A MAS NMR investigation of aluminosilicate, silicophosphate, and aluminosilicophosphate gels and the evolution of crystalline structures on heating the gels

Gels of various composition containing SiO2, Al2O3, and P2O5 have been investigated by employing high resolution magic-angle-spinning (MAS) 27Al, 29Si, and 31P NMR spectroscopy. Changes occurring in the NMR spectra as the gels are progressively heated have been examined to understand the nature of structural changes occurring during the crystallization of the gels. 27Al resonance is sensitive to changes in the coordination number even when the Al concentration is as low as 1 mol%. As the percentage of Al increases, the hydroxyl groups tend to be located on the Al sites while Si remains as SiO4/2 (Q4). Mullite is the major phase formed at higher temperature in the aluminosilicate gels. In the case of the silicophosphate gels, Si is present in the form of Q4 and Q3 species. There is a change in the coordination of Si from four to six as the gel is heated. The formation of six-coordinated Si is facilitated even at lower temperatures (~673 K) when the P2O5 content is high. The phosphorus atoms present as orthophosphoric acid units in the xerogels change over to metaphosphate-like units as the gel is heated to higher temperatures. In aluminosilicophosphates, Si is present as Q4 and Q3 species while P is present as metaphosphate units; Al in these gels seems to be inducted into the tetrahedral network positions.

Formation of lead pyrophosphate glass and the role of anion disproportionation

Thermal, spectroscopic and electrical properties of lead pyrophosphate glass prepared by melt quenching have been examined. A model based on the structural disproportionation of the P2O 7 4− ions has been proposed and is shown to consistently explain all the observations. The equilibrium of various anionic species has been discussed on the basis of their electronegativities which are in turn related to their basicities.

Switching studies and the effect of irradiation on ferroelectric properties of TAAP and DTAAP

Polarization switching processes in TAAP and DTAAP have been studied by the Merz method. The switching process in DTAAP is slower than in TAAP. The temperature dependence of switching time indicates that the crystal might contain groups of domain nuclei with different activation energies. X-ray irradiation causes an increase in the threshold field below which switching could not occur and decrease in the mobility of domain walls. Irradiation decreases the peak value of dielectric constant, Tc and increases the value of coercive field. Domain structure studies on TAAP crystals have shown that the crystals grow as both predominantly single domain and multi domains, depending on which the internal bias increases or remains unaffected upon irradiation.

Impedance parameters and the state-of-charge. III. Zinc-manganese dioxide and magnesium-manganese dioxide dry batteries

The problem of non-destructive determination of the state-of-charge of zinc- and magnesium-manganese dioxide dry batteries is examined experimentally from the viewpoint of internal impedance and open-circuit voltage at equilibrium. It is shown that the impedance is mainly charge-transfer controlled at relatively high states-of-charge and progressively changes over to diffusion control as the state-of-charge decreases in the case of zinc-manganese dioxide dry batteries. On the other hand, the impedance is mainly diffusion controlled for undischarged batteries but becomes charge-transfer controlled as soon as there is some discharge in the case of magnesium-manganese dioxide batteries. It is concluded that the determination of state-of-charge is not possible for both types of batteries by the measurement of impedance parameters due to film-induced fluctuations of these parameters. The measurement of open-circuit voltage at equilibrium can be used as a state-of-charge indicator for Zn-MnO2 batteries but not for Mg-MnO2 batteries.

Impedance parameters and the state-of-charge. II. Lead-acid battery

The determination of the state-of-charge of the lead-acid battery has been examined from the viewpoint of internal impedance. It is shown that the impedance is controlled by charge transfer and to a smaller extent by diffusion processes in the frequency range 15–100 Hz. The equivalent series/parallel capacitance as well as the a.c. phase-shift show a parabolic dependence upon the state-of-charge, with a maximum or minimum at 50% charge. These results are explained on the basis of a uniform transmission-line analog equivalent circuit for the battery electrodes.

Evaluation of Erosion Resistance of Metallic Materials and the Role of Material Properties in Correlations

A study of the correlations between material properties and normalized erosion resistance (inverse of erosion rates) of various materials tested in the rotating disk and the flow venturi at various intensities indicates that different individual properties influence different stages of erosion. At high and low intensities of erosion, energy properties predominate the phenomenon, whereas at intermediate intensities strength and acoustic properties become more significant. However, both strength and energy properties are significant in the correlations for the entire spectrum of erosion when extensive cavitation and liquid impingement data from several laboratories involving different intensities and hydrodynamic conditions are considered. The use of true material properties improved the statistical parameters by 3 to 37%, depending on the intensity of erosion. It is possible to evaluate qualitatively the erosion resistances of materials based on the true stress-true strain curves.

Impedance parameters and the state-of charge. I. Nickel-cadmium battery

The problem of nondestructive determination of the state-of-charge of nickel-cadmium batteries has been examined experimentally as well as theoretically from the viewpoint of internal impedance. It is shown that the modulus of the impedance is mainly controlled by diffusion at all states of charge. Even so, a prediction of the state of charge is possible if the equivalent series/parallel capacitance or the alternating current phase shift is measured at a sufficiently low a.c. test frequency (5–30 Hz) which also avoids inductive effects. These results are explained on the basis of a uniform transmission-line analog equivalent circuit for the battery electrodes.

A Series of Cu-II-Azide Polymers of Cu-6 Building Units and the Role of Chelating Diamine in Controlling their Dimensionality: Synthesis, Structures, and Magnetic Behavior

Four new neutral copper-azido polymers Cu-6(N-3)(12)(aem)(2)](n)(1), Cu-6(N-3)(12)(dmeen)(2)(H2O)(2)](n) (2), Cu-6(N-3)(12)(N,N'-dmen)(2)](n) (3), and Cu-6(N-3)(12)(hmpz)(2)](n) (4) aem = 4-(2-aminoethyl)morpholine; dmeen = N,N-dimethyl-N'-ethylethylenediamine; N,N'-dmen = N,N'-dimethylethylenediamine and hmpz = homopiperazine] have been synthesized by using 0.33 mol equiv of the chelating diamine ligands with Cu(NO3)(2)center dot 3H(2)O/CuCl2 center dot 2H(2)O and an excess of NaN3. Single crystal X-ray structures show that the basic unit of these complexes, especially 1-3, contains very similar Cu-6(II) building blocks. But the overall structures of these complexes vary widely in dimensionality. While 1 is three-dimensional (3D) in nature, 2 and 3 have a two-dimensional (2D) arrangement (with different connectivity) and 4 has a one-dimensional (1D) structure. Cryomagnetic susceptibility measurements over a wide range of temperature exhibit dominant ferromagnetic behavior in all the four complexes. The experimental susceptibility data have been analyzed by some theoretical model equations.

Effects of gender, and SLCO1B1 and CYP7A1 polymorphisms on plasma bile acids in humans and the pharmacokinetics of therapeutic ursodeoxycholic acid

Bile acids are important steroid-derived molecules essential for fat absorption in the small intestine. They are produced in the liver and secreted into the bile. Bile acids are transported by bile flow to the small intestine, where they aid the digestion of lipids. Most bile acids are reabsorbed in the small intestine and return to the liver through the portal vein. The whole recycling process is referred to as the enterohepatic circulation, during which only a small amount of bile acids are removed from the body via faeces. The enterohepatic circulation of bile acids involves the delicate coordination of a number of bile acid transporters expressed in the liver and the small intestine. Organic anion transporting polypeptide 1B1 (OATP1B1), encoded by the solute carrier organic anion transporter family, member 1B1 (SLCO1B1) gene, mediates the sodium independent hepatocellular uptake of bile acids. Two common SNPs in the SLCO1B1 gene are well known to affect the transport activity of OATP1B1. Moreover, bile acid synthesis is an important elimination route for cholesterol. Cholesterol 7α-hydroxylase (CYP7A1) is the rate-limiting enzyme of bile acid production. The aim of this thesis was to investigate the effects of SLCO1B1 polymorphism on the fasting plasma levels of individual endogenous bile acids and a bile acid synthesis marker, and the pharmacokinetics of exogenously administered ursodeoxycholic acid (UDCA). Furthermore, the effects of CYP7A1 genetic polymorphism and gender on the fasting plasma concentrations of individual endogenous bile acids and the bile acid synthesis marker were evaluated. Firstly, a high performance liquid chromatography-tandem mass spectrometry (HPLC-MS/MS) method for the determination of bile acids was developed (Study I). A retrospective study examined the effects of SLCO1B1 genetic polymorphism on the fasting plasma concentrations of individual bile acids and a bile acid synthesis marker in 65 healthy subjects (Study II). In another retrospective study with 143 healthy individuals, the effects of CYP7A1 genetic polymorphism and gender as well as SLCO1B1 polymorphism on the fasting plasma levels of individual bile acids and the bile acid synthesis marker were investigated (Study III). The effects of SLCO1B1 polymorphism on the pharmacokinetics of exogenously administered UDCA were evaluated in a prospective genotype panel study including 27 healthy volunteers (Study IV). A robust, sensitive and simple HPLC-MS/MS method was developed for the simultaneous determination of 16 individual bile acids in human plasma. The method validation parameters for all the analytes met the requirements of the FDA (Food and Drug Administration) bioanalytical guidelines. This HPLC-MS/MS method was applied in Studies II-IV. In Study II, the fasting plasma concentrations of several bile acids and the bile acid synthesis marker seemed to be affected by SLCO1B1 genetic polymorphism, but these findings were not replicated in Study III with a larger sample size. Moreover, SLCO1B1 polymorphism had no effect on the pharmacokinetic parameters of exogenously administered UDCA. Furthermore, no consistent association was observed between CYP7A1 genetic polymorphism and the fasting plasma concentrations of individual bile acids or the bile acid synthesis marker. In contrast, gender had a major effect on the fasting plasma concentrations of several bile acids and also total bile acids. In conclusion, gender, but not SLCO1B1 or CYP7A1 polymorphisms, has a major effect on the fasting plasma concentrations of individual bile acids. Moreover, the common genetic polymorphism of CYP7A1 is unlikely to influence the activity of CYP7A1 under normal physiological conditions. OATP1B1 does not play an important role in the in vivo disposition of exogenously administered UDCA.

Reduction behaviour of Fe3+/Al2O3 obtained from the mixed oxalate precursor and the formation of the Fe0-Al2O3 metal-ceramic composite

Reduction behaviour of Fe3+/Al2O3 obtained by the decomposition of the oxalate precursor has been investigated by employing X-ray diffraction (XRD), Mössbauer spectroscopy and electron paramagnetic resonance (EPR) spectroscopy. Calcination of Fe3+/Al2O3 at or below 1070 K yields mainly a poorly ordered, fine particulate form of ?-Al2�xFexO3. Calcination at or above 1220 K yields ?-Al2�xFexO3. Reduction of Fe3+/Al2O3 samples calcined at or below 1070 K gives the FeAl2O4 spinel on reduction at 870 K; samples calcined at or above 1220 K give Al2-xFexO3 with a very small proportion of metallic iron. Fe3+/Al2O3 samples calcined at 1220 K or above yield metallic iron and a very small proportion of the spinel on reduction below 1270 K. In the samples reduced at or above 1270 K, the main product is metallic iron in both ferromagnetic and superparamagnetic forms. The oxalate precursor route yields more metallic iron than the sol�gel route.

A study of the reaction of divalent transition metal chlorides with pyridinium poly(hydrogen fluoride), ppht, and the effect of potassium hydrogen fluoride on fluorination and complexation

Studies of the reaction of metal chlorides, MCl2 (M = Mn, Co, Ni, Cu, Zn) with PPHF at room temperature have shown that Mn, Co and Zn form the corresponding metal fluorides, MF2, while Ni and Cu form their dipyridine metal(II) dichloride complexes. Nickel and copper complexes further undergo fluorination and complexation by potassium hydrogen fluoride in PPHF to form KNiF3 and KCuF3.

Investigation on the Magnetic Anomaly and the Role of Orbital Moment on the Magnetic Properties of LaMn0.5Co0.5O3

Two distinct ferromagnetic phases are present in LaMn0.5Co0.5O3 for which the spin-only magnetic moment calculated from the high temperature dc susceptibility is found to be unusually high. Such a high moment can only be accounted for by assigning the valence state of the cations to Mn2+-Co4+. This is unrealistic as the earlier report based on X-ray absorption spectroscopy (XAS) has suggested the valence state to be mainly Mn4+-Co2+ with traces of Co3+. Also from our studies using XAS, it is found that the valence state is mainly Mn4+-Co2+. In addition, no notable difference is observed in the minor Co3+ present in both phases. Our results based on X-ray magnetic circular dichroism studies (XMCD) reveal the presence of ``distinct'' high orbital moment associated with Co2+ for both phases. Thus it is found that the distinctness of the orbital moment also plays a vital role in determining the magnetic moment and T-c of both phases of LaMn0.5Co0.5O3. By considering the orbital moment obtained from XMCD, the anomaly in the paramagnetic susceptibility is resolved and thus we are able to assign the valence state to Mn4+-Co2+ configuration. The difference in the magnitude of orbital moment in both phases is believed to be due to the crystal field effects.

The Reaction of a Nitro-Capped Cobalt(III) Cage Complex With Base: the Crystal Structure of a Contracted Cage Complex, and the Mechanism of Its Formation

The synthesis, properties and crystal structure of the cage complex (1-hydroxy-8-methyl-3,6,10,13,15,18-hexaazabicyclo[6.6.5]nonadecane)cobalt(III) chloride hydrate ([Co(Me,OH-absar)] C13.H2O) are reported. The mechanism of the formation of this contracted cavity cage from a nitro-capped hexaazabicycloicosane type cage has been investigated. Treatment of (1-methyl-8-nitro-3,6,10,13,16,19-hexaazabicyclo[6.6.6]icosane)cobalt(III) chloride ([Co(Me,NO2-sar)] 3+) with excess base in aqueous solution leads initially to rapid (t1/2 < 1 ms) and reversible deprotonation of one coordinated secondary amine. This species undergoes a retro-Mannich type reaction and imine hydrolysis (t1/2 almost-equal-to 90 s). Quenching the reaction with acid gives rise to a pair of isomeric intermediate species which have been isolated and characterized. They have a pendant arm macrocyclic structure, resulting from the loss of a methylene unit from one of the arms of the cap. Heating either isomer in aqueous solution gives the new cage compound with the contracted cap. It is postulated that this occurs through a Nef reaction, resulting in the formation of a ketone which then condenses with the coordinated primary amine. A comparison with the corresponding bicycloicosane analogue indicates a reduced chromophoric cavity size for the contracted cage. The reduction potential of the cobalt(III)/cobalt(II) couple is 170 mV more negative for the smaller cage, and, in the electronic spectrum of the cobalt(III) complex, the d-d transitions are both shifted to higher energy, corresponding to a stronger ligand field.