Direct and indirect electrochemical generation of alkoxycarbenium ion pools from thioacetals

Thioacetals were found to be effective precursors to generate and accumulate alkoxycarbenium ions based on direct and indirect cation pool methods. Alkoxycarbenium ions thus generated reacted with carbon nucleophiles such as allylsilanes and enol silyl ethers to give C-C bond formation products in good yields.     

Ruthenium-catalyzed [1,n]-metallotropic shift (n = 3, 5) of alkynyl carbene complex intermediates

The ruthenium-catalyzed isomerization of diynes and triynes involving propargyl carboxylate moieties affords dienynes and dienediynes, respectively. The [1,n]-metallotropic shift (n = 3, 5) (carbene walk) of in situ generated alkynyl carbene complexes has been proposed for the catalytic isomerization reaction.     

Indirect cation pool method. Rapid generation of alkoxycarbenium ion pools from thioacetals

A sequential one-pot indirect cation pool method has been developed. The method involves the electrochemical generation and accumulation of ArS(ArSSAr)+ at low temperature (step 1) and the follow-up reaction with a thioacetal to generate an alkoxycarbenium ion pool (step 2), which reacts with various carbon nucleophiles (step 3). Steps 2 and 3 are extremely fast. The electrogenerated ArS(ArSSAr)+ was well-characterized by 1H NMR and CSI-MS. The alkoxycarbenium ion pool generated by the present indirect method exhibited 1H and 13C NMR spectra and thermal stability similar to those of the alkoxycarbenium ion pool generated by the direct electrochemical method.     

Direct and selective benzylic oxidation of alkylarenes via C-H abstraction using alkali metal bromides

A direct benzylic oxidation of alkylarenes via C-H bond abstraction was developed using alkali metal bromides and oxidants under mild conditions. This reaction proceeded with excellent selectivity by thermal oxidation or photooxidation to provide a broad range of carbonyl compounds containing electron-deficient aryl carbonyl compounds in high yields.     

Ladder oligo(m-aniline)s: derivatives of azaacenes with cross-conjugated π-systems

We describe the synthesis and electronic properties of ladder oligomers of poly(m-aniline) that may be considered as derivatives of azaacenes with cross-conjugated π-systems. Syntheses of ladder oligo(m-aniline)s with 9 and 13 collinearly fused six-membered rings employed Pd-catalyzed aminations and Friedel-Crafts-based ring closures. Structures were confirmed by either X-ray crystallography or correlations between DFT-computed and experimental spectroscopic data such as (1)H, (13)C, and (15)N NMR chemical shifts and electronic absorption spectra. All compounds have planar "azaacene" moieties. The experimental band gaps E(g) ≈ 3.5-3.65 eV, determined by the UV-vis absorption onsets, were in agreement with the TD-DFT-computed vertical excitation energies to the S(1) state. Fluorescence quantum yields of up to 20% were found. Electrochemically estimated HOMO energies of -4.8 eV suggested propensity for a facile one-electron oxidation and just sufficient environmental stability toward oxygen (O(2)). For two oligomers with "tetraazanonacene" moieties, potentials of E(4+/3+) ≈ 1.6-1.7 V vs SCE were determined for four-electron oxidation to the corresponding tetraradical tetracations.     

On the security analysis of an image scrambling encryption of pixel bit and its improved scheme based on self-correlation encryption

An image scrambling encryption scheme for pixel bits was presented by Ye [Ye GD. Image scrambling encryption algorithm of pixel bit based on chaos map. Pattern Recognit Lett 2010;31:347-54], which can be seen as one kind of typical binary image scrambling encryption considering from the bit-plain of size M × (8N). However, recently, some defects existing in the original image encryption scheme, i.e., Ye’s scheme, have been observed by Li and Lo [Li CQ, Lo KT. Optimal quantitative cryptanalysis of permutation-only multimedia ciphers against plaintext attacks. Signal Process 2011;91:949-54]. In the attack proposed by Li and Lo at least 3 + ⌈log₂(MN)⌉ plain images of size M × N are used to reveal the permutation matrix W = [w(i, k)] (i ∈ {1, 2, … , M}; k ∈ {1, 2, … , 8N}) which can be applied to recover the exact plain image. In the current paper, at first, one type of special plain image/cipher image is used to analyze the security weakness of the original image scrambling scheme under study. The final encryption vectors TM and TN or the decryption vectors TM′ and TN′ are revealed completely according to our attack. To demonstrate the performance of our attack, a quantified comparison is drawn between our attack and the attack proposed by Li and Lo. Compared with Li and Lo’s attack, our attack is more efficient in the general conditions. In particular, when the sizes of images satisfy the condition M = N or M ? 8N, the number of the used plain images/cipher images is at most 9, which is sharply less than 3 + ⌈log₂(MN)⌉ when M and N are of large size. To overcome the weaknesses of the original scheme, in this paper, an improved image scrambling encryption scheme is proposed. In the improved scheme, the idea of the “self-correlation” method is used to resist the chosen-plaintext attack/known-plaintext attack. The corresponding simulations and analyses illustrate that the improved encryption method has good cryptographic properties, and can overcome the weakness of the original image encryption scheme. Finally, farther improvement is briefly presented for the future work.     

On Spectral Polynomials of the Heun Equation. II

The well-known Heun equation has the form

Detection Limits of Grazing-Exit EPMA for Particle Analysis

 In conventional electron probe microanalysis (EPMA), the electron-induced X-rays are measured at large take-off angles of about 45°. In the grazing exit EPMA (GE-EPMA) method, they are measured at small angles (< 1°). X-rays emitted from deep positions can not be detected at grazing exit angles due to refraction effects at sample-vacuum interface; therefore, it is possible to measure X-rays emitted only from near the surface with a low background. GE-EPMA is especially suitable for the analysis of particles deposited on a flat sample carrier. The detection limits of GE-EPMA were investigated for artificial particles (Al₂O₃, Fe₂O₃ and PbO₂ , particle sizes: 1 ∼ 18 μm) deposited on flat sample carriers of Au thin films–Si wafers. The detection limits improved with decreasing exit angle. The detection limits for characteristic X-rays at an exit angle of approximately 1.1° were 2–4 times lower than at 45°. A minimum detection limit of ca. 0.1% was obtained for Al in small particles.     

A theoretical study on the ionization of OCS with an analysis of vibrational structures of the photoelectron spectrum

 Ab initio calculations have been performed to study the molecular structures and vibrational levels of the four low-lying ionic states (1, 2²Π, and 1, 2²Σ⁺) of carbonyl sulfide. The global regions of the potential-energy surfaces have been obtained by multireference single and double excitation configuration interaction calculations. Vibrational calculations using explicit vibrational Hamiltonians have been used for vibrational analysis. The equilibrium molecular structures and a vibrational analysis of the four ionic states are presented. The theoretical ionization intensity curves including the vibrational structures of the ionic states are also presented and are compared with the photoelectron spectrum. Received: 20 January 2001 / Accepted: 22 August 2001 / Published online: 30 October 2001     

The Heun Equation and the Calogero-Moser-Sutherland System I: The Bethe Ansatz Method

 We propose and develop the Bethe Ansatz method for the Heun equation. As an application, holomorphy of the perturbation for the BC ₁ Inozemtsev model from the trigonometric model is proved. Received: 28 September 2001 / Accepted: 31 October 2002 Published online: 31 January 2003 Communicated by L. Takhtajan