Structural Changes Induced by Quinones: High-Resolution Microwave Study of 1,4-Naphthoquinone

1,4-Naphthoquinone (1,4-NQ) is an important product of naphthalene oxidation, and it appears as a motif in many biologically active compounds. We have investigated the structure of 1,4-NQ using chirped-pulse Fourier transform microwave spectroscopy and quantum chemistry calculations. The rotational spectra of the parent species, and its ¹³C and ¹⁸O isotopologues were observed in natural abundance, and their spectroscopic parameters were obtained. This allowed the determination of the substitution r_s, mass-weighted r_m and semi-experimental r_e^SE structures of 1,4-NQ. The obtained structural parameters show that the quinone moiety mainly changes the structure of the benzene ring where it is inserted, modifying the C−C bonds to having predominantly single or double bond character. Furthermore, the molecular electrostatic surface potential reveals that the quinone ring becomes electron deficient while the benzene ring remains a nucleophile. The most electrophilic areas are the hydrogens attached to the double bond in the quinone ring. Knowledge of the nucleophilic and electrophilic areas in 1,4-NQ will help understanding its behaviour interacting with other molecules and guide modifications to tune its properties.     

Some improvements in Neuberger's iteration procedure for solving partial differential equations

If m and n are positive integers then let S(m, n) denote the linear space over R whose elements are the real-valued symmetric n-linear functions on E_m with operations defined in the usual way. If $\text{U}$ is a function from some sphere S in E_m to R then let $\text{U}$⁽ⁱ⁾(x) denote the ith Frechet derivative of $\text{U}$ at x. In general $\text{U}$⁽ⁱ⁾(x)∈S(m,i). In the paper “An Iterative Method for Solving Nonlinear Partial Differential Equations” [Advances in Math. 19 (1976), 245–265] Neuberger presents an iterative procedure for solving a partial differential equation of the form

$\text{AU}{}^{\mathrm{n}}\text{(x)=F(x, U(x), U′(x),…,U}{}^{\mathrm{k}}\text{(x))}$

, where k > n, $\text{U}$ is the unknown from some sphere in E_m to R, A is a linear functional on S(m, n), and F is analytic. The defect in the theory presented there was that in order to prove that the iterates converged to a solution $\text{U}$ the condition $\text{k ?}\text{n}\text{2}$ was needed. In this paper an iteration procedure that is a slight variation on Neuberger's procedure is considered. Although the condition $\text{k ?}\text{n}\text{2}$ cannot as yet be eliminated, it is shown that in a broad class of cases depending upon the nature of the functional A the restriction $\text{k ?}\text{n}\text{2}$ may be replaced by the restriction $\text{k ?}\text{3n}\text{4}$.     

An inequality involving permanents of certain direct products

Let A denote a decomposable symmetric complex valued n-linear function on C^m. We prove

$\text{6A·A6}{}^2\text{?2}{}^{\mathrm{n}}\text{2n}\text{n}{}^{\mathrm{?1}}\text{6A?A6}{}^2$

, where · denotes the symmetric product and ? the tensor product. As a consequence we have per

$\text{M}\text{M}\text{M}\text{M}\text{?2}{}^{\mathrm{n}}\text{[per(M)]}{}^2$

, where M is a positive semidefinite Hermitian matrix and per denotes the permanent function. A sufficient condition for equality in the matrix inequality is that M is a nonnegative diagonal matrix.     

Probing the CH⋅⋅⋅π Weak Hydrogen Bond in Anesthetic Binding: The Sevoflurane–Benzene Cluster

Cooperativity between weak hydrogen bonds can be revealed in molecular clusters isolated in the gas phase. Here we examine the structure, internal dynamics, and origin of the weak intermolecular forces between sevoflurane and a benzene molecule, using multi‐isotopic broadband rotational spectra. This heterodimer is held together by a primary C? H???π hydrogen bond, assisted by multiple weak C? H???F interactions. The multiple nonbonding forces hinder the internal rotation of benzene around the isopropyl C? H bond in sevoflurane, producing detectable quantum tunneling effects in the rotational spectrum.     

Hydrogen Bond Cooperativity and the Three‐Dimensional Structures of Water Nonamers and Decamers

Broadband rotational spectroscopy of water clusters produced in a pulsed molecular jet expansion has been used to determine the oxygen atom geometry in three isomers of the nonamer and two isomers of the decamer. The isomers for each cluster size have the same nominal geometry but differ in the arrangement of their hydrogen bond networks. The nearest neighbor O? O distances show a characteristic pattern for each hydrogen bond network isomer that is caused by three‐body effects that produce cooperative hydrogen bonding. The observed structures are the lowest energy cluster geometries identified by quantum chemistry and the experimental and theoretical O? O distances are in good agreement. The cooperativity effects revealed by the hydrogen bond O? O distance variations are shown to be consistent with a simple model for hydrogen bonding in water that takes into account the cooperative and anticooperative bonding effects of nearby water molecules.     

Improved Information-Theoretic Generalization Bounds for Distributed,Federated, and Iterative Learning

We consider information-theoretic bounds on the expected generalization error for statistical learning problems in a network setting. In this setting, there are K nodes, each with its own independent dataset, and the models from the K nodes have to be aggregated into a final centralized model. We consider both simple averaging of the models as well as more complicated multi-round algorithms. We give upper bounds on the expected generalization error for a variety of problems, such as those with Bregman divergence or Lipschitz continuous losses, that demonstrate an improved dependence of 1/K on the number of nodes. These “per node” bounds are in terms of the mutual information between the training dataset and the trained weights at each node and are therefore useful in describing the generalization properties inherent to having communication or privacy constraints at each node.