Viscoelastic property mapping with contact resonance force microscopy

We demonstrate the accurate nanoscale mapping of near-surface loss and storage moduli on a polystyrene-polypropylene blend with contact resonance force microscopy (CR-FM). These viscoelastic properties are extracted from spatially resolved maps of the contact resonance frequency and quality factor of the AFM cantilever. We consider two methods of data acquisition: (i) discrete stepping between mapping points and (ii) continuous scanning. For point mapping and low-speed scanning, the values of the relative loss and storage modulus are in good agreement with the time-temperature superposition of low-frequency dynamic mechanical analysis measurements to the high frequencies probed by CR-FM.     

MS/MS fragmentation-guided search of TMG-chitooligomycins and their structure-activity relationship in specific β-N-acetylglucosaminidase inhibition

The reducing tetrasaccharide TMG-chitotriomycin (1) is an inhibitor of β-N-acetylglucosaminidase (GlcNAcase), produced by the actinomycete Streptomyces anulatus NBRC13369. The inhibitor shows a unique inhibitory spectrum, that is, selectivity toward enzymes from chitin-containing organisms such as insects and fungi. Nevertheless, its structure-selectivity relationship remains to be clarified. In this study, we conducted a structure-guided search of analogues of 1 in order to obtain diverse N,N,N-trimethylglucosaminium (TMG)-containing chitooligosaccharides. In this approach, the specific fragmentation profile of 1 on ESI-MS/MS analysis was used for the selective detection of desired compounds. As a result, two new analogues, named TMG-chitomonomycin (3) and TMG-chitobiomycin (2), were obtained from a culture filtrate of 1-producing Streptomyces. Their enzyme-inhibiting activity revealed that the potency and selectivity depended on the degree of polymerization of the reducing end GlcNAc units. Furthermore, a computational modeling study inspired the inhibitory mechanism of TMG-related compounds as a mimic of the substrate in the Michaelis complex of the GH20 enzyme. This study is an example of the successful application of a MS/MS experiment for structure-guided isolation of natural products.     

Sonochemically synthesized core-shell structured Au–Pd nanoparticles supported on γ-Fe2O3 particles

A sample of Au–Pd bimetallic nanoparticles supported on γ-Fe₂O₃ was synthesized in a sonochemically one-pot process. The structural analyses of the synthesized sample were performed by the techniques of X-ray Absorption Fine Structure (XAFS), X-ray Diffraction (XRD), Transmission Electron Microscopy (TEM) and UV–vis spectrometry. Results indicated that the synthesized sample formed a core-shell structure in which a gold core was surrounded by a thin palladium shell. The reaction rate constant for the hydrogenation of cyclohexene of the present sample showed higher value than that of Pd nanoparticles supported on γ-Fe₂O₃ and core-shell structured Au–Pd nanoparticles supported on SiO₂. The present sample is a promising catalyst material which has a high catalytic activity.     

Studies on the charge transfer complex and polymerization. XVI. Spontaneous copolymerization of cyclopentene and sulfur dioxide

The alternating copolymerization of cyclopentene and sulfur dioxide was studied. It takes place spontaneously at ?15°C. The rate of copolymerization in toluene was found to be proportional to [CPT]³ and [SO₂]² with the overall activation energy of 16.5 kcal/mole. Terpolymerizations with eight different third monomers were carried out to examine the character and behavior of the copolymerization system of CPT and SO₂. However, the polymerizations with styrene and methyl methacrylate as the third monomers were found to be extraordinary, in that all the three components are not incorporated into the polymer chain.     

Synthesis of 2,3-disubstituted benzofurans by platinum-olefin-catalyzed carboalkoxylation of o-alkynylphenyl acetals

The PtCl2-catalyzed cyclization reaction of o-alkynylphenyl acetals 1 in the presence of 1,5-cyclooctadiene produces 3-(alpha-alkoxyalkyl)benzofurans 2 in good to high yields. For example, the reaction of acetaldehyde ethyl 2-(1-octynyl)phenyl acetal (1a), acetaldehyde ethyl 2-(cyclohexylethynyl)phenyl acetal (1c), and acetaldehyde ethyl 2-(phenylethynyl)phenyl acetal (1f) in the presence of 2 mol % of platinum(II) chloride and 8 mol % of 1,5-cyclooctadiene in toluene at 30 degrees C gave the corresponding 2,3-disubstituted benzofurans 2a, 2c, and 2f in 91, 94, and 88% yields, respectively.     

Hierarchically organized architecture of potassium hydrogen phthalate and poly(acrylic acid): toward a general strategy for biomimetic crystal design

A hierarchically organized architecture in multiple scales was generated from potassium hydrogen phthalate crystals and poly(acrylic acid) based on our novel biomimetic approach with an exquisite association of polymers on crystallization.     

ν-Stable τ-Tilting Modules

Inspired by τ-tilting theory [3 Adachi , T. , Iyama , O. , Reiten , I. ( 2014 ). τ-tilting theory . Compos. Math. 150 ( 3 ): 415 – 452 .[Crossref], [Web of Science ®] , [Google Scholar]], we introduce the notion of ν-stable support τ-tilting modules. For any finite dimensional selfinjective algebra Λ, we give bijections between two-term tilting complexes in K ^b (proj Λ), ν-stable support τ-tilting Λ-modules, and ν-stable functorially finite torsion classes in modΛ. Moreover, these objects correspond bijectively to selfinjective cluster tilting objects in 𝒞 if Λ is a 2-CY tilted algebra associated with a Hom-finite 2-CY triangulated category 𝒞. We also study some properties of support τ-tilting modules over 2-CY tilted algebras, and we give a necessary condition such that algebras are 2-CY tilted in terms of support τ-tilting modules.     

Spin-inversion mechanisms in the reactions of transition metal cations (Sc+, Ti+, V+, Cr+, Mn+, Fe+, Co+, Ni+, and Cu+) with OCS in the gas phase: A perspective from automated reaction path search calculations

The mechanisms including spin-inversion have been systematically studied for the M⁺ + OCS → MS⁺ + CO/MO⁺ + CS (M denotes a transition metal from Sc to Cu) ion-molecule reactions using the automated reaction path search method. We used the lowest mixed-spin potential energy surface obtained from the diagonalization of the spin-coupled Hamiltonian matrix, whose diagonal elements are taken to be the lowest two spin states. This scheme can effectively locate approximate minimum energy crossing points between the two potential energy surfaces with different spin multiplicities. The spin-orbit couplings at spin-inversion points have been calculated to understand the efficiencies of nonadiabatic transitions. The obtained reaction pathways and the calculated spin-orbit couplings are employed to interpret previous experimental studies.