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Formation of C-N bonds is a quintessential transformation in organic synthesis. Among the various methods to access them, hydrogen borrowing catalysis offers a green, atom economical, and cost-effective approach with water as the sole by-product. In this reaction, amines are alkylated with alcohol coupling partners in the presence of a transition metal catalyst. Several catalytic systems have been developed and employed in the synthesis of pharmaceutical intermediates and complex natural products, replacing conventional amination reactions with hydrogen borrowing reactions that deliver improved selectivity and yield. In this short review, we compare hydrogen borrowing N-alkylation with other classical and modern C-N bond forming reactions and discuss applications in pharmaceutical synthesis. 

Intestinal microbes, whether resident or transient, influence the physiology of their hosts, altering both the chemical and the physical characteristics of the gut. An example of the latter is the human pathogenVibrio cholerae’sability to induce strong mechanical contractions, discovered in zebrafish. The underlying mechanism has remained unknown, but the phenomenon requires the actin crosslinking domain (ACD) ofVibrio’s type VI secretion system (T6SS), a multicomponent protein syringe that pierces adjacent cells and delivers toxins. By using a zebrafish-nativeVibrioand imaging-based assays of host intestinal mechanics and immune responses, we find evidence that macrophages mediate the connection between the T6SS ACD and intestinal activity. Inoculation withVibriogives rise to strong, ACD-dependent, gut contractions whose magnitude resembles those resulting from genetic depletion of macrophages.Vibrioalso induces tissue damage and macrophage activation, both ACD-dependent, recruiting macrophages to the site of tissue damage and away from their unperturbed positions near enteric neurons that line the midgut and regulate intestinal motility. Given known crosstalk between macrophages and enteric neurons, our observations suggest that macrophage redistribution forms a key link betweenVibrioactivity and intestinal motility. In addition to illuminating host-directed actions of the widespread T6SS protein apparatus, our findings highlight how localized bacteria-induced injury can reshape neuro-immune cellular dynamics to impact whole-organ physiology. IMPORTANCEGut microbes, whether beneficial, harmful, or neutral, can have dramatic effects on host activities. The human pathogenVibrio choleraecan induce strong intestinal contractions, though how this is achieved has remained a mystery. Using a zebrafish-nativeVibrioand live imaging of larval fish, we find evidence that immune cells mediate the connection between bacteria and host mechanics. A piece ofVibrio’s type VI secretion system, a syringe-like apparatus that stabs cellular targets, induces localized tissue damage, activating macrophages and drawing them from their normal residence near neurons, whose stimulation of gut contractions they dampen, to the damage site. Our observations reveal a mechanism in which cellular rearrangements, rather than bespoke biochemical signaling, drives a dynamic neuro-immune response to bacterial activity. 

Abstract Asymmetric and narrow infalling structures, often called streamers, have been observed in several Class 0/I protostars, which is not expected in the classical star formation picture. Their origin and impact on the disk formation remain observationally unclear. By combining data from the James Clerk Maxwell Telescope (JCMT) and Atacama Large Millimeter/submillimeter Array (ALMA), we investigate the physical properties of the streamers and parental dense core in the Class 0 protostar, IRAS 16544–1604. Three prominent streamers associated to the disk with lengths between 2800 and 5800 au are identified on the northern side of the protostar in the C¹⁸O emission. Their mass and mass infalling rates are estimated to be in the range of (1–4) × 10⁻³M_⊙and (1–5) × 10⁻⁸M_⊙yr⁻¹, respectively. Infall signatures are also observed in the more diffuse extended protostellar envelope observed with the ALMA from the comparison to the infalling and rotating envelope model. The parental dense core detected by the JCMT observation has a mass of ∼0.5M_⊙, a subsonic to transonic turbulence of $\mathcal{M}$ =  0.8–1.1, and a mass-to-flux ratio of 2–6. Our results show that the streamers in IRAS 16544–1604 only possess 2% of the entire dense core mass and contribute less than 10% of the mass infalling rate of the protostellar envelope. Therefore, the streamers in IRAS 16544–1604 play a minor role in the mass accretion process onto the disk, in contrast to those streamers observed in other sources and those formed in numerical simulations of collapsing dense cores with similar turbulence and magnetic field strengths. 

Carbon fiber reinforced polymers (CFRPs, or composites) are increasingly replacing traditional manufacturing materials used in the automobile, aerospace, and energy sectors. With this shift, it is vital to develop end-of-life processes for CFRPs that retain the value of both the carbon fibers and the polymer matrix. Here we demonstrate a strategy to upcycle pre- and post-con- sumer polystyrene-containing CFRPs, crosslinked with unsaturated polyesters or vinyl esters, to benzoic acid. The thermoset matrix is upgraded via biocatalysis utilizing an engineered strain of the filamentous fungus Aspergillus nidulans, which gives access to valuable secondary metabolites in high yields, exemplified here by (2Z,4Z,6E)-octa-2,4,6-trienoic acid. Reactions are engineered to preserve the carbon fibers, with much of their sizing, so that the isolated carbon fiber plies are manufactured into new composite coupons that exhibit mechanical properties comparable to virgin manufacturing substrates. In sum, this represents the first system to reclaim high value from both the fiber fabric and polymer matrix of a CFRP. 

Distinguishing ET and PCET processes is challenging. This paper used “protein charge ladders” to show that PCET occurs at the non-redox “structural” zinc sight of SOD1, when a Cu ion displaces Zn. 

Abstract We present Atacama Large Millimeter/submillimeter Array (ALMA) observations of the Class 0 protostar IRAS 04166+2706, obtained as part of the ALMA Large Program Early Planet Formation in Embedded Disks. These observations were made in the 1.3 mm dust continuum and molecular lines at angular resolutions of $\sim 0\stackrel{″}{.}05$(∼8 au) and $\sim 0\stackrel{″}{.}16$(∼25 au), respectively. The continuum emission shows a disklike structure with a radius of ∼22 au. Kinematical analysis of¹³CO (2–1), C¹⁸O (2–1), H₂CO (3_0,3–2_0,2), CH₃OH (4₂–3₁) emission demonstrates that these molecular lines trace the infalling-rotating envelope and possibly a Keplerian disk, enabling us to estimate the protostar mass to be 0.15M_⊙ < M_⋆ < 0.39M_⊙. The dusty disk is found to exhibit a brightness asymmetry along its minor axis in the continuum emission, probably caused by a flared distribution of the dust and the high optical depth of the dust emission. In addition, the¹²CO (2–1) and SiO (5–4) emissions show knotty and wiggling motions in the jets. Our high-angular-resolution observations revealed the most recent mass ejection events, which have occurred within the last ∼25 yr. 

The oxygen evolution reaction (OER) of water splitting is essential to electrochemical energy storage applications. While nickel electrodes are widely available heterogeneous OER catalysts, homogeneous nickel catalysts for OER are underexplored. Here we report two carbene-ligated nickel(II) complexes that are exceptionally robust and efficient homogeneous water oxidation catalysts. Remarkably, these novel nickel complexes can assemble a stable thin film onto a metal electrode through poly-imidazole bridges, making them supported heterogeneous electrochemical catalysts that are resilient to leaching and stripping. Unlike molecular catalysts and nanoparticle catalysts, such electrode-supported metal-complex catalysts for OER are rare and have the potential to inspire new designs. The electrochemical OER with our nickel-carbene catalysts exhibits excellent current densities with high efficiency, low Tafel slope, and useful longevity for a base metal catalyst. Our data show that imidazole carbene ligands stay bonded to the nickel(II) centers throughout the catalysis, which allows the facile oxygen evolution. 

The reconstruction of complete microbial metabolic pathways using ‘omics data from environmental samples remains challenging. Computational pipelines for pathway reconstruction that utilize machine learning methods to predict the presence or absence of KEGG modules in incomplete genomes are lacking. Here, we present MetaPathPredict, a software tool that incorporates machine learning models to predict the presence of complete KEGG modules within bacterial genomic datasets. Using gene annotation data and information from the KEGG module database, MetaPathPredict employs deep learning models to predict the presence of KEGG modules in a genome. MetaPathPredict can be used as a command line tool or as a Python module, and both options are designed to be run locally or on a compute cluster. Benchmarks show that MetaPathPredict makes robust predictions of KEGG module presence within highly incomplete genomes.