down to 0.5 K with strain rates between 10⁻³ and 10⁻⁵ s⁻¹. The activation volume was measured by stress relaxation tests. The dislocation structure of the deformed crystals (T → 1.85 K) was examined by high voltage electron microscopy. It was established that the low temperature increase of the critical shear stress exhibits three distinct temperature regimes with different temperature dependences. These non-uniformities are discussed in terms of recently developed theories of kink-pair formation and kink-kink interactions on screw dislocations in bcc metals. The HVEM observations suggest that the mobility of screw dislocations at very low temperatures should be determined by the combined effects of the PEIERLS barriers and the jog dragging.     

Sol–gel derived organic–inorganic hybrid electrolytes for thin film electrochromic devices

Sol–gel derived, lithium ion conducting organic–inorganic hybrid electrolytes for ambient temperatures applications, have been synthesized from tetraethyl orthosilicate (TEOS), poly(ethylene oxide) (PEO), propylene carbonate (PC), propylene oxide, butyl acrylate, butyl methacrylate, ethyl acetoacetate and LiClO₄ precursors. Mass fractions of the organic additions in the gels were of ca 30 mass% for gels 0/B, F–H and 40 mass% for gel J. The colorless transparent or translucent hybrid materials obtained in this work were aged at room temperature for at least three weeks and then dried at 80 °C for 3 h. The morphology and structure of all compositions were investigated by scanning electron microscopy equipped with energy dispersive X-ray spectroscopy (SEM/EDX), Fourier transform infrared spectroscopy and ²⁹Si MAS nuclear magnetic resonance. Amorphous nature of the hybrids was confirmed by X-ray diffraction. SEM, FTIR and NMR analysis showed structural properties and [SiO₄] tetrahedrons poly-condensation process to be strongly influenced by organic additives have been employed. Room temperature ionic conductivities of the hybrid electrolytes were in a range of 9.84 × 10⁻⁴–1.56 × 10⁻³ Ω⁻¹ cm⁻¹.     

Drug recrystallization using supercritical anti-solvent (SAS) process with impinging jets: Effect of process parameters

The aim of this study is to improve mixing in supercritical anti-solvent process (SAS) with impinging jets in order to form finer particles of sulfathiazole, a poorly water-soluble drug. The influence of several process parameters upon the powder characteristics is studied. Parameters are jets' velocity (0.25 m s^?1 to 25.92 m s^?1), molar ratio solvent/CO₂ (2.5% to 20%), temperature (313 K to 343 K), pressure (10 MPa to 20 MPa) and sulfathiazole concentration in the organic solution (0.5% to 1.8%). Two solvents are used: acetone and methanol. Smaller particles with a more homogeneous morphology are obtained from acetone solutions. For the smallest jets' velocity, corresponding to a non-atomized jet, the stable polymorphic form is obtained, pure or in mixture. At this velocity, pressure is the most influential parameter controlling the polymorphic nature of the powder formed. The pure stable polymorph is formed at 20 MPa. Concerning the particle size, the most influential parameters are temperature and sulfathiazole concentration.The use of impinging jets with different process parameters allows the crystallization of four polymorphs among the five known, and particle sizes are varied. This work demonstrates the studied device ability of the polymorph and the size control. A comparison with the classical SAS process shows that particle size, size distribution and morphology of particles crystallized with impinging jets are different from the ones obtained with classical SAS introduction device in similar operating conditions. Mean particle sizes are significantly smaller and size distributions are narrower with impinging jets device.     

The growth of high-quality MCT films by MBE using in-situ ellipsometry

The ellipsometry and RHEED study of high-quality MCT films grown on (112)- and (130) CdTe and GaAs by MBE was carried out. The dependence of the ellipsometric parameter ψ on MCT composition is evaluated. It was shown that such parameters as growth rate, the surface roughness, initial substrate temperature, and film composition may be measured by the in-situ ellipsometry. The appearance of surface roughness was observed in the initial stage of MCT growth under various compositions (x_CdTe = 0 ÷ 0.4). The further growth at optimum conditions leads to the smoothing of the surface and supplies us with high-quality MCT films. The concentration, mobility, and life time of carriers in MCT films were respectively: n = 1.8 × 10¹⁴ ÷ 8.2 × 10¹⁵ cm⁻³, μ_n = 44000 ÷ 370000 cm² V⁻¹ s⁻¹, τ_n = 40 ÷ 220 ns; p = 1.8 × 10¹⁵ ÷ 8.4 × 10¹⁵ cm⁻³, μ_p = 215 ÷ 284 cm² V⁻¹ s⁻¹, τ_p = 12 ÷ 20 ns.     

Confrontation of the BCF theory and computer simulation experiments with measured (R, σ) curves

A brief summary of crystal growth models – the surface diffusion model of Burton, Cabrera and Frank and computer simulation models – is given and these models are confronted with measured (R, σ) curves. It was found that the most (R, σ) curves measured so far can be fitted by BCF curves with 10⁻² ≲ σ₁ ≲ 10⁻¹ and C having an order of magnitude of 10⁻⁴ cm ≲ s⁻¹. ΔG turns out to be 12 ± 5 kcal ≲ mol⁻¹. – Some of the (R, σ) curves can be described better by a nucleus above nucleus formalism. The order of magnitude of A is 10⁻⁴ cm · s⁻¹ and 10⁻² ≲ B ≲ 10⁻¹. – It is concluded what kind of work should be done in future to check theoretical models.