Preparation, characterization, spectral and thermal analyses of (N2H5)2MCl4·2H2O (M = Fe, Co, Ni and Cu); crystal structure of the iron complex

Hydrazinium metal chlorides, (N2H5)2MCl4·2H2O (where M = Fe, Co, Ni and Cu), have been prepared from the aqueous solutions of the respective metal chlorides and hydrazine hydrochloride (N2H4·HCl or N2H4·2HCl) and investigated by spectral and thermal analyses. The crystal structure of the iron complex has been determined by direct methods and refined by full-matrix least-squares to an R of 0.023 and Rw of 0.031 for 1495 independent reflections. The structure shows ferrous ion in an octahedral environment bonded by two hydrazinium cations, two chloride anions and two water molecules. In the complex cation [Fe(N2H5)2(H2O)2Cl2]2+, the coordinated groups are in trans positions.

Synthesis and spectral studies of polyamide-phosphate esters from phosphine-oxide-containing diols with aryl phosphorodichloridates and their thermal and flammability behaviour

Polyamide-phosphate esters were synthesized by interfacial polycondensation of aryl phosphorodichloridates with the diols of phenoxaphosphine and phosphine oxide in the presence of a phase-transfer catalyst. The polymers were characterized by infra-red and 1H, 13C and 31P nuclear magnetic resonance (n.m.r.) spectroscopy. The molecular weights were determined by end-group analysis using 31P n.m.r. spectral data. The phenoxaphosphine-containing polymers showed superior thermostability and flame retardancy over the phosphine-oxide-containing polymers.

Synthesis, spectral and structural studies on metal complexes of Schiff bases involving vitamin B6 and histamine

Six metal complexes of Schiff bases involving Vitamin B6 and the decarboxylated amino acid histamine have been synthesised and characterized. Crystal structures have been determined for [CuL1(H2O)Br]-NO31(L1= pyridoxylidenehistamine) and [Cu2L22(NO3)2]·6H2O 2(L2= 5′-phosphopyridoxylidenehistaminate). The crystal structure of complex 1[space group P[1 with combining macron], a= 8.161(2), b= 10.368(2), c= 11.110(2)Å, α= 105.18(1), β= 102.12(1), γ= 72.10(1)° and Z= 2; R= 0.072, R′= 0.083] consists of square-pyramidally co-ordinated copper with the tridentate Schiff base in the zwitterionic form, whereas in 2[space group P[1 with combining macron], a= 8.727(1), b= 10.308(1), c= 12.845(2)Å, α= 110.00(1), β= 78.94(1), γ= 114.35(1)° and Z= 1; R= 0.035, R′= 0.034] the copper has the same co-ordination geometry but the tetradentate Schiff-base ligand exists as a monoanion. The conformational parameters deduced from such structures are important for understanding the stereochemical aspects of Vitamin B6-catalysed model reactions involving histidine.

Spectral element approach to wave propagation in uncertain beam structures

This paper presents a study on the uncertainty in material parameters of wave propagation responses in metallic beam structures. Special effort is made to quantify the effect of uncertainty in the wave propagation responses at high frequencies. Both the modulus of elasticity and the density are considered uncertain. The analysis is performed using a Monte Carlo simulation (MCS) under the spectral finite element method (SEM). The randomness in the material properties is characterized by three different distributions, the normal, Weibull and extreme value distributions. Their effect on wave propagation in beams is investigated. The numerical study shows that the CPU time taken for MCS under SEM is about 48 times less than for MCS under a conventional one-dimensional finite element environment for 50 kHz loading. The numerical results presented investigate effects of material uncertainties on high frequency modes. A study is performed on the usage of different beam theories and their uncertain responses due to dynamic impulse load. These studies show that even for a small coefficient of variation, significant changes in the above parameters are noticed. A number of interesting results are presented, showing the true effects of uncertainty response due to dynamic impulse load.

Direct Growth of Gold Nanorods on Gold and Indium Tin Oxide Surfaces: Spectral, Electrochemical, and Electrocatalytic Studies

The surfactant-assisted seed-mediated growth method was used for the formation of gold nanorods (GNRs) directly on gold (Au) and indium tin oxide (ITO) surfaces. Citrate-stabilized similar to 2.6 nm spherical gold nanoparticles (AuNPs) were first self-assembled on ITO or Au surfaces modified with (3-mercaptopropyl)-trimethoxysilane (MPTS) sol-gel film and then immersed in a cationic surfactant growth solution to form GNRs. The growth of GNRs on the MPTS sol gel film modified ITO surface was monitored by UV-visible spectroscopy. The ITO surface with the attached spherical AuNPs shows a surface plasmon resonance band at 550 nm. The intensity of this absorption band increases while increasing the immersion time of the AuNP-modified ITO surface into the growth solution, and after 5 h, an additional shoulder band around 680 nm was observed. The intensity of this shoulder band increases, and it was shifted to longer wavelength as the immersion time of the AuNP-modified ITO surface into the growth solution increases. After 20 h, a predominant wave at 720 nm was observed along with a band at 550 nm. Further immersion of the modified ITO surface into the growth solution did not change the absorption characteristics. The bands observed at 550 and 720 nm were characteristics of GNRs, corresponding to transverse and longitudinal waves, respectively. The AFM images showed the presence of GNRs on the surface of the MPTS sol gel modified ITO surface with a typical length of similar to 100-120 nm and a width of similar to 20-22 nm in addition to a few spherical AuNPs, indicating that seeded spherical AuNPs were not completely involved in the GNRs' formation. Finally, the electrocatalytic activity of the surface-grown GNRs on the MPTS sol gel film modified Au electrode toward the oxidation of ascorbic acid (AA) was studied. Unlike a polycrystalline Au electrode, the surface-grown GNR-modified electrode shows two well-defined voltammetric peaks for AA at 0.01 and 0.35 V in alkaline, neutral, and acidic pHs. The cause for the observed two oxidation peaks for AA was due to the presence of both nanorods and spherical nanoparticles on the electrode surface. The presence of spherical AuNPs on the MPTS sol gel film oxidized AA at more positive potential, whereas the GNRs oxidized AA at less positive potential. The observed 340 mV less positive potential shift in the oxidation of AA suggested that GNRs are better electrocatalysts for the oxidation of AA than the spherical AuNPs.

Monetary policy rules and estimated reaction functions for the European Central Bank

This thesis studies the interest-rate policy of the ECB by estimating monetary policy rules using real-time data and central bank forecasts. The aim of the estimations is to try to characterize a decade of common monetary policy and to look at how different models perform at this task.The estimated rules include: contemporary Taylor rules, forward-looking Taylor rules, nonlinearrules and forecast-based rules. The nonlinear models allow for the possibility of zone-like preferences and an asymmetric response to key variables. The models therefore encompass the most popular sub-group of simple models used for policy analysis as well as the more unusual non-linear approach. In addition to the empirical work, this thesis also contains a more general discussion of monetary policy rules mostly from a New Keynesian perspective. This discussion includes an overview of some notable related studies, optimal policy, policy gradualism and several other related subjects. The regression estimations are performed with either least squares or the generalized method of moments depending on the requirements of the estimations. The estimations use data from both the Euro Area Real-Time Database and the central bank forecasts published in ECB Monthly Bulletins. These data sources represent some of the best data that is available for this kind of analysis. The main results of this thesis are that forward-looking behavior appears highly prevalent, but that standard forward-looking Taylor rules offer only ambivalent results with regard to inflation. Nonlinear models are shown to work, but on the other hand do not have a strong rationale over a simpler linear formulation. However, the forecasts appear to be highly useful in characterizing policy and may offer the most accurate depiction of a predominantly forward-looking central bank. In particular the inflation response appears much stronger while the output response becomes highly forward-looking as well.

Crystal structures, spectral and magnetic properties of (µ-hydroxo)(µ-acetato)dicopper(II) complexes containing chelating amines

The reaction of [Cu2(O2CMe)4(H2O)2] with N, N, N′, N′-tetramethylethane- 1,2-diamine (tmen) in ethanol yielded the dicopper(II) complex [Cu2(OH)(O2CMe)(tmen)2][ClO4]21. A similar reaction with N, N- dimethylethane- 1,2-diamine (dmen) afforded a crystalline product 2 in which two dicopper(II) complexes, [Cu2(OH)(O2CMe)(dmen)2][ClO4]22a and [Cu2(OH)(O2CMe)(H2O)2(dmen)2][ClO4]22b, are cocrystallized in a 1 : 1 molar ratio along with 2NaClO4. The crystal structures of 1 and 2 have been determined. The complexes have an asymmetrically dibridged [Cu2(µ-OH)(µ-O2CMe)]2+ core. The co-ordination geometry of the metal is square planar (CuO2N2). The copper atoms in 2b have a square-pyramidal CuO3N2 co-ordination sphere. The Cu Cu distances and Cu–O–Cu angles in 1, 2a and 2b are 3.339(2), 3.368(3), 3.395(7)Å, 120.1(2), 116.4(1) and 123.6(2)°, respectively. Complex 1 exhibits an axial ESR spectrum in a methanol glass giving g∥= 2.26 (A∥= 164 × 10–4 cm–1) and g⊥= 2.04. The ESR spectra obtained from the bulk material of the dmen product are indicative of the presence of two dimers, viz. complex 2a(g∥= 2.25, A∥= 165 × 10–4 cm–1; g⊥= 2.03) and 2b(g∥= 2.19, A∥= 184 × 10–4 cm–1; g⊥= 2.0). Variable-temperature magnetic susceptibility measurements on these complexes show an intramolecular antiferromagnetic coupling in the dimeric core. The fitting parameters are J=–27.8 cm–1, g= 2.1 for complex 1 and J=–10.1 cm–1, g= 2.0 for 2. The magnetostructural properties of the complexes are discussed. There is a linear correlation of the –2J values with the Cu Cu distances among dibridged complexes having square-planar copper(II) centres.

NDDO-based CI methods for the prediction of electronic spectra and sum-over-states molecular hyperpolarization

NDDO-based (AM1) configuration interaction (CI) calculations have been used to calculate the wavelength and oscillator strengths of electronic absorptions in organic molecules and the results used in a sum-over-states treatment to calculate second-order-hyperpolarizabilities. The results for both spectra and hyperpolarizabilities are of acceptable quality as long as a suitable CI-expansion is used. We have found that using an active space of eight electrons in eight orbitals and including all single and pair-double excitations in the CI leads to results that agree well with experiment and that do not change significantly with increasing active space for most organic molecules. Calculated second-order hyperpolarizabilities using this type of CI within a sum-over-states calculation appear to be of useful accuracy.

Raman spectral studies of borate glasses

Raman spectroscopic measurements in borate glasses have been reviewe. The review shows that the technique is useful in identifying the structural groups present in the borate on the basis of the Krogh-Moe hypothesis. Vitreous B2O3 and alkali borates are extensvvely studied and a satisfactory assignment of bands is possible by a careful consideration of the literature. A cation effect on the borate netwoork is observed. Availaable measurements on binary borates other than alkali borates and on ternary borates are limited and more work is required to identify the structural modifications that take place with composition. Mixed alkali effect is reported only lithium-caesium borade and shows the formation of non-bridging oxygens, destroying the six-membered rings when Li2O is replaced by Cs2O. Fast ionic glasses (alkali borates containing alkali halides) yield the same Raman spectra as the alkali borates, except when the alkali is a fluoride.

Spectral approach for the soliton and periodic solutions of the nonlinear wave equation

A spectral method that obtains the soliton and periodic solutions to the nonlinear wave equation is presented. The results show that the nonlinear group velocity is a function of the frequency shift as well as of the soliton power. When the frequency shift is a function of time, a solution in terms of the Jacobian elliptic function is obtained. This solution is periodic in nature, and, to generate such an optical pulse train, one must simultaneously amplitude- and frequency-modulate the optical carrier. Finally, we extend the method to include the effect of self-steepening.

Synthesis, spectral characterisation and single-crystal structure of a bicyclic tetraphosphapentazane tetraoxide, N5P4ET5O4(OC6H3Me2-2,6)2

Reaction of the bicyclic phosphazane N5P4Et5Cl2 with 2,6-dimethylphenol and subsequent oxidation of the product by aqueous hydrogen peroxide yields N5P4Et5O4(OC6H3Me2-2,6)2 in 85% yield. Its structure has been established by NMR spectroscopy and single-crystal X-ray diffraction. The compound crystallises in the monoclinic space group C2/c with a= 21.245(5), b= 10.879(2), c= 16.450(6)Å, ?= 123.94(2)°, Z= 4, R= 0.066. The structural features are compared with those of bicyclic ?5-phosphazenes of type N5P4R3(NR1R2)5(NHR3)(R1,R3= Me or Et, R2= H or Me). The observed conformation of the N3P3 rings in the present compound is mainly dictated by the maximisation of the stabilising influence of �negative hyperconjugative interactions� between the nitrogen lone pairs and the adjacent P�X ?* orbitals.

Autoregressive spectral array for graphical display of EEG data

A graphical display of the frequency content of background,electroencephalogram (EEG) activity is obtained by calculating the spectral estimates using autocorrelation autoregressive method and the classical Fourier transform method, Display of spectral content of consecutive data segments is made using hidden-line suppression technique so as to get a spectral array, The autoregressive spectral array (ASA) is found to be sensitive to baseline drift, Following baseline correction the autoregressive technique is found to be superior to the Fourier method of compressed spectral array (CSA) in detecting the transitions in the frequencies of the signal. The smoothed ASA gives a better picture of transitions and changes in the background activity, The ASA can be made to adapt to specific changes of dominant frequencies while eliminating unnecessary peaks in the spectrum. The utility,of the ASA for background EEG analysis is discussed,

High Yield Room Temperature Synthesis And Spectral Studies Of Tri(Amino)Silanes: (R2n)3SIH

Tri(amino)silanes were prepared by the condensation of trichlorosilane with secondary amines in 1:6 molar ratio. Reactions of trichlorosilane with pyrrolidine, piperidine, hexamethyleneimine, morpholine, N-methylpiperazine and diethylamine afford the tri(amino)silanes in nearly quantitative yields. Their physical and spectroscopic properties are discussed. All these compounds are highly sensitive to moisture and hydrolyse to silica and the respective amine with the evolution of hydrogen. The compounds have been characterised by IR, 1H NMR, [1H]29Si NMR spectroscopic methods and CHN elemental analysis.

High-rate, Double-Symbol-Decodable STBCs from Clifford Algebras

For the number of transmit antennas N = 2(a) the maximum rate (in complex symbols per channel use) of all the Quasi-Orthogonal Designs (QODs) reported in the literature is a/2(a)-1. In this paper, we report double-symbol-decodable Space-Time Block Codes with rate a-1/2(a)-2 for N = 2(a) transmit antennas. In particular, our code for 8 and 16 transmit antennas offer rates 1 and 3/4 respectively, the known QODs offer only 3/4 and 1/2 respectively. Our construction is based on the representations of Clifford algebras and applicable for any number of transmit antennas. We study the diversity sum and diversity product of our codes. We show that our diversity sum is larger than that of all known QODs and hence our codes perform better than the comparable QODs at low SNRs for identical spectral efficiency. We provide simulation results for various spectral efficiencies.