Influences of local polymer-solvent π-π-interaction on dynamics of phenyl ring rotation and its role on photophysics of conjugated polymer

In this report, the role of local polymer-solvent π-π-interaction on rotational dynamics of phenyl rings of poly[2-methoxy-5-(2′-ethyl-hexyloxy)-1,4-phenylenevinylene] (MEH-PPV) is examined by utilizing nuclear magnetic resonance (NMR) spectroscopy. We have found that an aromatic solvent can couple strongly with the phenyl rings via favorable local π-π-interaction, causing a restriction of the ring rotation. The dynamic process takes place at much faster rate in a non-aromatic solvent. NMR line shape analysis indicates the existence of two side chain configurations with relatively long life-time in toluene and pyridine while a single time-averaged configuration is detected in chloroform and tetrahydrofuran. Addition of chloroform or cyclohexane to a solution of MEH-PPV in toluene is accompanied by an increase of the rotational dynamics. This indicates that the expansion or collapse of main chain upon varying solvent quality play a minor role on the rotational dynamics. The relationship between the dynamics of ring rotation and photophysics of MEH-PPV in solution is discussed.     

Electrospinning of polystyrene/poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene) blends

Ultrafine polystyrene (PS)/poly(2‐methoxy‐5‐(2′‐ethylhexyloxy)‐1,4‐phenylene vinylene) (MEH‐PPV) fibers were successfully prepared by electrospinning of PS/MEH‐PPV solutions in chloroform, 1,2‐dichloroethane, and tetrahydrofuran (THF). Three concentrations of the solutions were prepared: 8.5, 16, and 23.5% (w/v), with the compositional weight ratios between PS and MEH‐PPV being 7.5:1, 15:1, and 22.5:1, respectively. Smooth fibers only observed from 23.5% (w/v) PS/MEH‐PPV solution in chloroform. Improvement in the electrospinnability of 8.5% (w/v) PS/MEH‐PPV solution in chloroform was achieved by addition of an organic salt, pyridinium formate (PF), or by addition of a minor solvent with a high dielectric constant value. The average diameters of the as‐spun PS/MEH‐PPV fibers were between 0.30 and 5.11 μm. Last, photoluminescence of 8.5% (w/v) solutions of PS/MEH‐PPV in a mixed solvent system of chloroform and 1,2‐dichloroethane of various volumetric compositions and the resulting as‐spun fibers was investigated and compared. © 2005 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 43: 1881–1891, 2005     

Approaching Dissolved Species in Ammonoacidic GaN Crystal Growth: A Combined Solution NMR and Computational Study

Solutions of gallium trihalides GaX₃ (X=F, Cl, Br, I) and their ammoniates in liquid ammonia were studied at ambient temperature under autogenous pressure by multinuclear (⁷¹Ga, ³⁵Cl, ⁸¹Br) NMR spectroscopy. To unravel the role of pH, the analyses were done both in absence and in presence of ammonium halides, which are employed as mineralizers during ammonoacidic gallium nitride crystal growth. While gallium trifluoride and its ammoniate were found to be too sparingly soluble to give rise to a NMR signal, the spectra of solutions of the heavier halides reveal the presence of a single gallium-containing species in all cases. DFT calculations and molecular dynamics simulations suggest the identification of this species as consisting of a [Ga(NH₃)₆]³⁺ cation and up to six surrounding halide anions, resulting in an overall trend towards negative complex charge. Quantitative ⁷¹Ga NMR studies on saturated solutions of GaCl₃ containing various amounts of additional NH₄Cl revealed a near linear increase of GaCl₃ solubility with mineralizer concentration of about 0.023 mol GaCl₃ per mol NH₄Cl at room temperature. These findings reflect the importance of Coulombic shielding for the inhibition of oligomerization and precipitation processes and help to rationalize both the low solubility of gallium halides in neutral ammonia solution and, in turn, the proliferating effect of the mineralizer during ammonoacidic gallium nitride formation.     

On the Role of Amides and Imides for Understanding GaN Syntheses from Ammonia Solution: Molecular Mechanics Models of Ammonia,Amide and Imide Interactions with Gallium Nitride

A key requisite to characterizing GaN precipitation from ammonia solution from molecular simulations is the availability of reliable molecular mechanics models for the interactions of gallium ions with NH₃, NH₂⁻, and NH²⁻ species, respectively. Here, we present a tailor-made force field which is fully compatible to an earlier developed GaN model, thus bridging the analyses of Ga³⁺ ions in ammonia solution with the aggregation of [Ga_x(NH)_y(NH₂)_z]^+3x−2y−z precursors and the modelling of GaN crystals. For this, quantum mechanical characterization of a series of Ga-coordination clusters is used for parameterization and benchmarking the generalized amber force field (GAFF2) and tailor-made refinements needed to achieve good agreement of both structural features and formation energy, respectively. The perspectives of our models for larger scale molecular dynamics simulations are demonstrated by the analyses of amide and imide defects arrangement during the growth of GaN crystal faces.     

Kallikrein-11, in Association with Coiled-Coil Domain Containing 25, as a Potential Prognostic Marker for Cholangiocarcinoma with Lymph Node Metastasis

Cholangiocarcinoma (CCA) is a malignancy arising from cholangiocytes. Currently, the treatment and prognosis for CCA are mostly poor. Recently, we have reported that coiled-coil domain containing 25 (CCDC25) protein level in the sera may be a diagnostic marker for CCA. Subsequently, we identified three binding proteins of CCDC25 and found that kallikrein-11 (KLK11) expression was highest among those binding proteins. In this study, we investigated CCDC25 and KLK11 expression in CCA and adjacent normal tissues (n = 18) using immunohistochemistry. The results demonstrated that the expressions of CCDC25 and KLK11 in CCA tissues were both significantly higher than the adjacent tissues (p < 0.001 and p = 0.001, respectively). Then, using GEPIA bioinformatics analysis, KLK11 mRNA was significantly overexpressed in CCA tumor tissues compared with normal tissues (p < 0.05). Moreover, CCDC25 expression was positively correlated with KLK11 expression in CCA with lymph node metastasis (p = 0.028, r = 0.593). An analysis for the interaction of KLK11 with CCDC25 and other proteins, using STRING version 11.0, revealed that CCDC25 and KLK11 correlated with metastasis-related proteins. In addition, Kaplan-Meier survival curve analysis revealed that a high expression of KLK11 was associated with the poor prognosis of CCA. In conclusion, KLK11 is, as a binding protein for CCDC25, possibly involved in the metastatic process of CCA. KLK11 may be used as a prognostic marker for CCA.     

Bioinformatic Prediction of Signaling Pathways for Apurinic/Apyrimidinic Endodeoxyribonuclease 1 (APEX1) and Its Role in Cholangiocarcinoma Cells

Apurinic/apyrimidinic endodeoxyribonuclease 1 (APEX1) is involved in the DNA damage repair pathways and associates with the metastasis of several human cancers. However, the signaling pathway of APEX1 in cholangiocarcinoma (CCA) has never been reported. In this study, to predict the signaling pathways of APEX1 and related proteins and their functions, the effects of APEX1 gene silencing on APEX1 and related protein expression in CCA cell lines were investigated using mass spectrometry and bioinformatics tools. Bioinformatic analyses predicted that APEX1 might interact with cell division cycle 42 (CDC42) and son of sevenless homolog 1 (SOS1), which are involved in tumor metastasis. RNA and protein expression levels of APEX1 and its related proteins, retrieved from the Gene Expression Profiling Interactive Analysis (GEPIA) and the Human Protein Atlas databases, revealed that their expressions were higher in CCA than in the normal group. Moreover, higher levels of APEX1 expression and its related proteins were correlated with shorter survival time. In conclusion, the signaling pathway of APEX1 in metastasis might be mediated via CDC42 and SOS1. Furthermore, expression of APEX1 and related proteins is able to predict poor survival of CCA patients.     

Effects of chain conformation and chain length on degree of aggregation in assembled particles of conjugated polymer in solvents–nonsolvent: A spectroscopic study

This article explores photophysical properties and aggregation behaviors of conjugated polymer, poly[2‐methoxy, 5‐(2′‐ethylhexyloxy)‐1,4‐phenylenevinylene](MEH?PPV), in various solvent–nonsolvent systems by utilizing UV/vis absorption and photoluminescence (PL) spectroscopy. The isolated chains of MEH‐PPV dispersed in solvents including dichloromethane, chloroform, and tetrahydrofuran adopt either extended or collapsed conformations depending on local polymer–solvent interactions. Aggregation of the MEH‐PPV in these solvents is induced by addition of a poor solvent, cyclohexane. The formation of aggregates is indicated by the appearance of distinct red‐shift peaks in the absorption and PL spectra. The degree of aggregation in each solvent–nonsolvent system is compared by means of absorbance and PL intensity of the aggregate bands. In early stage of the aggregation, the amount of aggregates in system is controlled by the solubility of polymer. When the polymer chains are forced to densely pack within assembled particles by increasing ratio of cyclohexane to 99 v/v %, the conformation of individual chain plays important role. We have found that the extended chains facilitate the aggregation in the assembled particles. Increasing chain length of polymer promotes the aggregation in early stage and densely packed particles. Size distribution of the assembled particles is also found to depend on the choice of solvent. © 2010 Wiley Periodicals, Inc. J Polym Sci Part B: Polym Phys 48: 894–904, 2010