Selective extraction of catecholamines by packed fiber solid‐phase using composite nanofibers composing of polymeric crown ether with polystyrene

For the first time, electrospun composite nanofibers comprising polymeric crown ether with polystyrene (PCE‐PS) have been used for the selective extraction of catecholamines – dopamine (DA), norepinephrine (NE) and epinephrine (E) – prior to their analysis by high‐performance liquid chromatography–electrochemical detection. Using a minicartridge packed with PCE‐PS composite nanofibers, the target compounds were extracted effectively from urine samples to which diphenylborinic acid 2‐aminoethyl ester was added as a complexing reagent. The extracted catecholamines could be liberated from the fiber by the addition of acetic acid. A good linearity was observed for catecholamines in the range of 2.0–200 ng mL^?1 (NE, E and DA). The detection limits of catecholamines (signal‐to‐noise ratio = 3) were 0.5 ng mL^?1 (NE), 0.2 ng mL^?1 (E) and 0.2 ng mL^?1 (DA), respectively. Under the optimized conditions, the absolute recoveries of the above three catecholamines were 90.6% (NE), 88.5% (E) and 94.5% (DA). The repeatability of extraction performance was from 5.4 to 9.2% (expressed as relative standard deviation). Our results indicate that the proposed method could be used for the determination of NE, E and DA in urine. Copyright © 2014 John Wiley & Sons, Ltd.     

Synthesis and liquid crystalline behavior of bulky poly(methacrylamide)s

N‐(Bis(4‐(2‐ethylhexyloxy)phenyl)(phenyl)‐methyl)methacrylamide was synthesized and polymerized via reversible addition‐fragmentation chain‐transfer (RAFT) polymerization. The chain‐transfer agent (4‐cyano‐4‐(phenylcarbonothioylthio) pentanoic acid (CPADB)), combined with a chiral additive, and a radical initiator yielded polymers with dispersities between 1.2 and 1.4. At low concentrations, the polymers are soluble in hexanes and chloroform while at higher concentrations they swell in these solvents. Characterization of the polymers by wide‐angle X‐ray scattering (WAXS) revealed an interplanar distance of 19.0 Å. The WAXS data combined with polarized optical microscopy support a lamellar crystallization and lyotropic liquid crystalline behavior in hexanes and chloroform. © 2015 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2015 , 53, 2563–2568     

Synthesis,Crystal Structure,and Magnetic Properties of a New Dinuclear Iron Complex with Schiff Base Ligand

A new dinuclear iron(Ⅲ) complex has been synthesized and structurally characterized by X-ray crystallography: [FeⅢ2(L)(C6H5COO)(SO4)(CH3OH)2]·CH3CN·CH3OH(1, H3 L = N,N'-bis(salicylidene)-1,3-diamino-2-propanol). Complex 1 belongs to orthorhombic space group Pna21 with a = 11.4400(8), b = 22.9705(2), c = 12.5712(9) , V = 3303.5(4) 3, Z = 4, F(000) = 1576, Dc = 1.531 g·cm–3, Mr = 761.36, μ = 1.007 mm–1, S = 1.014, the final R = 0.0505 and wR = 0.1018. The crystal packing is stabilized by intermolecular O–H···O hydrogen bonds, forming an extended one-dimensional chain structure. The temperature dependence of magnetic susceptibility measurement shows that antiferromagnetic interaction is propagated between the metal centers. Fit as dinuclear arrangement gave parameters of J = 19.7 cm-1, g = 1.89 and R2 = 0.9999.     

Investigation of mononuclear,dinuclear, and trinuclear transition metal (II) complexes derived from an asymmetric Salamo‐based ligand possessing three different coordination modes

A new asymmetric Salamo‐based ligand H₂L was synthesized using 3‐tert‐butyl‐salicylaldehyde and 6‐methoxy‐2‐[O‐(1‐ethyloxyamide)]‐oxime‐1‐phenol. By adjusting the ratio of the ligand H₂L and Cu (II), Co (II), and Ni (II) ions, mononuclear, dinuclear, and trinuclear transition metal (II) complexes, [Cu(L)], [{Co(L)}₂], and [{Ni(L)(CH₃COO)(CH₃CH₂OH)}₂Ni] with the ligand H₂L possessing completely different coordination modes were obtained, respectively. The optical spectra of ligand H₂L and its Cu (II), Co (II) and Ni (II) complexes were investigated. The Cu (II) complex is a mononuclear structure, and the Cu (II) atom is tetracoordinated to form a planar quadrilateral structure. The Co (II) complex is dinuclear, and the two Co (II) atoms are pentacoordinated and have coordination geometries of distorted triangular bipyramid. The Ni (II) complex is a trinuclear structure, and the terminal and central Ni (II) atoms are all hexacoordinated, forming distorted octahedral geometries. Furthermore, optical properties including UV–Vis, IR, and fluorescence of the Cu (II), Co (II), and Ni (II) complexes were investigated. Finally, the antibacterial activities of the Cu (II), Co (II), and Ni (II) complexes were explored. According to the experimental results, the inhibitory effect was found to be enhanced with increasing concentrations of the Cu (II), Co (II), and Ni (II) complexes.     

The single-polarization filter composed of gold-coated photonic crystal fiber

A single-polarization filter comprising a gold-coated photonic crystal fiber based on surface plasmon resonance is designed and investigated. The pattern matching and coupled polarization characteristics analyzed by the full-vector finite element method (FEM) and losses at 1,540 nm are achieved to 1,016.01739 dB/cm (x-pol core mode) and 33.81917 dB/cm (y-pol core mode). The crosstalk (CT) value of the 1,540 nm band is ?853.12653 dB for fiber length $L=1,000\mathrm{\mu }\text{m}$ and the bandwidth is 850 nm. The working wavelength of the filter ranges from 1,280 nm to 1,540 nm by varying the diameter of outer air holes ($d_1$), the diameter of inner air holes ($d_4$), the metal film thickness (t), as well as the liquid refractive index (n).     

Selective Excitation of Band Extrema in Valley Photonic Crystals

Flexible control of building blocks of photonic crystals enables achieving desirable band structures. Exploration of photonic band extrema has brought many fantastic features to design artificial optical materials, such as Brillouin‐zone‐corner extrema for valley photonic materials and zone‐center extremum for zero‐index metamaterials. However, two such kinds of extrema are always found independently in different photonic crystals. In this work, a kind of valley photonic crystals possessing both zone‐center and zone‐corner band extrema almost at the same frequency is proposed. Inspired by antennas theory, a three‐antenna array (TAA) source is devoted to individually manipulate each extremum. The correlation coefficient is given to determine the coupling efficiency between the TAA source and extrema eigenmodes. By using a source with a high correlation coefficient, these extrema bulk states are selectively excited consistent with their eigenfields. Furthermore, three control cases are shown that multiple extrema points are simultaneously excited, in order to confirm the validity of the correlation coefficient. Finally, a potential application of a beam‐steering device is proposed through selective excitation of ternary extrema. This work develops binary valley states into ternary mix states, rendering more degrees of freedom for on‐chip optical information transport, particularly for beam steering and mode division multiplexing.     

Design of diamond-shape photonic crystal fiber polarization filter based on surface plasma resonance effect

A novel plasmonic polarization filter based on the diamond-shape photonic crystal fiber(PCF) is proposed. The resonant coupling characteristics of the PCF polarization filter are investigated by the full-vector finite-element method. By optimizing the geometric parameters of the PCF, when the fiber length is 5 mm, the polarization filter has a bandwidth of 990 nm and an extinction ratio(ER) of lower than -20 dB. Moreover, a single wavelength polarization filter can also be achieved, along with an ER of -279.78 dB at wavelength 1.55 μm. It is believed that the proposed PCF polarization filter will be very useful in laser and optical communication systems.     

Structure determination of KScS2, RbScS2 and KLnS2 (Ln = Nd,Sm, Tb,Dy, Ho,Er, Tm and Yb) and crystal–chemical discussion

The title structures of KScS₂ (potassium scandium sulfide), RbScS₂ (rubidium scandium sulfide) and KLnS₂ [Ln = Nd (potassium neodymium sufide), Sm (potassium samarium sulfide), Tb (potassium terbium sulfide), Dy (potassium dysprosium sulfide), Ho (potassium holmium sulfide), Er (potassium erbium sulfide), Tm (potassium thulium sulfide) and Yb (potassium ytterbium sulfide)] are either newly determined (KScS₂, RbScS₂ and KTbS₂) or redetermined. All of them belong to the α‐NaFeO₂ structure type in agreement with the ratio of the ionic radii r³⁺/r⁺. KScS₂, the member of this structural family with the smallest trivalent cation, is an extreme representative of these structures with rare earth trivalent cations. The title structures are compared with isostructural alkali rare earth sulfides in plots showing the dependence of several relevant parameters on the trivalent cation crystal radius; the parameters thus compared are c, a and c/a, the thicknesses of the S—S layers which contain the respective constituent cations, the sulfur fractional coordinates z(S²⁻) and the bond‐valence sums.     

Unsymmetrical Pyrene‐Fused Phthalocyanine Derivatives: Synthesis,Structure, and Properties

Novel pyrene‐fused unsymmetrical phthalocyanine derivatives 2,3,9,10,16,17‐hexakis(2,6‐dimethylphenoxy)‐22,25‐diaza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc complex Zn[Pc(Pz‐pyrene)(OC₈H₉)₆] ( 1 ) and 2,3,9,10‐tra(2,6‐dimethylphenoxy)‐15,18,22,25‐traza(2,7‐di‐tert‐butylpyrene)[4,5]phthalocyaninato zinc compound Zn[Pc(Pz‐pyrene)₂(OC₈H₉)₄] ( 2 ) were isolated for the first time. These unsymmetrical pyrene‐fused phthalocyanine derivatives have been characterized by a wide range of spectroscopic and electrochemical methods. In particular, the pyrene‐fused phthalocyanine structure was unambiguously revealed on the basis of single crystal X‐ray diffraction analysis of 1 , representing the first structurally characterized phthalocyanine derivative fused with an aromatic moiety larger than benzene.