Synthesis and optical and electrochemical properties of copolymers consisting of 9,9‐dihexylfluorene and aromatic triazole chromophores

Aromatic triazole chromophores were incorporated into polyfluorene in an attempt to increase electron affinity, to promote emission efficiency, and to diminish excimer formation. Poly(9,9‐dihexylfluorene) ( P1 ) and new copolymers with aromatic triazoles ( P2 – P4 ) were prepared by Suzuki coupling polymerization. In P2 , the aromatic triazole (3.8 mol %) was attached exclusively as terminal groups, whereas P3 and P4 were main‐chain copolymers containing 3.9 and 10.3 mol % aromatic triazole chromophores, respectively. The copolymers were soluble in common organic solvents and showed high decomposition temperatures (437–458 °C). The twisted structure between the triazole and fluorene increased the emission efficiency and effectively prevented excimer formation in P2 – P4 . After the introduction of the triazole units, the absorption spectra showed a blueshift (from 388 to 381 nm in chloroform) due to confined conjugation, but the photoluminescence spectra remained almost the same (417–418 nm); this was attributed to oligofluorene segments. No emission of triazole fluorophores was observed because of efficient energy transfer from the triazole to oligofluorene segments. However, incomplete energy transfer was observed in CH₃COOH. The optical stability upon thermal annealing was also improved by the incorporation of aromatic triazole segments. From cyclic voltammetry results, P2 – P4 , containing triazole groups, showed greater electron affinity (lowest unoccupied molecular orbital level = ?2.67 to ?2.71 eV) than P1 (?2.52 eV). Electroluminescence devices of P1 – P4 all exhibited excimer emissions (483–521 nm), which could also be diminished by the introduction of aromatic triazole chromophores. © 2006Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 45: 136–146, 2007     

Nanodiamond-based two-step sampling of multiply and singly phosphorylated peptides for MALDI-TOF mass spectrometry analysis

Simultaneous detection of multiply and singly phosphorylated peptides using matrix-assisted laser desorption/ionization time-of-flight mass spectrometry (MALDI-TOF MS) is challenging because of suppression effects during ionization. In oder to overcome this problem, this study presents a new approach to improve the detection of phosphopeptides by stepwise enrichment using polyarginine-coated (PA-coated) and titanium dioxide-coated (TiO(2)-coated) nanodiamonds for fractionation of multiply and singly phosphorylated peptides prior to on-probe MALDI MS analysis. The feasibility of this approach was demonstrated using synthetic peptides containing different numbers of phosphate groups, tryptic digests of α-casein, β-casein, and complex protein mixtures. The high specificity of the approach is shown in its effective enrichment and fractionation of phosphopeptides from the digest of β-casein and bovine serum albumin at a molar ratio as low as 1 : 1000, which out-performs the commercial Fe(3+)-IMAC and TiO(2) isolation kits. It offers a simple and effective alternative for the fractionation and identification of multiply and singly phosphorylated peptides by MALDI MS and allows for deduction of more information from limited starting materials.     

Monte Carlo approximation through Gibbs output in generalized linear mixed models

Geyer (J. Roy. Statist. Soc. 56 (1994) 291) proposed Monte Carlo method to approximate the whole likelihood function. His method is limited to choosing a proper reference point. We attempt to improve the method by assigning some prior information to the parameters and using the Gibbs output to evaluate the marginal likelihood and its derivatives through a Monte Carlo approximation. Vague priors are assigned to the parameters as well as the random effects within the Bayesian framework to represent a non-informative setting. Then the maximum likelihood estimates are obtained through the Newton Raphson method. Thus, out method serves as a bridge between Bayesian and classical approaches. The method is illustrated by analyzing the famous salamander mating data by generalized linear mixed models.     

The Synthesis and Chemistry of 9-Chlorobicyclo[6.1.0]Non-1(9)-Ene

9-Chlorobicyclo[6.1.0]non-l(9)-ene ( 4 ), a 2-chlorinated 1,3-fused cyclopropene, is synthesized and isolated from the dehalogenation of the l-bromo-9,9-dichlorobicyclo[6.1.0]nonane, itself derived from cyclooctene. Compound 4 undergoes ring opening reaction to generate cyclooctenyl chlorocarbene ( 9 ) which reacts with water via conjugate addition and ipso-addition to give ( E )-2-(chloromethylene)cyclooctanol ( 7 ) and cyclooctene-l-carboxaldehyde ( 8 ), respectively. The conjugate addition of 9 with water is more favorable than the ipso-addition by 3:1. Compound 4 , which is stable at ?25 °C for weeks without any decomposition, reacts with oxygen to produce 2-chlorocyclonon-2-enone ( 12 ) via the ring-opening reaction adduct, vinyl alkylcarbene 10 .     

Concurrent sympathetic activation and vagal withdrawal in hyperthyroidism: Evidence from detrended fluctuation analysis of heart rate variability

Despite many previous studies on the association between hyperthyroidism and the hyperadrenergic state, controversies still exist. Detrended fluctuation analysis (DFA) is a well recognized method in the nonlinear analysis of heart rate variability (HRV), and it has physiological significance related to the autonomic nervous system. In particular, an increased short-term scaling exponent α1 calculated from DFA is associated with both increased sympathetic activity and decreased vagal activity. No study has investigated the DFA of HRV in hyperthyroidism. This study was designed to assess the sympathovagal balance in hyperthyroidism. We performed the DFA along with the linear analysis of HRV in 36 hyperthyroid Graves’ disease patients (32 females and 4 males; age 30 ± 1 years, means ± SE) and 36 normal controls matched by sex, age and body mass index. Compared with the normal controls, the hyperthyroid patients revealed a significant increase (P<0.001) in α1 (hyperthyroid 1.28±0.04 versus control 0.91±0.02), long-term scaling exponent , overall scaling exponent , low frequency power in normalized units (LF%) and the ratio of low frequency power to high frequency power (LF/HF); and a significant decrease (P<0.001) in the standard deviation of the R-R intervals (SDNN) and high frequency power (HF). In conclusion, hyperthyroidism is characterized by concurrent sympathetic activation and vagal withdrawal. This sympathovagal imbalance state in hyperthyroidism helps to explain the higher prevalence of atrial fibrillation and exercise intolerance among hyperthyroid patients.     

Synthesis,structure, and electrochemistry of Ag-modified LiMn<Subscript>2</Subscript>O<Subscript>4</Subscript> cathode materials for lithium-ion batteries

The composite of silver-modified lithium manganese oxide were prepared using thermal decomposition method of different mole ratio. Structural characterization was carried out by X-ray diffraction (XRD). XRD analysis revealed different patterns as the content of the dopant in the spinel increases. Phase analysis shows that Ag particles were dispersed on the LiMn₂O₄ surface instead of entering the spinel structure. On the other hand, the electrochemical behavior of cathode powder was examined by using two-electrode test cells consisting of a cathode, metallic lithium as anode, and a solid polymer electrolyte of 0.87PEO-0.13LiCF₃SO₃-0.10DBP. According to the electrochemical tests results, the influence of the Ag additive content on the electrochemical properties of Ag/LiMn₂O₄ composites is clearly shown.     

A single-machine scheduling problem with two-agent and deteriorating jobs

Deteriorating jobs scheduling problems have been extensively studied in recent years. However, it is assumed that there is a common goal to minimize for all jobs in most of the research. In many management situations, multiple agents compete on the usage of a common processing resource. In this paper, we considered a single-machine scheduling problem with a linear deterioration assumption where the objective is to minimize the total weighted completion time of jobs from the first agent with the restriction that no tardy job is allowed for the second agent. We proposed a branch-and-bound algorithm and three heuristic algorithms to search for the optimal solution and near-optimal solutions, respectively. A computational experiment was conducted to evaluate the performance of the proposed algorithms.