Role of the diphosphine chelate in emissive, charge-neutral iridium(III) complexes.

A class of neutral tris-bidentate Ir(III) metal complexes incorporating a diphosphine as a chelate is prepared and characterized here for the first time. Treatment of [Ir(dppb)(tht)Cl3] (1) with fppzH afforded the dichloride complexes, trans-(Cl,Cl)[Ir(dppb)(fppz)Cl2] (2) and cis-(Cl,Cl)[Ir(dppb)(fppz)Cl2] (3). The reaction of 3 with the dianionic chelate precursor bipzH2 or mepzH2, in DMF gave the complex [Ir(dppb)(fppz)(bipz)] (4) or [Ir(dppb)(fppz)(mepz)] (5), respectively. In contrast, a hydride complex [Ir(dppb)(fppz)(bipzH)H] (6) was isolated instead of 4 in protic solvent, namely: DGME. All complexes 2 - 6 are luminescent in powder forms and thin films where the dichlorides (2, 3) emit with maxima at 590-627 nm (orange) and quantum yields (Q.Y.s) up to 90% whereas the tris-bidentate (4, 5) and hydride (6) complexes emit at 455-458 nm (blue) with Q.Y.s up to 70%. Hybrid TD-DFT calculations showed considerable MLCT contribution to the orange-emitting 2 and 3 but substantial ligand-centered 3ππ* transition character in the blue-emitting 4 - 6. The dppb does not participate to these radiative transitions in 4 - 6, but it provides the rigidity and steric bulk needed to promote the luminescence by suppressing the self-quenching in the solid state. Fabrication of an OLED with dopant 5 gave a deep blue CIE chromaticity of (0.16, 0.15). Superior blue emitters, which are vital in OLED applications, may be found in other neutral Ir(III) complexes containing phosphine chelates

On the left side are the power values (α = 0.05) as a function of the number of cases for different haplogroups (the circles refer to haplogroup H, triangles to haplogroup J and crosses to haplogroup I).

<p>The intensity of the symbols indicate different odds ratio control-case: the thinner symbols indicate odds 1∶1, the medium symbols odds 2∶1, while the bolded symbols odds 3∶1. Colors indicate different deviations from the null hypothesis; black: the frequency of the risky allele is 100% higher in cases than in controls, red: 50%; and green 25%. The graph indicates that there is not a relationship between the number of cases and the statistical power value. On the right side are the power values as a function of the statistic <i>N_sc</i>; in red is the theoretical curve for the statistical power for 2×2 tables when the number of controls is equal to the number of cases.</p

Bézier curves

<p>Execution times considering several BWA-based aligners running the BWA-MEM algorithm (axes are in log scale).</p

The left side shows power values (α = 0.05) as a function of <i>N_sc</i> without correction of number of haplogroups (<i>N_H</i>) for different number of haplogroups and when the number of cases equals the number of controls.

<p>The right side shows power corrected according to <i>N_H</i>, and the nonparametric estimated regression curve. Colored circles denote different number of haplogroups; black: 4 haplogroups; red: 8 haplogroups; green: 12 haplogroups; dark blue: 16; and light blue: 20. Haplogroup frequencies were built using a vector of probabilities where the risk allele takes values 0.30, 0.15 or 0.05 (other values led to the same results; data not shown). The risky haplogroup take relative frequency differences in cases with respect to control of 100%, 50% and 25%. The number of cases takes values of 100, 250, 500, 750 and 1000, and control-case odds of 1, 2 and 3. We noted that other values do not change the distribution. The red line indicates the theoretical curve for 2×2 tables and equal numbers of cases and controls, while the black line is the non-parametric estimator of regression between <i>N_sc</i> parameter and the statistical power.</p

Overhead of the RDDs sorting operation considering different datasets.

<p>Overhead of the RDDs sorting operation considering different datasets.</p

Estimates of statistical power (%) under the null hypothesis using the asymptotic distribution <i>versus</i> the permutation procedure, and elapsed computational times (in seconds) under different simulation scenarios.

<p>Estimates were computed for 1,000 and 10,000 simulated tables (ST), number of cases equal to number of controls, and level of significance α = 0.05 (therefore, estimated power values should be close to 5%). Time estimates were obtained using an Intel® Core™ I5 3.1 GHz. These values were averaged over ten simulations each.</p

estimates for a significance level α and a power value β using non-parametric regression.

<p>These values were averaged over ten simulations each. Note that these values differ slightly from those obtained by Samuels et al. (see their Table 3) <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0073567#pone.0073567-Samuels1" target="_blank">[26]</a> due to the simulation procedure implemented in both studies and because we consider unequal number of cases and controls.</p

Representation of power values for three haplogroups (H, J. and I) as a function of the number of cases and using the Chi-square test (significance level α = 0.05).

<p>Colors indicate different deviations from the null hypothesis; thus, black represents a frequency in cases 100% higher than in controls, red represents an increment of 50%, and green an increment of 25% (with the difference distributed proportionally between the remaining non-risky haplogroups). The different lines indicate different case-control odds. The continuous line denotes an odd control-case of 1∶1, the dotted line of 2∶1, and the pointed line of 3∶1. Frequencies in controls for each haplogroup are indicated above each plot. Note that the results can be directly comparable with Samuels et al. <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0073567#pone.0073567-Samuels1" target="_blank">[26]</a> (see their <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0073567#pone-0073567-g001" target="_blank"><b>Figure</b> 1</a>) when number of cases equals number of controls.</p

The simulations show that the parameter <i>N_H</i> raised to the power of 0.37 is the one that empirically allows a better fit of the data to the theoretical curve of statistical power even in scenarios where the number of cases differs from the number of controls.

<p>See legend of <a href="http://www.plosone.org/article/info:doi/10.1371/journal.pone.0073567#pone-0073567-g003" target="_blank"><b>Figure 3</b></a> for more information on the simulation.</p

Speedup considering several BWA-based aligners running the BWA-backtrack algorithm (axes are in log scale).

<p>Speedup considering several BWA-based aligners running the BWA-backtrack algorithm (axes are in log scale).</p