Field-induced anisotropy in concentrated systems of rigid particles and macromolecules

This paper presents experimental results on the use of spectroscopic optical polarimetry to study structure in dense systems of rigid particles and rigid polymer liquid crystals. These measurements probe microstructural anisotropy induced by the application of electric fields in the case of dense suspensions of rigid spheres, or flow fields in the case of polymer liquid crystals. It is demonstrated that conservative linear dichroism can measure moments of the particle pair distribution function in dense suspensions. In liquid crystals, the dichroism is a result of field-induced anisotropy in the defect structure of the material.     

Some experimental results on the development of Couette flow for non-Newtonian fluids

This paper reports some experimental results on the time development of a Couette flow following the start-up of shear flow using the technique of two-color flow birefringence. Measurements obtained on collagen solutions are consistent with two theoretical studies which predict that for some viscoelastic liquids, momentum is transferred from the moving Couette cell boundary to the interior of the fluid through a velocity wave propagating and reflecting between the cell boundaries. This non-Newtonian phenomenon, exhibited as an oscillatory response in the measured birefringence and orientation angle, is observed at shear rates above a critical value when the response time of the polymer solution approaches the flow development time in the Couette flow cell.     

Pulsed-field ionization electron spectroscopy and binding energies of alkali metal-dimethyl ether and -dimethoxyethane complexes

Lithium and sodium complexes of dimethyl ether (DME) and dimethoxyethane (DXE) were produced by reactions of laser-vaporized metal atoms with organic vapors in a pulsed nozzle cluster source. The mono-ligand complexes were studied by photoionization and pulsed field ionization zero electron kinetic energy (ZEKE) spectroscopy. Vibrationally resolved ZEKE spectra were obtained for Li(DME), Na(DME) and Li(DXE) and a photoionization efficiency spectrum for Na(DXE). The ZEKE spectra were analyzed by comparing with the spectra of other metal-ether complexes and with electronic structure calculations and spectral simulations. Major vibrations measured for the M(DME) (M=Li,Na) ions were M-O and C-O stretches and M-O-C and C-O-C bends. These vibrations and additional O-Li-O and O-C-C-O bends were observed for the Li(DXE) ion. The M(DME) complexes were in C2v symmetry with the metal atom binding to oxygen, whereas Li(DXE) was in a C2 ring configuration with the Li atom attaching to both oxygen atoms. Moreover, the ionization energies of these complexes were measured from the ZEKE or photoionization spectra and bond dissociation energies were derived from a thermodynamic cycle.     

Assay of89Sr in plant and soil samples by liquid scintillation counting

The Sr in plant and soil samples is converted to SrCl₂ by digestion with HNO₃ and HCl. The recovery of this digestion is 90% with a reproducibility of about 4%. SrCl₂ is solubilized in toluene by forming a complex with di-n-propyl phosphate (DNP). The DNP-toluene reagent was found to be a highly effective carrier of SrCl₂, and to have properties suitable for highly efficient liquid scintillation counting. An efficiency of 95% was obtained for⁸⁹Sr counting. The factors affecting the utility of the method are discussed.     

Studies on the synthesis of the inostamycin natural products: a reductive aldol/reductive Claisen approach to the C10-C24 ketone fragment

[reaction: see text] An approach to the C10-C24 ketone fragment of the inostamycin family of polyether antibiotics is described. The synthetic strategy utilizes an asymmetric Rh-catalyzed reductive aldol reaction and a stereoselective Rh-catalyzed reductive Claisen rearrangement as the key steps in formation of alkene and vinyl iodide synthons, respectively.     

Selective Debenzylation of Quaternary Salts. The Benzyl Group as an Excellent Protecting Group for Basic Nitrogen Compounds

In several synthetic problems in our laboratory it became essential to react a basic nitrogen atom with a suitable protecting group which could be subsequently removed under very mild conditions. The presence of sensitive functionality elsewhere in the molecule prevented serious consideration of most of the reagents which have been developed for dealkylation of quaternary ammonium salts^2–12. One of the most recent methods involving the highly nucleophilic system, lithium n-propylmercaptide in hexamethylphosphoramide¹² (HMPA) was thought to be most desirable but even in this instance demethylation of the quaternary system provided difficulties. For example, demethylation of the methiodide derivative of 18β-carbomethoxycleavamine (II, R [dbnd] CH₃, 3,4-double bond) provided only a 5% yield of the desired product. It was clear that a protecting group more susceptible to nucleophilic displacement was essential. During our studies directed to this end it has been established that the benzyl group satisfies the requirements in all respects. We present some of our results since they may be of interest to others involved in research on alkaloids and other basic nitrogen compounds.     

Birefringence and stress growth in uniaxial extension of polymer solutions

Simultaneous measurements of extensional stresses and birefringence are rare, especially for polymer solutions. This paper reports such measurements using the filament stretch rheometer and a phase modulated birefringence system. Both the extensional viscosity and the birefringence increase monotonically with strain and reach a plateau. Estimates of this saturation value for birefringence, using Peterlin’s formula for birefringence of a fully extended polymer chain are in agreement with the experimental results. However, estimates of the saturation value of the extensional viscosity using Batchelor’s formula for suspensions of elongated fibres are much higher than observed. Reasons for the inability of the flow field to fully unravel the polymer chain are examined using published Brownian dynamics simulations. It is tentatively concluded that the polymer chain forms a folded structure. Such folded chains can exhibit saturation in birefringence even though the stress is less than that expected for a fully extended molecule.Simultaneous measurements of stress and birefringence during relaxation indicate that the birefringence decays much more slowly than the stress. The stress-birefringence data show a pronounced hysteresis as predicted by bead-rod models. The failure of the stress optic coefficient in strong flows is noted.Experiments were also performed wherein the strain was increased linearly with time, then held constant for a short period before being increased again. The response of the stress and birefringence in such experiments is dramatically different and can be traced to the different configurations obtained during stretching and relaxation. The results cast doubt on the appropriateness of pre-averaging the non-linear terms in constitutive equations.