Promiscuity in Antibody Catalysis: Esterolytic Activity of the Decarboxylase 21D8

The high structural similarity of decarboxylase antibody 21D8 and esterase antibody 48G7 suggests that 21D8 might also possess hydrolytic activity. Kinetic investigations show that 21D8 does promote the selective hydrolysis of methyl 4‐nitrophenyl carbonate and sodium 4‐(acetoxy)benzenesulfonate with catalytic proficiencies (k_cat/K_m)/k_un of ca. 10⁵ M ^?1. The ability of 21D8 to accelerate a reaction for which it was not developed suggests that certain antibody scaffolds are intrinsically predisposed toward catalysis, a property that can be enhanced and refined during affinity maturation in response to a transition‐state analog. At the same time, however, the restricted structural diversity of the immune system may ultimately limit the catalytic efficiency that can be achieved.     

Total Positivity Properties of Generalized Hypergeometric Functions of Matrix Argument

In multivariate statistical analysis, several authors have studied the total positivity properties of the generalized (₀ F ₁) hypergeometric function of two real symmetric matrix arguments. In this paper, we make use of zonal polynomial expansions to obtain a new proof of a result that these ₀ F ₁functions fail to satisfy certain pairwise total positivity properties; this proof extends both to arbitrary generalized ( _r F _s ) functions of two matrix arguments and to the generalized hypergeometric functions of Hermitian matrix arguments. In the case of the generalized hypergeometric functions of two Hermitian matrix arguments, we prove that these functions satisfy certain modified pairwise TP₂properties; the proofs of these results are based on Sylvester's formula for compound determinants and the condensation formula of C. L. Dodgson [Lewis Carroll] (1866).     

High quality gate dielectrics formed by rapid thermal chemical vapor deposition of silane and nitrous oxide

In the present study, we have performed electrical characterization of oxides deposited via rapid thermal chemical vapor deposition using SiH₄ and N₂O. We have investigated the effect of temperature, pressure, and SiH₄ to N₂O ratio on the electrical and material properties of as-deposited films. We have found that as-deposited oxides deposited at low temperatures, low pressures, and with a low silane to nitrous oxide ratio of ～0.5% give good material and electrical properties. The as-deposited films are stoichiometric in nature and have high deposition rates. As-deposited films had very low D_it values, high breakdown fields, and excellent subthreshold swing. The leakage currents and metal oxide semiconductor field effect transistor current drive, although lower than thermal oxides, were found to be quite acceptable. We have also investigated the thickness dependence of the films and found that as the film thickness is reduced below 50Å, the reliability improves for all oxides including the silicon-rich deposited oxides.     

Generalized solutions of a class of nuclear-space-valued stochastic evolution equations

Generalized solutions are defined for stochastic evolution equations of the formdY _t =A ^* Y _t dt + dZ _t on the nuclear triplel(R ^d ) L²(R ^d ) l(R ^d ), whereA does not mapl(R ^d ) into itself. One case which is treated in detail involvesA = –(–) ^/2 ,0 < < 2. This example arises as the Langevin equation for the fluctuation limit of a system of particles migrating according to a symmetric stable process and undergoing critical branching in a random medium.The research of D. A. Dawson was supported by the Natural Sciences and Engineering Research Council of Canada. L. G. Gorostiza's research was supported in part by CONACyT Grants PCEXCNA-040319 and 140102 G203-006, Mexico.     

Consistency of decision processes

If a statistical or a voting decision procedure is used by several subpopulations and if each reaches an identical conclusion, then one might expect this conclusion to be the outcome for the full group. It is shown that this property fails to hold for large classes of decision procedures. The geometric reasons why the consistency does not hold are described. A general theorem is given to characterize the procedures that satisfy this property of weak consistency.This research was supported in part by NSF Grant IRI-8803505 and a Guggenheim Fellowship. Also, the author thanks a referee for some comments that stimulated certain revisions.     

Inversion of the exponential X-ray transform. I: Analysis

The exponential X-ray transform arises in single photon emission computed tomography and is defined on functions on ?ⁿ by , where μ is a constant. Approximate inversion, and inversion formulae of filtered back-projection type are derived for this operator in all dimensions. In particular, explicit formulae are given for convolution kernels (filters) K corresponding to a general point spread function E that can be used to invert the exponential X-ray transform via a filtered back-projection algorithm. The results extend and refine work of Tretiak and Metz¹⁷.     

Some examples of random walks on free products of discrete groups

Summary We consider the random walk (X_n) associated with a probability p on a free product of discrete groups. Knowledge of the resolvent (or Green's function) of p yields theorems about the asymptotic behaviour of the n-step transition probabilities p^*n(x)=P(X_n= x¦ X₀=e) as n. Woess [15], Cartwright and Soardi [3] and others have shown that under quite general conditions there is behaviour of the type p^*n(x)C_x^– n n^– 3/2. Here we show on the other hand that if G is a free product of m copies ofZ ^r and if (X_n) is the « average » of the classical nearest neighbour random walk on each of the factorsZ ^r, then while it satisfies an « n^–3/2 — law » for r small relative to m, it switches to an n^– r/2 -law for large r. Using the same techniques, we give examples of irreducible probabilities (of infinite support) on the free groupZ ^*m which satisfyn ^– for .     

Quantum relativistic action at a distance

A well-known relativistic action at a distance interaction of two unequal masses is altered so as to yield purely Newtonian radial forces with fixed particle rest masses in the system center-of-momentum inertial frame. Although particle masses experience no kinematic mass increase in this frame, speeds are naturally restricted to less than the speed of light. We derive a relation between the center-of-momentum frame total Newtonian energy and the composite rest mass. In a new proper time quantum formalism, we obtain an L²(R⁴ R⁴, C) Hilbert space by varying individual particle rest masses. We propose the use of density operators, recognizing that the auxiliary proper time parameter is not an observable. The quantum formalism is applied to our altered version of the relativistic harmonic oscillator. Our generalized coherent states yield four-dimensional wave packets which follow the correct classical world lines. Appendices contain reviews of classical Hamiltonian reparametrization (incorporating our notion of manifest covariance), and a comparison of this work with the literature.     

Thermodynamic properties of transition metals in aqueous solution. 2. The enthalpies of mixing of aqueous solutions of CoCl2, CuCl2, and MnCl2 with NaCl at varying ionic strength at 25°C

Enthalpies of mixing (_m H) aqueous solutions of CoCl₂, CuCl₂, and MnCl₂ with NaCl solutions were measured at constant ionic strengths of 0.5, 1.0, and 3.0 molal at 25°C. The excess enthalpy equations of Pitzer were then fit to the resulting _m H data. The resulting parameters are the temperature derivatives of the activity coefficient mixing parameters in the Pitzer system. The heat of mixing data for CoCl₂ and CuCl₂ were in agreement with earlier isomolal results by other workers.     

Reactions of [NiIII(cyclam)] with aqueous sulfur dioxide: Exhibition of a deuterium isotope effect and catalysis by chloride and bromide

One unit of S(IV) (SO₂ or SHO₃^?) is oxidized per 2 units of [Ni^III(cyclam)] species to obtain sulfate. Kinetic analyses have been done by varying the acidities (0.013 ? [H⁺] ? 1.0 M) and halide concentrations (0.000 ? [X^?] ? 0.012 M; X=Cl and Br) at constant ionic strength (μ = 1.0 M). The rate law that incorporates the [X^?] and [H⁺] dependence is ?d[Ni^III]_T/dt=2k[Ni^III]_T[S(IV)]_T where 2k={k_a[H⁺] + k_bK + kK′_X[H⁺] [X^?] + kK′_XK[X^?]} {[H⁺] + K}^?1 {1 + K′_X[X^?]}^?1, here k_a=87 ± 7 M^?1 s^?1, k_b=(2.5 ± 0.5)×10³ M^?1 s^?1 and pK = 1.8 ± 0.2. Rate constants k_a and k_b are attributed to the reactions of [Ni^III(cyclam) (H₂O)₂]³⁺ with SO₂ and SHO₃^?, respectively. Monohalo species apparent equilibrium constants K′_Cl=(1600 ± 400) M^?1 and K′_Br=(190 ± 20) M^?1 and rate constants k=80 ± 8 M^?1 s^?1 and k = 140 ± 15 M^?1 s^?1 are ascribed to the protonated pathway, involving the [Ni^III(cyclam) (H₂O)X]²⁺ and SO_2(aq) reaction pairs. The other two rate constants of k=(5 ± 1)×10³ M^?1 s^?1 and k=(3.1 ± 0.5)×10⁴ M^?1 s^?1, refer to the deprotonated pathway and are assigned to the [Ni^III(cyclam) (H₂O)X]²⁺ /SHO₃^? redox couple. A deuterium H₂O / D₂O isotope effect of 2.1–2.8 can be attributed partially to an equilibrium isotope effect at low acidity though a small kinetic isotope (2.5 ± 0.5) effect is evident for the dihydrogen sulfito pathway, k_a. The kinetic isotope effect and the absence of sulfite radical scavenging effects are explained by a mechanism entailing migration of a hydride from sulfur to the Ni^III center to produce a Ni^III—H species, which rapidly comproportionates, and S(VI). © 1993 John Wiley & Sons, Inc.