The swelling interface number as a criterion for prediction of diffusional solute release mechanisms in swellable polymers

When a glassy polymer containing a uniformly dispersed solute is brought in contact with a penetrant, solute diffusion will be associated with the transport mechanism and penetration velocity of the penetrant in the polymer. Analysis and prediction of mechanisms of diffusional solute release may be obtained through a new dimensionless number, the swelling interface number, Sw, which compares the relative mobilities of the penetrant and the solute in the presence of macromolecular relaxations in the polymer. It is shown that a sufficient and necessary criterion for time-independent diffusional solute release rates from these swellable systems is that the Sw be smaller than 10^?2. The swelling interface number Sw may be related to easily determined structural and thermodynamic parameters of the solute/polymer/penetrant system. Preliminary experimental results of dynamic water swelling of poly(2-hydroxyethyl methacrylate-co-methyl methacrylate) and diffusional release of theophylline from initially glassy copolymers show that decreasing values of Sw are related to increased pseudo-case-II transport kinetics of the solute.     

Oxidation Products of Retinylidene Dimedone

Several oxidation products of the retinoid retinylidene dimedone (RD) have been synthesized and characterized for biological testing in the expectation that they may be found as metabolites of RD.     

Scanning tunneling microscopy and surface simulation of zinc-blende GaN(001) intrinsic 4x reconstruction: linear gallium tetramers?

Scanning tunneling microscopy images confirm electron diffraction studies that the zinc-blende GaN(001)-4x reconstruction consists of rows aligned along [110] with a spacing along [110] of 4a. Dual-bias imaging shows a 180 degree shift of the corrugation maximum position between the profiles of empty and occupied states, in agreement with surface simulations based on the 4 x 1 linear tetramer model of Neugebauer et al. [Phys. Rev. Lett. 80, 3097 (1998)]. Electronic structure calculations predict a surface band gap of 1.1 eV, close to the measured value of 1.14 eV and the previously predicted value (1.2 eV). Despite the successes of this model, high-resolution images reveal an unexpected 3x periodicity (not seen in diffraction) along the [110] row direction, indicating the need for a 4 x 3 model, and putting into question the existence of linear Ga tetramers.     

Efficient synthesis of enantiomerically pure alpha-alkyl cyclopropanecarbonitrile derivatives from pyrazolines

[reaction: see text] Thermolysis of enantiopure sulfonyl pyrazolines 4 and 5, easily obtained from (Z)-3-p-tolylsulfinylacrylonitriles (1), afforded sulfonyl cyclopropanes (6, 7) in a completely stereoselective manner in almost quantitative yields. Both cyclopropanes and alkylidenecyclopropanes, containing one or two chiral carbon atoms, one of them being quaternary, were obtained by hydrogenolysis of the C-S bonding and under the conditions reported by Julia, respectively. The highly stereoselective extrusion of nitrogen suggests a concerted mechanism.     

Tetrabromobutatriene: completing the perhalocumulene series

[structure: see text] Tetrabromobutatriene, C(4)Br(4), can be prepared directly from dibromobutadiyne by reaction with Br(2) at -25 degrees C in concentrated hexanes solution. The cumulene precipitates out of the reaction mixture as a yellow powder. Under palladium-catalyzed coupling conditions, C(4)Br(4) can undergo allylic rearrangement, giving a mixture of products, including some with butenyne backbones. However, in furan solution, C(4)Br(4) reacts cleanly at its central double bond to give the furan Diels-Alder adduct. Under Suzuki conditions, this adduct reacts at the furan double bond rather than at bromide.     

Lattice invariants and the center of the generic division ring

Let be a finite group, let be a -lattice, and let be a field of characteristic zero containing primitive roots of 1. Let be the quotient field of the group algebra of the abelian group . It is well known that if is quasi-permutation and -faithful, then is stably equivalent to . Let be the center of the division ring of generic matrices over . Let be the symmetric group on symbols. Let be a prime. We show that there exist a split group extension of by a -elementary group, a -faithful quasi-permutation -lattice , and a one-cocycle in such that is stably isomorphic to . This represents a reduction of the problem since we have a quasi-permutation action; however, the twist introduces a new level of complexity. The second result, which is a consequence of the first, is that, if is algebraically closed, there is a group extension of by an abelian -group such that is stably equivalent to the invariants of the Noether setting .

     

Aberro-polariscope for the human eye

We have developed an aberro-polariscope that simultaneously measures spatially resolved polarization properties and wave-front aberration in a living human eye. The setup consists of an infrared Hartmann-Shack sensor that incorporates a polariscope. A series of four Hartmann-Shack images corresponding to independent polarization states were recorded. The corresponding wave-front aberration was computed from each image. Moreover, from each set of four images spatially resolved (over the pupil plane) parameters of polarization were also determined. This instrument allows useful information on both the optical and the biomechanical properties of the eye to be obtained.     

Naphthalene analogues of lignans

The methodology for the synthesis of podophyllotoxin and thuriferic acid-type lignans has been applied to derivatives carrying a naphthalene moiety. Starting from the 1,3-dithiane of 2-naphthaldehyde afforded the expected analogues in the 2,1-naphthalene series. The preferred conformations of these compounds are influenced by the bulky naphthalene system. By contrast, 1,8-bridged products were obtained from the 1,3-dithiane of 1-naphthaldehyde. In this series, polycyclic naphthalene lignan analogues were isolated after deprotection and/or desulfurization reactions. The cyclizations produced in this process are due to the proximity between the 3,4,5-trimethoxyphenyl moiety and the reacting C-2 of the 1,3-dithiane ring.     

Stereodifferentiation of chiral compounds using reversed-phase liquid chromatography coupled with capillary gas chromatography

A method is described for the enantiomeric quantitation of some chiral compounds via online coupling of reversed-phase liquid chromatography-gas chromatography. The evaluation of some variables affecting the experimentation (i.e., the packing material used in the interface, volume of the transferred fraction, desorption time, initial temperature of the interface, and purge time) makes it possible to optimize the recoveries obtained for some chiral terpenes and lactones using a capillary column of beta-cyclodextrin dissolved in OV-1701. The proposed method allows the enantiomeric analysis of aqueous matrices obtaining relative standard deviations lower than 9% and detection limits ranging from 0.26-0.93 ppm for the investigated compounds.