Quantitative photoacoustic spectrometry : Determination of copper(II) and iron(III) complexed on modified silica gel samples

Calibration curves for copper(II) and iron(III) complexed with N-2-aminoethyl-3-aminoprophyltrimethoxysilane (AEAPS) immobilized on silica gel were prepared separately by photoacoustic spectroscopy (p.a.s.) based on a response function that combines the amplitude and phase values. The concentration of copper and iron in two-component samples are determined by obtaining the response at 600 and 400 nm, respectively, and referring to the calibration graphs. The relative errors in the concentrations determined by p.a.s. compared to atomic absorption spectrometry for copper range from ?9.3 to 3.2%, while for iron the range is ?52.7 to 4.5%. The large error for iron was due to its low concentration and absorptivity. With suitable chromophores and matrix, the response function extends the linear range of the calibration graph and can be used for nondestructive determination of two components.     

Synthesis and characterisation of the methylene-inserted mixed-chalcogenide compounds Fe2(CO)6(μ-SeCH2Te) and Fe2(CO)6(μ-SCH2Te)

The methylene-bridged, mixed-chalogen compounds Fe₂(CO)₆(μ-SeCH₂Te) (1) and Fe₂(CO)₆(μ-SCH₂Te) (3) have been synthesised from the room temperature reaction of diazomethane with Fe₂(CO)₆(μ-SeTe) and Fe₂(CO)₆(μ-STe), respectively. Compounds 1 and 3 have been characterised by IR, ¹H, ¹³C, ⁷⁷Se and ¹²⁵Te NMR spectroscopy. The structure of 1 has been elucidated by X-ray crystallography. The crystalsare monoclinic,space group P2₁/n, A = 6.695(2), B = 13.993(5), C = 14.007(4)Å, β = 103.03(2)°, V = 1278(7) ų, Z = 4, D_c = 2.599 g cm⁻³ and R = 0.030 (R_w = 0.047).     

Solvent‐Free One‐Pot Synthesis of Amidoalkyl Naphthols Catalyzed by Silica Sulfuric Acid

An efficient, inexpensive, and mild method for the synthesis of amidoalkyl naphthols, catalyzed by ‘silica sulfuric acid’ (SSA), was elaborated under solvent‐free conditions at room temperature. Various amidoalkyl naphthols were synthesized in high yields from aromatic or aliphatic aldehydes, α‐ or β‐naphthols, and amides or urea or thiourea.     

Rearrangements in the mass spectra of α-phenylcinnamic acid and its derivatives

The electron impact ionization and collisional activation mass spectra of α-phenylcinnamic acid and its derivatives have been studied. The loss of a phenylic hydrogen is not an important process in these molecules, unlike the unsubstituted cinnamic acids. However, in o-chloro-α-phenylcinnamic acid and its methyl and trimethylsilyl derivatives loss of Cl resulting in the formation of 2-substituted-3-phenylbenzopyrilium ion is an important fragmentation pathway. The rearrangement ions observed at m/z 118 and 107 in the Spectrum of α-phenylcinnamic acid have been found to have the structures of the M⁺˙ of benzofuran and PhCH?$ \mathop {\rm O}\limits^{\rm +} $H, respectively. The ion at m/z 121 in the spectrum of the methyl ester of α-phenylcinnamic acid has been found to have the structure PhCH?$ \mathop {\rm O}\limits^{\rm +} $Me.     

Estimation of trace elements in water matrix from photon attenuation coefficients

The method of elemental analysis based on the measurement of attenuation coefficient has been used to estimate the impurity introduced in a water matrix using a scintillation detector with a single channel analyser. For a 2% change in the mass attenuation coefficient the minimum detectable fractions of impurities were estimated to be of the order of 625–1250 μg/g for uranium and thorium compounds at photon energies 32.1 and 59.5 keV.     

Hydrogen bonding,mobility, and structural transitions in aliphatic polyamides

Some salient results in nylon research are reviewed to identify the fundamental principles that are applicable to other strongly interacting or hydrogen‐bonded polymers, including proteins. The effects of hydrogen bonds on stress‐, heat‐, and solvent‐induced changes in macroscopic properties are discussed. These data provide a window into the chain mobility and linkages between the crystalline and amorphous domains, both of which are important for any predictive model. The changes in the characteristics of the amorphous phase with the crystallinity and orientation require that it be modeled with at least two components: a rigid/immobile/anisotropic component and a soft/mobile/isotropic component. The deformation and shrinkage behavior of these polymers are discussed in terms of the relative contributions of the amorphous and crystalline domains and of the interactions between them. The premelting crystalline transition is accompanied by the merging of intersheet and intrasheet diffraction peaks in some nylons, as observed by Brill, and not in others even though the underlying mechanism that gives rise to these transitions, the onset of volume‐increasing librational motion of the crystalline stems, is the same. Because the effects of the temperature, deformation, and solvent have a common origin associated with mobility, a fictive temperature can be associated with a given solvent activity or stress level. The magnitude of this fictive temperature is the amount by which the glass or Brill transition temperature is reduced in the presence of solvents (～50 °C) or stress or by which the annealing temperature can be reduced in the presence of a solvent (or active stress) to achieve the same structural state as that of a dry (or static) polymer. © 2006 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 44: 1763–1782, 2006     

Finite Difference Methods for the Heat Equation with a Nonlocal Boundary Condition

We consider the numerical solution by finite difference methods of the heat equation in one space dimension, with a nonlocal integral boundary condition, resulting from the truncation to a finite interval of the problem on a semi-infinite interval. We first analyze the forward Euler method, and then the $θ$-method for $0 < θ ≤ 1$, in both cases in maximum-norm, showing $O(h^2 + k)$ error bounds, where $h$ is the mesh-width and $k$ the time step. We then give an alternative analysis for the case $θ = 1/2$, the Crank-Nicolson method, using energy arguments, yielding a $O(h^2$ + $k^{3/2}$) error bound. Special attention is given the approximation of the boundary integral operator. Our results are illustrated by numerical examples.