Steric isotope effects gauged by the bowl-inversion barrier in selectively deuterated pentaarylcorannulenes

Motivated by a greater bowl depth and barrier to bowl inversion in sym-1,3,5,7,9-pentamanisylcorannulene compared to corannulene, an experimental plan is developed to measure the effective hydrogen/deuterium steric kinetic isotope effect (KIE). Symmetry arguments are used to design orthogonal isotope labeling patterns so that the barrier for the CD3 compound can be measured in the presence of the CH3 compound. This scheme eliminates the differential uncertainty in the temperature measurement by allowing both barriers to be measure in the same sample, which in turn reduces the error in determining the differential barrier. Ab initio computations corroborate the structure and isotope effect found experimentally. The predicted and determined steric KIE at 250 K is 1.08 (modified QUIVER at M06-2X/cc-pVDZ) and 1.22 +/- 0.06 (VT-NMR), respectively. The results stem from differences in zero-point energy of the CH and CD motions; however, the phenomenology makes the CD3 group appear effectively "stickier" than CH3. The more the C-H...X interaction steepens the well, the "stickier" C-D should appear to be relative to C-H--an important consideration for molecular recognition and one supported by stronger binding constants for deuterated substrates.     

Large positive magnetoresistance of insulating organic crystals in the non-ohmic region

We report a large positive magnetoresistance ratio in insulating organic crystals theta-(ET)(2)CsZn(SCN)(4) at low temperatures at which they exhibit highly nonlinear current-voltage characteristics. Despite the nonlinearity, the magnetoresistance ratio is independent of the applied voltage. The magnetoresistance ratio depends little on the magnetic field direction and is described by a simple universal function of mu(B)B/k(B)T, where mu(B) is the Bohr magneton. The positive magnetoresistance may be caused by magnetic-field-induced parallel alignment of spins of mobile and localized electrons, and a resulting blockade of electrical conduction due to the Pauli exclusion principle.     

Unique Separation Behavior of a C60 Fullerene‐Bonded Silica Monolith Prepared by an Effective Thermal Coupling Agent

Herein, we report a newly developed C₆₀ fullerene‐bonded silica monolith in a capillary with unique retention behavior due to the structure of C₆₀ fullerene. N‐Hydroxysuccinimide (NHS)‐conjugated C₆₀ fullerene was successfully synthesized by a thermal coupling agent, perfluorophenyl azide (PFPA), and assigned by spectroscopic analyses. Then, NHS‐PFPA‐C₆₀ fullerene was attached onto the surface of a silica monolith in a capillary. The capillary provided specific separation ability for polycyclic aromatic hydrocarbons in liquid chromatography by an effective π–π interaction. Furthermore, corannulene, which has a hemispherical structure, was selectively retained in the capillary based on the specific structural recognition due to the spherical C₆₀ fullerene. This is the first report revealing the spherical recognition ability by C₆₀ fullerene in liquid chromatographic separation.     

Determination of bismuth in geological materials by automated hydride generation and electrothermal atomic absorption spectrometry

The rapid and precise determination of bismuth (>5 μg kg^?1 in geological materials is described. The sample is decomposed with a HClO₄/HNO₃/HF mixture; interferences are eliminated by addition of aluminium chloride, ascorbic acid and thiourea. Bismuth hydride is introduced into a quartz cell atomizer.     

Epitaxial thin films of ATiO(3-x)H(x) (A = Ba, Sr, Ca) with metallic conductivity

Epitaxial thin films of titanium perovskite oxyhydride ATiO(3-x)H(x) (A = Ba, Sr, Ca) were prepared by CaH(2) reduction of epitaxial ATiO(3) thin films deposited on a (LaAlO(3))(0.3)(SrAl(0.5)Ta(0.5)O(3))(0.7) substrate. Secondary ion mass spectroscopy detected a substantial amount and uniform distribution of hydride within the film. SrTiO(3)/LSAT thin film hydridized at 530 °C for 1 day had hydride concentration of 4.0 × 10(21) atoms/cm(3) (i.e., SrTiO(2.75)H(0.25)). The electric resistivity of all the ATiO(3-x)H(x) films exhibited metallic (positive) temperature dependence, as opposed to negative as in BaTiO(3-x)H(x) powder, revealing that ATiO(3-x)H(x) are intrinsically metallic, with high conductivity of 10(2)-10(4) S/cm. Treatment with D(2) gas results in hydride/deuteride exchange of the films; these films should be valuable in further studies on hydride diffusion kinetics. Combined with the materials' inherent high electronic conductivity, new mixed electron/hydride ion conductors may also be possible.     

Novel surface-modification techniques for polymer-based separation media. Stimulus-responsive phenomena based on double polymeric selectors

A pair of polymeric selectors potentially responding to stimulation was introduced onto monosized porous polymer particles to be evaluated as a packing material for HPLC. Possible complexes formed between polyacrylamide (PAAm) and poly(methacrylic acid) (PMAA) were utilized as stimulus responsive polymeric selectors. Uniformly sized base polymer particle was prepared by multi-step swelling and polymerization method, while the introduction of PAAm and PMAA was done by newly invented modification technique. In this technique, a solvent in which both acrylamide (AAm) and methacrylic acid (MAA) monomers are soluble, but PAAm and PMAA are insoluble, was utilized as a modification medium. The polymer particle doubly modified with PAAm and PMAA was utilized as packing material for HPLC and the stimulus responses were evaluated by changing temperature or pH to check change of the slope of a Van't Hoff plot. By using water as a mobile phase, the expected inflection point of the Van't Hoff plot was observed at upper critical solution temperature (UCST) of the polymer complexes and the temperature responsive ability was observed. Moreover, pH responsive ability was studied by using buffer of either pH 4 or 10 as mobile phase. Slope of the plot was changed in buffer of pH 4, but no change of slope was observed in the buffer of pH 10.     

Amphiphilic fluorous random copolymer self‐assembly for encapsulation of a fluorinated agrochemical

Amphiphilic self‐folding random copolymers exhibit different solution behaviors depending on the identity of the hydrophobic/hydrophilic units. Herein, it is demonstrated that changing the hydrophilic unit from poly(ethylene glycol) to the sugar trehalose causes increased discrepancy in the polarity difference with a fluorinated hydrophobic segment and changes the aggregation state of the polymer in water. The PEG‐fluorinated and trehalose/PEG‐fluorinated amphiphilic random copolymers were the most efficient at encapsulating a fluorinated agrochemical. The small‐molecule agrochemical exerts a strong influence on the self‐assembly of the polymers, demonstrating that fluorous interactions result in not only intramolecular self‐folding behavior but also intermolecular polymer association to form well‐defined nanoparticles. © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2019 , 57, 352–359     

Synthesis of diversely functionalized hexahydropyrrolo[2,3-b]indoles using domino reactions, olefination, isomerization and Claisen rearrangement followed by reductive cyclization

Hexahydropyrrolo[2,3-b]indoles 6 were synthesized in five steps from indolin-3-one 8 by a general and efficient method, in which elements of molecular diversity were readily added onto the 3a-position of the pyrrolo[2,3-b]indole ring system. Horner-Wadsworth-Emmons reaction of 2-allyloxyindolin-3-ones 7, derived from indolin-3-one 8 and a variety of allylic alcohols, smoothly proceeded with successive Claisen rearrangement to give the corresponding 3-allyl-3-cyanomethylindolin-2-ones 15. Indolin-2-ones 15 were converted into pyrrolo[2,3-b]indoles 6 using partial hydrolysis followed by reductive cyclization with LiAlH(4). Synthesis of N-methylated pyrrolo[2,3-b]indole derivatives 23 and 26 is also described.     

Fabrication of Ge-channel MOSFETs by using replacement gate process and selective epitaxial growth

We fabricated Ge-channel metal-oxide-semiconductor field-effect transistors (MOSFETs) by using replacement gate process and selective epitaxial growth. In our method, thin Ge layers were selectively grown on the channel region of MOSFETs after the removal of a sacrificial gate stack structure and the etching of the channel region. Ge layers with a smooth surface and a good morphology could be obtained by using the thin Si_0.5Ge_0.5 buffer layer. Dislocations were observed in the epitaxial layers and near the interface between the epitaxial layer and the substrates. We consider that these dislocations degrade the device performance. Although the electrical characteristics of the obtained MOSFETs need further improvement, our method is one of the promising candidates for the practical fabrication process of Ge-channel MOSFETs.