Structure Solution of Nano-Crystalline Small Molecules Using MicroED and Solid-State NMR Dipolar-Based Experiments

Three-dimensional electron diffraction crystallography (microED) can solve structures of sub-micrometer crystals, which are too small for single crystal X-ray crystallography. However, R factors for the microED-based structures are generally high because of dynamic scattering. That means R factor may not be reliable provided that kinetic analysis is used. Consequently, there remains ambiguity to locate hydrogens and to assign nuclei with close atomic numbers, like carbon, nitrogen, and oxygen. Herein, we employed microED and ssNMR dipolar-based experiments together with spin dynamics numerical simulations. The NMR dipolar-based experiments were ¹H-¹⁴N phase-modulated rotational-echo saturation-pulse double-resonance (PM-S-RESPDOR) and ¹H-¹H selective recoupling of proton (SERP) experiments. The former examined the dephasing effect of a specific ¹H resonance under multiple ¹H-¹⁴N dipolar couplings. The latter examined the selective polarization transfer between a ¹H-¹H pair. The structure was solved by microED and then validated by evaluating the agreement between experimental and calculated dipolar-based NMR results. As the measurements were performed on ¹H and ¹⁴N, the method can be employed for natural abundance samples. Furthermore, the whole validation procedure was conducted at 293 K unlike widely used chemical shift calculation at 0 K using the GIPAW method. This combined method was demonstrated on monoclinic l-histidine.     

Cyclization of 5-amino-1-β-d-ribofuranosylimidazole-4-carboxamide (AICA-riboside): A review

The synthesis of various purine nucleosides by cyclization of AICA-riboside(5-amino-1-β-D-ribofuranosylimidazole-4-carboxamide) is described. A variety of cyclization reactions provide new synthetic routes to inosine and guanosine. In this review, emphasis will be placed on the synthesis of the latter.     

Design and synthesis of dual inhibitors of acetylcholinesterase and serotonin transporter targeting potential agents for Alzheimer's disease

Highly efficient acetylcholinesterase (AChE) and serotonin transporter (SERT) dual inhibitors, (S)-4 and (R)-13 were designed and synthesized on the basis of the hypothetical model of AChE active site. Both compounds showed potent inhibitory activities against AChE and SERT. [structure: see text]     

Mixed magnetic phases in (Ga,Mn)As epilayers

Two different ferromagnetic-paramagnetic transitions are detected in (Ga,Mn)As/GaAs(001) epilayers from ac susceptibility measurements: transition at a higher temperature results from (Ga,Mn)As cluster phases with [110] uniaxial anisotropy and that at a lower temperature is associated with a ferromagnetic (Ga,Mn)As matrix with 100 cubic anisotropy. A change in the magnetic easy axis from [100] to [110] with increasing temperature can be explained by the reduced contribution of 100 cubic anisotropy to the magnetic properties above the transition temperature of the (Ga,Mn)As matrix.     

Molecular mechanisms of the photostability of indigo

The photophysics of indigo as well as of bispyrroleindigo, the basic chromophore of indigo, has been investigated with ab initio electronic-structure calculations. Vertical electronic excitation energies and excited-state potential-energy profiles have been calculated with the CASSCF, CASPT2 and CC2 methods. The calculations reveal that indigo and bispyrroleindigo undergo intramolecular single-proton transfer between adjacent N-H and C=O groups in the (1)ππ* excited state. The nearly barrierless proton transfer provides the pathway for a very efficient deactivation of the (1)ππ* state via a conical intersection with the ground state. While a low-lying S(1)-S(0) conical intersection exists also after double-proton transfer, the latter reaction path exhibits a much higher barrier. The reaction path for trans→cis photoisomerization via the twisting of the central C=C bond has been investigated for bispyrroleindigo. It has been found that the twisting of the central C=C bond is unlikely to play a role in the photochemistry of indigo, because of a large potential-energy barrier and a rather high energy of the S(1)-S(0) conical intersection of the twisted structure. These findings indicate that the exceptional photostability of indigo is the result of rapid internal conversion via intramolecular single-proton transfer, combined with the absence of a low-barrier reaction path for the generation of the cis isomer via trans→cis photoisomerization.     

Construction of regulated nanospace around a porphyrin core

A series of 1,3,5-phenylene-based rigid dendritic porphyrins were synthesized by Suzuki coupling between a porphyrin core and dendron units. The intramolecular energy transfer was studied by absorption and fluorescence spectroscopies. The encapsulation of the porphyrin core within the 1,3,5-phenylene dendron units was found to provide highly efficient energy transfer from the dendron units to the porphyrin core. The dendritic wedge structure affected the energy transfer efficiency. The 1,3,5-phenylene-based rigid dendron units act as highly efficient light-harvesting antennae. These dendritic porphyrins have also been examined as C(60) hosts and substrate-selective oxidation catalysts. The attachment of the second generation of 1,3,5-phenylene-based dendron units with the porphyrin core enabled a stable inclusion of C(60) in toluene. Furthermore, the size and shape of the nanospace in the rigid dendritic porphyrins were found to affect the selectivity of substrates in the catalytic olefin oxidations.     

Pion-transfer (n, d) and (d, He) reactions leading to deeply bound pionic atoms

Theoretical studies are given on the (n, d) and (d, ³He) reactions leading to deeply bound pionic atoms in heavy nuclei of configuration [(nl)_π·j_n⁻¹]J. The cross sections for various pionic and neutron-hole configurations in the case of a ²⁰⁸Pb target are calculated at incident energies 300–1000 MeV/u by using the effective number approach and the eikonal approximation for distortion. The effective number with a pion in the 1s or 2p state and a neutron hole in the orbit peaks around the same incident energy (T_n = 600 MeV) as the elementary cross section n+n→d+π⁻, where the momentum transfer matches the angular-momentum transfer of L = 5–7. The DWIA cross section for (n,d) producing a pion in the 1s or 2p orbit at T_n = 600 MeV is found to be around 42 or 75 μb/sr, respectively. At T_n = 350 MeV, where the momentum transfer is small, quasi-substitutional states of configurations and are preferentially populated with (n, d) cross sections of 95 and 190 μb/sr, respectively. The (d, ³He) cross sections are estimated to be an order of magnitude smaller than the (n, d) cross sections. Thus, the (n, d) and (d, ³He) reactions are found to be suited for the production of deeply bound pionic atoms.     

Reduced Norm Map of Division Algebras over Complete Discrete Valuation Fields of Certain Type

We study a ramification theory for a division algebra D of the following type: The center of D is a complete discrete valuation field K with the imperfect residue field F of certain type, and the residue algebra of D is commutative and purely inseparable over F. Using Swan conductors of the corresponding element of Br(K), we define -function of D/K, and it describe the action of the reduced norm map on the filtration of D-. We also gives a relation among the Swan conductors and the ramification number of D, which is defined by the commutator group of D-.     

Alternative method for reconstruction of antihydrogen annihilation vertices

The ALPHA experiment, located at CERN, aims to compare the properties of antihydrogen atoms with those of hydrogen atoms. The neutral antihydrogen atoms are trapped using an octupole magnetic trap. The trap region is surrounded by a three layered silicon detector used to reconstruct the antiproton annihilation vertices. This paper describes a method we have devised that can be used for reconstructing annihilation vertices with a good resolution and is more efficient than the standard method currently used for the same purpose.