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.     

(2‐Aminoethanethiolato‐N,S)bis(ethylenediamine‐N,N′)cobalt(III) dinitrate

In the title compound, [Co(C₂H₆NS)(C₂H₈N₂)₂](NO₃)₂, the Co^III atom has a slightly distorted octahedral geometry, coordinated by one 2‐amino­ethane­thiol­ate and two ethyl­enedi­amine ligands. The three five‐membered chelate rings adopt a gauche conformation with the unfavoured (lel)₂(ob) form, which is ascribed to hydrogen bonds between the amine groups in the complex cation and the nitrate counter‐anions [N?O 2.900 (3)–3.378 (3) Å].     

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...     

Cover Picture: Electrochemical Method for G-quartet RNA Detection of COVID-19 Based on Cyclic Ferrocenylnaphthalene Diimide (Electroanalysis 4/2023)

To develop an electrochemical detection method for COVID-19, we have investigated the interaction between RG-1, a characteristic parallel four-strand RNA component of the COVID-19 genome, and cyclic ferrocenylnaphthalene diimides carrying different linker lengths 1 and 2 , which bind to RG-1 more strongly than cyclic naphthalene diimide 3 that lacks a ferrocene moiety. In particular, the binding affinity of 1 having short one showed the highest binding affinity to RG-1, and the redox current of 1 increased in the presence of RG-1 using a glassy carbon electrode. This increasing current of 1 in the presence of c-myc as a parallel G4 DNA or single-stranded RNA was lower than that in the presence of RG-1. Several RG-1 was electrochemically detected at the nanomolar level by 1 .     

A facile method for generation of carbon oxide sulfide

Carbon oxide sulfide was easily generated upon heating of amine salts of carbamothioic acids at 85°C which were produced in situ from amines, carbon monoxide, and elemental sulfur in the presence of a catalytic amount of selenium under mild conditions.