Electrophilicity Scale of Activated Amides: 17O NMR and 15N NMR Chemical Shifts of Acyclic Twisted Amides in N−C(O) Cross-Coupling

The structure and properties of amides are of tremendous interest in organic synthesis and biochemistry. Traditional amides are planar and the carbonyl group non-electrophilic due to n_N→π*_C=O conjugation. In this study, we report electrophilicity scale by exploiting ¹⁷O NMR and ¹⁵N NMR chemical shifts of acyclic twisted and destabilized acyclic amides that have recently received major attention as precursors in N-C(O) cross-coupling by selective oxidative addition as well as precursors in electrophilic activation of N-C(O) bonds. Most crucially, we demonstrate that acyclic twisted amides feature electrophilicity of the carbonyl group that ranges between that of acid anhydrides and acid chlorides. Furthermore, a wide range of electrophilic amides is possible with gradually varying carbonyl electrophilicity by steric and electronic tuning of amide bond properties. Overall, the study quantifies for the first time that steric and electronic destabilization of the amide bond in common acyclic amides renders the amide bond as electrophilic as acid anhydrides and chlorides. These findings should have major implications on the fundamental properties of amide bonds.     

Probenecid and benzamide: DSC applied to the study of an “impossible” pharmaceutical system

Journal of Thermal Analysis and Calorimetry - The study of the binary system probenecid–benzamide is an excellent example of the power and the limits of thermal analysis applied to the...     

The Physico-Chemical Properties of Glipizide: New Findings

The present work is a concrete example of how physico-chemical studies, if performed in depth, are crucial to understand the behavior of pharmaceutical solids and constitute a solid basis for the control of the reproducibility of the industrial batches. In particular, a deep study of the thermal behavior of glipizide, a hypoglycemic drug, was carried out with the aim of clarifying whether the recognition of its polymorphic forms can really be done on the basis of the endothermic peak that the literature studies attribute to the melting of the compound. A number of analytical techniques were used: thermal techniques (DSC, TGA), X-ray powder diffraction (XRPD), FT-IR spectroscopy and scanning electron microscopy (SEM). Great attention was paid to the experimental design and to the interpretation of the combined results obtained by all these techniques. We proved that the attribution of the endothermic peak shown by glipizide to its melting was actually wrong. The DSC peak is no doubt triggered by a decomposition process that involves gas evolution (cyclohexanamine and carbon dioxide) and formation of 5-methyl-N-[2-(4-sulphamoylphenyl) ethyl] pyrazine-2-carboxamide, which remains as decomposition residue. Thermal treatments properly designed and the combined use of DSC with FT-IR and XRPD led to identifying a new polymorphic form of 5-methyl-N-[2-(4-sulphamoylphenyl) ethyl] pyrazine-2-carboxamide, which is obtained by crystallization from the melt. Hence, our results put into evidence that the check of the polymorphic form of glipizide cannot be based on the temperature values of the DSC peak, since such a peak is due to a decomposition process whose Tonset value is strongly affected by the particle size. Kinetic studies of the decomposition process show the high stability of solid glipizide at room temperature.     

Numerical Analysis of Structural Systems Subjected to Non-Gaussian Random Fields

This paper deals with the stochastic response of structures loaded by non-Gaussian random fields. A finite element model is used to describe a cantilever beam assuming both linear and non-linear behavior. The cross-correlated stochastic field is generated by a numerical procedure based on the translation processes theory. The marginal distribution of the load is assumed to be lognormal and the correlation structure is based on the second-order Markov process. The statistical analysis of the results highlights the effects of the involved non-linearity and non-Gaussianity properties on the structures response.     

Permanent Waves in Slow Free-Surface Flow of a Herschel–Bulkley fluid

Unsteady flow of a viscoplastic fluid on an inclined plane is examined. The fluid is described by the three-parameter Herschel–Bulkley constitutive equation. The set of equations governing the flow is presented, recovering earlier results for a Bingham fluid and steady uniform motion. A permanent wave solution is then derived, and the relation between wave speed and flow depth is discussed. It is shown that more types of gravity currents are possible than in a Newtonian fluid; these include some cases of flows propagating up a slope. The speed of permanent waves is derived and the possible surface profiles are illustrated as functions of the flow behavior index.     

An exact solution for one-dimensional unsteady nonlinear groundwater flow

After a brief review of the validity of Darcy's law, a nonlinear flow law is adopted for the analytical solution of a groundwater flow problem. A one-dimensional unsteady flow in plane geometry, with prescribed head at the boundaries, is studies. The solution of the analogous linear case is reviewed through the use of Boltzmann's transformation. A solution for nonlinear flow is obtained through a generalization of this transformation. Detailed expressions for specific discharge and drawdown are derived for two significant values of the exponent of the flow law. All results are presented in dimensionless form for a comparative analysis. Some significant cases are plotted. Finally, some implications of the adoption of a nonlinear flow law are discussed.

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Sommario Dopo un breve riepilogo sui limiti di validità della legge di Darcy, si adotta una formulazione non lineare della legge del moto per la risoluzione analitica di un problema di filtrazione. Si studia un moto non stazionario monodimensionale in geometria piana, con carico assegnato al contorno. Viene richiamata la soluzione dell'analogo caso lineare, tramite l'applicazione della trasformata di Boltzmann. Una soluzione per il moto non lineare è ottenuta mediante la generalizzazione di tale trasformazione. Si ricavano le espressioni della velocità apparente di filtrazione e del drawdown per due valori significativi dell'esponente della legge del moto. Tutti i risultati sono presentati in forma adimensionale per una analisi comparativa. Alcuni casi significativi sono diagrammati. In conclusione, sono discusse alcune implicazioni dell'adozione di una legge del moto non lineare.

     

Homology computation for a class of contact structures on T^3

We consider a family of tight contact forms on the three-dimensional torus and we compute the relative Contact Homology by using the variational theory of critical points at infinity. We will also show local stability.     

Electrochemical Approach for the Production of Layered Double Hydroxides with a Well-Defined Co/MeIII Ratio

Layered double hydroxides (LDHs) have been widely studied for their plethora of fascinating features and applications. The potentiostatic electrodeposition of LDHs has been extensively applied in the literature as a fast and direct method to substitute classical chemical routes. However, the electrochemical approach does not usually allow for a fine control of the M^II/M^III ratio in the synthesized material. By employing a recently proposed potentiodynamic method, LDH films of controlled composition are herein prepared with good reproducibility, using different ratios of the trivalent (Fe or Al) to bivalent (Co) cations in the electrolytic solution. All the obtained materials are shown to be effective oxygen evolution reaction (OER) catalysts, and are thoroughly characterized by a multi-technique approach, including FE-SEM, XRD, Raman, AES and a wide range of electrochemical procedures.     

Structures of Highly Twisted Amides Relevant to Amide N−C Cross‐Coupling: Evidence for Ground‐State Amide Destabilization

Herein, we show that acyclic amides that have recently enabled a series of elusive transition‐metal‐catalyzed N?C activation/cross‐coupling reactions are highly twisted around the N?C(O) axis by a new destabilization mechanism of the amide bond. A unique effect of the N‐glutarimide substituent, leading to uniformly high twist (ca. 90°) irrespective of the steric effect at the carbon side of the amide bond has been found. This represents the first example of a twisted amide that does not bear significant steric hindrance at the α‐carbon atom. The ¹⁵N NMR data show linear correlations between electron density at nitrogen and amide bond twist. This study strongly supports the concept of amide bond ground‐state twist as a blueprint for activation of amides toward N?C bond cleavage. The new mechanism offers considerable opportunities for organic synthesis and biological processes involving non‐planar amide bonds.     

Numerical simulation of a double-gate MOSFET with a subband model for semiconductors based on the maximum entropy principle

A nanoscale double-gate MOSFET is simulated with an energy-transport subband model for semiconductors formulated starting from the moment system derived from the Schr?dinger–Poisson–Boltzmann equations. The system is closed on the basis of the maximum entropy principle and includes scattering of electrons with acoustic and non-polar optical phonons. The proposed expression of the entropy combines quantum effects and semiclassical transport by weighting the contribution of each subband with the square modulus of the envelope functions arising from the Schr?dinger–Poisson subsystem. The simulations show that the model is able to capture the relevant confining and transport features and assess the robustness of the numerical scheme.