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Phosphorylation and dephosphorylation of proteins by kinases and phosphatases are central to cellular responses and function. The structural effects of serine and threonine phosphorylation were examined in peptides and in proteins, by circular dichroism, NMR spectroscopy, bioinformatics analysis of the PDB, small-molecule X-ray crystallography, and computational investigations. Phosphorylation of both serine and threonine residues induces substantial conformational restriction in their physiologically more important dianionic forms. Threonine exhibits a particularly strong disorder-to-order transition upon phosphorylation, with dianionic phosphothreonine preferentially adopting a cyclic conformation with restricted φ (φ ~ –60 ̊) stabilized by three noncovalent interactions: a strong intraresidue phosphate-amide hydrogen bond, an n→π* interaction between consecutive carbonyls, and an n→σ* interaction between the phosphate Oγ lone pair and the antibonding orbital of C–Hβ that restricts the χ2 side chain conformation. Proline is unique among the canonical amino acids for its covalent cyclization on the backbone. Phosphothreonine can mimic proline's backbone cyclization via noncovalent interactions. The preferred torsions of dianionic phosphothreonine are φ,ψ = polyproline II helix > α-helix (φ ~ –60 ̊); χ1 = g–; χ2 ~ +115 ̊ (eclipsed C–H/O–P bonds). This structural signature is observed in diverse proteins, including in the activation loops of protein kinases and in protein-protein interactions. In total, these results suggest a structural basis for the differential use and evolution of threonine versus serine phosphorylation sites in proteins, with serine phosphorylation typically inducing smaller, rheostat-like changes, versus threonine phosphorylation promoting larger, step function-like switches, in proteins. 

We present optical and near-infrared stellar polarization observations toward the dark filamentary clouds associated with IC5146. The data allow us to investigate the dust properties (this paper) and the magnetic field structure (Paper II). A total of 2022 background stars were detected in the R c , I\prime , H, and/or K bands to {A}V≲ 25 mag. The ratio of the polarization percentage at different wavelengths provides an estimate of {λ }\max , the wavelength of the peak polarization, which is an indicator of the small-size cutoff of the grain size distribution. The grain size distribution seems to significantly change at {A}V˜ 3 mag, where both the average and dispersion of {P}{Rc}/{P}H decrease. In addition, we found {λ }\max ˜ 0.6{--}0.9 μm for {A}V> 2.5 mag, which is larger than the ˜0.55 μm in the general interstellar medium (ISM), suggesting that grain growth has already started in low-A V regions. Our data also reveal that polarization efficiency ({PE}\equiv {P}λ /{A}V) decreases with A V as a power law in the R c , I\prime , and K bands with indices of -0.71 ± 0.10, -1.23 ± 0.10, and -0.53 ± 0.09. However, H-band data show a power index change; the PE varies with A V steeply (index of -0.95 ± 0.30) when {A}V< 2.88+/- 0.67 mag, but softly (index of -0.25 ± 0.06) for greater A V values. The soft decay of PE in high-A V regions is consistent with the radiative alignment torque model, suggesting that our data trace the magnetic field to {A}V˜ 20 mag. Furthermore, the breakpoint found in the H band is similar to that for A V , where we found the {P}{Rc}/{P}H dispersion significantly decreased. Therefore, the flat PE-A V in high-A V regions implies that the power-index changes result from additional grain growth.