34 research outputs found

    Effect of Side-Chain Architecture on the Optical and Crystalline Properties of Two-Dimensional Polythiophenes

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    The present study reported here synthesis of three novel two-dimensional (2D) polythiophene derivatives with conjugated terthiophene–vinylene side chainpoly­{3-(5″-hexyl-2,2′:5′,2″-terthiophenyl-5-vinyl)­thiophene-alt-thiophene} (<b>P1</b>), poly­{3-(5,5″-dihexyl-2,2′:5′,2″-terthiophenyl-3′-vinyl)­thiophene-alt-thiophene} (<b>P2</b>), and poly­{3-(4,4″-dihexyl-2,2:5′,2″-terthiophene-3′-vinyl)­thiophene-alt-thiophene} (<b>P3</b>)that were synthesized via stille coupling reaction. The terthiophene side chain with different conformations conjugated to the polythiophene main chain via vinyl linkage provided the ability to control the molecular organization, hence affecting the optoelectronic and electrochemical properties of 2D polymers. TD-DFT calculation with the B3LYP/6-31+g­(d) function on electronic structures of the monomers was consistent with the experimental results. It suggested that the energetic states of HOMO and LUMO were highly dependent on the side-chain architectures. These polythiophene thin films fabricated by spin-casting show a broader absorption ranges from 300 to 700 nm which was significantly wider than the absorption of pure poly­(3-hexylthiophene). When comparing the solid-state absorption spectra of these polymers before and after thermal annealing, <b>P3</b> displayed the most red-shift in the wavelength range between 450 and 700 nm. It was presumably due to an extended conjugation length resulting from the linear conformation and preferred chain packing, as manifested in the X-ray diffraction. Molecular dynamics (MD) simulation on polymers with different side chains in isolated and packed states suggests planar conformation of the main chain was adopted and regulated by the side chains which were placed in parallel with the main-chain direction. Interestingly, <b>P1</b> solution revealed an excitation-dependent emission property, suggesting a structural inhomogeneity in solution. Contrary to <b>P1</b>, the PL spectra of <b>P2</b> and <b>P3</b> showed only one emission peak at 460 nm, regardless of the excitation energy. Orientation and regiochemistry of the terthiophene side chain had a major impact on the overall optical and electronic properties of the polymer. Moreover, the HOMO and LUMO of these three polymers had been determined through cyclic voltammetry. HOMO of the three polymers were in the following order: <b>P1</b> > <b>P2</b> > <b>P3</b>. It implied that the energy level was regiochemistry dependent and directly associated with the linked position between backbone and conjugated side chain. Most importantly, through mesogen-jacketed-like design strategy employed in the present study, the improved packing of these two-dimensional polymers offered insights into structure design to enhance properties that have strong ties to the electronic devices

    The impact of an additional extra-hepatic primary malignancy on the outcomes of patients with hepatocellular carcinoma

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    <div><p>Background</p><p>The impact of additional extra-hepatic primary cancer (EHPC) on the outcomes of patients with hepatocellular carcinoma (HCC) remains uncertain.</p><p>Methods</p><p>We retrospectively analyzed the cancer registration database from a tertiary hospital in Southern Taiwan. Patients who were diagnosed with HCC from 2008 to 2012 were enrolled. Overall survival (OS), HCC-specific survival and recurrence after curative therapy were analyzed and compared between the patients with and the patients without EHPC.</p><p>Results</p><p>EHPC was found in 121/1506 (8.0%) patients. HCC patients with EHPC were older, more likely to be classified as Child-Pugh A, less likely to have viral hepatitis B or C, more likely to be single, had early stage HCC and received curative therapy for HCC. The OS did not significantly differ between the patients with and without EHPC(p = 0.061). However, significantly higher HCC-specific survival was observed in patients with EHPC (p<0.001), and a higher rate of non-HCC mortality was demonstrated in patients with EHPC (54.4% vs 9.3%). The subgroup analysis revealed better OS in patients with EHPC who were older than 65, had viral hepatitis B or C, had non-stage 1 HCC, had non-early stage BCLC and received non-curative therapy. Conversely, patients with HCC stage 1 who received curative therapy exhibited worse OS if they also had EHPC. The analysis of recurrence after curative therapy showed no difference between the two groups.</p><p>Conclusions</p><p>Our results implied that EHPC did not affect OS, but HCC-related survival was better in patients with EHPC. Based on these findings, the management of additional primary cancer is warranted.</p></div

    The correlation of measurements and limits of agreement between RealT<i>ime</i> and TaqMan assay in the 434 samples of HBV DNA level <3 log<sub>10</sub> IU/mL.

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    <p>The correlation of HBV DNA in the 434 samples between the two assays was not as good as all samples (R<sup>2</sup> = 0.457; <i>P</i><0.001). (A) The mean difference was 0.40±0.77 log<sub>10</sub> IU/ml (limits of agreement, −1.15 to 1.95 log<sub>10</sub> IU/ml). (B)</p
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