All Non-Carbon B3NO2 Exotic Heterocycles: Synthesis,Dynamics, and Catalysis

The B₃NO₂ six-membered heterocycle (1,3-dioxa-5-aza-2,4,6-triborinane=DATB), comprising three different non-carbon period 2 elements, has been recently demonstrated to be a powerful catalyst for dehydrative condensation of carboxylic acids and amines. The tedious synthesis of DATB, however, has significantly diminished its utility as a catalyst, and thus the inherent chemical properties of the ring system have remained virtually unexplored. Here, a general and facile synthetic strategy that harnesses a pyrimidine-containing scaffold for the reliable installation of boron atoms is disclosed, giving rise to a series of Pym-DATBs from inexpensive materials in a modular fashion. The identification of a soluble Pym-DATB derivative allowed for the investigation of the dynamic nature of the B₃NO₂ ring system, revealing differential ring-closing and -opening behaviors depending on the medium. Readily accessible Pym-DATBs proved their utility as efficient catalysts for dehydrative amidation with broad substrate scope and functional-group tolerance, offering a general and practical catalytic alternative to reagent-driven amidation.     

Assessing the Error Probability of the Model Selection Test

The asymptotic error probability of Linhart's model selection test isevaluated, and compared with the nominal significance level. We examine thecase where the expected discrepancies of the candidate models from the truemodel are asymptotically equal. The local alternatives method is employed inthe limiting operation of the asymptotic evaluation. Although the errorprobability under the null hypothesis is actually shown to be equal to orless than the level for most situations, intolerable violations of the errorcontrol are observed for nested models: It is often erroneously concludedthat the smaller model is significantly better than the larger model. Toprevent this violation, a modification of Linhart's test statistic isproposed. The effectiveness of the proposed test is confirmed throughtheoretical analysis and numerical simulations.     

Chemically modified proton‐conducting membranes based on sulfonated polyimides: Improved water stability and fuel‐cell performance

A series of branched/crosslinked sulfonated polyimide (B/C‐SPI) membranes were prepared and evaluated as proton‐conducting ionomers based on the new concept of in situ crosslinking from sulfonated polyimide (SPI) oligomers and triamine monomers. Chemical branching and crosslinking in SPI oligomers with 1,3,5‐tris(4‐aminophenoxy)benzene as a crosslinker gave the polymer membranes very good water stability and mechanical properties under an accelerated aging treatment in water at 130 °C, despite their high ion‐exchange capacity (2.2–2.6 mequiv g^?1). The resulting polymer electrolytes displayed high proton conductivities of 0.2–0.3 S cm^?1 at 120 °C in water and reasonably high conductivities of 0.02–0.03 S cm^?1 at 50% relative humidity. In a single H₂/O₂ fuel‐cell system at 90 °C, they exhibited high fuel‐cell performances comparable to those of Nafion 112. The B/C‐SPI membranes also displayed good performances in a direct methanol fuel cell with methanol concentrations as high as 50 wt % that were superior to those of Nafion 112. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 3751–3762, 2006     

Improvement of Dispersion and Release Properties of Nifedipine in Suppositories by Complexation with 2-Hydroxypropyl-β-cyclodextrin

Geometries, electronic properties and NMR-shielding of cucurbit[5]uril, decamethylcucurbit[5]uril, cucurbit[6]uril, cucurbit[7]uril, and cucurbit[8]uril are investigated with DFT calculations. All molecules are highly symmetrical with a distinct geometric flexibility. In addition with a characteristic partial charge distribution these findings account for their chemical complex building ability.     

Electrochiroptical systems based on biphenyl-2,2′-diyl-type dicationic dyes: strong chiroptical signals through the transmission of point chirality to axial chirality

Huge CD amplitude (A = +538) was attained by diastereomeric preference (50% de) for the title dication with two bis[4-(R)-sec-butoxyphenyl]methylium units in benzene at 23 °C. Intramolecular π-π stacking is the origin for effective transmission of point chirality to axial chirality to attain the chiroptical enhancement of 400-times. Thanks to the strong CD signaling, chiroptical changes upon electrolysis could be readily detected, thus realizing a new class of electrochiroptical response systems. Chiroptical properties could also be modified by solvent polarity.     

Thermochromic and solvatochromic zinc biladienones: dynamic equilibria of a metal complex having a flexible framework sensitive to environment

Dehydration of zinc biladienone was catalyzed by zinc acetate, while the reverse reaction was catalyzed by triethylamine. The transformation can be performed thermally without catalyst, and the ratio of the hydrated form to the dehydrated form depended on the solvents: the dehydrated form is favored in CHCl₃ and CH₂Cl₂, while the hydrated form is favored in hexane, pyridine, and DMF. Kinetic studies on the thermal transformation of zinc biladienone from its hydrated blue form to the dehydrated yellow-brown form were performed in toluene and THF. The rate law was half order with respect to the zinc biladienone concentration in toluene, while first order in THF, leading to a slow transformation in concentrated solution in toluene.     

Three-way-output response system by electric potential: UV-vis, CD, and fluorescence spectral changes upon electrolysis of the chiral ester of tetracyanoanthraquinodimethane

The newly prepared tetracyanoanthraquinodimethane (TCNAQ) derivatives 1a,b with a chiral auxiliary are good electron acceptors and exhibit weak circular dichroism (CD) based on the absorption of TCNAQ. The twin-type electron acceptor 1c with two TCNAQ units shows larger ellipticity by exciton coupling. UV-vis, CD, and fluorescence spectra were changed drastically upon electrochemical reduction of 1c, which demonstrates the unprecedented three-way-output response system.     

Novel catalytic asymmetric sulfoxidation in water using the hypervalent iodine reagent iodoxybenzene

A new catalytic asymmetric oxidation of sulfides to sulfoxides in water using the hypervalent iodine(V) reagent iodoxybenzene (PhIO2) has been developed. This methodology is distinctly different from the previously reported use of cyclodextrins or biological catalysts and provides a new route to asymmetric sulfoxidation in water.     

Multi‐input–Multi‐output Molecular Response System Based on Dynamic Redox Behavior of Hexaphenylethane‐type Electron Donors with the Tetrahydrophenanthrazepine Skeleton: Strong Chiroptical Signals through the Transmission of Point Chirality to Helicity

The title heterocyclic donors undergo reversible C? C bond formation/cleavage upon electron transfer (dynamic redox behavior). The helical sense in both neutral and cationic states is interconvertible by facile ring flipping. The π‐type asymmetric center on the azepine nitrogen atom induces a significant degree of diasteromeric preference, thus endowing strong CD activity based on exciton coupling. Chiroptical properties could be modified not only by redox reactions but also by heat and protonation. The present redox pairs can serve as unprecedented three‐way‐input (e, H⁺, Δ) and two‐way‐output (UV/Vis, CD) response systems.