Group graded rings

Let R be a group graded ring . The map ( , ): R × R →₁ defined by: (x,y) = (xy)₁ , is an inner product on R. In this paper we investigate aspects of nondegeneracy of the product, which is a generalization of the notion of strongly G —graded rings,introduced by Dade. We show that various chain conditions are satisfied by R if and only if they are satisfied by R₁ , and that when R₁ is simple artinian, then R is a crossed product R₁ ^* G. We give conditions for simple R-modules to be completely reducible R₁ -modules . Finally, we prove an incomparability theorem,when G is finite abelian.     

On the nature of ion-stabilized cytosine pairs in DNA i-motifs: The importance of charge transfer processes

Recent experimental results indicate that the stability of non-Watson-Crick DNA i-motif structures can be influenced by the presence of various metal cations. Whereas Au⁺, Cu⁺, and Ag⁺ are stabilizing agents, alkali metal ions like Na⁺ or Li⁺ are known to destabilize the i-motif. In terms of reduced ion-cytosine complexes, we rationalize the experimental observations with the help of standard and conceptual density functional theory (DFT) calculations. Our results highlight the importance of coordinating electrostatic bonds with partially covalent character for the stability of the ion-cytosine complex. The occurrence of these bonds can be mainly attributed to charge transfer processes between two cytosines and the transition metal ions, which can be either explained by frontier molecular orbital theory in combination with a bond critical point analysis, or by the concept of chemical reactivity indices within a conceptual DFT approach. The results of our calculations establish a consistent theoretical framework to understand the experimentally observed behavior, and are also important in order to achieve more detailed insights into nucleobase pairing mechanisms in general.     

Catenation and Aggregation of Multi‐Cavity Coordination Cages

A series of metal‐mediated cages, having multiple cavities, was synthesized from Pd^II cations and tris‐ or tetrakis‐monodentate bridging ligands and characterized by NMR spectroscopy, mass spectrometry, and X‐ray methods. The peanut‐shaped [Pd₃L¹₄] cage deriving from the tris‐monodentate ligand L¹ could be quantitatively converted into its interpenetrated [5Cl@Pd₆L¹₈] dimer featuring a linear {[Pd‐Cl‐]₅Pd} stack as an unprecedented structural motif upon addition of chloride anions. Small‐angle neutron scattering (SANS) experiments showed that the cigar‐shaped assembly with a length of 3.7 nm aggregates into mono‐layered discs of 14 nm diameter via solvophobic interactions between the hexyl sidechains. The hepta‐cationic [5Cl@Pd₆L¹₈] cage was found to interact with polyanionic oligonucleotide double‐strands under dissolution of the aggregates in water, rendering the compound class interesting for applications based on non‐covalent DNA binding.     

Dynamic Covalent Identification of an Efficient Heparin Ligand

Despite heparin being the most widely used macromolecular drug, the design of small‐molecule ligands to modulate its effects has been hampered by the structural properties of this polyanionic polysaccharide. Now a dynamic covalent selection approach is used to identify a new ligand for heparin, assembled from extremely simple building blocks. The amplified molecule strongly binds to heparin (K_D in the low μm range, ITC) by a combination of electrostatic, hydrogen bonding, and CH–π interactions as shown by NMR and molecular modeling. Moreover, this ligand reverts the inhibitory effect of heparin within an enzymatic cascade reaction related to blood coagulation. This study demonstrates the power of dynamic covalent chemistry for the discovery of new modulators of biologically relevant glycosaminoglycans.     

EThcD Discrimination of Isomeric Leucine/Isoleucine Residues in Sequencing of the Intact Skin Frog Peptides with Intramolecular Disulfide Bond

Our scientific interests involve de novo sequencing of non-tryptic natural amphibian skin peptides including those with intramolecular S–S bond by means of exclusively mass spectrometry. Reliable discrimination of the isomeric leucine/isoleucine residues during peptide sequencing by means of mass spectrometry represents a bottleneck in the workflow for complete automation of the primary structure elucidation of these compounds. MS³ is capable of solving the problem. Earlier we demonstrated the advanced efficiency of ETD-HCD method to discriminate Leu/Ile in individual peptides by consecutive application of ETD to the polyprotonated peptides followed by HCD applied to the manually selected primary z-ions with the targeted isomeric residues at their N-termini and registration of the characteristic w-ions. Later this approach was extended to deal with several (4–7) broad band mass ranges, without special isolation of the primary z-ions. The present paper demonstrates an advanced version of this method when EThcD is applied in the whole mass range to a complex mixture of natural non-tryptic peptides without their separation and intermediate isolation of the targeted z-ions. The proposed EThcD method showed over 81% efficiency for the large natural peptides with intact disulfide ring, while the interfering process of radical site migration is suppressed. Due to higher speed and sensitivity, the proposed EThcD approach facilitates the analytical procedure and allows for the automation of the entire experiment and data processing. Moreover, in some cases it gives a chance to establish the nature of the residues in the intact intramolecular disulfide loops.

Open image in new window

Graphical Abstract ?

     

Electrochemical Hydroxylation of Arenes Catalyzed by a Keggin Polyoxometalate with a Cobalt(IV) Heteroatom

The sustainable, selective direct hydroxylation of arenes, such as benzene to phenol, is an important research challenge. An electrocatalytic transformation using formic acid to oxidize benzene and its halogenated derivatives to selectively yield aryl formates, which are easily hydrolyzed by water to yield the corresponding phenols, is presented. The formylation reaction occurs on a Pt anode in the presence of [Co^IIIW₁₂O₄₀]^5? as a catalyst and lithium formate as an electrolyte via formation of a formyloxyl radical as the reactive species, which was trapped by a BMPO spin trap and identified by EPR. Hydrogen was formed at the Pt cathode. The sum transformation is ArH+H₂O→ArOH+H₂. Non‐optimized reaction conditions showed a Faradaic efficiency of 75 % and selective formation of the mono‐oxidized product in a 35 % yield. Decomposition of formic acid into CO₂ and H₂ is a side‐reaction.     

Green and Rapid Hydrothermal Crystallization and Synthesis of Fully Conjugated Aromatic Compounds

Highly fused, fully conjugated aromatic compounds are interesting candidates for organic electronics. With higher crystallinity their electronic properties improve. It is shown here that the crystallization of three archetypes of such molecules—pentacenetetrone, indigo, and perinone—can be achieved hydrothermally. Given their molecular structure, this is a truly startling finding. In addition, it is demonstrated that perinone can also be synthesized in solely high‐temperature water from the starting compounds naphthalene bisanhydride and o‐phenylene diamine without the need for co‐solvents or catalysts. The transformation can be drastically accelerated by the application of microwave irradiation. This is the first report on the hydrothermal generation of two fused heterocycles.     

Crystal and molecular structure of triacanthine, 6-amino-3-dimethylallylpurine,a naturally occurring N(3)-substituted purine

The crystal and molecular structures of the naturally occurring, N(3)-substituted purine triacanthine (6-amino-3-dimethylallylpurine) are presented. Triacanthine crystallizes, from a saturated DMSO solution, in the monoclinic system, space groupP2₁/c. Crystallographic data are as follows:a = 12.451(4),b = 8.508(4),c = 11.365(3) Å, = 122.74(2) °,V _c = 1012.66 ų,Z = 4,D _m = 1.335(1),D _x = 1.333 g cm^–3. The structural solution was obtained by direct methods and has been refined, based on full-matrix least squares with 2124 observedF _o data, to a finalR value of 0.075. The principal molecular features are (1) the occurrence of the substituted purine as the amino tautomer, (2) a nearly planar purine ring system, and (3) a highly planar dimethylallyl group oriented approximately orthogonally to the purine ring system. The crystal packing is dominated by intermolecular hydrogen bonds involving the exocyclic amino group and the acceptor sites N(1) and N(9). Sheets of such hydrogen-bonded molecules are stacked along [10¯1]. Two distinct types of molecular overlaps are observed within these stacks.