Poly(diphenylacetylene)s with Electron‐Donating Alkoxy and Electron‐Withdrawing Fluoroalkyl Groups: Effect of the Substituent on Fluorescence

New poly(diphenylacetylene)s with alkoxy and fluoroalkyl groups as electron‐donating and electron‐withdrawing groups, respectively, were synthesized by using a WCl₆‐n‐Ph₄Sn catalyst. The polymer solutions emitted strong, bluish‐green lights when photo‐excited. The polymers that contained the electron‐donating alkoxy groups showed longer fluorescence‐maximum peaks when compared to the polymers that contained the electron‐withdrawing fluoroalkyl groups. However, such an effect of the substituent on the absorption property was not clearly seen. The emission bands of the solid films did not show any significant red shift, relative to that of the dilute solution.

     

Effect of surfactant on retention behaviors of polystyrene latex particles in sedimentation field-flow fractionation: effective boundary slip model approach

A retention theory in sedimentation field-flow fractionation (SdFFF) was developed by exploiting the effective slip boundary condition (BC) that allows a finite velocity for particles to have at the wall, thereby alleviating the limitations set by the no-slip BC constraint bound to the standard retention theory (SRT). This led to an expression for the retention ratio R as R = (R(o) + v*(b))/(R(o) + v*(b)), where R(o) is the sterically corrected SRT retention ratio and v*(b) is the reduced boundary velocity. Then, v*(b) was modeled as v*(b) = v*(b,o)/[1 + (7K*S(o))(1/2)], where S(o) is the surfactant (FL-70) concentration and K* is the distribution coefficient associated with the langmuirian isotherm of the apparent effective mass against S(o). We applied this to study the surfactant effect on the retention behaviors of polystyrene (PS) latex beads of 170-500 nm in diameter. As a result, an empirical relation was found to hold between v*(b,o) and d(o) (estimated from R(o) at S(o) = 0) as v*(b,o) - v*(o,o)[1 - (d(c)/d(o))], where v*(o,o) is the asymptotic value of v*(b,o) in the vanishing d(c)/d(o) limit and d(c) is the cutoff value at which v*(b,o) would vanish. According to the present approach, the no-slip BC (v*(b,o) = 0) was predicted to recover when d(o) ～ d(c), and the boundary slip effect could be significant for S(o) ≤ 0.05%, particularly for large latex beads.     

Polyatomic anion versus acetonitrile in coordinating ability: structural properties of AgX-bearing 1,4-bis(2-isonicotinoyloxyethyl)piperazine (X??=?NO3?, CF3SO3?, ClO4?, BF4?, and PF6?)

Type studies on competitive polyatomic anion versus acetonitrile coordination in the self-assembly of a series of [Ag₂(X) _m (bip)(NCCH₃) _n ](X)_2−m (X⁻ = NO₃ ⁻, CF₃SO₃ ⁻, ClO₄ ⁻, BF₄ ⁻, and PF₆ ⁻; m = 0, 2; n = 0, 2, 4; bip = 1,4-bis(2-isonicotinoyloxyethyl)piperazine) were carried out. Each bip spacer acts as an N₄ tetradentate ligand and is linked to four silver(I) centers through two pyridine and two piperazine moieties, producing a double strand consisting of two 20-membered ring units. The coordinating environment around the silver(I) center is subtly determined by the competition of the polyatomic anions with acetonitrile, that is, by the Ag···NCCH₃ versus Ag···X interactions. The coordinating ability of acetonitrile is inversely proportional to the order of the coordination ability of the Hoffmeister series of polyatomic anions, NO₃ ⁻ ≫ CF₃SO₃ ⁻ > ClO₄ ⁻ > BF₄ ⁻ ≫ PF₆ ⁻.     

Preparation of blue-emitting CaMgSi2O6:Eu phosphors in reverse micellar system and their application to transparent emissive display devices

Blue-emitting Eu²⁺-doped CaMgSi₂O₆ phosphors were prepared by the reverse micelle method. The resultant particles were nanocrystalline with a grain size of about <300 nm and exhibited a characteristic blue emission spectrum centered at 445 nm induced by the oxygen coordinated Eu²⁺ ions. By using the corresponding nanophosphors followed by the formation of a uniform phosphor layer, we have demonstrated the mini-sized transparent plasma-discharge panels and investigated their luminance characteristics. Phosphor coated panel is properly transparent, ≥65%, at the visible wavelength region and illuminates a characteristic blue emission under Ne/Xe plasma discharge conditions. Thus, we can obtain a fast decaying, robust blue-emitting silicate phosphor layer under excited plasma radiation for upcoming emissive display devices like as transparent and three-dimensional plasma display panels.     

BF3·SiO2-catalyzed one-pot synthesis of α-aminophosphonates in ionic liquid and neat conditions

α-Aminophosphonates were synthesized in a simple and efficient method from the three-component condensation reaction of 5-amino 2,2-difluoro-1,3-benzodioxole, aromatic aldehydes, and diethyl phosphite by silica-supported boron trifluoride (BF₃·SiO₂) in ionic liquid ([bmim][HCl]) under solvent-free conditions at room temperature in good to excellent yields and short reaction times. The catalyst can be recovered and reused for several times without any significant loss of activity. It was observed that a homogeneous reaction medium proved beneficial for the yield of the reaction.     

Synthesis of 2-arylacrylic esters from aryl methyl ketones via Wittig reaction/singlet oxygen ene reaction

An efficient synthetic method has been developed for the synthesis of 2-arylacrylic esters from the corresponding aryl methyl ketones via Wittig reaction and singlet oxygen ene reaction. Wittig reaction to aryl methyl ketones with (methoxymethyl)triphenylphosphonium chloride in basic condition afforded the methyl enol ethers, and then 2-arylacrylic esters were obtained by singlet oxygen ene reaction, followed by tosylation and elimination in one-pot to the methyl enol ethers in good yields.     

Development of a peptide inhibitor-based cantilever sensor assay for cyclic adenosine monophosphate-dependent protein kinase

A highly sensitive nanomechanical cantilever sensor assay based on an electrical measurement has been developed for detecting activated cyclic adenosine monophosphate (cyclic AMP)-dependent protein kinase (PKA). Employing a peptide derived from the heat-stable protein kinase inhibitor (PKI), a magnetic bead system was first selected as a vehicle to immobilize the PKI-(5-24) peptide for capturing PKA catalytic subunit and the activity assay was applied for indirectly assessing the binding. Synergistic interactions of adenosine triphosphate (ATP) and the peptide inhibitor with the kinase were then investigated by a solution phase capillary electrophoretic assay, and by surface plasmon resonance technology which involved immobilization of the peptide inhibitor. After systemically evaluated by a homogeneous direct binding assay, the ATP-dependent recognition of the catalytic subunit of PKA by PKI-(5-24) was successfully transferred on to the nanomechanical cantilevers at protein concentrations of 6.6 pM-66 nM, exhibiting much higher sensitivity and wider dynamic range than the conventional activity assay. Thus, direct assessment of activated kinases using the cantilever sensor system functionalized with specific peptide inhibitors holds great promise in analytical applications and clinical medicine.     

α-MoO3 nanowire-based amperometric biosensor for l-lactate detection

Large-scale orthorhombic single-crystalline molybdenum trioxide nanowires were synthesized using a facile one-pot hydrothermal method. Lactate oxidase enzyme was immobilized on the nanowires to produce a highly sensitive electrochemical biosensor for l-lactate detection. At an applied potential of 0.5 V, the sensor exhibited a high sensitivity of 0.87 μA/mM with a fast response to l-lactate (90% of response times within 10 s). A linear response was obtained over a concentration range from 0.5 to 8 mM with a detection limit of 0.15 mM (S/N?=?3). The developed biosensor showed excellent reproducibility and operational stability, as well as the ability to be stored long term.     

Synthesis and structure of ansa-cyclopentadienyl pyrrolyl titanium complexes: [(η-C5H4)CH2(2-C4H3N)]Ti(NMe2)2 and [1,3-{CH2(2-C4H3N)}2(η-C5H3)]Ti(NMe2)

Reaction of ansa-cyclopentadienyl pyrrolyl ligand (C₅H₅)CH₂(2-C₄H₃NH) (2) with Ti(NMe₂)₄ affords bis(dimethylamido)titanium complex [(η⁵-C₅H₄)CH₂(2-C₄H₃N)]Ti(NMe₂)₂ (3) via amine elimination. A cyclopentadiene ligand with two pendant pyrrolyl arms, a mixture of 1,3- and 1,4-{CH₂(2-C₄H₃NH)}₂C₅H₄ (4), undergoes an analogous reaction with Ti(NMe₂)₄ to give [1,3-{CH₂(2-C₄H₃N)}₂(η⁵-C₅H₃)]Ti(NMe₂) (5). Molecular structures of 3 and 5 have been determined by single crystal X-ray diffraction studies.