Metal-Free Aziridination of Unactivated Olefins via Transient -Pyridinium Iminoiodinanes.

We describe a metal-free aziridination of unactivated olefins to generate pyridinium aziridines. Subsequent cross-coupling affords -aryl aziridines, and reductive depyridylation affords N-H aziridines. Kinetics experiments, based on a variable time normalization analysis (VTNA), indicate that aziridination proceeds via a highly electrophilic -pyridinium iminoiodinane intermediate.

Opportunity Cost of Surgical Management of Craniomaxillofacial Trauma: A Longitudinal Study.

Study Design: Single-institution retrospective financial analysis.

Objective: Trauma care is consistently linked to inadequate reimbursement, posing a significant financial burden for large trauma centers. Data show that declining Medicare reimbursement rates have indirectly led to declining payment for all procedures covered by insurance.

Aziridine Group Transfer via Transient -Aziridinyl Radicals.

Aziridines are the smallest nitrogen-containing heterocycles. Strain-enhanced electrophilicity renders aziridines useful synthetic intermediates and gives rise to biological activity. Classical aziridine syntheses─based on either [2 + 1] cycloadditions or intramolecular substitution chemistry─assemble aziridines from acyclic precursors.

Defining Golden Batches in Biomanufacturing Processes From Internal Metabolic Activity to Detect Process Changes That May Affect Product Quality.

Cellular metabolism plays a role in the observed variability of a drug substance's Critical Quality Attributes (CQAs) made by biomanufacturing processes. Therefore, here we describe a new approach for monitoring biomanufacturing processes that measures a set of metabolic reaction rates (named Critical Metabolic Parameters (CMP) in addition to the macroscopic process conditions currently being used as Critical Process Parameters (CPP) for biomanufacturing. Constraint-based systems biology models like Flux Balance Analysis (FBA) are used to estimate metabolic reaction rates, and metabolic rates are used as inputs for multivariate Batch Evolution Models (BEM).

Hydrogen-bond activation enables aziridination of unactivated olefins with simple iminoiodinanes.

Iminoiodinanes comprise a class of hypervalent iodine reagents that is often encountered in nitrogen-group transfer (NGT) catalysis. In general, transition metal catalysts are required to effect efficient NGT to unactivated olefins because iminoiodinanes are insufficiently electrophilic to engage in direct aziridination chemistry. Here, we demonstrate that 1,1,1,3,3,3-hexafluoroisopropanol (HFIP) activates -arylsulfonamide-derived iminoiodinanes for the metal-free aziridination of unactivated olefins.

Bidirectional Electron Transfer Strategies for Anti-Markovnikov Olefin Aminofunctionalization via Arylamine Radicals.

Arylamines are common structural motifs in pharmaceuticals, natural products, and materials precursors. While olefin aminofunctionalization chemistry can provide entry to arylamines, classical polar reactions typically afford Markovnikov products. Nitrogen-centered radical intermediates provide the opportunity to access anti-Markovnikov selectivity; however, anti-Markovnikov arylamination is unknown in large part due to the lack of arylamine radical precursors.

Understanding and Navigating the Unique Barriers Rural Primary Care Settings Face when Implementing Collaborative Care for Mental Health.

Rural primary care (RPC) clinics may face unique barriers to implementing the Collaborative Care Model (CoCM). We used mixed methods to explore RPC staff and practice facilitator (PF) perspectives on CoCM implementation. PFs reported on barriers and facilitators experienced after each monthly meeting with clinics (n = 459 surveys across 23 clinics).

-mucus interactions encompass shifts in gene expression, metabolism, and biofilm formation.

Unlabelled: In a healthy colon, the stratified mucus layer serves as a crucial innate immune barrier to protect the epithelium from microbes. Mucins are complex glycoproteins that serve as a nutrient source for resident microflora and can be exploited by pathogens. We aimed to understand how the intestinal pathogen, , independently uses or manipulates mucus to its benefit, without contributions from members of the microbiota.

Synthesis of Secondary Amines via Self-Limiting Alkylation.

-centered nucleophilicity increases upon alkylation, and thus selective partial alkylation of ammonia and primary amines can be challenging: Poor selectivity and overalkylation are often observed. Here we introduce -aminopyridinium salts as ammonia surrogates for the synthesis of secondary amines via self-limiting alkylation chemistry. Readily available -aryl--aminopyridinium salts engage in -alkylation and depyridylation to afford secondary aryl-alkyl amines without any overalkylation products.

β-Phenethylamine Synthesis: N-Pyridinium Aziridines as Latent Dual Electrophiles.

β-Phenethylamines are widely represented in biologically and pharmacologically active organic small molecules. Here, we introduce N-pyridinium aziridines as latent dual electrophiles for the synthesis of β-phenethylamines. Bromide-promoted ring opening generates β-halopyridinium amines.

-mucus interactions encompass shifts in gene expression, metabolism, and biofilm formation.

In a healthy colon, the stratified mucus layer serves as a crucial innate immune barrier to protect the epithelium from microbes. Mucins are complex glycoproteins that serve as a nutrient source for resident microflora and can be exploited by pathogens. We aimed to understand how the intestinal pathogen, , independently uses or manipulates mucus to its benefit, without contributions from members of the microbiota.

A wing-assisted incline running exercise regime during rearing increases initial flight velocity during descent in adult white- and brown-feathered laying hens.

Domestic laying hens rely primarily on their hindlimbs for terrestrial locomotion. Although they perform flapping flight, they appear to use maximal power during descent and thus may lack control for maneuvering and avoiding injuries on landing. This in turn may result in injury in open rearing systems.

A global comparative study of wealth-pain gradients: Investigating individual- and country-level associations.

Pain is a significant yet underappreciated dimension of population health. Its associations with individual- and country-level wealth are not well characterized using global data. We estimate both individual- and country-level wealth inequalities in pain in 51 countries by combining data from the World Health Organization's World Health Survey with country-level contextual data.

Mixed methods, single case design, feasibility trial of a motivational conversational agent for rehabilitation for adults with traumatic brain injury.

Objective: Rehabilitation for adults with traumatic brain injury (TBI) incorporates client-centred goal-setting and motivational support to achieve goals. However, face-to-face rehabilitation is time-limited. New therapy approaches which leverage care are warranted.

Reduction of wing area affects estimated stress in the primary flight muscles of chickens.

In flying birds, the pectoralis (PECT) and supracoracoideus (SUPRA) generate most of the power required for flight, while the wing feathers create the aerodynamic forces. However, in domestic laying hens, little is known about the architectural properties of these muscles and the forces the wings produce. As housing space increases for commercial laying hens, understanding these properties is important for assuring safe locomotion.

Unlocking Solid-State Organometallic Photochemistry with Optically Transparent, Porous Salt Thin Films.

Synthetic porous materials continue to garner attention as platforms for solid-state chemistry and as designer heterogeneous catalysts. Applications in photochemistry and photocatalysis, however, are plagued by poor light harvesting efficiency due to light scattering resulting from sample microcrystallinity and poor optical penetration that arises from inner filter effects. Here we demonstrate the layer-by-layer growth of optically transparent, photochemically active thin films of porous salts.

-Amino Pyridinium Salts in Organic Synthesis.

C-N bond forming reactions hold immense significance to synthetic organic chemistry. In pursuit of efficient methods for the introduction of nitrogen in organic small molecules, myriad synthetic methods have been developed, and methods based on both nucleophilic and electrophilic aminating reagents have received sustained research effort. In response to continued challenges - the need for substrate prefunctionalization, the requirement for vestigial -activating groups, and the need to incorporate nitrogen in ever more complex molecular settings - the development of novel aminating reagents remains a central challenge in method development.

Systems-ecology designed bacterial consortium protects from severe infection.

Fecal Microbiota Transplant (FMT) is an emerging therapy that has had remarkable success in treatment and prevention of recurrent infection (rCDI). FMT has recently been associated with adverse outcomes such as inadvertent transfer of antimicrobial resistance, necessitating development of more targeted bacteriotherapies. To address this challenge, we developed a novel systems biology pipeline to identify candidate probiotic strains that would be predicted to interrupt pathogenesis.

Development of Nonclassical Photoprecursors for Rh Nitrenes.

Characterization of reactive intermediates in C-H functionalization is challenging due to the fleeting lifetimes of these species. Synthetic photochemistry provides a strategy to generate post-turnover-limiting-step intermediates in catalysis under cryogenic conditions that enable characterization. We have a long-standing interest in the structure and reactivity of Rh nitrene intermediates, which are implicated as transient intermediates in Rh-catalyzed C-H amination.

Iodanyl Radical Catalysis.

ConspectusHypervalent iodine reagents find application as selective chemical oxidants in a diverse array of oxidative transformations. The utility of these reagents is often ascribed to (1) the proclivity to engage being selective two-electron redox transformations; (2) facile ligand exchange at the three-centered, four-electron (3c-4e) hypervalent iodine-ligand (I-X) bonds; and (3) the hypernucleofugacity of aryl iodides. One-electron redox and iodine radical chemistry is well-precedented in the context of inorganic hypervalent iodine chemistry─for example, in the iodide-triiodide couple that drives dye-sensitized solar cells.