Thermodynamics of a μ‑oxo Dicopper(II) Complex for Hydrogen Atom Abstraction

The mono-μ-hydroxo complex {[Cu­(tmpa)]₂-(μ-OH)}³⁺ (<b>1</b>) can undergo reversible deprotonation at −30 °C to yield {[Cu­(tmpa)]₂-(μ-O)}²⁺ (<b>2</b>). This species is basic with a p<i>K</i>_a of 24.3. <b>2</b> is competent for concerted proton–electron transfer from TEMPOH, but is an intrinsically poor hydrogen atom abstractor (BDFE­(OH) of 77.2 kcal/mol) based on kinetic and thermodynamic analyses. Nonetheless, DFT calculations experimentally calibrated against <b>2</b> reveal that [Cu₂O]²⁺ is likely thermodynamically viable in copper-dependent methane monoxygenase enzymes

Thermodynamics of a μ‑oxo Dicopper(II) Complex for Hydrogen Atom Abstraction

The mono-μ-hydroxo complex {[Cu­(tmpa)]₂-(μ-OH)}³⁺ (<b>1</b>) can undergo reversible deprotonation at −30 °C to yield {[Cu­(tmpa)]₂-(μ-O)}²⁺ (<b>2</b>). This species is basic with a p<i>K</i>_a of 24.3. <b>2</b> is competent for concerted proton–electron transfer from TEMPOH, but is an intrinsically poor hydrogen atom abstractor (BDFE­(OH) of 77.2 kcal/mol) based on kinetic and thermodynamic analyses. Nonetheless, DFT calculations experimentally calibrated against <b>2</b> reveal that [Cu₂O]²⁺ is likely thermodynamically viable in copper-dependent methane monoxygenase enzymes

Pedigree of a consanguineous Pakistani family segregating an autosomal recessive form of a novel type of ectodermal dysplasia.

<p>Circles and squares represent females and males, respectively. Clear symbols represent unaffected individuals while filled symbols represent affected individuals. Symbols with asterisk represent DNA samples available for the molecular analysis.</p

Ideogram of chromosome 18 displaying positions of the functional genes along the linkage interval (Chr18p11.32-p11.31 on GRCH37/hg19 assembly) of 3.03 Mb identified in the family.

<p>Ideogram of chromosome 18 displaying positions of the functional genes along the linkage interval (Chr18p11.32-p11.31 on GRCH37/hg19 assembly) of 3.03 Mb identified in the family.</p

Two-point LOD score between ED syndrome and SNP markers on chromosome 18p11.32-p11.31.

<p><b>a</b> Physical positions of the SNPs are according to the dbSNP132 (<a href="http://genome.ucsc.edu/cgi-bin/hgGateway" target="_blank">http://genome.ucsc.edu/cgi-bin/hgGateway</a>)</p><p><b>b</b> Recombination fraction.</p><p>Two-point LOD score between ED syndrome and SNP markers on chromosome 18p11.32-p11.31.</p