Structural and Functional Characterization of 4-Hydroxyphenylacetate 3-Hydroxylase from Escherichia coli

The hydroxylation of phenols into polyphenols, which are valuable chemicals and pharmaceutical products, is a challenging reaction. The search for green synthetic processes has led to considering microorganisms and pure hydroxylases as catalysts for phenol hydroxylation. Herein, we report the structural and functional characterization of the flavin adenine dinucleotide (FAD)-dependent 4-hydroxyphenylacetate 3-monooxygenase from Escherichia coli, named HpaB. It is shown that this enzyme enjoys a relatively broad substrate specificity, which allows the conversion of a number of non-natural phenolic compounds, such as tyrosol, hydroxymandelic acid, coumaric acid, hydroxybenzoic acid and its methyl ester, and phenol, into the corresponding catechols. The reaction can be performed by using a simple chemical assay based on formate as the electron donor and the organometallic complex [Rh(bpy)Cp*(H₂O)]²⁺ (Cp*: 1,2,3,4,5-pentamethylcyclopentadiene, bpy: 2,2′-bipyridyl) as the catalyst for FAD reduction. The availability of a crystal structure of HpaB in complex with FAD at 1.8 Å resolution opens up the possibility of the rational tuning of the substrate specificity and activity of this interesting class of phenol hydroxylases.     

Adventitial Tertiary Lymphoid Organs as Potential Source of MicroRNA Biomarkers for Abdominal Aortic Aneurysm

Abdominal aortic aneurysm (AAA) is an inflammatory disease associated with marked changes in the cellular composition of the aortic wall. This study aims to identify microRNA (miRNA) expression in aneurysmal inflammatory cells isolated by laser microdissection from human tissue samples. The distribution of inflammatory cells (neutrophils, B and T lymphocytes, mast cells) was evaluated in human AAA biopsies. We observed in half of the samples that adventitial tertiary lymphoid organs (ATLOs) with a thickness from 0.5 to 2 mm were located exclusively in the adventitia. Out of the 850 miRNA that were screened by microarray in isolated ATLOs (n = 2), 164 miRNAs were detected in ATLOs. The three miRNAs (miR-15a-3p, miR-30a-5p and miR-489-3p) with the highest expression levels were chosen and their expression quantified by RT-PCR in isolated ATLOs (n = 4), M1 (n = 2) and M2 macrophages (n = 2) and entire aneurysmal biopsies (n = 3). Except for the miR-30a-5p, a similar modulation was found in ATLOs and the two subtypes of macrophages. The modulated miRNAs were then evaluated in the plasma of AAA patients for their potential as AAA biomarkers. Our data emphasize the potential of miR-15a-3p and miR-30a-5p as biomarkers of AAA but also as triggers of ATLO evolution. Further investigations will be required to evaluate their targets in order to better understand AAA pathophysiology.     

Physico-Chemical Characterizations of Poly(vinylidene fluoride)/Cu3(BTC)2 Composite Membranes Prepared by In Situ Crystal Growth

In this work, we present a simple and fast method for elaborating hybrid membranes by growing metal–organic framework crystals inside a polymer solution. The solution thus obtained was casted then annealed at 90°C for 5 h. This method was tested with poly(vinylidene fluoride) (PVDF) as a piezoelectric polymer and the Cu₃(BTC)₂, BTC = 1,3,5-benzene tricarboxylate, as a filler. The characterization of the obtained membranes by attenuated total reflectance Fourier transform infrared spectroscopy and X-ray diffraction showed the presence of the characteristic signatures of Cu₃(BTC)₂ and the β-phase of PVDF. Moreover, scanning electron microscopy images reveal that the Cu₃(BTC)₂ crystallites have grown along the PVDF membranes. The effect of the filler on both thermal and mechanical properties of the membranes was also studied. POLYM. ENG. SCI., 60:464–473, 2020. © 2019 Society of Plastics Engineers     

Transport Map sampling with PGD model reduction for fast dynamical Bayesian data assimilation

The motivation of this work is to address real-time sequential inference of parameters with a full Bayesian formulation. First, the proper generalized decomposition (PGD) is used to reduce the computational evaluation of the posterior density in the online phase. Second, Transport Map sampling is used to build a deterministic coupling between a reference measure and the posterior measure. The determination of the transport maps involves the solution of a minimization problem. As the PGD model is quasi-analytical and under a variable separation form, the use of gradient and Hessian information speeds up the minimization algorithm. Eventually, uncertainty quantification on outputs of interest of the model can be easily performed due to the global feature of the PGD solution over all coordinate domains. Numerical examples highlight the performance of the method.     

Learning of grasp selection based on shape-templates

The ability to grasp unknown objects still remains an unsolved problem in the robotics community. One of the challenges is to choose an appropriate grasp configuration, i.e., the 6D pose of the hand relative to the object and its finger configuration. In this paper, we introduce an algorithm that is based on the assumption that similarly shaped objects can be grasped in a similar way. It is able to synthesize good grasp poses for unknown objects by finding the best matching object shape templates associated with previously demonstrated grasps. The grasp selection algorithm is able to improve over time by using the information of previous grasp attempts to adapt the ranking of the templates to new situations. We tested our approach on two different platforms, the Willow Garage PR2 and the Barrett WAM robot, which have very different hand kinematics. Furthermore, we compared our algorithm with other grasp planners and demonstrated its superior performance. The results presented in this paper show that the algorithm is able to find good grasp configurations for a large set of unknown objects from a relatively small set of demonstrations, and does improve its performance over time.     

Oxidation Kinetics of Carbon Deposited on Cerium‐Doped FePO4 during Dehydration of Glycerol to Acrolein

A cerium‐doped FePO₄ catalyst dehydrates glycerol to acrolein in the gas phase but carbon accumulation reduces the reaction rate with time. Reaction rates may be maintained for longer times by co‐feeding low concentrations of oxygen together with the glycerol, but the acrolein yield drops proportionally to the oxygen concentration. The catalyst is easily regenerated by air and the reaction rate is proportional to both the oxygen concentration and quantity of carbon. The carbonaceous deposits may be due to both glycerol and acrolein: when either is fed to the catalyst, the CO₂/CO ratio is close to 1; during the regeneration step, the CO₂/CO ratio is near 4. A kinetic model of first order in both oxygen concentration and adsorbed sites characterizes the transient data very well.     

Guaranteed error bounds on pointwise quantities of interest for transient viscodynamics problems

A new method is developed to obtain guaranteed error bounds on pointwise quantities of interest for linear transient viscodynamics problems. The calculation of strict error bounds is based on the concept of “constitutive relation error” (CRE) and the solution of an adjoint problem. The central and original point of this work is the treatment of the singularity in space and time introduced by the loading of the adjoint problem. Hence, the adjoint solution is decomposed into two parts: (i) an analytical part determined from Green’s functions; (ii) a residual part approximated with classical numerical tools (finite element method, Newmark integration scheme). The capabilities and the limits of the proposed approach are analyzed on a 2D example.