Photoassisted Synthesis of Luminescent Mannose–Au Nanodots for the Detection of Thyroglobulin in Serum

We have employed mannose‐modified gold nanodots (Man–Au NDs) as a luminescence sensor for the detection of the thyroid‐cancer marker thyroglobulin (Tg) in homogeneous solutions. The luminescent Man–Au NDs are prepared through the reaction of 2.9 nm‐diameter gold nanoparticles (Au NPs) with 11‐mercapto‐3,6,9‐trioxaundecyl‐α‐D ‐mannopyranoside (Man‐RSH) under the irradiation of a light‐emitting diode (LED). We have found that the irradiation enhances the quantum yield (～11 %), alters the emission wavelength and lifetimes, and shortens the preparation time. A luminescence assay has been developed for Tg based on the competition between Tg and Man–Au NDs for the interaction with the concanavalin A (Con A). Because luminescence quenching of the Man–Au NDs by Con A is inhibited by Tg selectivity, we have obtained a highly sensitive and selective assay for Tg.     

Syntheses,Structures, and Biological Activity of NiII,PdII, and PtII Complexes with New Tetradentate Benzamidine Ligands

N‐(Dialkylthiocarbamoyl)benzimidoyl chlorides react with o‐(salicylidenimine)benzylamine with formation of a novel class of tetradentate benzamidine ligands (H₂L^Et and H₂L^Morph), which readily react with Ni(CH₃COO)₂, [PdCl₂(CH₃CN)₂], and [PtCl₂(PPh₃)₂] under formation of complexes of the composition [M(L^R)] [M = Ni ( 4 ), Pd ( 5 ), Pt ( 6 )]. In all complexes, H₂L^R is doubly deprotonated and bonded to the metal ion via its N₂OS donor set and establishes a distorted square‐planar coordination sphere. The antiproliferative effects of the compounds on MCF‐7 and Hep‐G2 cells were studied. The complexes of H₂L^Morph are generally more active than those of H₂L^Et. While H₂L^Et and its complexes exhibit stronger effects on the Hep‐G2 line, the corresponding compounds of H₂L^Morph show almost equal effects on the two cell lines. In each series of compounds, the cytotoxicity increases in the order H₂L^R << 4 < 5 < 6 .     

Synthesis,photoluminescence, and electrochromic properties of wholly aromatic polyamides bearing naphthylamine chromophores

A series of novel polyamides with pendent naphthylamine units having inherent viscosities of 0.15–1.02 dL/g were prepared via direct phosphorylation polycondensation from various diamines and a naphthylamine‐based aromatic dicarboxylic acid, 1‐[N,N‐di(4‐carboxyphenyl)amino]naphthalene. These amorphous polyamides were readily soluble in various organic solvents and could be cast into transparent and tough films. The aromatic polyamides had useful levels of thermal stability associated with high glass‐transition temperatures (268–355 °C), 10% weight loss temperatures in excess of 480 °C, and char yields at 800 °C in nitrogen higher than 60%. These polymers showed maximum ultraviolet–visible absorption at 350–358 nm and exhibited fluorescence emission maxima around 435–458 nm in N‐methyl‐2‐pyrrolidinone solutions with fluorescence quantum yields ranging from 0.4 to 15.0%. The hole‐transporting and electrochromic properties were examined with electrochemical and spectroelectrochemical methods. Cyclic voltammograms of the polyamide films cast onto an indium tin oxide coated glass substrate exhibited one oxidative redox couple around 1.08–1.16 V (oxidation onset potential) versus Ag/AgCl in an acetonitrile solution and revealed good stability of the electrochromic characteristics, with a color change from colorless to green at applied potentials ranging from 0 to 1.6 V. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 6094–6102, 2006     

Photolytic transformation of aryl benzobisoxazole and aryl benzobisthiazole compounds into carbon dioxide

Solid‐state aryl benzobisoxazole and aryl benzobisthiazole compounds photolyzed in the presence of O₂ undergo cleavage to produce benzobisoxazoles (or benzobisthiazoles), benzonitriles, and benzamides. A very high percentage of the carbon atoms in one of the two segments from chain cleavage are converted to CO₂. This very unusual observation has been carefully confirmed by gas chromatography/mass spectroscopy analysis of the gaseous components in the photolysis vessel before and after photolysis, labeling experiments, and the correlation of the mass reduction in photolyzed polymers and the amount of CO₂ that evolves. The rate of CO₂ generation is used to compare the relative photostability of aryl benzobisoxazole and aryl benzobisthiazole model compounds, films, and fibers. © 2006 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1868–1877, 2007     

Functional Dihydro‐1H‐Imidazole Derivatives for MALDI Signal Enhancement of a Lysine‐Specific Chemical Modification

The enhancement of signal sensitivity and quantification of low‐abundance proteins is of great importance in proteomic analysis. The preparation of 2‐methoxy‐4,5‐dihydro‐1H‐imidazole (MeO‐DHIM) derivatives was accomplished by one‐step synthesis of O‐methyl‐isourea. The signal enhancement induced by these attached moieties increases in an order of compound 1 ≈? 4 < 2 < 5 ≈? 6 < 3 in MALDI mass spectrometry. Peptide‐compound 3 adduct was approximately 20 times signal enhancement of the unmodified peptide and of 9 times of the peptide‐compound 1 adduct. This result demonstrates that the rational designed organic molecules are capable of providing a sensitive tool in the detection of low‐abundance proteins in proteomics.     

Synthesis and interfacial behaviors of amphiphilic poly(oxypropylene) amidoacids

A series of hydrophobic poly(oxypropylene) (POP)‐backboned and hydrophilic poly(oxyethylene)‐backboned amidoacids and imidoacids were prepared through the reaction of poly(oxyalkylene) diamines and trimellitic anhydride (TMA) under mild conditions. The synthesized copolymers were characterized with nuclear magnetic resonance and Fourier transform infrared. Their ability to lower the water surface tension and toluene/water interfacial tension was measured and correlated with the hydrophobic/hydrophilic balance with multiple sodium carboxylate functionalities. The specific POP2000/TMA copolymers, consisting of a 2000 g/mol POP segment and multiple amidoacid functionalities, enabled the demonstration of a strong surfactant tendency and a critical micelle concentration at 0.1 wt %. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 44: 646–652, 2006     

Synthesis of highly conductive EDOT copolymer films via oxidative chemical in situ polymerization

Poly(3,4‐ethylenedioxythiophene)s (PEDOT) represent a class of conjugated polymers that can be potentially used as an electrode material for flexible organic electronics due to their superior conductivity and transparency. In this study, we demonstrate that the conductivity of a PEDOT containing copolymer film can be further enhanced by the oxidative chemical in situ copolymerization of a liquid film spun coated from monomer mixture (3,4‐ethylenedioxythiophene (EDOT) and 3‐thienyl ethoxybutanesulfonate (TEBS)), oxidant (iron(III) p‐toluenesulfonate (Fe(OTs)₃)), weak base (imidazole), and solvent (methanol). We investigated that the effect of the processing parameters such as the molar ratios TEBS/EDOT, IM/EDOT, and Fe(OTs)₃/EDOT on the surface morphology, optical property, and the conductivity of the resulting copolymer films. These parameters have been optimized to achieve conductivities for the copolymer films as high as 170 S/cm compared with a conductivity of 30 S/cm for the pure PEDOT film synthesized using the same fabrication method. This conductivity enhancement for the copolymer films was found to be resulted from the fact that the addition of TEBS monomer reduces the copolymerization rate, leading to the formation of much more uniform film surface without defects and copolymers of higher molecular weight which increase the conductivity of the resulting copolymer film. The composition of two monomers in the copolymer film is not related to the variation of conductivity. © 2008 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 46: 1662–1673, 2008     

Theory and experiment of ultrahigh-gain gyrotron traveling waveamplifier

Physics and technology issues of importance to the high-gain gyrotron traveling wave amplifier (gyro-TWT) are investigated in theory and experiment. The gyro-TWT is known to be highly susceptible to spurious oscillations, especially in high gain operations. In the current study, oscillations of various origins are classified and characterized with detailed theoretical modeling. They are shown to be intricately connected to the interplay between the absolute/convective instabilities, circuit losses, and reflective feedback. Knowledge of these processes leads to the concept of an ultra high gain scheme which employs distributed wall losses for the suppression of spurious oscillations. A proof-of-principle Ka-band gyro-TWT experiment stable at zero drive has produced 93 kW saturated peak power at 26.5% efficiency and 70 dB gain, with a 3 dB saturated output power bandwidth of 3 GHz. The saturated gain is more than 30 dB beyond that previously achieved     

Poly(triarylamine): Its synthesis,properties, and blend with polyfluorene for white‐light electroluminescence

A new high‐molecular‐weight poly(triarylamine), poly[di(1‐naphthyl)‐4‐anisylamine] (PDNAA), was successfully synthesized by oxidative coupling polymerization from di(1‐naphthyl)‐4‐anisylamine (DNAA) with FeCl₃ as an oxidant. PDNAA was readily soluble in common organic solvents and could be processed into freestanding films with high thermal decomposition and softening temperatures. Cyclic voltammograms of DNAA and PDNAA exhibited reversible oxidative redox couples at the potentials of 0.85 and 0.85 V, respectively, because of the oxidation of the main‐chain triarylamine unit. This suggested that PDNAA is a hole‐transporting material with an estimated HOMO level of 5.19 eV. The absorption maximum of a PDNAA film appeared at 370 nm, with an estimated band gap of 2.86 eV from the absorption edge. Unusual multiple photoluminescence maxima were observed at 546 nm, and this suggested its potential application in white‐light‐emission devices. Nearly white‐light‐emission devices could be obtained with either a bilayer‐structure approach {indium tin oxide/poly(ethylenedioxythiophene):poly(styrene sulfonate)/PDNAA/poly[2,7‐(9,9‐dihexylfluorene)] (PF)/Ca} or a polymer‐blend approach (PF/PDNAA = 95:5). The luminance yield and maximum external quantum efficiency of the light‐emitting diode with the PF/PDNAA blend as the emissive layer were 1.29 cd/A and 0.71%, respectively, and were significantly higher than those of the homopolymer. This study suggests that the PDNAA is a versatile material for electronic and optoelectronic applications. © 2007 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 1727–1736, 2007     

非水电导滴定法测定磺化聚醚砜

在分析测试磺化聚醚砜时，包裹在ＳＰＥＳ中的自由硫酸常影响着测试结果。为此本文提出利用非水溶剂的区分效应和对ＳＰＥＳ的良好溶解性能，通过电导滴定分析ＳＰＥＳ和自由硫酸的混合产物。经过透析实验和采用不同碱式滴定剂进行非水滴定实验表明：电导滴定能简便，快速、准确地测出自由硫酸含量和磺化度。同时了相关实验和理论方面的讨论。