Straightforward α‐Amino Nitrile Synthesis Through Mo(CO)6‐Catalyzed Reductive Functionalization of Carboxamides

The selective reduction of amides into an intermediate hemiaminal catalyzed by Mo(CO)₆ together with the inexpensive and easy to handle TMDS (1,1,3,3‐tetramethyldisiloxane) as reducing agent, followed by subsequent trapping of the hemiaminal with a cyanide source, allows for the straightforward synthesis of α‐amino nitriles. The methodology presented here, displays high levels of chemoselectivity allowing for the reduction of amides in the presence of functional groups such as ketones, imines, aldehydes, and acids, which affords a simple route for the synthesis of α‐amino nitriles with a broad scope of functionalities in high yields. Furthermore, the applicability of this methodology is demonstrated by scale up experiments and by derivatization of the target compounds into synthetically interesting products. The selective cyanation is successfully applied in late stage functionalizations of amide containing drugs and prolinol derivatives.     

Multiple Stable Conformations Account for Reversible Concentration‐Dependent Oligomerization and Autoinhibition of a Metamorphic Metallopeptidase

Molecular plasticity controls enzymatic activity: the native fold of a protein in a given environment is normally unique and at a global free‐energy minimum. Some proteins, however, spontaneously undergo substantial fold switching to reversibly transit between defined conformers, the “metamorphic” proteins. Here, we present a minimal metamorphic, selective, and specific caseinolytic metallopeptidase, selecase, which reversibly transits between several different states of defined three‐dimensional structure, which are associated with loss of enzymatic activity due to autoinhibition. The latter is triggered by sequestering the competent conformation in incompetent but structured dimers, tetramers, and octamers. This system, which is compatible with a discrete multifunnel energy landscape, affords a switch that provides a reversible mechanism of control of catalytic activity unique in nature.     

Dispersive shock waves in phase-mismatched second-harmonic generation

We investigate wave-breaking and dispersive shock wave formation driven by a pulse undergoing second-harmonic generation in a quadratic medium. We show that the process is accessible in the regime of high phase-mismatch (cascading limit) and weak dispersion. Insight into the phenomenon is obtained by means of a suitable hydrodynamic reduction of the equations that govern the mixing.     

Cavityless oscillation through backward quasi-phase-matched second-harmonic generation

In an amplifier, nonlinear feedback from mismatched backward second-harmonic generation leads to strong enhancement of parametric conversion. With reference to LiNbO(3) quasi-phase-matched waveguides, we propose a parametric bistable device that operates simultaneously in two colors and in the cw or the self-pulsed regime.     

Excitation of stable transverse wavepackets with quadratic and cubic susceptibilities

We have identified a family of (2+1)D spatial solitary waves which can stably propagate in bulk media in the presence of coexisting diffraction, self-focusing Kerr and quadratic nonlinearities. In a conspicuous range of excitation conditions close to the stationary solutions, the emerging wavepackets are immune to the detrimental occurrence of filamentation and collapse, typical of pure Kerr media. The presence of a second-order contribution to the cubic nonlinear response is, therefore, able to prevent optical damage in applications relying on self-guidance. We show that the cross-phase modulation plays an important effect on stability. Our estimate shows that the effects of the cubic susceptibility cannot be neglected below a certain beam size in realistic crystals (e.g. KTP or similar).     

Spontaneously generated X-shaped light bullets

We observe the formation of an intense optical wave packet fully localized in all dimensions, i.e., both longitudinally (in time) and in the transverse plane, with an extension of a few tens of fsec and microns, respectively. Our measurements show that the self-trapped wave is an X-shaped light bullet spontaneously generated from a standard laser wave packet via the nonlinear material response (i.e., second-harmonic generation), which extend the soliton concept to a new realm, where the main hump coexists with conical tails which reflect the symmetry of linear dispersion relationship.     

An FDTD approach to the simulation of quantum-well infrared photodetectors

A Finite Difference Time Domain approach is used to design and to optimize quantum-well based infrared photodetectors. Results showing the influence of some parameters on the performance of these devices are presented and discussed.     

In Situ Functionalized Polymers for siRNA Delivery

A new method is reported herein for screening the biological activity of functional polymers across a consistent degree of polymerization and in situ, that is, under aqueous conditions and without purification/isolation of candidate polymers. In brief, the chemical functionality of a poly(acryloyl hydrazide) scaffold was activated under aqueous conditions using readily available aldehydes to obtain amphiphilic polymers. The transport activity of the resulting polymers can be evaluated in situ using model membranes and living cells without the need for tedious isolation and purification steps. This technology allowed the rapid identification of a supramolecular polymeric vector with excellent efficiency and reproducibility for the delivery of siRNA into human cells (HeLa‐EGFP). The reported method constitutes a blueprint for the high‐throughput screening and future discovery of new polymeric functional materials with important biological applications.     

Discrete breathers for understanding reconstructive mineral processes at low temperatures

Reconstructive transformations in layered silicates need a high temperature in order to be observed. However, very recently, some systems have been found where transformation can be studied at temperatures 600 degrees C below the lowest experimental results previously reported, including sol-gel methods. We explore the possible relation with the existence of intrinsic localized modes, known as discrete breathers. We construct a model for nonlinear vibrations within the cation layer, obtain their parameters, and calculate them numerically, obtaining their energies. Their statistics show that, although there are far less breathers than phonons, there are much more above the activation energy, making them good candidates to explain the reconstructive transformations at low temperatures.