Self-assembly of ionic liquid (BMI-PF6)-stabilized gold nanoparticles on a silicon surface: chemical and structural aspects

Ultrafine monodisperse gold nanoparticles (AuNPs) were synthesized by an elegant sputtering of gold onto 1- n-butyl-3-methylimidazolium hexafluorophosphate (BMI-PF(6)) ionic liquid. It was found that the BMI-PF(6) supramolecular aggregates were loosely coordinated to the gold nanoparticles and were replaceable with thiol molecules. The self-assembly of BMI-PF(6)-stabilized AuNPs onto a (3-mercaptopropyl)trimethoxysilane (MPS)-functionalized silicon surface in 2D arrays, followed by dodecanethiol (DDT) treatment, have been demonstrated using X-ray photoelectron spectroscopy, field emission scanning electron microscopy, and contact angle measurements. DDT treatment of tethered AuNPs revealed two types of interactions between AuNPs and the MPS-functionalized surface: (a) AuNPs anchor through Au-S chemisorption linkage resulting in strong immobilization and (b) some of the AuNPs are supported by physisorption, driven by BMI-PF(6). The attachment of these particles remains unchanged with sonication. The replacement of BMI-PF(6) aggregates from physisorbed AuNPs with DDT molecules advances the dilution of their interaction with the MPS-functionalized surface, and they subsequently detach from the silicon surface. The present finding is promising for the immobilization of ionic liquid-stabilized nanoparticles, which is very desirable for electronic and catalytic device fabrication. Additionally, these environmentally friendly AuNPs are expected to replace conventional citrate-stabilized AuNPs.     

Superiority of a new gradient system utilizing a critical threshold for the adsorption capacity of polypeptides to column packing when compared with a standard gradient system for the simultaneous and quantitative analysis of polypeptides

Compared with a standard gradient system, the new gradient system which we developed has a major advantage because it permits a wide range of acetonitrile content, e.g. more than the critical threshold, in the polypeptide solution and allows the quantitative analysis of the polypeptide with satisfactory analytical precision. Additionally, this new gradient system allows the enhancement of the sensitivity of the polypeptide analysis proportionate to the increased volume of solution loaded with the same levels of precision. In contrast, when using a standard gradient system it is difficult to analyze a polypeptide quantitatively with good precision due to either adsorption to various materials or to irregular change in the ratio between a retained and a passed peak of the polypeptide. Additionally, the appearance of a passed peak results in a loss in the sensitivity of the polypeptide analysis, although no adsorption of a polypeptide to various materials occurs in a solution with acetonitrile content more than the critical threshold. Consequently, the new gradient system is effective for the simultaneous and quantitative analysis of different polypeptides with good precision and without any loss of sensitivity due to either adsorption to various materials or the appearance of a passed peak.     

Stable ion NMR and GIAO-DFT study of novel cations from 8,16-dicyano[2.2]metacyclophanedienes and from strategically substituted/benzannelated dihydropyrenes: charge-induced tropicity modulation and pi-switching

The dicyanometacyclophanediene 1 is diprotonated at the cyano groups (1H2 2+) in various superacid media. Upon quenching, intact 1 and the ring-closed CPD 2 were obtained in a 3:2 or 3:1 ratio, depending on the superacid system. Compound 2 undergoes ring opening in the superacid to give the ipso-monoprotonated 2H+, which on quenching furnishes 1-cyanopyrene as a major product together with 2 and 1. The dication 3 2+, with strongly deshielded internal methyls, was generated from the epoxyannulene 3. Ketones 4-6 and ester 7 are O/C diprotonated to give paratropic carboxonium-annulenium dications (4H2 2+, 5H2 2+, 6H2 2+, and 7H2 2+, respectively). Ester 8 gives a trication by two-electron oxidation and O-protonation. Conjugated carboxylic acid 9 gives a mixture of two dications by CO and ring protonation. The dibromo derivatives 10 and 11 form carboxonium ions, whereas the monobromo derivative 12 is O/C diprotonated to give an oxonium-annulenium dication. Charge delocalization modes and tropicity in the resulting species are evaluated by NMR and GIAO-DFT. Facile formation of 2 from 1 in quenching experiments indicates that thermal closing can be achieved with the diprotonated dinitrile, without imposing skeletal rearrangement.     

The Chemistry of Stable Silabenzenes

Stable silabenzenes ( 1a; R = Tbt, 1b; R = Bbt) were synthesized by taking advantage of extremely bulky and efficient steric protection groups, 2,4,6‐tris[bis(trimethylsilyl)methyl]phenyl (Tbt) and 2,6‐bis‐[bis(trimethylsilyl)methyl]‐4‐[tris(trimethylsilyl)methyl]phenyl (Bbt). The structure of Tbt‐substituted 1a was determined by X‐ray crystallographic analysis, which demonstrated the complete delocalization of the π‐electrons of the silabenzene ring. It was found that silabenzene 1a reacted with C–C and C–O multiple bond compounds to give the corresponding [4+2]‐cycloadducts via 1,4‐addition, while 1a underwent both 1,2‐ and 1,4‐additions by the reaction with methanol. Silabenzene 1a dimerized very gradually to afford its [4+2]‐dimer, although 1b showed no change under the same conditions. Photochemical reaction of 1a gave the corresponding silabenzvalene isomer instead of the Dewar silabenzene isomer.     

Toric Rings Arising from Cyclic Polytopes

Let d and n be positive integers with n ≥ d + 1 and 𝒫 ? ? ^d an integral cyclic polytope of dimension d with n vertices, and let K[𝒫] = K[?_≥0𝒜_𝒫] denote its associated semigroup K-algebra, where 𝒜_𝒫 = {(1, α) ∈ ? ^d+1: α ∈ 𝒫} ∩ ? ^d+1 and K is a field. In the present paper, we consider the problem when K[𝒫] is Cohen–Macaulay by discussing Serre's condition (R ₁), and we give a complete characterization when K[𝒫] is Gorenstein. Moreover, we study the normality of the other semigroup K-algebra K[Q] arising from an integral cyclic polytope, where Q is a semigroup generated by its vertices only.     

Internal reflectance spectroscopy associated with cyclic staircase voltammetry using a microcomputer

In order to obtain extensive information on electrode-solution interfaces, a rapid-scan internal reflectance spectroscopic system is combined with cyclic staircase voltammetry; the staircase wave generated by computer software is applied to an optically transparent tin oxide electrode. The internal reflectance spectrum is measured at each step of the applied staircase voltage simultaneously with the instantaneous current.     

ESR study on the structure of the ethylene radical cation stabilized in frozen SF6 and some fluoroalkanes: An evidence for a twisted structure

ESR spectra of the ethylene radical cation were detected at cryogenic temperatures in SF₆, C₂F₆ and C₃F₈. From the unusually small hyperfine couplings estimated for¹H and¹³C, it has been shown that the ethylene radical cation has a non-planar structure with a torsional angle in the range of 8°–23°. Upon annealing the sample at a temperature above 93 K, the ethylene radical cation in SF₆ changed into a monofluoroethyl radical through charge recombination with fluoride anion or SF ₆ ^? .     

Identification of a dehydrodimer of avenanthramide phytoalexin in oats

A new compound (1) was found to accumulate when oat leaves were treated with elicitors. A reaction with peroxidase and avenanthramide B, an oat phytoalexin, in the presence of hydrogen peroxide resulted in the formation of 1. The chemical structure of 1 was determined to be a cyclic dehydrodimer of avenanthramide B based on spectroscopic analyses and chemical derivatization, and 1 was named bisavenanthramide B.