A study of the proposed Santa Fe extension from the present Redondo Branch at El Segundo to Los Angeles Harbor

The Los Angeles Harbor at San Pedro with its natural advantages, and the big development of these now underway, will very soon be the key to the traffic routes of Southern California. The Atchison, Topeka, and Santa Fe railway company realizing this and, not wishing to be caught asleep, has planned to build a line from El Segundo to the harbor. The developments of the harbor are not the only developments taking place in these localities and the proposed new line is intended to include these also.

The development of an asymmetric palladium-catalyzed conjugate addition and its application toward the total syntheses of taiwaniaquinoid natural products

The asymmetric synthesis of quaternary stereocenters remains a challenging problem in organic synthesis. Past work from the Stoltz laboratory has resulted in methodology to install quaternary stereocenters α- or γ- to carbonyl compounds. Thus, the asymmetric synthesis of β-quaternary stereocenters was a desirable objective, and was accomplished by engineering the palladium-catalyzed addition of arylmetal organometallic reagents to α,β-unsaturated conjugate acceptors.

Herein, we described the rational design of a palladium-catalyzed conjugate addition reactions utilizing a catalyst derived from palladium(II) trifluoroacetate and pyridinooxazole ligands. This reaction is highly tolerant of protic solvents and oxygen atmosphere, making it a practical and operationally simple reaction. The mild conditions facilitate a remarkably high functional group tolerance, including carbonyls, halogens, and fluorinated functional groups. Furthermore, the reaction catalyzed conjugate additions with high enantioselectivity with conjugate acceptors of 5-, 6-, and 7-membered ring sizes. Extension of the methodology toward the asymmetric synthesis of flavanone products is presented, as well.

A computational and experimental investigation into the reaction mechanism provided a stereochemical model for enantioinduction, whereby the α-methylene protons adjacent the enone carbonyl clashes with the tert-butyl groups of the chiral ligand. Additionally, it was found that the addition of water and ammonium hexafluorophosphate significantly increases the reaction rate without sacrificing enantioselectivity. The synergistic effects of these additives allowed for the reaction to proceed at a lower temperature, and thus facilitated expansion of the substrate scope to sensitive functional groups such as protic amides and aryl bromides. Investigations into a scale-up synthesis of the chiral ligand (S)-tert-butylPyOx are also presented. This three-step synthetic route allowed for synthesis of the target compound of greater than 10 g scale.

Finally, the application of the newly developed conjugate addition reaction toward the synthesis of the taiwaniaquinoid class of terpenoid natural products is discussed. The conjugate addition reaction formed the key benzylic quaternary stereocenter in high enantioselectivity, joining together the majority of the carbons in the taiwaniaquinoid scaffold. Efforts toward the synthesis of the B-ring are presented.

On the set of eigenvalues of a class of equimodular matrices

The structure of the set ϐ(A) of all eigenvalues of all complex matrices (elementwise) equimodular with a given n x n non-negative matrix A is studied. The problem was suggested by O. Taussky and some aspects have been studied by R. S. Varga and B.W. Levinger.

If every matrix equimodular with A is non-singular, then A is called regular. A new proof of the P. Camion-A.J. Hoffman characterization of regular matrices is given.

The set ϐ(A) consists of m ≤ n closed annuli centered at the origin. Each gap, ɤ, in this set can be associated with a class of regular matrices with a (unique) permutation, π(ɤ). The association depends on both the combinatorial structure of A and the size of the a_ii. Let A be associated with the set of r permutations, π₁, π₂,…, π_r, where each gap in ϐ(A) is associated with one of the π_k. Then r ≤ n, even when the complement of ϐ(A) has n+1 components. Further, if π(ɤ) is the identity, the real boundary points of ɤ are eigenvalues of real matrices equimodular with A. In particular, if A is essentially diagonally dominant, every real boundary point of ϐ(A) is an eigenvalues of a real matrix equimodular with A.

Several conjectures based on these results are made which if verified would constitute an extension of the Perron-Frobenius Theorem, and an algebraic method is introduced which unites the study of regular matrices with that of ϐ(A).

On the distribution of the signs of the conjugates of the cyclotomic units in the maximal real subfield of the qth cyclotomic field, q A prime

Let F = Ǫ(ζ + ζ ^–1) be the maximal real subfield of the cyclotomic field Ǫ(ζ) where ζ is a primitive qth root of unity and q is an odd rational prime. The numbers u₁=-1, u_k=(ζ^k-ζ^-k)/(ζ-ζ^-1), k=2,…,p, p=(q-1)/2, are units in F and are called the cyclotomic units. In this thesis the sign distribution of the conjugates in F of the cyclotomic units is studied.

Let G(F/Ǫ) denote the Galoi's group of F over Ǫ, and let V denote the units in F. For each σϵ G(F/Ǫ) and μϵV define a mapping sgn_σ: V→GF(2) by sgn_σ(μ) = 1 iff σ(μ) ˂ 0 and sgn_σ(μ) = 0 iff σ(μ) ˃ 0. Let {σ₁, ... , σ_p} be a fixed ordering of G(F/Ǫ). The matrix M_q=(sgn_σj(v_i) ) , i, j = 1, ... , p is called the matrix of cyclotomic signatures. The rank of this matrix determines the sign distribution of the conjugates of the cyclotomic units. The matrix of cyclotomic signatures is associated with an ideal in the ring GF(2) [x] / (x^p+ 1) in such a way that the rank of the matrix equals the GF(2)-dimension of the ideal. It is shown that if p = (q-1)/ 2 is a prime and if 2 is a primitive root mod p, then M_q is non-singular. Also let p be arbitrary, let ℓ be a primitive root mod q and let L = {i | 0 ≤ i ≤ p-1, the least positive residue of defined by ℓⁱ mod q is greater than p}. Let H_q(x) ϵ GF(2)[x] be defined by H_q(x) = g. c. d. ((Σ xⁱ/I ϵ L) (x+1) + 1, x^p + 1). It is shown that the rank of M_q equals the difference p - degree H_q(x).

Further results are obtained by using the reciprocity theorem of class field theory. The reciprocity maps for a certain abelian extension of F and for the infinite primes in F are associated with the signs of conjugates. The product formula for the reciprocity maps is used to associate the signs of conjugates with the reciprocity maps at the primes which lie above (2). The case when (2) is a prime in F is studied in detail. Let T denote the group of totally positive units in F. Let U be the group generated by the cyclotomic units. Assume that (2) is a prime in F and that p is odd. Let F₍₂₎ denote the completion of F at (2) and let V₍₂₎ denote the units in F₍₂₎. The following statements are shown to be equivalent. 1) The matrix of cyclotomic signatures is non-singular. 2) U∩T = U². 3) U∩F²₍₂₎ = U². 4) V₍₂₎/ V₍₂₎² = ˂v₁ V₍₂₎²˃ ʘ…ʘ˂v_p V₍₂₎²˃ ʘ ˂3V₍₂₎²˃.

The rank of M_q was computed for 5≤q≤929 and the results appear in tables. On the basis of these results and additional calculations the following conjecture is made: If q and p = (q -1)/ 2 are both primes, then M_q is non-singular.

A nonlinear systems model for the control mechanism of free fatty acid-glucose metabolosm in normal humans

A mathematical model is proposed in this thesis for the control mechanism of free fatty acid-glucose metabolism in healthy individuals under resting conditions. The objective is to explain in a consistent manner some clinical laboratory observations such as glucose, insulin and free fatty acid responses to intravenous injection of glucose, insulin, etc. Responses up to only about two hours from the beginning of infusion are considered. The model is an extension of the one for glucose homeostasis proposed by Charette, Kadish and Sridhar (Modeling and Control Aspects of Glucose Homeostasis. Mathematical Biosciences, 1969). It is based upon a systems approach and agrees with the current theories of glucose and free fatty acid metabolism. The description is in terms of ordinary differential equations. Validation of the model is based on clinical laboratory data available at the present time. Finally procedures are suggested for systematically identifying the parameters associated with the free fatty acid portion of the model.

On the uniqueness of singular solutions to boundary-initial value problems in linear elastodynamics

This investigation deals with certain generalizations of the classical uniqueness theorem for the second boundary-initial value problem in the linearized dynamical theory of not necessarily homogeneous nor isotropic elastic solids. First, the regularity assumptions underlying the foregoing theorem are relaxed by admitting stress fields with suitably restricted finite jump discontinuities. Such singularities are familiar from known solutions to dynamical elasticity problems involving discontinuous surface tractions or non-matching boundary and initial conditions. The proof of the appropriate uniqueness theorem given here rests on a generalization of the usual energy identity to the class of singular elastodynamic fields under consideration.

Following this extension of the conventional uniqueness theorem, we turn to a further relaxation of the customary smoothness hypotheses and allow the displacement field to be differentiable merely in a generalized sense, thereby admitting stress fields with square-integrable unbounded local singularities, such as those encountered in the presence of focusing of elastic waves. A statement of the traction problem applicable in these pathological circumstances necessitates the introduction of "weak solutions'' to the field equations that are accompanied by correspondingly weakened boundary and initial conditions. A uniqueness theorem pertaining to this weak formulation is then proved through an adaptation of an argument used by O. Ladyzhenskaya in connection with the first boundary-initial value problem for a second-order hyperbolic equation in a single dependent variable. Moreover, the second uniqueness theorem thus obtained contains, as a special case, a slight modification of the previously established uniqueness theorem covering solutions that exhibit only finite stress-discontinuities.