Effect of Self-Poisoning on Crystallization Kinetics of Dimorphic Precision Polyethylenes with Bromine

High molar mass polyethylenes with bromine atoms placed on each and every 21st, 19th, 15th, or 9th backbone carbon crystallize into two distinctive layered polymorphs by changing undercooling. Crystallization at low temperatures produces Form I, a planar <i>all-trans</i> conformation, while at higher temperatures <i>gauche</i> conformers set for backbone bonds adjacent to the methine due to a close intermolecular staggering of bromines resulting in a herringbone Form II structure. In this work, the sharp range of isothermal crystallization temperatures for the transition between Form I and Form II is first identified via WAXD and melting behaviors for all members of the series. Furthermore, the temperature dependence of the isothermal linear spherulitic growth rates of Form II has been studied for a wide range of crystallization temperatures. The linear growth rates display a discrete minimum with decreasing temperature at a crystallization temperature near the melting point of Form I, a feature which is reminiscent of the minimum found in the crystallization rate of long-chain <i>n</i>-alkanes. Changes in spherulitic morphology and the growth rate minima are analyzed on the basis of self-poisoning at the growth front resulting from frequent but unstable Form I depositions on the growth surface of Form II. The similarity with the behavior observed in the growth of long-chain <i>n</i>-alkanes crystallites supports a polymer crystallization process controlled by events that take place at the crystal growth front

Distribution of selected characteristics among ESCC cases and controls.

<p>Abbreviation: ESCC, esophageal squamous cell carcinoma.</p>1<p>Two-sided χ² test.</p>2<p>Median age of cases is 59 years.</p><p>Distribution of selected characteristics among ESCC cases and controls.</p

<i>TNFAIP2</i> mRNA expression (mean ±SD) in normal and cancerous esophagus tissues grouped by <i>TNFAIP2</i> rs8126 T>C genotypes.

<p>The individual <i>TNFAIP2</i> mRNA expression was calculated relative to expression of <i>β-actin</i> mRNA using the 2^−dCt method. In normal esophagus tissues, significantly lower <i>TNFAIP2</i> mRNA levels among subjects with the rs8126 CC and CT genotypes were observed compared with the TT genotypes (0.0319±0.0167 [<i>n = </i>8] vs. 0.0602±0.0132 [<i>n = </i>10], <i>P<</i>0.05). However, there were no statistically significant differences of <i>TNFAIP2</i> mRNA expression were found between CC, CT and TT genotypes in ESCC tissue specimens (CC and CT: 0.0517±0.0207 [<i>n = </i>8] vs. TT: 0.0566±0.0163 [<i>n = </i>10], <i>P></i>0.05, n.s., not significant).</p

Genotype frequencies of the <i>TNFAIP2</i> rs8126 polymorphism among ESCC cases and controls and their association with ESCC risk.

<p>Abbreviation: ESCC, esophageal squamous cell carcinoma; OR, odds ratio; CI, confidence interval.</p>1<p>Data were calculated by logistic regression with adjustment for age, sex, smoking and drinking status.</p>2<p>Test for trend of odds was two-sided and based on likelihood ratio test assuming an additive model.</p><p>Genotype frequencies of the <i>TNFAIP2</i> rs8126 polymorphism among ESCC cases and controls and their association with ESCC risk.</p

Additional file 1: of Vemurafenib in Chinese patients with BRAFV600 mutation–positive unresectable or metastatic melanoma: an open-label, multicenter phase I study

Schedule of assessments. (DOCX 19 kb

Additional file 5: of Vemurafenib in Chinese patients with BRAFV600 mutation–positive unresectable or metastatic melanoma: an open-label, multicenter phase I study

Table S2. Comparison of efficacy between study YO28390 (Chinese patients) and the BRIM-2 and BRIM-3 studies (predominantly Caucasian patients). (DOCX 18 kb

Additional file 5: of Vemurafenib in Chinese patients with BRAFV600 mutation–positive unresectable or metastatic melanoma: an open-label, multicenter phase I study

Table S2. Comparison of efficacy between study YO28390 (Chinese patients) and the BRIM-2 and BRIM-3 studies (predominantly Caucasian patients). (DOCX 18 kb

Additional file 6: of Vemurafenib in Chinese patients with BRAFV600 mutation–positive unresectable or metastatic melanoma: an open-label, multicenter phase I study

Table S3. Comparison of safety between study YO28390 (Chinese patients) and the BRIM-3 study (predominantly Caucasian patients). (DOCX 18 kb

Additional file 2: of Vemurafenib in Chinese patients with BRAFV600 mutation–positive unresectable or metastatic melanoma: an open-label, multicenter phase I study

Figure S1. Vemurafenib Ctrough concentrations (mean ± SD) after day 28 in the pharmacokinetics and expansion cohorts. SD standard deviation, CV coefficient of variation. (PDF 71 kb

Additional file 3: of Vemurafenib in Chinese patients with BRAFV600 mutation–positive unresectable or metastatic melanoma: an open-label, multicenter phase I study

Figure S2. Kaplan-Meier plots of (A) progression-free survival (PFS) and (B) overall survival (OS). (PDF 80 kb