trans-acetonide controlled endo-selective intramolecular nitrone-alkene cycloaddition of hept-6-enoses: a facile entry to calystegines, tropanes, and hydroxylated aminocycloheptanes

High-yielding endo-selective intramolecular nitrone-alkene cycloaddition (INAC) reactions of hept-6-enoses controlled by a trans-acetonide to give bridged bicyclo[4.2.1]isoxazolidines exclusively are realized for the first time. The cycloadducts were readily transformed into calystegine, tropane, and hydroxylated aminocycloheptane frameworks. [reaction: see text].     

Ambipolar diphenylamino end-capped oligofluorenylthiophenes as excellent electron-transporting emitters

In addition to hole transport, diphenylamino-end-capped oligofluorenylthiophenes can exhibit efficient electron transport, in which the oligothiophene central core acts as an excellent electron-transporting moiety. The highly efficient undoped multilayer OLEDs using OF(2)TTP-NPh and OF(2)QTP-NPh as an electron-transporting emitter exhibited a maximum luminance of 19,800 and 11,800 cd m(-2) with a luminance efficiency up to 5.3 and 1.0 cd A(-1), respectively.     

Novel butterfly-shaped fused heteroacenes: synthesis, properties, and device performance of solution-processed field-effect transistors

Two tetrabrominated intermediates obtained by bromination of naphthodithiophene in different solvents were used to construct novel highly π-extended butterfly-shaped heteroarenes 1-6, containing either an 8- or 10-fused ring. The solution-processed organic field-effect transistors based on compound 1 exhibited promising device performance with a hole mobility of 0.072 cm(2) V(-1) s(-1) and a current on/off ratio of 10(6) under ambient atmosphere.     

Efflorescence relative humidity for ammonium sulfate particles

The classical homogeneous nucleation theory was employed to calculate the efflorescence relative humidity (ERH) of airborne ammonium sulfate particles with a wide size range (8 nm to 17 microm) at room temperature. The theoretical predictions are in good agreement with the experimentally measured values. When the ammonium sulfate particle is decreased in size, the ERH first decreases, reaches a minimum around 30% for particle diameter equal to about 30 nm, and then increases. It is for the first time that the Kelvin effect is theoretically verified to substantially affect the ERH of ammonium sulfate particles smaller than 30 nm, while the aerosol size is the dominant factor affecting the efflorescent behavior of ammonium sulfate particles larger than 50 nm.     

Computer simulations of diffusion and dynamics of short-chain polyelectrolytes

Brownian dynamics simulations are conducted to investigate the diffusional and dynamic properties of polyelectrolytes in dilute salt-free solutions. The polyelectrolyte molecule is represented by a bead-spring chain in a primitive model. The long-range hydrodynamic and Coulomb interactions are both taken into consideration through the Ewald summations for the first time. The major finding of our simulations is that the dependence of the long-time chain diffusivity on the Coulomb interaction strength is very different from that of the Kirkwood short-time diffusivity, which simply shows a trend nearly opposite to the chain size. When ignoring the hydrodynamic interaction (HI), the coupling effect between the chain and its counterions gives rise to a noticeable increase in the long-time diffusivity at intermediate electrostatic interaction strengths. However, the incorporation of HI suppresses this effect to a degree that one can no longer discern it. Moreover, the rotational relaxation is found to show a dependence opposite to that of the gyration radius relaxation.     

Experimental and theoretical studies on stereo- and regioselectivity in intramolecular nitrone-alkene cycloaddition of hept-6-enoses derived from carbohydrates

The effect of blocking groups and stereochemistry of the substituents on the regio- and stereoselectivity in intramolecular nitrone-alkene cycloaddition (INAC) of hept-6-enoses are reported. L-ribo-Hept-6-enose 12 and D-lyxo-hept-6-enose 15, both containing a 2,3-O-isopropylidene blocking group, and L-xylo-hept-6-enose 23 and D-arabino-hept-6-enose 30, both with a 2,3-O-trans-diacetal blocking group, were prepared from D-ribose and D-arabinose, respectively. With N-alkyl hydroxylamine, lactols 12 and 15 underwent an INAC reaction to give cis-fused isoxazolidines exclusively whereas lactols 23 and 30 gave a mixture of cis-, trans-fused isoxazolidines (cyclohexanols) and bridged isoxazolidines (cycloheptanols). With the 2,3-O-trans-diacetal protecting group, the bridged bicyclo[4.2.1]isoxazolidines (cycloheptanols), via the endo mode of INAC cyclization, were synthesized for the first time from unbranched sugar derivatives 23 and 30. The stereochemical outcomes of these reactions were rationalized on the basis of transition state energies obtained by computation. The present INAC showed trivial temperature, but significant solvent dependence. For lactols 23 and 30, performing the INAC in 2-propanol gave the best yields of fused isoxazolidines (cyclohexanols) whereas in dichloromethane afforded the best yields of bridged isoxazolidines (cycloheptanols).     

Synthesis of oligophenylene-substituted calix[4]crown-4s and their silver(I) ion-induced nanocones formation

A novel series of oligophenylene OPP(n)-substituted calix[4]crown-4s bearing up to three phenylene units, 1a-d, has been efficiently synthesized by means of either microwave-assisted or silver(I) ion-assisted Pd-catalyzed Suzuki cross-coupling of tetraiodocalix[4]crown-4 and the corresponding oligophenylboronic acids. Complexation of OPP(n)-substituted calix[4]crown-4s with silver (I) ion was substantiated by 1H NMR spectroscopic and high-resolution ESI- or MALDI-TOF- MS studies. The weak binding affinities of OPP(n)-substituted calix[4]crown-4s for silver (I) ion, which were estimated from 1H NMR titrations with binding association in the range of 30-90 M(-1), allows reversible disassembling in the presence of KI at ambient temperature. Remarkably, the single-crystal X-ray structures of OPP(n)-calix[4]crown-4.Ag+ complexes indicate the atypical silver (I) ion-crown ether binding mode resulting in the formation of rigid nanocones with volume created up to approximately 1500 A(3). Our results suggested that despite the weak binding affinity of crown ether ligands for silver (I) ion, this weak interaction is still be useful as a tool to construct supramolecular architectures.     

Analysing persistent organic pollutants in eggs, blood and tissue of the green sea turtle (Chelonia mydas) using gas chromatography with tandem mass spectrometry (GC-MS/MS)

Investigation into persistent organic pollutants (POPs) in sea turtles is an important area of conservation research due to the harmful effects of these chemicals. However, the analysis of POPs in the green sea turtle (Chelonia mydas) has been limited by methods with relatively high limits of detection and high costs associated with multiple sample injections into complex arrangements of analytical equipment. The present study aimed to develop a method that could detect a large number of POPs in the blood, eggs and tissue of C. mydas at trace concentrations. A gas chromatography with tandem mass spectrometry (GC-MS/MS) method was developed that could report 125 POP compounds to a limit of detection of <35 pg g^?1 using a single sample injection. The recoveries of internal standards ranged from 30% to 96%, and the standard reference materials were reported to within 70% of the certified values. The coefficient of variation of ten replicates of pooled egg sample was <20% for all compounds, indicating low within-run variation. This GC-MS/MS method is an improvement of previous methods for analysing POPs in C. mydas in that more compounds can be reported at lower concentrations and the accuracy and precision of the method are sound. This is particularly important for C. mydas as they occupy a low trophic level and have lower concentrations of POPs. This method is also simple to set up, and there are minimal differences in sample preparation for the different tissue types.     

Derivations on the algebra of operators in hilbert C*-modules

Let M be a full Hilbert C*-module over a C*-algebra A,and let End*A(M) be the algebra of adjointable operators on M.We show that if A is unital and commutative,then every derivation of End A(M) is an inner derivation,and that if A is σ-unital and commutative,then innerness of derivations on "compact" operators completely decides innerness of derivations on End*A(M).If A is unital(no commutativity is assumed) such that every derivation of A is inner,then it is proved that every derivation of End*A(Ln(A)) is also inner,where Ln(A) denotes the direct sum of n copies of A.In addition,in case A is unital,commutative and there exist x0,y0 ∈ M such that x0,y0 = 1,we characterize the linear A-module homomorphisms on End*A(M) which behave like derivations when acting on zero products.