Catalytic enantioselective desymmetrization of meso-glutaric anhydrides using a stable Ni2-Schiff base catalyst

We describe the desymmetrization of meso-glutaric anhydrides to chiral hemiesters using a bench-stable homodinuclear Ni(2)-(Schiff base) complex as the catalyst in good to excellent yield (up to 99%) and enantioselectivity (up to 94%). Using the opposite enantiomer of the catalyst, we obtained the same yield and enantioselectivity with the opposite configuration, thereby gaining access to both hemiester enantiomers.     

Amycolamicin: A Novel Broad‐Spectrum Antibiotic Inhibiting Bacterial Topoisomerase

The abuse of antibacterial drugs imposes a selection pressure on bacteria that has driven the evolution of multidrug resistance in many pathogens. Our efforts to discover novel classes of antibiotics to combat these pathogens resulted in the discovery of amycolamicin (AMM). The absolute structure of AMM was determined by NMR spectroscopy, X‐ray analysis, chemical degradation, and modification of its functional groups. AMM consists of trans‐decalin, tetramic acid, two unusual sugars (amycolose and amykitanose), and dichloropyrrole carboxylic acid. The pyranose ring named as amykitanose undergoes anomerization in methanol. AMM is a potent and broad‐spectrum antibiotic against Gram‐positive pathogenic bacteria by inhibiting DNA gyrase and bacterial topoisomerase IV. The target of AMM has been proved to be the DNA gyrase B subunit and its binding mode to DNA gyrase is different from those of novobiocin and coumermycin, the known DNA gyrase inhibitors.     

Application of paramagnetic NMR-validated molecular dynamics simulation to the analysis of a conformational ensemble of a branched oligosaccharide

Oligosaccharides of biological importance often exhibit branched covalent structures and dynamic conformational multiplicities. Here we report the application of a method that we developed, which combined molecular dynamics (MD) simulations and lanthanide-assisted paramagnetic NMR spectroscopy, to evaluate the dynamic conformational ensemble of a branched oligosaccharide. A lanthanide-chelating tag was attached to the reducing end of the branched tetrasaccharide of GM2 ganglioside to observe pseudocontact shifts as the source of long distance information for validating the conformational ensemble derived from MD simulations. By inspecting the results, the conformational space of the GM2 tetrasaccharide was compared with that of its nonbranched derivative, the GM3 trisaccharide.     

Whose deletion does not affect your payoff? The difference between the Shapley value, the egalitarian value, the solidarity value, and the Banzhaf value

This study provides a unified axiomatic characterization method of one-point solutions for cooperative games with transferable utilities. Any one-point solution that satisfies efficiency, the balanced cycle contributions property (BCC), and the axioms related to invariance under a player deletion is characterized as a corollary of our general result. BCC is a weaker requirement than the well-known balanced contributions property. Any one-point solution that is both symmetric and linear satisfies BCC. The invariance axioms necessitate that the deletion of a specific player from games does not affect the other players’ payoffs, and this deletion is different with respect to solutions. As corollaries of the above characterization result, we are able to characterize the well-known one-point solutions, the Shapley, egalitarian, and solidarity values, in a unified manner. We also studied characterizations of an inefficient one-point solution, the Banzhaf value that is a well-known alternative to the Shapley value.     

Ferromagnetic coupling promoted by kappa3N:kappa2N bridging system

Syntheses, structures, and magnetic properties of novel trinuclear complexes of the same motif [M{Cu(pz2bg)2}M]4+ (M = CuII, NiII, CoII, MnII), catena-[Cu2{Cu(pz2bg)2}(Hpz)2(PhSO3)2](PhSO3)2.4H2O (2.4H2O), [Ni2{Cu(pz2bg)2}(MeOH)2(H2O)4](NO3)4 (3), [Co2{Cu(pz2bg)2}(NO3)2(EtOH)2](NO3)2 (4), and [Mn2{Cu(pz2bg)2}(NO3)4(MeCN)2] (5), which include the complex ligand [Cu(pz2bg)2] (1), are reported (Hpz = pyrazole, pz2bg- = di(pyrazolecarbimido)aminate; bispyrazolyl derivative of biguanidate). The reaction of Cu(ClO4)2.6H2O, sodium dicyanamide, Hpz, and PhSO3H.H2O (1:2:4:4) in MeOH yielded blue crystals of [Cu2(1)(Hpz)2(PhSO3)2](PhSO3)2.4H2O (2.4H2O). In 2, the tricopper(II) units, which consist of two Cu(II) ions bridged by 1, are linked by benzenesulfonate anions to form a ladder structure. Complex 1 was isolated by removing the terminal Cu(II) ions from 2 with use of Na(4)edta. Complexes 3-5 were obtained by the reaction of 1 with an excess of each M(II) ion. In 2-5, the adjoining metal ions are ferromagnetically coupled via the pz2bg- ligand with J values of +7.2(1), +7.5(1), +2.7(1), and +0.3(1) cm(-1), respectively, using a spin Hamiltonian H = -2J(S(M1)S(Cu) + S(Cu)S(M2)). The ferromagnetic interaction was attributed to the strict orthogonality of magnetic dsigma orbitals, which are controlled by the kappa3N:kappa2N bridging geometry of the pz2bg- ligands.     

The Structural Rule Distinguishing a Superfold: A Case Study of Ferredoxin Fold and the Reverse Ferredoxin Fold

Superfolds are folds commonly observed among evolutionarily unrelated multiple superfamilies of proteins. Since discovering superfolds almost two decades ago, structural rules distinguishing superfolds from the other ordinary folds have been explored but remained elusive. Here, we analyzed a typical superfold, the ferredoxin fold, and the fold which reverses the N to C terminus direction from the ferredoxin fold as a case study to find the rule to distinguish superfolds from the other folds. Though all the known structural characteristics for superfolds apply to both the ferredoxin fold and the reverse ferredoxin fold, the reverse fold has been found only in a single superfamily. The database analyses in the present study revealed the structural preferences of αβ- and βα-units; the preferences separate two α-helices in the ferredoxin fold, preventing their collision and stabilizing the fold. In contrast, in the reverse ferredoxin fold, the preferences bring two helices near each other, inducing structural conflict. The Rosetta folding simulations suggested that the ferredoxin fold is physically much more realizable than the reverse ferredoxin fold. Therefore, we propose that minimal structural conflict or minimal frustration among secondary structures is the rule to distinguish a superfold from ordinary folds. Intriguingly, the database analyses revealed that a most stringent structural rule in proteins, the right-handedness of the βαβ-unit, is broken in a set of structures to prevent the frustration, suggesting the proposed rule of minimum frustration among secondary structural units is comparably strong as the right-handedness rule of the βαβ-unit.     

Compressed sensing by two-directional line sensing

Optical Review - We propose an imaging method using commercially available profile sensor. Specifically, we use a multipixel CMOS area sensor capable of acquiring projection profiles and perform...     

Structural-transformation-induced Drastic Luminescence Changes in an Organic-Inorganic Hybrid [ReN(CN)4]2− Salt Triggered by Chemical Stimuli

We synthesized a (1-propylpyridinium)₂[ReN(CN)₄]-type organic–inorganic hybrid exhibiting water-vapor-induced drastic structural changes of the [ReN(CN)₄]²⁻ assemblies. Specifically, upon exposure to water vapor, dehydrated nitrido-bridged chains were converted to hydrated cyanido-bridged tetranuclear clusters via rearrangements of large molecular building units in the crystals. These switchable assembly forms display substantially different photo-physical properties, although in both cases the emission is caused by a metal-centered d–d transition. The nitrido-bridged chain exhibited a near-infrared (749 nm) emission, which blue-shifted as the temperature increased, while a visible (561 nm) emission and its red shift was demonstrated by the cyanido-bridged cluster.     

Measurement of image sensor tilt based on amplitude and phase of image

Optical Review - In this study, we present a new method for measuring the tilt of an image sensor to the lens. The assembly accuracy of the lens and image sensor units has a significant influence...