Developments of nano-polycrystalline diamond anvil cells for neutron diffraction experiments

ABSTRACT

A new high pressure cell for neutron diffraction experiments using nano-polycrystalline anvils is presented. The cell design, off-line pressure generation tests and a gas-loading procedure for this cell are described. The performance is illustrated by powder neutron diffraction patterns of ice VII to ～82?GPa. We also demonstrate the feasibility of single crystal neutron diffraction experiments of Fe₃O₄ at ambient conditions using this cell and discuss the current limitation and future developments.     

A tensor product of the Steinberg module and a certain simple kG(pr)-module

Let G be a connected, semisimple, and simply connected algebraic group defined and split over the finite field of order p, and let G(q) be the corresponding finite Chevalley or twisted group, where q = p^r. Recently, Anwar determines the direct sum decomposition of the tensor product of the rth Steinberg module and a simple G-module with a (p,r)-minuscule highest weight λ. In this paper, we determine that of the tensor product regarded as a module for G(q) under some weak assumptions for λ.     

Controlled Reduction of Carboxamides to Alcohols or Amines by Zinc Hydrides

New protocols for controlled reduction of carboxamides to either alcohols or amines were established using a combination of sodium hydride (NaH) and zinc halides (ZnX₂). Use of a different halide on ZnX₂ dictates the selectivity, wherein the NaH‐ZnI₂ system delivers alcohols and NaH‐ZnCl₂ gives amines. Extensive mechanistic studies by experimental and theoretical approaches imply that polymeric zinc hydride (ZnH₂)_∞ is responsible for alcohol formation, whereas dimeric zinc chloride hydride (H?Zn?Cl)₂ is the key species for the production of amines.     

Synthesis of bis(N-heterocyclic carbene) palladium complexes derived from (S,S)-1,2-bis(1-hydroxypropyl)benzene

New o-xylylene-linked bis(benzimidazolium) salts were synthesized in six-steps from C₂-symmetric chiral 1,4-diol, 1,2-bis(1-hydroxypropyl)benzene, as a starting material. The silver complex of bis(benzimidazol-2-ylidene) was obtained on treatment of bis(benzimidazolium) salt with silver oxide. The reaction of the silver bis-NHC with [PdCl₂(PhCN)₂] afforded the bis-NHC complex of palladium. The X-ray diffraction studies on Pd complexes revealed that these complexes have distorted square planar geometry around the Pd center coordinating the NHC ligand in mutually cis-position. The arene ring of o-xylylene unit hanged over the Pd center and thus these complexes showed C₁-symmetric structures. The variable temperature NMR spectroscopy revealed that these Pd complexes showed fluxional behavior between C₁- and C₂-symmetric structures in solution state.     

Improvement of water vapor adsorption ability of natural mesoporous material by impregnating with chloride salts for development of a new desiccant filter

The aim of this study is the development of a new adsorbent for the desiccant material which can be regenerated by the domestic exhaust heat by using natural mesoporous material, Wakkanai siliceous shale. To improve this shale’s performance to adsorb/desorb the water vapor, lithium chloride, calcium chloride or sodium chloride was supported into the mesopores by impregnating with each chloride solution. Especially sodium chloride was effective to increase the water vapor adsorption amount 5–7 times of that of natural shale in the relative humidity range from 50 to 70%. Moreover, the appropriate impregnating concentrations were determined as 5wt% from the relationship between the maximum water vapor adsorption amount and the mesopore volume. Based on these results, a new desiccant filter has been developed by impregnated original paper with lithium chloride and sodium chloride. This paper contained shale powder in the synthetic fibers. The dehumidification performance of this filter was evaluated under the simulated summer condition in Tokyo. From the cyclic adsorption/regeneration test, this shale and chlorides filter could adsorb and desorb 60 g/h water vapor repeatedly at the regeneration temperature of 40°C. On the other hand, a silica gel filter and a zeolite filter adsorbed and desorbed only 10 g/h and 25 g/h, respectively. These results suggested that the shale impregnated with the chlorides has the best dehumidification ability as a new desiccant material. Further, the desiccant filter made from the shale will achieve the effective use of the low temperature exhaust heat.     

Fast multipole method for three-dimensional systems with periodic boundary condition in two directions

We derived a new expression for the electrostatic interaction of three-dimensional charge-neutral systems with two-dimensional periodic boundary conditions (slab geometry) using a fast multipole method (FMM). Contributions from all the image cells are expressed as a sum of real and reciprocal space terms, and a self-interaction term. The reciprocal space contribution consists of two parts: zero and nonzero terms of the absolute value of the reciprocal lattice vector. To test the new expressions, electrostatic interactions were calculated for a randomly placed charge distribution in a cubic box and liquid water produced by molecular dynamics calculation. The accuracy could be controlled by the degree of expansion of the FMM. In the present expression, the computational complexity of the electrostatic interaction of N-particle systems is order N, which is superior to that of the conventional two-dimensional periodic Ewald method for a slab geometry and the particle mesh Ewald method with a large empty space at an interface of the unit cell. © 2020 Wiley Periodicals, Inc.     

Simultaneous determination of tetracyclines and their degradation products in environmental waters by liquid chromatography–electrospray tandem mass spectrometry

A sensitive method was developed for the trace determination of six tetracyclines and ten of their degradation products in influent, effluent, and river waters using liquid chromatography–electrospray tandem mass spectrometry detection, combined with Oasis hydrophilic–lipophilic balance (HLB) cartridge extraction and Oasis mixed-mode strong anion exchange (MAX) cartridge cleanup. Tetracyclines and their products were separated by liquid chromatography in 9.5 min, and the instrument detection limits were generally between 0.03 and 0.1 μg/L except for minocycline (0.5 μg/L). The chromatograms were improved through the MAX cleanup and no apparent matrix effect was found. The recoveries of all the target compounds except for 4-epianhydrochlortetracycline and anhydrochlortetracycline (34–52%) were 75–120% for influent, 61–103% for effluent, and 64–113% for river waters. The method detection limits (MDLs) of the analytes varied in the range of 0.8–17.5 ng/L in all studied matrices. The method was applied for the determination of tetracyclines and their products in a sewage treatment plant (STP) and surface waters in Beijing, China. Oxytetracycline (3.8–72.5 ng/L), tetracycline (1.9–16.5 ng/L), and five products including 4-epitetracycline, 4-epioxytetracycline, isochlortetracycline, anhydrotetracycline, and 4-epianhydrochlortetracycline (5.7–25.3 ng/L) were detected in wastewater, while only oxytetracycline and tetracycline (2.2 and 2.1 ng/L) were detected in surface water samples.     

Total Synthesis and Biological Evaluation of (+)‐Neopeltolide and Its Analogues

The stereocontrolled total synthesis of the originally proposed ( 1 ) and correct ( 2 ) structures of (+)‐neopeltolide, a novel marine macrolide natural product with highly potent antiproliferative activity against several cancer cell lines as well as potent antifungal activity, has been achieved by exploiting a newly developed Suzuki–Miyaura coupling/ring‐closing metathesis strategy. Alkylborate 44 , which was generated in situ from iodide 34 , was coupled with enol phosphate 8 by a Suzuki–Miyaura coupling. Ring‐closing metathesis of the derived diene 45 followed by stereoselective hydrogenation afforded tetrahydropyran 47 as a single stereoisomer in high overall yield from 34 . Our convergent strategy enabled us to construct the 14‐membered macrolactone core structure of 2 in a rapid and efficient manner. Total synthesis and biological evaluation of synthetic intermediates and designed synthetic analogues, performed to establish the structure–activity relationships of 2 , led to the discovery of a structurally simple yet potent cytotoxic analogue, 9‐demethylneopeltolide ( 54 ).     

Radiation Crosslinking of Chlorinated Poly(Isobutylene-co-Isoprene) with Polyfunctional Monomers

Abstract

It is well known that poly(isobutylene-co-isoprene) (butyl rubber, IIR) is degraded by irradiation. However, we demonstrated that IIR, after chlorination (CIIR) crosslinks by electron beam (EB) irradiation. The gel dose for CIIR was 3.8 kGy. To avoid scission of the main chain, various polyfunctional monomers were added for crosslinking of CIIR at lower doses. It was found that trimethylolpropane trimethacrylate (TMPT) is the most effective accelerator for crosslinking of CIIR at a lower dose. The tensile strength of EB crosslinked by CIIR increases almost linearly with increasing TMPT content.     

Synthesis of chiral 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine and their application to enantioselective borane reduction of prochiral ketones as chiral catalysts

Chiral diamines, 2-(anilinophenylmethyl)pyrrolidines and 2-(anilinodiphenylmethyl)pyrrolidine, were prepared from N-(tert-butoxycarbonyl)pyrrolidine or (S)-proline as a starting material, respectively. These chiral diamines were efficient for the catalytic enantioselective borane reduction of acetophenone. Using (S)-2-(anilinodiphenylmethyl)pyrrolidine, chiral secondary alcohols were obtained from prochiral ketones with good to excellent enantiomeric excesses (up to 98% ee).