Heterogeneous Solution NMR Signal Amplification by Reversible Exchange

A novel variant of an iridium‐based organometallic catalyst was synthesized and used to enhance the NMR signals of pyridine in a heterogeneous phase by immobilization on polymer microbead solid supports. Upon administration of parahydrogen (pH₂) gas to a methanol mixture containing the HET‐SABRE catalyst particles and the pyridine, up to fivefold enhancements were observed in the ¹H NMR spectra after sample transfer to high field (9.4 T). Importantly, enhancements were not due to any residual catalyst molecules in solution, thus supporting the true heterogeneity of the SABRE process. Further significant improvements may be expected by systematic optimization of experimental parameters. Moreover, the heterogeneous catalyst is easy to separate and recycle, thus opening a door to future potential applications varying from spectroscopic studies of catalysis, to imaging metabolites in the body without concern of contamination from expensive and potentially toxic metal catalysts or accompanying organic molecules.     

B-MWW Zeolite: The Case Against Single-Site Catalysis

Boron-containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron-containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B₂(OH)_xO_(3−x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM-22 isomorphously substituted with boron (B-MWW). Using ¹¹B solid-state NMR spectroscopy, we show that the majority of boron species in B-MWW exist as isolated BO₃ units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B-MWW for ODH of propane falsifies the hypothesis that site-isolated BO₃ units are the active site in boron-based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium-based catalysts and provides an important piece of the mechanistic puzzle.     

Surface Design for Immobilization of an Antimicrobial Peptide Mimic for Efficient Anti-Biofouling

Microbial surface attachment negatively impacts a wide range of devices from water purification membranes to biomedical implants. Mimics of antimicrobial peptides (AMPs) constituted from poly(N-substituted glycine) „peptoids“ are of great interest as they resist proteolysis and can inhibit a wide spectrum of microbes. We investigate how terminal modification of a peptoid AMP-mimic and its surface immobilization affect antimicrobial activity. We also demonstrate a convenient surface modification strategy for enabling alkyne–azide „click“ coupling on amino-functionalized surfaces. Our results verified that the N- and C-terminal peptoid structures are not required for antimicrobial activity. Moreover, our peptoid immobilization density and choice of PEG tether resulted in a „volumetric“ spatial separation between AMPs that, compared to past studies, enabled the highest AMP surface activity relative to bacterial attachment. Our analysis suggests the importance of spatial flexibility for membrane activity and that AMP separation may be a controlling parameter for optimizing surface anti-biofouling.     

B‐MWW Zeolite: The Case Against Single‐Site Catalysis

Boron‐containing materials have recently been identified as highly selective catalysts for the oxidative dehydrogenation (ODH) of alkanes to olefins. It has previously been demonstrated by several spectroscopic characterization techniques that the surface of these boron‐containing ODH catalysts oxidize and hydrolyze under reaction conditions, forming an amorphous B₂(OH)_xO_(3?x/2) (x=0–6) layer. Yet, the precise nature of the active site(s) remains elusive. In this Communication, we provide a detailed characterization of zeolite MCM‐22 isomorphously substituted with boron (B‐MWW). Using ¹¹B solid‐state NMR spectroscopy, we show that the majority of boron species in B‐MWW exist as isolated BO₃ units, fully incorporated into the zeolite framework. However, this material shows no catalytic activity for ODH of propane to propene. The catalytic inactivity of B‐MWW for ODH of propane falsifies the hypothesis that site‐isolated BO₃ units are the active site in boron‐based catalysts. This observation is at odds with other traditionally studied catalysts like vanadium‐based catalysts and provides an important piece of the mechanistic puzzle.     

A Concise Total Synthesis of the Fungal Isoquinoline Alkaloid TMC-120B

Recent reports of antiepileptic activity of the fungal alkaloid TMC-120B have renewed the interest in this natural product. Previous total syntheses of TMC-120B comprise many steps and have low overall yields (11–17 steps, 1.5–2.9% yield). Thus, to access this compound more efficiently, we herein present a concise and significantly improved total synthesis of the natural product. Our short synthesis relies on two key cyclization steps to assemble the central scaffold: isoquinoline formation via an ethynyl-imino cyclization and an intramolecular Friedel-Crafts reaction to form the furanone.     

Overview of finite elements simulation of temperature profile to estimate properties of materials 3D-printed by laser powder-bed fusion

Laser powder bed fusion(LPBF),like many other additive manufacturing techniques,offers flexibility in design expected to become a disruption to the manufacturing industry.The current cost of LPBF process does not favor a try-anderror way of research,which makes modelling and simulation a field of superior importance in that area of engineering.In this work,various methods used to overcome challenges in modeling at different levels of approximation of LPBF process are reviewed.Recent efforts made towards a reliable and computationally effective model to simulate LPBF process using finite element(FE)codes are presented.A combination of ray-tracing technique,the solution of the radiation transfer equation and absorption measurements has been used to establish an analytical equation,which gives a more accurate approximation of laser energy deposition in powder-substrate configuration.When this new analytical energy deposition model is used in in FE simulation,with other physics carefully set,it enables us to get reliable cooling curves and melt track morphology that agree well with experimental observations.The use of more computationally effective approximation,without explicit topological changes,allows to simulate wider geometries and longer scanning time leading to many applications in real engineering world.Different applications are herein presented including:prediction of printing quality through the simulated overlapping of consecutive melt tracks,simulation of LPBF of a mixture of materials and estimation of martensite inclusion in printed steel.     

Maze exploration and learning in C. elegans

The soil dwelling nematode, Caenorhabditis (C.) elegans, is a popular model system for studying behavioral plasticity. Noticeably absent from the C. elegans literature, however, are studies evaluating worm behavior in mazes. Here, we report the use of microfluidic mazes to investigate exploration and learning behaviors in wild-type C. elegans, as well as in the dopamine-poor mutant, cat-2. The key research findings include: (1)C. elegans worms are motivated to explore complex spatial environments with or without the presence of food/reward, (2) wild-type worms exhibit a greater tendency to explore relative to mutant worms, (3) both wild-type and mutant worms can learn to make unconditioned responses to food/reward, and (4) wild-type worms are significantly more likely to learn to make conditioned responses linking reward to location than mutant worms. These results introduce microfluidic mazes as a valuable new tool for biological behavioral analysis.     

Visible-Light Switching of Metallosupramolecular Assemblies**

A photoswitchable ligand and palladium(II) ions form a dynamic mixture of self-assembled metallosupramolecular structures. The photoswitching ligand is an ortho-fluoroazobenzene with appended pyridyl groups. Combining the E-isomer with palladium(II) salts affords a double-walled triangle with composition [Pd₃L₆]⁶⁺ and a distorted tetrahedron [Pd₄L₈]⁸⁺ (1 : 2 ratio at 298 K). Irradiation with 410 nm light generates a photostationary state with approximately 80 % of the E-isomer of the ligand and results in the selective disassembly of the tetrahedron, the more thermodynamically stable structure, and the formation of the triangle, the more kinetically inert product. The triangle is then slowly transformed back into the tetrahedron over 2 days at 333 K. The Z-isomer of the ligand does not form any well-defined structures and has a thermal half-life of 25 days at 298 K. This approach shows how a thermodynamically preferred self-assembled structure can be reversibly pumped to a kinetic trap by small perturbations of the isomer distribution using non-destructive visible light.     

Probing the Intracellular Glutathione Redox Potential by In‐Cell NMR Spectroscopy

Non‐invasive and real‐time analysis of cellular redox processes has been greatly hampered by lack of suitable measurement techniques. Here we describe an in‐cell nuclear magnetic resonance (NMR) based method for measuring the intracellular glutathione redox potential by direct and quantitative measurement of isotopically labeled glutathione introduced exogenously into living yeast. By using this approach, perturbations in the cellular glutathione redox homeostasis were also monitored as yeast cells were subjected to oxidative stress.