Azetidine‐Containing Alkaloids Produced by a Quorum‐Sensing Regulated Nonribosomal Peptide Synthetase Pathway in Pseudomonas aeruginosa

Pseudomonas aeruginosa displays an impressive metabolic versatility, which ensures its survival in diverse environments. Reported herein is the identification of rare azetidine‐containing alkaloids from P. aeruginosa PAO1, termed azetidomonamides, which are derived from a conserved, quorum‐sensing regulated nonribosomal peptide synthetase (NRPS) pathway. Biosynthesis of the azetidine motif has been elucidated by gene inactivation, feeding experiments, and biochemical characterization in vitro, which involves a new S‐adenosylmethionine‐dependent enzyme to produce azetidine 2‐carboxylic acid as an unusual building block of NRPS. The mutants of P. aeruginosa unable to produce azetidomonamides had an advantage in growth at high cell density in vitro and displayed rapid virulence in Galleria mellonella model, inferring functional roles of azetidomonamides in the host adaptation. This work opens the avenue to study the biological functions of azetidomonamides and related compounds in pathogenic and environmental bacteria.     

Correction to: EQRAIN: uranium and plutonium interlaboratory exercises from 1997 to 2016—comparison to ITVs-2010

Journal of Radioanalytical and Nuclear Chemistry - In the original publication of the article, the values of u(s), u(r) and ITV for HKED were published incorrectly in Table 6.     

Thermal studies,degradation kinetic,equilibrium solubility,DFT, MIR,and XRPD analyses of a new cocrystal of gemfibrozil and isonicotinamide

Journal of Thermal Analysis and Calorimetry - A synthesis of a novel pharmaceutical cocrystal of the gemfibrozil (GEM) with the isonicotinamide (INCT) as coformer was carried out using the...     

Correction to: Synthesis and characterization of a biopolymer of glycerol and macadamia oil

Journal of Thermal Analysis and Calorimetry - In the original publication of the article, the Figures 6, 7, and 8 are in disagreement with their figure captions. Moreover, in the result...     

Dynamic Wetting Properties of Mesh Substrates with Tunable Water Adhesion

In nature, wetting phenomena are present nearly everywhere and are a source of inspiration for liquid transportation. A good understanding of the underlying dynamic phenomena that governs wettability is therefore extremely important for researchers involved in bio-inspired surfaces. Herein, we study the adhesive behavior with water of mesh substrates modified with structured copolymers in order to tune the surfaces from parahydrophobic states (high water adhesion) to superhydrophobic states (low water adhesion). Using the ejection test method (ETM), a new technique that consists of the ejection of water droplets deposited onto a substrate with the aid of a catapult system, we experimentally demonstrate that the elasticity of the mesh substrate can be exploited for efficient vertical actuation of droplets.     

Mimicking the Ice Recrystallization Activity of Biological Antifreezes. When is a New Polymer “Active”?

Antifreeze proteins and ice‐binding proteins have been discovered in a diverse range of extremophiles and have the ability to modulate the growth and formation of ice crystals. Considering the importance of cryoscience across transport, biomedicine, and climate science, there is significant interest in developing synthetic macromolecular mimics of antifreeze proteins, in particular to reproduce their property of ice recrystallization inhibition (IRI). This activity is a continuum rather than an “on/off” property and there may be multiple molecular mechanisms which give rise to differences in this observable property; the limiting concentrations for ice growth vary by more than a thousand between an antifreeze glycoprotein and poly(vinyl alcohol), for example. The aim of this article is to provide a concise comparison of a range of natural and synthetic materials that are known to have IRI, thus providing a guide to see if a new synthetic mimic is active or not, including emerging materials which are comparatively weak compared to antifreeze proteins, but may have technological importance. The link between activity and the mechanisms involving either ice binding or amphiphilicity is discussed and known materials assigned into classes based on this.     

Monotonic convergent optimal control theory with strict limitations on the spectrum of optimized laser fields

We present a modified optimal control scheme based on the Krotov method, which allows for strict limitations on the spectrum of the optimized laser fields. A frequency constraint is introduced and derived mathematically correct, without losing monotonic convergence of the algorithm. The method guarantees a close link to learning loop control experiments and is demonstrated for the challenging control of nonresonant Raman transitions, which are used to implement a set of global quantum gates for molecular vibrational qubits.     

Synthetic and computational assessment of a chiral metal–organic framework catalyst for predictive asymmetric transformation

Understanding and controlling molecular recognition mechanisms at a chiral solid interface is a continuously addressed challenge in heterogeneous catalysis. Here, the molecular recognition of a chiral peptide-functionalized metal–organic framework (MOF) catalyst towards a pro-chiral substrate is evaluated experimentally and in silico. The MIL-101 metal–organic framework is used as a macroligand for hosting a Noyori-type chiral ruthenium molecular catalyst, namely (benzene)Ru@MIL-101-NH-Gly-Pro. Its catalytic perfomance toward the asymmetric transfer hydrogenation (ATH) of acetophenone into R- and S-phenylethanol are assessed. The excellent match between the experimentally obtained enantiomeric excesses and the computational outcomes provides a robust atomic-level rationale for the observed product selectivities. The unprecedented role of the MOF in confining the molecular Ru-catalyst and in determining the access of the prochiral substrate to the active site is revealed in terms of highly face-specific host–guest interactions. The predicted surface-specific face differentiation of the prochiral substrate is experimentally corroborated since a three-fold increase in enantiomeric excess is obtained with the heterogeneous MOF-based catalyst when compared to its homogeneous molecular counterpart.

Understanding and controlling molecular recognition mechanisms at a chiral solid interface has been addressed in metal–organic framework catalysts for the asymmetric transfer hydrogenation reaction.     

A Selective Sulfide Oxidation Catalyzed by Heterogeneous Artificial Metalloenzymes Iron@NikA

Performing a heterogeneous catalysis with proteins is still a challenge. Herein, we demonstrate the importance of cross-linked crystals for sulfoxide oxidation by an artificial enzyme. The biohybrid consists of the insertion of an iron complex into a NikA protein crystal. The heterogeneous catalysts displays a better efficiency-with higher reaction kinetics, a better stability and expand the substrate scope compared to its solution counterpart. Designing crystalline artificial enzymes represents a good alternative to soluble or supported enzymes for the future of synthetic biology.