Rearrangement during cyclisation of some 3-(2-pyrrolyl) propionic acids and related compounds

Cyclisation of the title compounds leads to mixtures of the expected 4H-cyclopental[b]pyrrol-4-ones (1), the corresponding 6-ones (3) by a single rearrangement, and the cyclopenta[c]pyrrol-4-ones (4) by a double rearrangement, the proportions depending upon the substituents.The ¹H NMR spectra of 2-methyl-4H-cyctopenta[b]thiophen-6-one (3f) shows 6J long range $\text{CH}{}_3\text{CH}{}_2$ coupling, but this is absent in the corresponding pyrroles (3c,d). The ¹³C spectra of 1 and 3 cannot be interpreted on the basis of substituent chemical shifts in pyrroles and thiophens, and are clearly -CH = CH-X (X = NMe, NPh, S) bridged derivatives of cyclopent-2-enone.     

The effect of crown ethers on the alkylation of a cyclic β-keto ester

The effects of crown ethers (6 and 7) on the reactions of sodium (2a) and potassium enolates (2b) of 2-ethoxycarbonylcyclohexanone (1) with isopropyl iodide in dimethylsulfoxide and dimethoxyethane have been investigated. When the addition of crown ether promoted dissociation of ion pair 2 in either of the two solvents, the total rate of reaction (k_t) increased and the ratio of carbon- (3) to oxygen-alkylation (4 and 5) products decreased. The results are consistent with the involvement of both the ion pair and more dissociated species in alkylation and with greater reactivity for the latter.     

THE MOLECULAR WEIGHT OF HAEMATOPORPHYRIN DERIVATIVE, ITS GEL COLUMN FRACTIONS and SOME OF ITS COMPONENTS IN AQUEOUS SOLUTION

Abstract— The average molecular weights of haematoporphyrin derivative (HPD), the fractions of HPD that can he obtained by gel chromatography and of purified haematoporphyrin and protoporphyrin in aqueous solution have been determined by ultracentrifugation. The results show that HPD contains polymeric material with the excluded fraction from the gel column (HPD aggregate) having an average molecular weight of greater than 20000. The two remaining gel column fractions of HPD have lower molecular weights and their similarity indicates that these fractions do not separate because of molecular weight differences. Purified haematoporphyrin has a comparatively low molecular weight in aqueous solution but the data is not capable of discriminating between monomer, dimer or slightly higher oligomer. In contrast, protoporphyrin sediments to the bottom of the centrifuge tube under the conditions of sedimentation equilibrium indicating that it has an average molecular weight considerably greater than that of HPD aggregate.     

Dysrhythmias of the respiratory oscillator

Breathing is regulated by a central neural oscillator that produces rhythmic output to the respiratory muscles. Pathological disturbances in rhythm (dysrhythmias) are observed in the breathing pattern of children and adults with neurological and cardiopulmonary diseases. The mechanisms responsible for genesis of respiratory dysrhythmias are poorly understood. The present studies take a novel approach to this problem. The basic postulate is that the rhythm of the respiratory oscillator can be altered by a variety of stimuli. When the oscillator recovers its rhythm after such perturbations, its phase may be reset relative to the original rhythm. The amount of phase resetting is dependent upon stimulus parameters and the level of respiratory drive. The long-range hypothesis is that respiratory dysrhythmias can be induced by stimuli that impinge upon or arise within the respiratory oscillator with certain combinations of strength and timing relative to the respiratory cycle. Animal studies were performed in anesthetized or decerebrate preparations. Neural respiratory rhythmicity is represented by phrenic nerve activity, allowing use of open-loop experimental conditions which avoid negative chemical feedback associated with changes in ventilation.In animal experiments, respiratory dysrhythmias can be induced by stimuli having specific combinations of strength and timing. Newborn animals readily exhibit spontaneous dysrhythmias which become more prominent at lower respiratory drives. In human subjects, swallowing was studied as a physiological perturbation of respiratory rhythm, causing a pattern of phase resetting that is characterized topologically as type 0. Computational studies of the Bonhoeffer-van der Pol (BvP) equations, whose qualitative behavior is representative of many excitable systems, supports a unified interpretation of these experimental findings. Rhythmicity is observed when the BvP model exhibits recurrent periods of excitation alternating with refractory periods. The same system can be perturbed to a state in which amplitude of oscillation is attenuated or abolished. We have characterized critical perturbations which induce transitions between these two states, giving rise to patterns of dysrhythmic activity that are similar to those seen in the experiments. We illustrate the importance of noise in initiation and termination of rhythm, comparable to normal respiratory rhythm intermixed with spontaneous dysrhythmias. In the BvP system the incidence and duration of dysrhythmia is shown to be strongly influenced by the level of noise. These studies should lead to greater understanding of rhythmicity and integrative responses of the respiratory control system, and provide insight into disturbances in control mechanisms that cause apnea and aspiration in clinical disease states. (c) 1995 American Institute of Physics.     

Multiple time scale analysis of two models for the peroxidase-oxidase reaction

A multiple time scale analysis of two four-variable models of the peroxidase-oxidase reaction, the DOP, and the Olsen model, is carried out. It is shown that autonomous limit cycle oscillations are exhibited by the fast subsets of these two models, but only in certain regions of parameter space, confirming the prior suggestion that the slow variable (NADH) is not essential for oscillatory behavior. However, it is found that the slow variable is essential for oscillatory behavior over other ranges of parameter values, and is always essential for complex oscillatory and chaotic behavior. This latter conclusion is based on a study involving driving the fast subset with a sinusoidally varying (NADH). This study suggests the level of coupling between fast and slow variables of an autonomous system necessary to cause the chaos observed in the DOP model. Further study of the driven system allows for the identification of a natural period of the nonoscillatory but bistable fast subsystem and a set of rules for applying a parametric driving in such a way as to generate a more complete Farey sequence from a truncated Farey sequence. These conclusions are used to compare the very similar DOP and Olsen models, which, nevertheless, exhibit quite different Farey sequences and routes to chaos. (c) 1995 American Institute of Physics.     

Error estimates in the determination of rigid body displacements in protein crystals

We report the estimation of random errors in the refinement of the rigid body displacements of the -helices of the enzyme 6-phosphogluconate dehydrogenase. Least-squares refinement of the TLS parameters of the helices has been carried out using X-ray reflection data of 2.1 Å resolution, resulting in anR-factor of 19.5%. Standard deviations were estimated from the normal matrix. The results show that the translational mean-square displacements of nearly all the helices are significant at this resolution. However the libration parameters are only significant when the helices have at least four turns. Screw-rotation tensor values cannot be determined at this resolution.     

Moment closure hierarchies for kinetic theories

This paper presents a systematicnonperturbative derivation of a hierarchy of closed systems of moment equations corresponding to any classical kinetic theory. The first member of the hierarchy is the Euler system, which is based on Maxwellian velocity distributions, while the second member is based on nonisotropic Gaussian velocity distributions. The closure proceeds in two steps. The first ensures that every member of the hierarchy is hyperbolic, has an entropy, and formally recovers the Euler limit. The second involves modifying the collisional terms so that members of the hierarchy beyound the second also recover the correct Navier-Stokes behavior. This is achieved through the introduction of a generalization of the BGK collision operator. The simplest such system in three spatial dimensions is a 14-moment closure, which also recovers the behavior of the Grad 13-moment system when the velocity distributions lie near local Maxwellians. The closure procedure can be applied to a general class of kinetic theories.     

Global (and local) analyticity for second order operators constructed from rigid vector fields on products of tori

We prove global analytic hypoellipticity on a product of tori for partial differential operators which are constructed as rigid (variable coefficient) quadratic polynomials in real vector fields satisfying the Hörmander condition and where satisfies a ``maximal' estimate. We also prove an analyticity result that is local in some variables and global in others for operators whose prototype is

(with analytic , naturally, but not identically zero). The results, because of the flexibility of the methods, generalize recent work of Cordaro and Himonas in [4] and Himonas in [8] which showed that certain operators known not to be locally analytic hypoelliptic (those of Baouendi and Goulaouic [1], Hanges and Himonas [6], and Christ [3]) were globally analytic hypoelliptic on products of tori.

     

Chemistry of 1-Alkoxy-1-glycosyl Radicals: The Manno- and Rhamnopyranosyl Series. Inversion of alpha- to beta-Pyranosides and the Fragmentation of Anomeric Radicals

The formation and stereoselective quenching of 1-mannopyranosyl radicals by a tributyltin hydride-mediated intramolecular 1,5-hydrogen abstraction sequence is described. A competing process is 1,4-hydrogen atom abstraction leading principally to glucopyran-2-ulosides. Fragmentation of the anomeric radical resulting in the formation of ring opened products is a problem in certain series. The chemistry is dictated to a considerable extent by the nature of the protecting groups employed with the 4,6-benzylidene series and, for rhamnose, the Ley 3,4-dispiroketal, being particularly susceptible to the 1,4-hydrogen atom abstraction but less to the fragmentation. Photochemical conditions are described, in which these side reactions are practically eliminated, and applied to the inversion of an alpha- to a beta-mannoside in a disaccharide.