Directed ortho-lithiation of unprotected diphenylphosphinic acids

Directed ortho lithiation of diphenylphosphinic acid and subsequent electrophilic trapping provides mono ortho-functionalized derivatives including enantiopure γ-aminophosphinic acids in moderate yields. Copper catalyzed coupling of the ortho anion leads to biphenyl-2,2′-diylbis(phenylphosphinic acid), a phosphorus analogue of biphenyl-2,2′-dicarboxylic acid. Preliminary studies of the metal-binding abilities of this O,O-chelating ligand towards a series of metal cations are included.     

Unexpected reactivity of trifluoromethylated olefins with indole: a mechanistic investigation

Several trifluoromethylated compounds were reacted with indole sodium salt, leading to monofluorinated compounds. The unexpected products formation was rationalized by DFT calculations.     

Multiple Keys for a Single Lock: The Unusual Structural Plasticity of the Nucleotidyltransferase (4′)/Kanamycin Complex

The most common mode of bacterial resistance to aminoglycoside antibiotics is the enzyme‐catalysed chemical modification of the drug. Over the last two decades, significant efforts in medicinal chemistry have been focused on the design of non‐ inactivable antibiotics. Unfortunately, this strategy has met with limited success on account of the remarkably wide substrate specificity of aminoglycoside‐modifying enzymes. To understand the mechanisms behind substrate promiscuity, we have performed a comprehensive experimental and theoretical analysis of the molecular‐recognition processes that lead to antibiotic inactivation by Staphylococcus aureus nucleotidyltransferase 4′(ANT(4′)), a clinically relevant protein. According to our results, the ability of this enzyme to inactivate structurally diverse polycationic molecules relies on three specific features of the catalytic region. First, the dominant role of electrostatics in aminoglycoside recognition, in combination with the significant extension of the enzyme anionic regions, confers to the protein/antibiotic complex a highly dynamic character. The motion deduced for the bound antibiotic seem to be essential for the enzyme action and probably provide a mechanism to explore alternative drug inactivation modes. Second, the nucleotide recognition is exclusively mediated by the inorganic fragment. In fact, even inorganic triphosphate can be employed as a substrate. Third, ANT(4′) seems to be equipped with a duplicated basic catalyst that is able to promote drug inactivation through different reactive geometries. This particular combination of features explains the enzyme versatility and renders the design of non‐inactivable derivatives a challenging task.     

A general and systematic framework for the kinematic analysis of complex gear systems

It is presented an integral approach for the velocity analysis of complex gear systems. Due to the intrinsic nature of the method, it can be systematically applied for gear trains with arbitrary architecture, including bevel gears with non-parallel motion axes. As a result, not only velocity ratios can be computed, but also angular velocities of any body composing the gear system. Several application examples are presented to prove the feasibility and the validity of the proposed method.     

The spherical-model limit in a random field

The spherical-model limitn of then-vector model in a random field, with either a statistically independent distribution or with long-range correlated random fields, is studied to demonstrate the correctness of the replica method in which then and replica limits limits are interchanged, provided the replica and thermodynamic limits are taken in the right order, in the case of long-range correlated random fields. A scaling form for the two-point correlation function relevant to the first-order phase transition below the lower critical dimensionality of the random system is also obtained.     

Kinematical and gravitational analysis of the rocket-borne clock experiment by Vessot and Levine using the revised Robertson's test theory of special relativity

The kinematic aspects of the rocket-borne clock experiment by Vessot and Levine are analyzed with the revised Robertson's test theory of special relativity (Found. Phys. 14, 625 (1984)). Besides the expected time-dilation, it is found that the intermediate steps of this experiment yield in principle Michelson-Morley type information (a relation between longitudinal and transverse length contractions) in the third order of the velocities involved, but no relativity-of-simultaneity related effects.The flat space-time test theory induces a family of spherically symmetric line elements that become the Schwarzschild line element in the relativistic case and also in theabinito rest frame of the theory. These line elements represent the same space-time manifold, but pertain in a one-to-one correspondence to the different flat space-time coordinate transformations of the test theory. The conserved energy is related to the family of local energies in the tangent plane. No deviations from the orthodoxy appear at the pertinent levels of approximation. Hence the unexplained residuals of the Vessot-Levine experiment are not due in obvious ways to kinematic and gravitational frequency shifts caused by deviations of the real coordinate transformations from the Lorentz transformations.This work was started while the author was at Departamento de Fisica, Facultad Experimental de Ciencias, Universidad del Zulia, Maracaibo, Venezuela. It was completed at the Department of Physics, Utah State University, Logan, Utah 83422.     

Revised Robertson's test theory of special relativity: Space-time structure and dynamics

The experimental testing of the Lorentz transformations is based on a family of sets of coordinate transformations that do not comply in general with the principle of equivalence of the inertial frames. The Lorentz and Galilean sets of transformations are the only member sets of the family that satisfy this principle. In the neighborhood of regular points of space-time, all members in the family are assumed to comply with local homogeneity of space-time and isotropy of space in at least one free-falling elevator, to be denoted as Robertson'sab initio rest frame [H. P. Robertson,Rev. Mod. Phys. 21, 378 (1949)].Without any further assumptions, it is shown that Robertson's rest frame becomes a preferred frame for all member sets of the Robertson family except for, again, Galilean and Einstein's relativities. If one now assumes the validity of Maxwell-Lorentz electrodynamics in the preferred frame, a different electrodynamics spontaneously emerges for each set of transformations. The flat space-time of relativity retains its relevance, which permits an obvious generalization, in a Robertson context, of Dirac's theory of the electron and Einstein's gravitation. The family of theories thus obtained constitutes a covering theory of relativistic physics.A technique is developed to move back and forth between Einstein's relativity and the different members of the family of theories. It permits great simplifications in the analysis of relativistic experiments with relevant Robertson's subfamilies. It is shown how to adapt the Clifford algebra version of standard physics for use with the covering theory and, in particular, with the covering Dirac theory.Part of this work was done at the Department of Physics, Utah State University, Logan, Utah 84322.