A reactivity/affinity switch for parallel kinetic resolution: alpha-amino acid quasienantiomers and the resolution of cyclopropene carboxylic acids

A new type of parallel kinetic resolution (PKR) is reported in which quasienantiomers with very similar reactivities give products whose chromatographic properties diverge upon the addition of fluoride. This concept of a reactivity/affinity switch is applied to the PKR of cyclopropene carboxylic acids with all-carbon quaternary centers. This is the first application of alpha-amino acid quasienantiomers in PKR, and it is a complementary approach for acyltransfer systems where the asymmetry is induced by the nucleophile rather than the leaving group. Excellent diastereoselectivities (ranging from 90:10 to 99.5:5) and good yields were obtained for both quasienantiomeric products, and the reactions can be run on significant scale because the separation is trivial. High-level DFT calculations (B3LYP functional with the 6-31+G(d,p) basis set) provided transition-state structures with relative energies that are in accord with the experimental observations.     

Enhanced infrared transmission through subwavelength coaxial metallic arrays

We report the observation of enhanced near-infrared transmission through arrays of subwavelength coaxial metallic structures compared with that through comparable diameter hole arrays as a result of localized electromagnetic modes supported by the complex coaxial unit cell. Polarization and angle-dependent transmission measurements clearly demonstrate the coupling between this localized mode and delocalized surface plasmon modes. A generalized, multiple discrete states Fano line shape provides a good fit to the experimental results.     

Polarity switching and transient responses in single nanotube nanofluidic transistors

We report the integration of inorganic nanotubes into metal-oxide-solution field effect transistors (FETs) which exhibit rapid field effect modulation of ionic conductance. Surface functionalization, analogous to doping in semiconductors, can switch the nanofluidic transistors from p-type to ambipolar and n-type field effect transistors. Transient study reveals the kinetics of field effect modulation is controlled by ion-exchange step. Nanofluidic FETs have potential implications in subfemtoliter analytical technology and large-scale nanofluidic integration.     

Stress analysis of ZrO2/SiO2 multilayers deposited on different substrates with different thickness periods

The effects of repeating thickness periods on stress are studied in ZrO2/SiO2 multilayers deposited by electron-beam evaporation on BK7 glass and fused-silica substrates. The results show that the residual stress is compressive and decreases with an increase of the periods of repeating thickness in the ZrO2/SiO2 multilayers. At the same time, the residual stress in multilayers deposited on BK7 glass is less than that of samples deposited on fused silica. The variation of the microstructure examined by x-ray diffraction shows that microscopic deformation does not correspond to macroscopic stress, which may be due to variation of the interface stress.     

Distinguishability and indistinguishability by local operations and classical communication

It is well known that orthogonal quantum states can be distinguished perfectly. However, if we assume that these orthogonal quantum states are shared by spatially separated parties, the distinguishability of these shared quantum states may be completely different. We show that a set of linearly independent quantum states [formula: see text] where U(m,n) are generalized Pauli matrices, cannot be discriminated deterministically or probabilistically by local operations and classical communication. On the other hand, any l maximally entangled states from this set are locally distinguishable if l(l-1)< or =2d. The explicit projecting measurements are obtained to locally discriminate these states. As an example, we show that four Werner states are locally indistinguishable.     

A unique reaction pathway of fluorine-substituted ethyl groups on Cu(111): successive alpha,alpha-fluoride elimination

Fluorine-substituted ethyl groups on Cu(111) were generated by thermal scission of the C-I bond in the adsorbed C2F5I. Temperature-programmed reaction spectrometry observed a novel pathway resulting in the evolution of C4F6 above 400 K. Among the various isomers, this product was identified as hexafluro-2-butyne. Although abstraction of two fluorine atoms from the starting Cu-CF2CF3 was required, Cu-CCF3 (trifluoroethylidyne) was favored over Cu-CF=CF2 (trifluorovinyl) as the intermediate because this ethyl-ethylidyne-butyne pathway was suppressed on a Cu(100) surface devoid of the key threefold hollow binding sites for ethylidyne. Once formed, perfluoroethylidyne readily coupled to afford a tightly surface-bound hexafluoro-2-butyne up to 400 K. Therefore, the C-F bonds adjacent to the metal were found to be more susceptible to the bond activation, leading the chemisorbed perfluoroethyl to eliminate two F atoms successively from the alpha-carbon. This preference for alpha-elimination rather than beta-elimination (the most favorable route in hydrocarbons) may be quite general for metal surface-mediated reactions involving fluorinated alkyl groups.     

Structure,transport and magnetic properties of the double perovskite (Ca<Subscript>2-2x</Subscript>Sr<Subscript>2x</Subscript>)FeMoO<Subscript>6</Subscript>

In this paper we report the results of a detailed investigation of the double perovskite (Ca_2-2xSr_2x)FeMoO₆ system. Chemical size effects on structural, electrical, and magnetic properties caused by the substitution of isovalent, larger Sr ions into the smaller Ca sites, resulting in (Ca_2-2xSr_2x)FeMoO₆, have been examined. The compounds crystallize in the monoclinic space group P2₁/n for 0.0x<0.2, the orthorhombic space group Pbnm for 0.2x<0.4, and the tetragonal space group I4/m and I4/mmm for x0.4. Examination of the resistivity of all compounds reveals a metallic behavior which is well described by a Tⁿ dependence except for x=1.0. These n values change from 1 to 2 as T decreases lower than T_c. This is indicative of a variation in the transport mechanism at T_c. The ferrimagnetic transition temperature T_c increases with increasing x from 318 (x=0.0) to 393 K (x=1.0). For all samples, the saturation magnetization at 82 K obeys M_s3.5_B/(formula unit), compared to a theoretical spin-only moment of 4_B/(formula unit) for a perfectly ordered compound. PACS 74.25.Fy; 74.25.Ha     

Fabrication of alternating polycation and albumin multilayer coating onto stainless steel by electrostatic layer-by-layer adsorption

Multilayer films consisting of polyethylenimine (PEI) and albumin were successfully prepared on biomedical 316L stainless steel surface via electrostatic self-assembly of the PEI and albumin. The process of electrostatic self-assembly of PEI/albumin was monitored by125I radiolabeling, electrochemical impedance spectroscopy (EIS) and atomic force microscopy (AFM). The EIS data revealed that the multilayer coating was stable in Tris-HCl (pH 7.35) buffer solution for 21 days. 125I radiolabeling experiments indicated that less than 10% albumin was eluted by PBS in 45 days. Static platelet adhesion experiments indicated that the PEI/albumin deposited on stainless steel could resist platelet adhesion effectively. Such an easy processing and shape-independent method may have good potential for surface modification of cardiovascular devices.     

Capacitive sensors using electropolymerized o-phenylenediamine film doped with ion-pair complex as selective elements for the determination of pentoxyverine

A capacitive sensing method based on electropolymerized o-phenylenediamine film doped with pentoxyverine ion-pair complex as selective element was successfully developed for the determination of pentoxyverine. Ion-pair complex, pentoxyverine-tetraphenylborate or pentoxyverine-picrolonate, was embedded in electropolymerized o-phenylenediamine film by electropolymerizing technique. The effects of working frequency and test solution pH on the detection of pentoxyverine were investigated in detail and optimized. For the sensor modified with pentoxyverine-tetraphenylborate, calibration curve was linear over the concentration range of 5.0×10⁻⁷ to 1.0×10⁻⁴ M with a detection limit of 1.0×10⁻⁷ M at pH 7. The proposed sensor exhibited high selectivity and sensitivity to pentoxyverine. The results in sample analysis confirmed the usefulness of the proposed ISC sensor for quantitative analysis, and also indicated that this method might find applications in the assay of other drugs.