Hyperaromatic stabilization of arenium ions

Benzene-cis- and trans-1,2-dihydrodiols undergo acid-catalyzed dehydration at remarkably different rates: k(cis)/k(trans) = 4500. This is explained by formation of a β-hydroxycarbocation intermediate in different initial conformations, one of which is stabilized by hyperconjugation amplified by an aromatic no-bond resonance structure (HOC(6)H(6)(+) ? HOC(6)H(5) H(+)). MP2 calculations and an unfavorable effect of benzoannelation on benzenium ion stability, implied by pK(R) measurements of -2.3, -8.0, and -11.9 for benzenium, 1-naphthalenium, and 9-phenanthrenium ions, respectively, support the explanation.     

Statistical quality control for ternary ordinal quality data

The paper considers various aspects of statistical quality control by means of sample data received on a ternary ordinal scale. A new method for evaluating quality level and dispersion, free of any latent numerical scale assumptions, is proposed. The emphasis is on working with large samples, which enable the statistical analysis, estimation and control by the use of approximate analytical expressions of these measures to be considerably simplified. Two complementary studies demonstrate the usage of the proposed approach. Copyright © 2010 John Wiley & Sons, Ltd.     

Synthesis and characterization of LaB6 thin films on tungsten, rhenium, silicon and other substrates and their investigations as?field emitters

The paper deals with the comparative study of nanocrystalline Lanthanum hexaboride (LaB₆) thin films grown on various substrates by Pulsed laser deposition and Arc plasma method. Field emission studies were carried out on LaB₆ films deposited on various substrates show metallic behavior of the emitters. The high value of field enhancement factors, indicating that the electron emission from LaB₆ nanoscale protrusions deposited on emitter surface. The post field emission surface morphology of the emitters showed no significant erosion of the films during continuous operation. The observed behavior indicates that it is linked with the growth of LaB₆ films on substrate crystal structure. The LaB₆ nanocrystallites/nanowires films were synthesized using arc plasma method shows good emission current stability. The LaB₆ micro/nanocrystallites were also obtained by picosecond laser irradiation which gives high enhancement β factor, and good emission current stability along with high current density. The results reveal that nanocrystalline LaB₆ films, exhibit high resistance to ion bombardment and excellent structural stability and are more promising emitters for practical applications in field emission based new generation devices.     

Excellent Stability of a Lithium‐Ion‐Conducting Solid Electrolyte upon Reversible Li+/H+ Exchange in Aqueous Solutions

Batteries with an aqueous catholyte and a Li metal anode have attracted interest owing to their exceptional energy density and high charge/discharge rate. The long‐term operation of such batteries requires that the solid electrolyte separator between the anode and aqueous solutions must be compatible with Li and stable over a wide pH range. Unfortunately, no such compound has yet been reported. In this study, an excellent stability in neutral and strongly basic solutions was observed when using the cubic Li₇La₃Zr₂O₁₂ garnet as a Li‐stable solid electrolyte. The material underwent a Li⁺/H⁺ exchange in aqueous solutions. Nevertheless, its structure remained unchanged even under a high exchange rate of 63.6 %. When treated with a 2 M LiOH solution, the Li⁺/H⁺ exchange was reversed without any structural change. These observations suggest that cubic Li₇La₃Zr₂O₁₂ is a promising candidate for the separator in aqueous lithium batteries.     

A Facile Diversity‐Oriented Multicomponent One‐Pot Synthesis of 3‐Amino‐6,7‐dihydrobenzo[c]thiophen‐4(5H)‐one Derivatives from α‐Oxo‐N,S‐ketene Acetal

A convenient one‐pot multicomponent method for the preparation of 3‐amino‐6,7‐dihydrobenzo[c]thiophen‐4(5H)‐one derivative has been developed. Reaction of 1,3‐cyclohexanedione and phenyl isothiocynate gave α‐oxo‐N,S‐ketene acetal that were reacted in situ with 2‐chloromethylquniazoline‐4‐one derivatives, in the presence of sodium hydride to afford the target compound in reasonable overall yields.     

Some metrological aspects of the comparison between two ordinal measuring systems

The usage of ordinal scales (sometimes called ‘semi-quantitative’ scales) for performing measurements in the area of applied chemical metrology and quality assurance is widespread. This paper presents a method for handling actions such as calibration, measuring systems’ capabilities comparison and reproducibility evaluation as a comparison between two measuring systems (MSs) referring to a known/unknown reference standard. The strength of the agreement between these MSs is evaluated through two known versions of Cohen’s kappa statistics (the traditional one and the modified one). The effectiveness of these statistics from the metrological point of view is examined, and the preferability of the modified kappa statistics is demonstrated via an example.     

Multi-component, regio-selective aldol addition of β-ketoesters to aldehydes: scope and applications

Simple and effective multi-component one-pot aldol addition/protection reactions of β-ketoesters to a series of aldehydes in the presence Me(3)SiCl and i-Pr(2)EtN have been described. The analysis of the scope of the reaction revealed a dramatic dependence of the reactivity on the substrates used. Thus the effect of a catalytic amount of DMF and different reaction conditions was widely investigated. Further transformations of the aldol adducts were particularly useful to give valuable diols and compounds with quaternary stereocenters, while X-ray structural analysis gave also important stereochemical information about this challenging reaction.     

Logic of secrets in collaboration networks

The article proposes Logic of Secrets in Collaboration Networks, a formal logical system for reasoning about a set of secrets established over a fixed configuration of communication channels. The system’s key feature, a multi-channel relation called independence, is a generalization of a two-channel relation known in the literature as nondeducibility. The main result is the completeness of the proposed system with respect to a semantics of secrets.     

Hyperaromatic stabilization of arenium ions: a remarkable cis stereoselectivity of nucleophilic trapping of β-hydroxyarenium ions by water

Cis- and trans-1,2-dihydrodiol isomers of benzene undergo acid-catalyzed dehydration to form phenol. In principle the isomeric substrates react through a common β-hydroxybenzenium (cyclohexadienyl) carbocation. Notwithstanding, the isomers show a large difference in reactivity, k(cis)/k(trans) = 4500. This difference is reduced to k(cis)/k(trans) = 440 and 50 for the 1,2-dihydrodiols of naphthalene and 9,10-dihydrodiols of phenanthrene, respectively, and to 6.9 for the dihydrodiols of the nonaromatic 7,8-double bond of acenaphthylene. Because the difference in stabilities of cis- and trans-dihydrodiols should be no more than 2-3-fold, these results imply a high cis stereoselectivity for nucleophilic trapping of a β-hydroxyarenium cation by water in the reverse of the carbocation-forming reaction. This is confirmed by studies of the 10-hydroxy-9-phenanthrenium ion generated from aqueous solvolyses of the trans-9,10-bromohydrin derivative of phenanthrene and the monotrichloroacetate ester of the phenanthrene cis-9,10-dihydrodiol. The cis stereoselectivity of forward and reverse reactions is explained by the formation (in the "forward" reaction) of different conformations of carbocation from cis- and trans-dihydrodiol reactants with respectively β-C-H and β-C-OH bonds in pseudoaxial positions with respect to the charge center of the carbocation optimal for hyperconjugation. Formation of different conformations is constrained by departure of the (protonated) OH leaving group from a pseudoaxial position. The difference in stability of the carbocations is suggested to stem (a) from the greater hyperconjugative ability of a C-H than a C-OH bond and (b) from enhanced conjugation arising from the stabilizing influence of an aromatic ring in the no-bond resonance structures representing the hyperconjugation (C(6)H(6)OH(+) ? C(6)H(5)OH H(+)). This is consistent with an earlier suggestion by Mulliken and a demonstration by Schleyer that the benzenium ion is subject to hyperconjugative aromatic stabilization. It is proposed that, in analogy with the terms homoconjugation and homoaromaticity, arenium ions should be considered as "hyperaromatic".     

Guidelines for choosing molecular "alligator clip" binding motifs in electron transport devices

We employ a one-electron, tight-binding model of an electrode-molecule-electrode junction to explore the fundamental relationship between adsorption geometry and electron transport, producing exact results (within this model). By varying the chemisorption location (e.g., atop a surface atom or in a hollow site between surface atoms) and the molecule-electrode coupling, we find that the largest currents are realized when the molecule (i) is highly coordinated by the surface and (ii) has favorable overlap with electrode states near the Fermi level. We also show the importance of electrode-induced molecular level shifting for certain adsorption geometries, which can cause molecular levels far from the Fermi level to conduct better than those near the Fermi level. Since all of these factors are greatly influenced by the chemical moiety used to link the molecule to an electrode, these results present a set of guidelines to help choose "alligator clips" for molecular electronic devices.