The Role of Electron Transfer in Copper-Mediated C(sp)-H Trifluoromethylation.

We report copper(II) and copper(III) trifluoromethyl complexes supported by a pyridinedicarboxamide ligand (L) as a platform for investigating the role of electron transfer in C(sp)-H trifluoromethylation. While the copper(II) trifluoromethyl complex is unreactive towards (hetero)arenes, the formal copper(III) trifluoromethyl complex performs C(sp)-H trifluoromethylation of a wide range of (hetero)arenes. Mechanistic studies using the copper(III) trifluoromethyl complex suggest that the mechanism of arene trifluoromethylation is substrate-dependent.

A dinuclear nickel peroxycarbonate complex: CO addition promotes HO release.

Nickel coordination compounds featuring Ni-O bonds are key structural motifs in both bioinorganic and synthetic chemistries. They serve as precursors for organic substrate oxidation and are commonly invoked intermediates in water oxidation and oxygen reduction schemes. Herein, we disclose a series of well-defined dinuclear nickel complexes that, upon treatment with CO and HO, afford the first nickel-bound peroxycarbonate.

Nb Doping and Alloying of 2D WS by Atomic Layer Deposition for 2D Transition Metal Dichalcogenide Transistors and HER Electrocatalysts.

We utilize plasma-enhanced atomic layer deposition to synthesize two-dimensional Nb-doped WS and NbWS alloys to expand the range of properties and improve the performance of 2D transition metal dichalcogenides for electronics and catalysis. Using a supercycle deposition process, films are prepared with compositions spanning the range from WS to NbS. While the W-rich films form crystalline disulfides, the Nb-rich films form amorphous trisulfides.

Kohn-Sham Density in a Slater Orbital Basis Set.

Finite, atom-centered Slater basis sets are used to determine approximate Kohn-Sham molecular orbitals. This is achieved by minimizing the kinetic energy plus the sum-squared difference between the Kohn-Sham density and the full configuration interaction density. As a result of the finite basis, a weight factor is introduced to balance the two minimization components.

Transannular Functionalization of Multiple C(sp)-H Bonds of Tropane via an Alkene-Bridged Palladium(I) Dimer.

This communication describes the Pd-catalyzed C(sp)-H functionalization of a tropane derivative to generate products with functionalization at two (β/γ) or three (β/γ/β) different sites on the alicyclic amine core. These reactions proceed via an initial dehydrogenation to generate an alkene product that can react further to form a Pd(I) alkene-bridged dimer. Functionalization of this dimer affords β/γ/β-functionalized allylic arylation and allylic acetoxylation products.

Substituent Impact on Quinoxaline Performance and Degradation in Redox Flow Batteries.

Aqueous redox flow batteries (RFBs) are attractive candidates for low-cost, grid-scale storage of energy from renewable sources. Quinoxaline derivatives represent a promising but underexplored class of charge-storing materials on account of poor chemical stability in prior studies (with capacity fade rates >20%/day). Here, we establish that 2,3-dimethylquinoxaline-6-carboxylic acid (DMeQUIC) is vulnerable to tautomerization in its reduced form under alkaline conditions.

Ultrafast X-ray Absorption Spectroscopy Reveals Excited-State Dynamics of B Coenzymes Controlled by the Axial Base.

Polarized time-resolved X-ray absorption spectroscopy at the Co K-edge is used to probe the excited-state dynamics and photolysis of base-off methylcobalamin and the excited-state structure of base-off adenosylcobalamin. For both molecules, the final excited-state minimum shows evidence for an expansion of the cavity around the Co ion by ca. 0.

Selective and Potent PROTAC Degraders of c-Src Kinase.

Using dasatinib linked to E3 ligase ligands, we identified a potent and selective dual Csk/c-Src PROTAC degrader. We then replaced dasatinib, the c-Src-directed ligand, with a conformation-selective analogue that stabilizes the αC-helix-out conformation of c-Src. Using the αC-helix-out ligand, we identified a PROTAC that is potent and selective for c-Src.

Accessing Ta/Cu Architectures via Metal-Metal Salt Metatheses: Heterobimetallic C-H Bond Activation Affords μ-Hydrides.

We employ a metal-metal salt metathesis strategy to access low-valent tantalum-copper heterometallic architectures (Ta-μ -H -Cu and Ta-μ -H -Cu ) that emulate structural elements proposed for surface alloyed nanomaterials. Whereas cluster assembly with carbonylmetalates is well precedented, the use of the corresponding polyarene transition metal anions is underexplored, despite recognition of these highly reactive fragments as storable sources of atomic M . Our application of this strategy provides structurally unique early-late bimetallic species.

Backbone Conformational Equilibrium in Mismatched DNA Correlates with Enzyme Activity.

T:G mismatches in mammals arise primarily from the deamination of methylated CpG sites or the incorporation of improper nucleotides. The process by which repair enzymes such as thymine DNA glycosylase (TDG) identify a canonical DNA base in the incorrect pairing context remains a mystery. However, the abundant contacts of the repair enzymes with the DNA backbone suggest a role for protein-phosphate interaction in the recognition and repair processes, where conformational properties may facilitate the proper interactions.

Coordinatively Unsaturated Nickel Nitroxyl Complex: Structure, Physicochemical Properties, and Reactivity toward Dioxygen.

For its important roles in biology, nitrogen monoxide (·NO) has become one of the most studied and fascinating molecules in chemistry. ·NO itself acts as a "noninnocent" or "redox active" ligand to transition metal ions to give metal-NO (M-NO) complexes. Because of this uncertainty due to redox chemistry, the real description of the electronic structure of the M-NO unit requires extensive spectroscopic and theoretical studies.

Characterization and Reactivity of Copper(II) and Copper(III) σ-Aryl Intermediates in Aminoquinoline-Directed C-H Functionalization.

Over the past decade, numerous reports have focused on the development and applications of Cu-mediated C-H functionalization reactions; however, to date, little is known about the Cu intermediates involved in these transformations. This paper details the observation and characterization of Cu and Cu intermediates in aminoquinoline-directed C(sp)-H functionalization of a fluoroarene substrate. An initial C(sp)-H activation at Cu occurs at room temperature to afford an isolable anionic cyclometalated Cu complex.

Watching Excited State Dynamics with Optical and X-ray Probes: The Excited State Dynamics of Aquocobalamin and Hydroxocobalamin.

Femtosecond time-resolved X-ray absorption (XANES) at the Co K-edge, X-ray emission (XES) in the Co Kβ and valence-to-core regions, and broadband UV-vis transient absorption are combined to probe the femtosecond to picosecond sequential atomic and electronic dynamics following photoexcitation of two vitamin B compounds, hydroxocobalamin and aquocobalamin. Polarized XANES difference spectra allow identification of sequential structural evolution involving first the equatorial and then the axial ligands, with the latter showing rapid coherent bond elongation to the outer turning point of the excited state potential followed by recoil to a relaxed excited state structure. Time-resolved XES, especially in the valence-to-core region, along with polarized optical transient absorption suggests that the recoil results in the formation of a metal-centered excited state with a lifetime of 2-5 ps.

Glass Transition Temperatures of Organic Mixtures from Isoprene Epoxydiol-Derived Secondary Organic Aerosol.

The phase states and glass transition temperatures () of secondary organic aerosol (SOA) particles are important to resolve for understanding the formation, growth, and fate of SOA as well as their cloud formation properties. Currently, there is a limited understanding of how changes with the composition of organic and inorganic components of atmospheric aerosol. Using broadband dielectric spectroscopy, we measured the of organic mixtures containing isoprene epoxydiol (IEPOX)-derived SOA components, including 2-methyltetrols (2-MT), 2-methyltetrol-sulfate (2-MTS), and 3-methyltetrol-sulfate (3-MTS).

Structure of pre-miR-31 reveals an active role in Dicer processing.

As an essential post-transcriptional regulator of gene expression, microRNA (miR) levels must be strictly maintained. The biogenesis of many, but not all, miRs is mediated by trans-acting protein partners through a variety of mechanisms, including remodeling of the RNA structure. miR-31 functions as an oncogene in numerous cancers and interestingly, its biogenesis is not known to be regulated by protein binding partners.

Engineering a Conformationally Switchable Artificial Metalloprotein.

Many naturally occurring metalloenzymes are gated by rate-limiting conformational changes, and there exists a critical interplay between macroscopic structural rearrangements of the protein and subatomic changes affecting the electronic structure of embedded metallocofactors. Despite this connection, most artificial metalloproteins (ArMs) are prepared in structurally rigid protein hosts. To better model the natural mechanisms of metalloprotein reactivity, we have developed conformationally switchable ArMs (swArMs) that undergo a large-scale structural rearrangement upon allosteric effector binding.

Atomic Layer Deposition of Large-Area Polycrystalline Transition Metal Dichalcogenides from 100 °C through Control of Plasma Chemistry.

Two-dimensional transition metal dichalcogenides, such as MoS, are intensely studied for applications in electronics. However, the difficulty of depositing large-area films of sufficient quality under application-relevant conditions remains a major challenge. Herein, we demonstrate deposition of polycrystalline, wafer-scale MoS, TiS, and WS films of controlled thickness at record-low temperatures down to 100 °C using plasma-enhanced atomic layer deposition.

Cobalamin-Dependent Radical -Adenosylmethionine Enzymes: Capitalizing on Old Motifs for New Functions.

The members of the radical -adenosylmethionine (SAM) enzyme superfamily are responsible for catalyzing a diverse set of reactions in a multitude of biosynthetic pathways. Many members of this superfamily accomplish their transformations using the catalytic power of a 5'-deoxyadenosyl radical (5'-dAdo•), but there are also enzymes within this superfamily that bind auxiliary cofactors and extend the catalytic repertoire of SAM. In particular, the cobalamin (Cbl)-dependent class synergistically uses Cbl to facilitate challenging methylation and radical rearrangement reactions.

Solution Structure of NPSL2, A Regulatory Element in the oncomiR-1 RNA.

The miR-17 ∼ 92a polycistron, also known as oncomiR-1, is commonly overexpressed in multiple cancers and has several oncogenic properties. OncomiR-1 encodes six constituent microRNAs (miRs), each enzymatically processed with different efficiencies. However, the structural mechanism that regulates this differential processing remains unclear.

Chorioretinal Hypoxia Detection Using Lipid-Polymer Hybrid Organic Room-Temperature Phosphorescent Nanoparticles.

Ischemia-induced hypoxia is a common complication associated with numerous diseases and is the most important prognostic factor in retinal vein occlusions (RVOs). Early detection and long-term visualization of retinal tissue hypoxia is essential to understand the pathophysiology and treatment of ischemic retinopathies. However, no effective solution exists to evaluate extravascular retinal tissue oxygen tension.

pH dependence of C•A, G•A and A•A mismatches in the stem of precursor microRNA-31.

MicroRNAs (miRNAs) are important regulators of post-transcriptional gene expression. Mature miRNAs are generated from longer transcripts (primary, pri- and precursor, pre-miRNAs) through a series of highly coordinated enzymatic processing steps. The sequence and structure of these pri- and pre-miRNAs play important roles in controlling their processing.

FDA-Approved Oximes and Their Significance in Medicinal Chemistry.

Despite the scientific advancements, organophosphate (OP) poisoning continues to be a major threat to humans, accounting for nearly one million poisoning cases every year leading to at least 20,000 deaths worldwide. Oximes represent the most important class in medicinal chemistry, renowned for their widespread applications as OP antidotes, drugs and intermediates for the synthesis of several pharmacological derivatives. Common oxime based reactivators or nerve antidotes include pralidoxime, obidoxime, HI-6, trimedoxime and methoxime, among which pralidoxime is the only FDA-approved drug.

Probing the Formation and Conformational Relaxation of Previtamin D and Analogues in Solution and in Lipid Bilayers.

The photosynthesis of vitamin D in mammalian skin results from UV-B irradiation of provitamin D (7-dehydrocholesterol, DHC) at ca. 290 nm. Upon return to the ground state, the hexatriene product, previtamin D, undergoes a conformational equilibration between helical gZg and more planar tZg and tZt forms.

NMR chemical shift assignments of RNA oligonucleotides to expand the RNA chemical shift database.

RNAs play myriad functional and regulatory roles in the cell. Despite their significance, three-dimensional structure elucidation of RNA molecules lags significantly behind that of proteins. NMR-based studies are often rate-limited by the assignment of chemical shifts.