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1. On the reciprocal relationship between σ-hole bonding and (anti)aromaticity gain in ketocyclopolyenes

   https://doi.org/10.1039/D0OB01076F  

   Paudel, Hari Ram; Karas, Lucas José; Wu, Judy I-Chia (July 2020, Organic & Biomolecular Chemistry)

   null (Ed.)

   σ-Hole bonding interactions ( e.g. , tetrel, pnictogen, chalcogen, and halogen bonding) can polarize π-electrons to enhance cyclic [4 n ] π-electron delocalization ( i.e. , antiaromaticity gain) or cyclic [4 n + 2] π-electron delocalization ( i.e. , aromaticity gain). Examples based on the ketocyclopolyenes: cyclopentadienone, tropone, and planar cyclononatetraenone are presented. Recognizing this relationship has implications, for example, for tuning the electronic properties of fulvene-based π-conjugated systems such as 9-fluorenone. 

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2. Competition Between the Two σ‐Holes in the Formation of a Chalcogen Bond

   https://doi.org/10.1002/cphc.202200936  

   Scheiner, Steve (February 2023, ChemPhysChem)

   Abstract A chalcogen atom Y contains two separate σ‐holes when in a R₁YR₂molecular bonding pattern. Quantum chemical calculations consider competition between these two σ‐holes to engage in a chalcogen bond (ChB) with a NH₃base. R groups considered include F, Br, I, and tert‐butyl (tBu). Also examined is the situation where the Y lies within a chalcogenazole ring, where its neighbors are C and N. Both electron‐withdrawing substituents R₁and R₂act cooperatively to deepen the two σ‐holes, but the deeper of the two holes consistently lies opposite to the more electron‐withdrawing group, and is also favored to form a stronger ChB. The formation of two simultaneous ChBs in a triad requires the Y atom to act as double electron acceptor, and so anti‐cooperativity weakens each bond relative to the simple dyad. This effect is such that some of the shallower σ‐holes are unable to form a ChB at all when a base occupies the other site. 

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3. Collision cross‐section analysis of self‐assembled metallomacrocycle isomers and isobars via ion mobility mass spectrometry

   https://doi.org/10.1002/rcm.8717  

   Endres, Kevin_J; Barthelmes, Kevin; Winter, Andreas; Antolovich, Robert; Schubert, Ulrich_S; Wesdemiotis, Chrys (February 2020, Rapid Communications in Mass Spectrometry)

   RationaleCoordinatively driven self‐assembly of transition metal ions and bidentate ligands gives rise to organometallic complexes that usually contain superimposed isobars, isomers, and conformers. In this study, the double dispersion ability of ion mobility mass spectrometry (IM‐MS) was used to provide a comprehensive structural characterization of the self‐assembled supramolecular complexes by their mass and charge, revealed by the MS event, and their shape and collision cross‐section (Ω), revealed by the IM event. MethodsSelf‐assembled complexes were synthesized by reacting a bis(terpyridine) ligand exhibiting a 60^odihedral angle between the two ligating terpyridine sites (T) with divalent Zn, Ni, Cd, or Fe. The products were isolated as (Metal²⁺[T])_n(PF₆)_2nsalts and analyzed using IM‐MS after electrospray ionization (ESI) which produced several charge states from eachn‐mer, depending on the number of PF₆ˉ anions lost upon ESI. Experimental Ω data, derived using IM‐MS, and computational Ω predictions were used to elucidate the size and architecture of the complexes. ResultsOnly macrocyclic dimers, trimers, and tetramers were observed with Cd²⁺, whereas Zn²⁺formed the same plus hexameric complexes. These two metals led to the simplest product distributions and no linear isomers. In sharp contrast, Ni²⁺and Fe²⁺formed all possible ring sizes from dimer to hexamer as well as various linear isomers. The experimental and theoretical Ω data indicated rather planar macrocyclic geometries for the dimers and trimers, twisted 3D architectures for the larger rings, and substantially larger sizes with spiral conformation for the linear congeners. Adding PF₆ˉ to the same complex was found to mainly cause size contraction due to new stabilizing anion–cation interactions. ConclusionsComplete structural identification could be accomplished using ESI‐IM‐MS. Our results affirm that self‐assembly with Cd²⁺and Zn²⁺proceeds through reversible equilibria that generate the thermodynamically most stable structures, encompassing exclusively macrocyclic architectures that readily accommodate the 60^oligand used. In contrast, complexation with Ni²⁺and Fe²⁺, which form stronger coordinative bonds, proceeds through kinetic control, leading to more complex mixtures and kinetically trapped less stable architectures, such as macrocyclic pentamers and linear isomers. 

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4. An upper bound for the first nonzero Steklov eigenvalue

   https://doi.org/10.1051/cocv/2024088  

   Li, Xiaolong; Wang, Kui; Wu, Haotian (January 2025, ESAIM: Control, Optimisation and Calculus of Variations)

   Let (Mⁿ,g) be a complete simply connectedn-dimensional Riemannian manifold with curvature bounds Sect_g≤ κ for κ ≤ 0 and Ric_g≥ (n− 1)KgforK≤ 0. We prove that for any bounded domain Ω ⊂Mⁿwith diameterdand Lipschitz boundary, if Ω* is a geodesic ball in the simply connected space form with constant sectional curvature κ enclosing the same volume as Ω, then σ₁(Ω) ≤Cσ₁(Ω*), where σ₁(Ω) and σ₁(Ω*) denote the first nonzero Steklov eigenvalues of Ω and Ω* respectively, andC=C(n, κ,K,d) is an explicit constant. When κ =K, we haveC= 1 and recover the Brock–Weinstock inequality, asserting that geodesic balls uniquely maximize the first nonzero Steklov eigenvalue among domains of the same volume, in Euclidean space and the hyperbolic space. 

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5. Electronic Control of Polyproline II Helix Stability via the Identity of Acyl Capping Groups: the Pivaloyl Group Particularly Promotes PPII

   https://doi.org/10.1002/chem.202401454  

   Bhatt, Megh_R; Zondlo, Neal_J (June 2024, Chemistry – A European Journal)

   Abstract The type II polyproline helix (PPII) is a fundamental secondary structure of proteins, important in globular proteins, in intrinsically disordered proteins, and at protein‐protein interfaces. PPII is stabilized in part byn→π* interactions between consecutive carbonyls, via electron delocalization between an electron‐donor carbonyl lone pair (n) and an electron‐acceptor carbonyl (π*) on the subsequent residue. We previously demonstrated that changes to the electronic properties of the acyl donor can predictably modulate the strength ofn→π* interactions, with data from model compounds, in solution in chloroform, in the solid state, and computationally. Herein, we examined whether the electronic properties of acyl capping groups could modulate the stability of PPII in peptides in water. InX−PPGY‐NH₂peptides (X=10 acyl capping groups), the effect of acyl group identity on PPII was quantified by circular dichroism and NMR spectroscopy. Electron‐rich acyl groups promoted PPII relative to the standard acetyl (Ac−) group, with the pivaloyl andiso‐butyryl groups most significantly increasing PPII. In contrast, acyl derivatives with electron‐withdrawing substituents and the formyl group relatively disfavored PPII. Similar results, though lesser in magnitude, were also observed inX−APPGY‐NH₂peptides, indicating that the capping group can impact PPII conformation at both proline and non‐proline residues. The pivaloyl group was particularly favorable in promoting PPII. The effects of acyl capping groups were further analyzed inX–DfpPGY‐NH₂andX−ADfpPGY‐NH₂peptides, Dfp=4,4‐difluoroproline. Data on these peptides indicated that acyl groups induced order Piv‐ > Ac‐ > For‐. These results suggest that greater consideration should be given to the identity of acyl capping groups in inducing structure in peptides. 

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