2‐Oxazoline Formation for Selective Chemical Labeling of 5‐Hydroxylysine

Hydroxylation of lysine, one of posttranslational modifications of proteins, generates 5‐hydroxylysine (Koh) and plays a crucial role in regulating protein functions in cellular activity. We have developed a chemical labeling method of Koh. The 1,2‐aminoalcohol moiety of Koh in synthetic peptide sequences was trapped by an alkyne‐containing benzimidate to form a 2‐oxazoline ring. An additional ammonia treatment process removed the undesirable amidine residue formed between benzimidate and lysine. During the ammonia treatment, the oxazoline residue formed at Koh mainly remained intact, and the ring opening to the amide form was observed for only part of oxazoline, indicating that the chemical labeling is amino acid selective. Azide‐substituted biotin or fluorescent dye was attached to the peptide through Huisgen cycloaddition at Koh and converted into an alkyne‐labeled oxazoline form. The Koh‐labeling assay could provide a platform to enhance proteomic research of lysine hydroxylation.     

Pyridine-Stabilized Cationic Silanethione Tungsten Complexes: Synthesis,Structures, and Reactivity

Silanethione compounds, R₂Si=S, have been recognized as highly reactive species. One reliable way to stabilize silanethione is its coordination to transition metal fragments to convert silanethione-coordinated transition metal complexes. Herein, we report the synthesis, structure, and reactivity of a second cationic silanethione tungsten complex [Cp*(OC)₃W{S=SiR₂(py)}]TFPB (R=Me ( 5 a ), Ph ( 5 b ), Cp*: η⁵-C₅Me₅, py: pyridine, and TFPB⁻: [B{3,5-(CF₃)₂C₆H₃}₄]⁻). Complex 5 was obtained by H⁻ abstraction from the Si atom in the corresponding silylsulfanyl complex Cp*(OC)₃W(SSiR₂H) ( 4 ) with Ph₃CTFPB, followed by the addition of pyridine. The reaction of 5 with PhNCS and PMe₃ produced [Cp*(OC)₃W{SSiR₂N(Ph)C(PMe₃)₂}]TFPB (R=Me ( 6 a ), Ph ( 6 b )) via the elimination of pyridine and the addition of the 1,3-dipolar species PhNC(PMe₃)₂ ( A ) to the Si atom.     

High-Spin and Reactive Fe13 Cluster with Exposed Metal Sites

Atomically defined large metal clusters have applications in new reaction development and preparation of materials with tailored properties. Expanding the synthetic toolbox for reactive high nuclearity metal complexes, we report a new class of Fe clusters, Tp*₄W₄Fe₁₃S₁₂ , displaying a Fe₁₃ core with M−M bonds that has precedent only in main group and late metal chemistry. M₁₃ clusters with closed shell electron configurations can show significant stability and have been classified as superatoms. In contrast, Tp*₄W₄Fe₁₃S₁₂ displays a large spin ground state of S=13. This compound performs small molecule activations involving the transfer of up to 12 electrons resulting in significant cluster rearrangements.     

Iron–Oxalato Framework with One‐Dimensional Open Channels for Electrochemical Sodium‐Ion Intercalation

Discovery of a new class of ion intercalation compounds is highly desirable due to its relevance to various electrochemical devices, such as batteries. Herein, we present a new iron–oxalato open framework, which showed reversible Na⁺ intercalation/extraction. The hydrothermally synthesized K₄Na₂[Fe(C₂O₄)₂]₃ ? 2 H₂O possesses one‐dimensional open channels in the oxalato‐bridged network, providing ion accessibility up to two Na⁺ per the formula unit. The detailed studies on the structural and electronic states revealed that the framework exhibited a solid solution state almost entirely during Na⁺ intercalation/extraction associated with the reversible redox of Fe. The present work demonstrates possibilities of the oxalato frameworks as tunable and robust ion intercalation electrode materials for various device applications.     

Copper‐Catalyzed Stereoselective Aminoboration of Bicyclic Alkenes

A copper‐catalyzed aminoboration of bicyclic alkenes, including oxa‐ and azabenzonorbornadienes, has been developed. With this method, amine and boron moieties are simultaneously introduced at an olefin with exo selectivity. Subsequent stereospecific transformations of the boryl group can provide oxygen‐ and nitrogen‐rich cyclic molecules with motifs that may be found in natural products or pharmaceutically active compounds. Moreover, a catalytic asymmetric variant of this transformation was realized by using a copper complex with a chiral bisphosphine ligand, namely (R,R)‐Ph‐BPE.     

A Triphenylamine with Two Phenoxy Radicals Having Unusual Bonding Patterns and a Closed‐Shell Electronic State

Reported herein is the structure and the electronic properties of a novel triphenylamine derivative having two phenoxy radicals appended to the amino nitrogen atom. X‐ray single crystal analysis and the magnetic resonance measurements demonstrates the unexpected closed‐shell electronic structure, even at room temperature, of the molecule and two unusual C? N bonds with multiple‐bond character. The theoretical calculations support the experimentally determined molecular geometry with the closed‐shell electronic structure, and predicted a small HOMO–LUMO gap originating from the nonbonding character of the HOMO. The optical and electrochemical measurements show that the molecule has a remarkably small HOMO–LUMO gap compared with its triphenylamine precursor.     

Fast and Robust Nanocellulose Width Estimation Using Turbidimetry

The dimensions of nanocelluloses are important factors in controlling their material properties. The present study reports a fast and robust method for estimating the widths of individual nanocellulose particles based on the turbidities of their water dispersions. Seven types of nanocellulose, including short and rigid cellulose nanocrystals and long and flexible cellulose nanofibers, are prepared via different processes. Their widths are calculated from the respective turbidity plots of their water dispersions, based on the theory of light scattering by thin and long particles. The turbidity‐derived widths of the seven nanocelluloses range from 2 to 10 nm, and show good correlations with the thicknesses of nanocellulose particles spread on flat mica surfaces determined using atomic force microscopy.

     

Radiation in a hypersonic shock layer generated around a projectile

Radiation emitted from the shock layer generated around a hypersonic flight model is experimentally investigated by using a ballistic range (two-stage light-gas gun). A polyethylene projectile of 1.2 cm in diameter is launched in this facility at the velocity of 5 km/sec (M=15), and the emission from the induced shock layer around the projectile is observed with a spectroscope. As a result, molecular band-spectra from NO and N₂ are detected along with those from carboncontaining molecules. Total emission power is measured with a diode-type powermeter. In addition, dimension effect of the flight model is theoretically and numerically examined, and a scaling law on thermochemical structure of the shock layer is developed. It shows that the thickness of thermal boundary-layer formed on the model surface does not follow the conventional scaling law based on the reaction distance and on the energy relaxation distance. Finally, the radiative field around the projectile is numerically computed, and the total power emitted from the shock layer is estimated. From the comparison between computed and measured results, the validity of the calculation model is discussed.