Pyrimidino- and Proton-ionizable Pyrimidono-crown Ether Ligands: Synthesis and Preliminary Complexation Studies

Pyrimidino-crown ethers were prepared in 30-50% yields by reactingthe ditosylate derivative of the appropriate oligoethylene glycol with4-methoxy-5-methyl-2,6-pyrimidinedimethanol under basic conditions. A newmacrocyclic ligand containing a proton-ionizable pyrimidone subcyclic unitwas prepared in 88% yield by treating the appropriatepyrimidino-crown ether with 5 M NaOH in 50% (v/v) aqueous methanol.Preliminary complexation properties of some of these new compounds werestudied using various NMR spectral techniques. Good enantiomeric recognitionwas exhibited by a chiral pyrimidino-crown ether for the enantiomers of1-(-naphthyl)ethylammonium perchlorate.     

New pyrimidino-crown ether ligands

Eight new macrocyclic ligands containing the pyrimidine subcyclic unit ( 3-10 , Figure 1) have been prepared. Two of these new crown ethers are chiral. Pyrimidino-crowns 3-8 were prepared by treating the di-tosylate derivative of the appropriate oligoethylene glycol with 4-methoxy-5-raethyl-2,6-pyrimidinedimeth-anol in basic conditions. The yields were in the 30-50% range giving the crowns as viscous oils. Chiral dimethyl-substituted pyrimidino-crown 9 was prepared from 4-methoxy-5-methyl-2,6-pyrimidinedimethyl di-tosylate and chiral dimethyl-substituted tetraethylene glycol. Treatment of dimethyl 4-methoxy-5-methyl-2,6-pyrimidinedicarboxylate with the diamine derivative of chiral dibenzyl-substituted tetraethylene glycol gave the chiral dibenzyl-substituted pyrimidino-crown diamide 10. Starting 4-methoxy-5-methyl-2,6-pyrimidinedi-methanol was prepared by a six step process from acetamidine hydrochloride and diethyl oxalpropionate.     

Temperament Development Modeled as a Nonlinear Complex Adaptive System

Using approach-withdrawal (AW) as a specific instance of temperament, a theoretical model of temperament as a complex dynamic system is proposed. Developmental contextualism (Lerner, 1998) serves as a guiding theory in determining the structural components of the system and Kauffman's (1993) Boolean models of self-organization are adapted to estimate the parameter functions. In this model P(AW) = f(, ) where P(AW) is the probability density function of an approach or a withdrawal response, ( is a standardized parameter estimate of the biological sensitivity to stimulation, and is a standardized parameter estimate of the contextual response to an approach or withdrawal response. It is theorized that the functions of ( and follow a Hill function of the forms: d /dt = (²/c² + ²) – K₁ d /dt = ( ²/c² + ²) – K₂, where K₁, K₂, and c are system constants. This results in a double sigmoid function in which at extreme values of and the system stabilizes on a steady state of either approach or withdrawal response patterns. At intermediate parameter values the probability density functions of approach and withdrawal responses are wider. Thus, AW can be modeled as representing two basins of attraction. In addition, considerations are given to the systems sensitivity to initial conditions.     

Use and Abuse of Entropy in Biology: A Case for Caliber

Here, I discuss entropy and its use as a tool in fields of biology such as bioenergetics, ecology, and evolutionary biology. Statistical entropy concepts including Shannon’s diversity, configurational entropy, and informational entropy are discussed in connection to their use in describing the diversity, heterogeneity, and spatial patterning of biological systems. The use of entropy as a measure of biological complexity is also discussed, and I explore the extension of thermodynamic entropy principles to open, nonequilibrium systems operating in finite time. I conclude with suggestions for use of caliber, a metric similar to entropy but for time-dependent trajectories rather than static distributions, and propose the complementary notion of path information.     

A SAXS study of the internal structure of dendritic polymer systems

Small-angle x-ray scattering was used to characterize the single-particle scattering factors produced by poly(amidoamine) dendrimers, poly(propleneimine) dendrimers, and polyol hyperbranched polymers in dilute solutions with methanol as solvent. Fits from electron density modeling reveal similar overall densities of the dendrimers as a function of dendrimer generation. The seventh through tenth generation poly(amidoamine) dendrimers exhibit higher order scattering features that require nearly monodisperse, spherical particles with essentially uniform internal segment densities. Dilute hyperbranched polymer solutions exhibit scattering more indicative of the inherent irregularity of internal segment densities and overall sizes to be expected within these systems. Radii of gyration estimated from electron density modeling agree reasonably well with those estimated by standard Guinier methods used in previous studies. © 1997 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 35: 2913–2924, 1997     

Asymmetric dihydroxylation of disubstituted allenes

Asymmetric dihydroxylation of 1,1-disubstituted and 1,3-disubstituted allenes can be used to synthesize chiral α-hydroxy ketones. We have also obtained α,α′-dihydroxy ketones with high enantioselectivity from 1,3-disubstituted allenes. Low conversion of the dihydroxylation of chiral allenes can be used as a kinetic resolution of sterically hindered allenes.     

Novikov numbers

Translated from Matematicheskii Zametki, Vol. 47, No. 1, pp. 98–104, January, 1990.     

Probabilistic determination of two-phase flow regimes in horizontal tubes utilizing an automated image recognition technique

Probabilistic two-phase flow map data is experimentally obtained for R134a at 25.0, 35.0, and 49.7°C, R410A at 25.0°C, mass fluxes from 100 to 600 kg/m²-s, qualities from 0 to1 in 8.00, 5.43, 3.90, and 1.74 mm I.D. single, smooth, adiabatic, horizontal tubes in order to extend probabilistic two-phase flow map modeling techniques to single tubes. A new web camera based flow visualization technique utilizing an illuminated diffuse striped background was used to enhance images, detect fine films, and aid in the automated image recognition process developed in the present study. This technique has an average time fraction classification error of less than 0.01.