Micro-phase sorbent extraction for trace analysis via in situ sorbent formation: application to the spectrophotometric determination of nitrite in environmental waters.

A micro-phase sorbent in situ formation from an aqueous solution was proposed for the sensitive spectrophotometric determination of nitrite in environmental waters. Nitrite in a 10 mL sample solution was converted into a cationic azo dye by the reaction with 4-trifluoromethylanilinium ion and N-1-naphthylethylenediammonium ion in an acidic medium. Addition of dodecylbenzenesulfonate ion caused the formation of a suspension of ion associate in the solution. Centrifugation of the solution led to the isolation of a liquid organic phase that extracted the azo dye at the bottom of the centrifuge tube. The volume of the new phase was ca. 5 microL. After the aqueous phase was discarded, the organic phase was dissolved with 1 mL of 2-methoxyethanol to measure the absorbance. Nitrogen as NO2- at concentrations from 1.5 to 30 microg L(-1) was determined with sufficient precision. When 0.2 mL of 2-methoxyethanol was applied to dissolve the organic phase, 0.3-4.8 microg NO2--N L(-1) was determined. The recovery tests for nitrite added to some river water and seawater were satisfactory. This method is very simple and rapid. It takes only 30 min from the dye formation to the measurement of the absorbance.     

Discrete palladium clusters that consist of two mutually bisecting perpendicular planes

The construction of novel molecules with unprecedented alignments of the constituent elements has revolutionized the field of functional materials. The arrangement of two or more planar subunits in a mutually perpendicular fashion is a frequently encountered approach to produce novel functional materials. Previous examples of such materials can be categorized into two well-investigated families: spiro-conjugated and dumbbell-shaped structures, wherein the two planes are aligned orthogonally via a single atom or an axis, respectively. This article describes a third family: reaction of [Pd(CN^tBu)₂]₃ with Sn₃Me₈ or Ge₆Me₁₂ afforded a Pd₇Sn₄ cluster and a Pd₈Ge₆ cluster that consist of two mutually bisecting perpendicular planes. In the Pd₇Sn₄ cluster, the two equivalent Pd₅Sn₂ planes share three palladium atoms that include a dihedral angle of 85.6°.

The construction of Pd₇Sn₄ and Pd₈Ge₆ clusters that consist of two mutually bisecting perpendicular planes was accomplished by the reaction of [Pd(CN^tBu)₂]₃ with Me₃Sn–SnMe₂–SnMe₃ or Ge₆Me₁₂.     

Induced Fitting and Polarization of a Bromine Molecule in an Electrophilic Inorganic Molecular Cavity and Its Bromination Reactivity

Dodecavanadate, [V₁₂O₃₂]^4? (V12), possesses a 4.4 Å cavity entrance, and the cavity shows unique electrophilicity. Owing to the high polarizability, Br₂ was inserted into V12, inducing the inversion of one of the VO₅ square pyramids to form [V₁₂O₃₂(Br₂)]^4? (V12(Br2)). The inserted Br₂ molecule was polarized and showed a peak at 185 cm^?1 in the IR spectrum. The reaction of V12(Br2) and toluene yielded bromination of toluene at the ring, showing the electrophilicity of the inserted Br₂ molecule. Compound V12(Br2) also reacted with propane, n‐butane, and n‐pentane to give brominated alkanes. Bromination with V12(Br2) showed high selectivity for 3‐bromopentane (64 %) among the monobromopentane products and preferred threo isomer among 2‐,3‐dibromobutane and 2,3‐dibromopenane. The unique inorganic cavity traps Br₂ leading the polarization of the diatomic molecule. Owing to its new reaction field, the trapped Br₂ shows selective functionalization of alkanes.     

Synthesis,characterization, photo‐induced alignment,and surface orientation of poly(9,9‐dioctylfluorene‐alt‐azobenzene)s

Three types of bi‐functionalized copolymers ( P1FAz , P2FAz , and P3FAz ) with different numbers of fluorene units and an azobenzene unit were synthesized and characterized using UV–vis and polarized absorption spectroanalysis. The trans‐cis photoisomerization was conformed under 400 nm light irradiation for all copolymers in chloroform. However, in the film state, only the trans‐cis photoisomerization occurred by mono‐fluorene attached copolymer poly[(9,9‐di‐n‐octylfluorenyl‐2,7‐diyl)‐alt‐4,4′‐azobenzene)] ( P1FAz ). Photo‐induced alignment was achieved using the P1FAz film after irradiation with linear polarized 400 nm light and subsequent annealing at 60 °C. Surface orientation of a spin‐coating film of poly(9,9‐didodecylfluorene) ( F12 ) was achieved using the photo‐induced alignment layer of the P1FAz film after annealing at 90 °C. The photo‐induced alignment layer of P1FAz has potential application to the surface orientation technique for appropriate polymers, which will be useful for the fabrication of optoelectronics devices. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Dynamic behaviors of ferroelectric liquid crystal molecules under an applied electric field

The dynamic changes in ferroelectric liquid crystal (FLC) molecular alignments under an applied electric field are examined by observing the formation of conoscopic figures with a time resolution of 0.1 ms. Close agreements between observed and simulated conoscopic figures under low voltage (30 V) were obtained. Under high voltage (120 V), however, the observed conoscopic figures became blurred between 0.8 ms and 1.1 ms after reversal of the electric field. The light scattering producing the blurriness occurred due to the development of fast transient molecular alignments during the switching transition above the applied voltage 70 V.     

Lanthanide complexes of macrocyclic polyoxovanadates by VO4 units: synthesis, characterization, and structure elucidation by X-ray crystallography and EXAFS spectroscopy

Reactions of a tetravanadate anion, [V(4)O(12)](4-), with a series of lanthanide(III) salts yield three types of lanthanide complexes of macrocyclic polyoxovanadates: (Et(4)N)(6)[Ln(III)V(9)O(27)] [Ln = Nd (1), Sm (2), Eu (3), Gd (4), Tb (5), Dy (6)], (Et(4)N)(5)[(H(2)O)Ho(III)(V(4)O(12))(2)] (7), and (Et(4)N)(7)[Ln(III)V(10)O(30)] [Ln = Er (8), Tm (9), Yb (10), Lu (11)]. Lanthanide complexes 1-11 are isolated and characterized by IR, elemental analysis, single-crystal X-ray diffraction, and extended X-ray absorption fine structure spectroscopy (EXAFS). Lanthanide complexes 1-6 are composed of a square-antiprism eight-coordinated Ln(III) center with a macrocyclic polyoxovanadate that is constructed from nine VO(4) tetrahedra through vertex sharing. The structure of 7 is composed of a seven-coordinated Ho(III) center, which exhibits a capped trigonal-prism coordination environment by the sandwiching of two cyclic tetravanadates with a capping H(2)O ligand. Lanthanide complexes 8-11 have a six-coordinated Ln(III) center with a 10-membered vanadate ligand. The structural trend to adopt a larger coordination number for a larger lanthanide ion among the three types of structures is accompanied by a change in the vanadate ring sizes. These lanthanide complexes are examined by EXAFS spectroscopies on lanthanide L(III) absorption edges, and the EXAFS oscillations of each of the samples in the solid state and in acetonitrile are identical. The Ln-O and Ln···V bond lengths obtained from fits of the EXAFS data are consistent with the data from the single-crystal X-ray studies, reflecting retention of the structures in acetonitrile.     

Analysis of liquid structure without construction of any structure models by the X-ray scattering method.

A simple approach for determining a liquid structure using X-ray scattering data, in which a liquid structure is uniquely evaluated without construction of any plausible structure models, has been applied to liquid acetonitrile, acetone and cyclohexane. For a pair of molecules, a given point within a molecule is located at the origin with a given molecular orientation. The site of the given point of another molecule is defined by the polar coordinates and the molecular orientation is treated by three Eulerian angles. These parameters are optimized by a non-linear least-squares calculation applied to X-ray scattering data. The reliability of the method was examined by determining the liquid structure of polar acetonitrile and the obtained intermolecular interatomic distances are in good agreement with the previously reported values. The method was then successfully applied to the determination of the liquid structure of acetone and cyclohexane. Especially for nonpolar cyclohexane, the construction of a variety of plausible structural models is very difficult. It was revealed that acetone has an ordered liquid arrangement similar to that found in its crystal, although the intermolecular distances in liquid acetone are different from those in the crystal. On the other hand, the liquid structure of cyclohexane is disordered.