Kinetics of phase transformation from hBN to cBN in the presence of Mg3BN3 catalyst

Abstract

Transformation kinetics from hBN to cBN has been studied at 6 GPa with changing reaction temperature and content of catalyst mixed with hBN powder. At lower catalyst content (3–10 wt %), rate of transformation was extraordinary rapid between 1300 and 1350 C. At higher catalyst content (30–50 wt %), rate of transformation was decreased. Normal nucleation kinetics was observed at about 1500 C. The rapid transformation temperature region correlates characteristic behavior of the sintering process.     

Enhancement of Magneto-Optic Effect in Optical Isolator with Semiconductor Guiding Layer by Selective Oxidation of AlInAs

Selective oxidation of an AlInAs layer was investigated for enhancement of magneto-optic effect in an optical isolator. Twelve times nonreciprocal phase shift enhancement was estimated from a measured AlInAs-oxide refractive index.     

Direct Addition of Amides to Glycals Enabled by Solvation‐Insusceptible 2‐Haloazolium Salt Catalysis

The direct 2‐deoxyglycosylation of nucleophiles with glycals leads to biologically and pharmacologically important 2‐deoxysugar compounds. Although the direct addition of hydroxyl and sulfonamide groups have been well developed, the direct 2‐deoxyglycosylation of amide groups has not been reported to date. Herein, we show the first direct 2‐deoxyglycosylation of amide groups using a newly designed Brønsted acid catalyst under mild conditions. Through mechanistic investigations, we discovered that the amide group can inhibit acid catalysts, and the inhibition has made the 2‐deoxyglycosylation reaction difficult. Diffusion‐ordered two‐dimensional NMR spectroscopy analysis implied that the 2‐chloroazolium salt catalyst was less likely to form aggregates with amides in comparison to other acid catalysts. The chlorine atom and the extended π‐scaffold of the catalyst played a crucial role for this phenomenon. This relative insusceptibility to inhibition by amides is more responsible for the catalytic activity than the strength of the acidity.     

Single-crystal-to-single-crystal photocyclization of 4-(2,4,6-triisopropylbenzoyl)benzoic acid in the salt crystal with (S)-phenylethylamine

Ultraviolet irradiation of a salt crystal of 4-(2,4,6-triisopropylbenzoyl)benzoic acid with (S)-phenylethylamine promoted single-crystal-to-single-crystal photocyclization to give an enantiopure (R,R)-cyclopentenol and almost racemic cyclobutenol. The reaction paths were elucidated by X-ray crystallographic analysis of the crystal before and after irradiation.     

Fabrication of novel layer-by-layer assembly films composed of poly(lactic acid) and polylysine through cation-dipole interactions

Novel layer-by-layer (LbL) assembly films composed of poly( L-lysine) (PLL) and poly( D-lactic acid) (PDLA) were prepared by the alternate immersion of a gold substrate into an aqueous PLL solution and an acetonitrile solution of PDLA. The formation of the LbL assembly film was confirmed by quartz crystal microbalance (QCM) analysis, atomic force microscopy observation, and attenuated total reflection Fourier transform infrared spectroscopy measurement. The driving force responsible for the LbL assembly was determined by investigating the formation behavior of the LbL assembly under various conditions. The formation of the LbL assembly was not affected either by the stereochemistry of polylysine and poly(lactic acid) or by the addition of urea, which is known to inhibit hydrogen bonding interaction between polymers, into the aqueous PLL solution. The LbL assembly was also formed by the combination of PDLA and polycations other than polylysine, such as poly(diallyldimethylammonium chloride). On the other hand, the combination of PDLA and any polyanions such as poly(styrene sulfonate sodium salt) produced little corresponding LbL assembly. The increase in positive charge on the amino nitrogen atom of PLL enhanced the LbL assembly. These results suggest that the LbL assembly film composed of PLL and PDLA was fabricated by cation-dipole interactions between the positive charge on the amino nitrogen atom of PLL and the lone pairs of the carbonyl oxygen atom of PDLA.     

Photoinduced tandem three-component coupling of propanedinitrile, 2,5-dimethylhexa-2,4-diene, and cyanoarenes

A tandem three-component coupling photoreaction proceeds upon photoirradiation of MeCN/H2O solutions containing propanedinitrile (1, malononitrile), 2,5-dimethylhexa-2,4-diene (2), and polycyanoarenes in the presence of phenanthrene and carbonate, leading to selective alpha-monoalkylation of 1. The reaction proceeds via photo-NOCAS (Nucleophile-Olefin Combination, Aromatic Substitution) type mechanism: nucleophilic attack of the anion of 1 to photogenerated 2(*+) is followed by ipso-substitution on the radical anion of the polycyanoarene. It advances under mild, safe, and environmentally friendly conditions such as proceeding at ambient temperature without metals and halogens, and in the presence of weak base. The reaction also represents a novel and metal-free cross-coupling reaction that leads to ipso-substitution on polycyanoarene via aryl-cyano bond cleavage. In addition, the reaction is a rare example of introducing carbon nucleophile in the photoinduced electron transfer reaction, except that of cyanide ion.     

Synthesis and spectroscopic studies of CoII, NiII, FeIII and ThIV complexes derived from 2,2'-dihydroxy-3,3'-di(carboxymethyl)-1,1'-binaphthyl

The synthesis of 2,2'-dihydroxy-3,3'-di(carboxymethyl)-1,1'-binaphthyl (H2L) and its novel metal complexes with Co(II), Ni(II), Fe(III) and Th(IV) salts are reported. The ligand and its metal complexes have been characterized on the basis of analytical, conductance, spectral (IR, UV-vis, 1H NMR, mass) and magnetic susceptibility measurements. The M?ssbauer spectrum of the Fe(III) complex indicates a low-spin octahedral geometry around the Fe(III) ion. The IR and 1H NMR spectral data show that the ligand behaves in a dibasic bidentate fashion coordinating to two metal atoms through the two deprotonated naphthyl OH groups and acts in a dibasic tetradentate manner using both carbonyl oxygen's and the deprotonated naphthyl OH groups coordinating to two metal ions. Thermal studies (TGA, DTA) confirm the presence of solvents either inside or outside the coordination sphere and support the mechanism of the decomposition process. The value of [alpha]D20 for the ligand has been determined in DMSO.     

Surface structure and interface dynamics of alkanethiol self-assembled monolayers on Au(111)

Scanning tunneling microscopy (STM) and high-resolution electron energy loss spectroscopy (HREELS) were used to examine the structural transitions and interface dynamics of octanethiol (OT) self-assembled monolayers (SAMs) caused by long-term storage or annealing at an elevated temperature. We found that the structural transitions of OT SAMs from the c(4 x 2) superlattice to the (6 x square root 3) superlattice resulting from long-term storage were caused by both the dynamic movement of the adsorbed sulfur atoms on several adsorption sites of the Au(111) surface and the change of molecular orientation in the ordered layer. Moreover, it was found that the chemical structure of the sulfur headgroups does not change from monomer to dimer by the temporal change of SAMs at room temperature. Contrary to the results of the long-term-stored SAMs, it was found that the annealing process did not modify either the interfacial or chemical structures of the sulfur headgroups or the two-dimensional c(4 x 2) domain structure. Our results will be very useful for a better understanding of the interface dynamics and stability of sulfur atoms in alkanethiol SAMs on Au(111) surfaces.     

Phosphatidylcholine vesicle-mediated decomposition of hydrogen peroxide

The decomposition of hydrogen peroxide (H2O2) was examined in aqueous solution (50 mM Tris-HCl buffer, pH 7.4, containing 100 mM NaCl) at 25 degrees C in pure buffer or in the presence of either vesicles or micelles formed from various phosphatidylcholines (PCs). In the absence of PCs, more than 90% of the initially added H2O2 (1.0 mM) remained intact after incubation for 120 h. The effect of the PCs on the decomposition of H2O2 was studied by using different PCs that varied in terms of number of carbon atoms in the two acyl chains n as well as in terms of the degree of unsaturation. PCs with short hydrocarbon chains (n = 4, 6-8) were dissolved in the buffer solution in the form of nonassociated monomers or as micelles in equilibrium with monomers at a fixed PC concentration of 10 mM. The presence of these short-chain PCs slightly enhanced the H2O2 decomposition rate. Micelles formed by non-lipid detergents (sodium cholate, Triton X-100, and sodium dodecylsulfate) had a similar effect. In marked contrast, PCs with long hydrocarbon chains (n > or = 10) dispersed in buffer solution as vesicles (liposomes) significantly enhanced the rate of H2O2 decomposition, with the most effective PC being 1,2-dimyristoyl-sn-glycero-3-phosphocholine (DMPC) at 25 degrees C. This indicates that the packing density of the PC molecules influences the reactivity, presumably through the direct interaction of the PC assemblies with H2O2 molecules. Furthermore, in the case of vesicles formed from PCs with unsaturated acyl chains (1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine, POPC; 1,2-dioleoyl-sn-glycero-3-phosphocholine, DOPC), carbon-carbon double bond oxidation did not occur extensively under the conditions used. This indicates that the observed effect of PCs on the decomposition of H2O2 is indeed related to the assembly structure (vesicle vs micelles vs monomers) and is clearly not related to the presence of unsaturated hydrocarbon chains. Fluorescence polarization measurements of two fluorescent probes embedded either in the acyl chain region of the vesicles (DPH, 1,6-diphenyl-1,3,5-hexatriene) or on the surface of the vesicles (TMA-DPH, 1-(4-trimethylammoniumphenyl)-6-phenyl-1,3,5-hexatriene iodide) show that the presence of H2O2 leads to a decrease in the fluidity of the lipid-water surface and not to a change in the fluidity of the hydrophobic region of the vesicle bilayer. This indicates that the decomposition of H2O2 is triggered through interactions between H2O2 and the polar head group area of PC vesicles.     

Competing forward and reversed chain reactions in one-dimensional molecular line growth on the Si(100)-(2 x 1)-H surface

To explore the role of competing forward and reversed chain reactions in the growth of a one-dimensional (1D) molecular line on the Si(100)-(2 x 1)-H surface, controlled experiments were performed with various alkene molecules by scanning tunneling microscopy (STM) at various temperatures. It was observed that the end dangling bond (DB) of a styrene line, fabricated by a chain reaction on the Si(100)-(2 x 1)-H surface at 300 K, initiated a reverse chain reaction at 400 K, leading to the complete disappearance of the styrene line with zero-order desorption kinetics (rate constant k = 1.17 x 10-2 s-1 at 400 K). In the case of 2,4-dimethylstyrene, the reversed chain reaction was observed even at 300 K. These results suggest that the appearance of a molecular line in an STM image is determined by the rates of competing forward and reversed chain reactions at a given temperature. As predicted, 1D lines formed by the DB-initiated chain reaction of 1-hexene and 1-heptene on Si(100)-(2 x 1)-H were observed at 180 K because of the reduced desorption rate, despite the fact that those molecules showed no line growth at 300 K. These results indicate that the scope of forming 1D molecular lines on the Si(100)-(2 x 1)-H surface with various alkenes is much wider than anticipated in previous studies.