Biocatalysis as Useful Tool in Asymmetric Synthesis: An Assessment of Recently Granted Patents (2014–2019)

The broad interdisciplinary nature of biocatalysis fosters innovation, as different technical fields are interconnected and synergized. A way to depict that innovation is by conducting a survey on patent activities. This paper analyses the intellectual property activities of the last five years (2014–2019) with a specific focus on biocatalysis applied to asymmetric synthesis. Furthermore, to reflect the inventive and innovative steps, only patents that were granted during that period are considered. Patent searches using several keywords (e.g., enzyme names) have been conducted by using several patent engine servers (e.g., Espacenet, SciFinder, Google Patents), with focus on granted patents during the period 2014–2019. Around 200 granted patents have been identified, covering all enzyme types. The inventive pattern focuses on the protection of novel protein sequences, as well as on new substrates. In some other cases, combined processes, multi-step enzymatic reactions, as well as process conditions are the innovative basis. Both industries and academic groups are active in patenting. As a conclusion of this survey, we can assert that biocatalysis is increasingly recognized as a useful tool for asymmetric synthesis and being considered as an innovative option to build IP and protect synthetic routes

Renormings of Lp(Lq)L^p(L^q)

We investigate the best order of smoothness of $L^p(L^q)$. We prove in particular that there exists a $C^\infty$-smooth bump function on $L^p(L^q)$ if and only if $p$ and $q$ are both even integers and $p$ is a multiple of $q$.Comment: 18 pages; AMS-Te

Gaussian to Exponential Crossover in the Attenuation of Polarization Echoes in NMR

An ingenious pulse sequence devised by S. Zhang, B. H. Meier, and R. R. Ernst (Phys. Rev. Lett. {\bf 69}, 2149 (1992)) reverses the time evolution (``spin diffusion'') of the local polarization in a dipolar coupled $^{1}$H spin system. This refocusing originates a Polarization Echo whose amplitude attenuates by increasing the time $t_R$ elapsed until the dynamics is reversed. Different functional attenuations are found for a set of dipolar coupled systems: ferrocene, (C$_5$H$_5$)$_2$Fe, cymantrene, (C$_5$H$_5$)Mn(CO)$_3$, and cobaltocene, (C$_5$H$_5$)$_2$Co. To control a relevant variable involved in this attenuation a pulse sequence has been devised to progressively reduce the dipolar dynamics. Since it reduces the evolution of the polarization echo it is referred as REPE sequence. Two extreme behaviors were found while characterizing the materials: In systems with a strong source of relaxation and slow dynamics, the attenuation follows an exponential law (cymantrene). In systems with a strong dipolar dynamics the attenuation is mainly Gaussian. By the application of the REPE sequence the characteristic time of the Gaussian decay is increased until the presence of an underlying dissipative mechanism is revealed (cobaltocene). For ferrocene, however, the attenuation remains Gaussian within the experimental time scale. These two behaviors suggest that the many body quantum dynamics presents an extreme intrinsic instability which, in the presence of small perturbations, leads to the onset of irreversibility. This experimental conclusion is consistent with the tendencies displayed by the numerical solutions of model systems.Comment: 7 pages + 7 Postscript figure

Autonomous thermal machine for amplification and control of energetic coherence

We present a model for an autonomous quantum thermal machine comprised of two qubits capable of manipulating and even amplifying the local coherence in a non-degenerate external system. The machine uses only thermal resources, namely, contact with two heat baths at different temperatures, and the external system has a non-zero initial amount of coherence. The method we propose allows for an interconversion between energy, both work and heat, and coherence in an autonomous configuration working in out-of-equilibrium conditions. This model raises interesting questions about the role of fundamental limitations on transformations involving coherence and opens up new possibilities in the manipulation of coherence by autonomous thermal machines.Comment: v1: 5 + 3 pages, 2 figures. v2: Restructured version with several new results and a new appendix, 11 + 14 pages, 4 + 3 figures. v3: Improved and corrected version with new discussions, 8 + 8 pages, 4 + 3 figure

Nonequilibrium potential and fluctuation theorems for quantum maps

We derive a general fluctuation theorem for quantum maps. The theorem applies to a broad class of quantum dynamics, such as unitary evolution, decoherence, thermalization, and other types of evolution for quantum open systems. The theorem reproduces well-known fluctuation theorems in a single and simplified framework and extends the Hatano-Sasa theorem to quantum nonequilibrium processes. Moreover, it helps to elucidate the physical nature of the environment inducing a given dynamics in an open quantum system.Comment: 10 page

Quantum fluctuation theorems for arbitrary environments: adiabatic and non-adiabatic entropy production

We analyze the production of entropy along non-equilibrium processes in quantum systems coupled to generic environments. First, we show that the entropy production due to final measurements and the loss of correlations obeys a fluctuation theorem in detailed and integral forms. Second, we discuss the decomposition of the entropy production into two positive contributions, adiabatic and non-adiabatic, based on the existence of invariant states of the local dynamics. Fluctuation theorems for both contributions hold only for evolutions verifying a specific condition of quantum origin. We illustrate our results with three relevant examples of quantum thermodynamic processes far from equilibrium.Comment: 20 pages + 6 of appendices; 7 figures; v2: New example added (example A) and some minor corrections; accepted in Phys. Rev.