A novel proton-selective sensor based on a sugar with hinge flexibility

A hinge sugar, a 2,4-diamino-2,4-dideoxy-beta-D-xylopyranoside derivative, turns its four equatorial substituents into axial orientations through a (4)C(1)-to-(1)C(4) ring flip in response to chelation to a metal ion. This hinge-like motion enables two components attached at the 1- and 3-positions to switch between far and near states. In this study, we examined the effect of N-alkylation on the bendability of the hinge molecule and synthesized a 2,4-dipyrenylmethyl derivative as a proton-selective sensor. (1)H NMR studies showed that N-alkylations of the hinge sugar facilitated (1)C(4) formation in the presence of an acid, probably because the increased basicity of the amino group promoted the intramolecular hydrogen bond between the 2- and 4-amino substituents, whereas chelation to a metal ion was hampered by the increased bulkiness. In accordance with the above results, N,N'-dipyrenylmethyl hinge sugar 3 emitted excimer fluorescence (445 nm) owing to the pyrene stacking as a result of the (1)C(4) formation at lower concentrations of trifuluoroacetic acid (TFA), while no significant changes in fluorescence spectra were observed when metal ions were added. Increase of the monomer fluorescence (375 nm) at higher TFA concentrations was also observed. These observations indicate that 3 could be used as a proton-selective sensor that covers a wide range of proton concentrations through monitoring of the two fluorescence maxima.     

Process research on arylnaphthalene lignan aza-analogues: a new palladium-catalyzed benzannulation of α,β-bisbenzylidenesuccinic acid derivatives

The discovery of a new Pd-catalyzed benzannulation reaction of bisbenzylidenesuccinimide during process research on arylnaphthalene lignan aza-analogues is described. An extension of the Pd-catalyzed benzannulation to the regiospecific synthesis of various arylnaphthalene lignan aza-analogues utilizing classical Stobbe condensation is included.     

Dzyaloshinskii–Moriya interaction: How to measure its sign in weak ferromagnets?

Three experimental techniques sensitive to the sign of the Dzyaloshinskii-Moriya interaction are discussed: neutron diffraction, Mössbauer γ-ray diffraction, and resonant x-ray scattering. Classical examples of hematite (α-Fe₂O₃) and MnCO₃ crystals are considered in detail.     

Application of Parallel Hybrid Algorithm in Massively Parallel GPGPU—The Improved Effective and Efficient Method for Calculating Coulombic Interactions in Simulations of Many Ions with SIMION

In our previous study, we introduced a new hybrid approach to effectively approximate the total force on each ion during a trajectory calculation in mass spectrometry device simulations, and the algorithm worked successfully with SIMION. We took one step further and applied the method in massively parallel general-purpose computing with GPU (GPGPU) to test its performance in simulations with thousands to over a million ions. We took extra care to minimize the barrier synchronization and data transfer between the host (CPU) and the device (GPU) memory, and took full advantage of the latency hiding. Parallel codes were written in CUDA C++ and implemented to SIMION via the user-defined Lua program. In this study, we tested the parallel hybrid algorithm with a couple of basic models and analyzed the performance by comparing it to that of the original, fully-explicit method written in serial code. The Coulomb explosion simulation with 128,000 ions was completed in 309?s, over 700 times faster than the 63?h taken by the original explicit method in which we evaluated two-body Coulomb interactions explicitly on one ion with each of all the other ions. The simulation of 1,024,000 ions was completed in 2650?s. In another example, we applied the hybrid method on a simulation of ions in a simple quadrupole ion storage model with 100,000 ions, and it only took less than 10 d. Based on our estimate, the same simulation is expected to take 5-7 y by the explicit method in serial code.     

Reaction of Cu+ with dimethoxyethane: competition between association and multiple dissociation channels

The reaction of Cu+ with dimethoxyethane (DXE) is studied using kinetic-energy dependent guided ion beam mass spectrometry. The bimolecular reaction forms an associative Cu(+)(DXE) complex that is long-lived and dissociates into several competitive channels: C4H9O2(+)+CuH, Cu(+)(C3H6O)+CH3OH, back to reactants, and other minor channels. The kinetic-energy dependences of the cross sections for the three largest product channels are interpreted with several different models (including rigorous phase space theory) to yield 0 K bond energies after accounting for the effects of multiple ion-molecule collisions, internal energy of the reactant ions, Doppler broadening, and dissociation lifetimes. These values are compared with bond energies obtained from collision-induced dissociation (CID) studies of the Cu(+)(DXE) complex and found to be self-consistent. Although all models provide reasonable thermochemistry, phase space theory reproduces the details of the cross sections most accurately. We also examine the dynamics of this reaction using time-of-flight methods and a retarding potential analysis. This provides additional insight into the unimolecular decay of the long-lived Cu(+)(DXE) association complex. Comparison of results from this study with those from the complementary CID study, thus forming the same energized Cu(+)(DXE) complex in two distinct ways, allows an assessment of the models used to interpret CID thresholds.     

Enzymatic formation of an unnatural hexacyclic C35 polyprenoid by bacterial squalene cyclase

A C35 polyprene in which a farnesyl C15 unit is connected in a head-to-head fashion to a geranylgeranyl C20 unit was enzymatically converted to an unnatural hexacyclic polyprenoid by squalene:hopene cyclase from Alicyclobacillus acidocaldarius. This is the first demonstration of the remarkable ability of the squalene cyclizing enzyme to perform construction of unnatural hexacyclic skeleton. The cyclization of the C35 polyprene was initiated by a proton attack on the terminal double bond of the C15 unit and proceeded without rearrangement of carbon and hydrogen. The substrate should be folded in chair-chair-chair-chair-boat-boat conformation to achieve the stereochemistry of the cyclization product.     

Enzymatic formation of indole-containing unnatural cyclic polyprenoids by bacterial squalene:hopene cyclase

[reaction: see text] Two indole-containing substrate analogues, in which a C20 isoprene unit is connected to indole (3-(geranylgeranyl)indole and 3-(farnesyldimethylallyl)indole), were synthesized and tested for enzymatic cyclization by squalene:hopene cyclase from Alicyclobacillus acidocaldarius. Interestingly, 3-(geranylgeranyl)indole was not a substrate for the bacterial squalene cyclase, while 3-(farnesyldimethylallyl)indole was efficiently converted to a 2:1 mixture of unnatural novel products.     

Single-crystalline platinum nanosheets from nonionic surfactant 2-D self-assemblies at solid/aqueous solution interfaces

Single-crystalline platinum nanosheets have been prepared via a new methodology based on the chemical reduction of a platinum salt (H2PtCl6) with hydrazine at a graphite/solution interface, using polyoxyethylene (20) sorbitan monostearate (Tween 60) based self-assembly (hemicylindrical micelle) templates. The platinum nanosheets with a uniform thickness of as thin as 3.5 +/- 1 nm are surface-smooth and continuous over relatively large length scales of micrometer sizes. In striking contrast to the Tween 60 based system, no Pt nanosheets are obtained with nonaethylene glycol monododecyl ether (C12EO9) and polyoxyethylene (23) dodecyl ether (C12EO23). No Pt nanosheets are also obtainable with a laterally homogeneous layer of Tween 60 formed at the silica/solution interface. These results indicate that surfactant Tween 60 molecules with a triple polyoxyethylene structure, as well as their hemicylindrical micelle templates, play an essential role for the formation of the Pt nanosheets. It is also suggested that the interfacially directed growth of Pt metals within the aqueous shells of the Tween 60 hemicylindrical micelles induces the thin Pt crystals as thick as the aqueous shells. The present approach could be extended to prepare a wide range of novel nanostructures of noble metals, using various micelle-like self-assemblies at interfaces.     

The role of hydroxyl groups in interchain interactions in cellulose Iα and Iβ

Complex networks of hydrogen bonds within the cellulose I_α and I_β contribute greatly to cellulose's anisotropic physical properties such as material stiffness. The interchain hydrogen bonding interactions through hydroxyl groups are isolated in each of the three lattice planes of the adjacent chains within the unit cell of two allomorphs of natural cellulose. In our density function theory study with dispersion corrected Perdew–Burke–Ernzerhof (PBE‐D2) functional, these hydroxyl groups participate in strong hydrogen bonding interactions (?24.8 and ?24.8 kcal/mol for cellulose I_α and I_β, respectively) in the side‐to‐side lattice plane. Unexpectedly, the hydroxyl groups also participate significantly in hydrogen bonding interactions (?11.0 and ?12.4 kcal/mol for cellulose I_α and I_β, respectively) in one of the diagonal lattice planes in both cellulose I_α and I_β. Both PM7 and PBE‐D2 method predict that the overall interaction is asymmetric and stronger in the right diagonal lattice plane. While hydrogen bonding interactions are strongest in side‐to‐side lattice plane as expected, the role of hydrogen bonding interactions for keeping the sheet together is more significant than previously thought.