Synthetic thermally reversible gel systems. V

Differential thermal analysis has been used to study the fusion of aqueous thermally reversible gels of gelatin and polyacrylylglycinamide (PAG). In the case of gelatin gels, endotherms close to the melting point are readily observed and these are sometimes preceeded by a small exothermic heat of gel reorganization. Calculations are presented to show that breaking of the gelatin gel network requires only a small fraction of the observed endothermic heat of fusion and that most of the heat is required for melting larger crystallites within gelatin aggregates and for perhaps a helix → coil transition. Failure to observe endotherms by DTA over the known temperature range of fusion of PAG gels is consistent with prior measurements and conclusions. The noncrystallinity of PAG gels and soluble aggregates together with a heat of crosslinking of only ?5 to ?10 kcal/mole of crosslinks places the heat of fusion of PAG gels outside the lower limits of DTA sensitivity.     

High-resolution spectroscopy of induced chiral dimers: a study of the dimers of ethanol by Fourier transform microwave spectroscopy

We present the first recording of the high-resolution spectrum of an induced chiral dimer. Three conformers of the induced chiral dimers of ethanol have been observed using a pulsed molecular-beam Fourier transform microwave spectrometer. The rotational constants of the normal isotopomers of the three species have been determined to be (a) A=5113.826(5), B=1329.7214(4), and C=1257.5151(3) MHz, (b) A=5086.459(5), B=1316.6508(4), and C=1243.6329(4) MHz, and (c) A=4851.608(5), B=1369.7558(6), and C=1243.4184(4) MHz. The observed species have been assigned to calculated structures via Kraitchman double substitution analyses and ab initio calculations. The Kraitchman analyses and the fitted centrifugal distortion parameters suggest that the deuterium bond is significantly stronger than the hydrogen bond in the dimers of ethanol.     

Processes of flats induced by higher dimensional processes III

Stationary processes of k-flats in ^d can be thought of as point processes on the Grassmannian _k ^d of k-dimensional subspaces of ^d . If such a process is sampled by a (d–k+ j)-dimensional space F, it induces a process of j-flats in F. In this work we will investigate the possibility of determining the original k-process from knowledge of the intensity measures of the induced j-processes. We will see that this is impossible precisely when 1<k<d–1 and j=0,...,2[r/2]–1, where r is the rank of the manifold _k ^d . We will show how the problem is equivalent to the study of the kernel of various integral transforms, these will then be investigated using harmonic analysis on Grassmannian manifolds.The research of the first and third authors was supported in part by NSF grants DMS-9207019 and DMS-9304284. The research of the second author was supported in part by NFR contract number R-RA 4873-306 and the Swedish Academy of Sciences.     

Nitrato- and fluoroboracites M3B7O13NO3 and M3B7O13F

New boracites containing nitrato- or fluoroanions that appear to be true low-pressure phases have been synthesized at superatmospheric pressures. The M₃B₇O₁₃NO₃ compounds (M = Co, Ni, Cu, Zn, Cd) transform rapidly and reversibly in the temperature region 300–500°C between probable orthorhombic and face centered cubic symmetry, while the M₃B₇O₁₃F compounds (M = Mg, Mn, Fe, Co, Zn) appear to maintain rhombohedral symmetry up to their decomposition temperatures of 800–900°C. True high-pressure boracite-like phases containing F and Cr, Mn, Fe, or Co that decompose upon heating to M₃B₇O₁₃F have also been isolated.     

Obtaining partial widths from siegert wavefunctions

It is shown that a simple expression for the partial widths in a multichannel decay problem can be readily obtained from a Siegert wavefunction.     

Metal-ligand bonding and rutile- versus CdI2-type structural preference in platinum dioxide and titanium dioxide

First principles electronic structure calculations were carried out to determine the relative stabilities of the rutile- and CdI₂-type structures of platinum dioxide (PtO₂) and titanium dioxide (TiO₂). The orbital interactions between the transition metal d- and oxygen p-orbitals were analyzed to gain insight into why PtO₂ has both the rutile- and CdI₂-type structures, but TiO₂ has only the rutile-type structure. The cause for the large difference in the c/a ratios of the CdI₂-type structures of TiO₂ and PtO₂ was examined.