Sometimes, the Least Demanding Solution Is the Most Suitable: A Careful Survey of NMR Spectra of a Phosphonium Salt Accounted for Its “Unusual Wittig Reaction”

Careful product analysis in combination with appropriate supporting experiments unambiguously proves that in contrast to what was previously reported, generation of the phosphonium salt from a β-cyclocitral-derived allylic alcohol and PPh₃HBr takes place via a proton-driven elimination/addition path

Characteristics of patients.

<p>Characteristics of patients.</p

ESAS items at admission and at discharge in patients with complete data.

<p>ESAS items at admission and at discharge in patients with complete data.</p

Data regarding the previous disease-oriented treatment, the setting where patients were previously cared and who referred the patient at admission, and care setting, physicians to refer patients and clinical pathways suggested at discharge from the unit.

<p>APSCU = acute palliative-supportive care unit.</p

Baseline characteristics of mCRC patients (n = 133 patients).

<p>Baseline characteristics of mCRC patients (n = 133 patients).</p

The boxplot of time to progression according to the 5FUDR-based metabolic classes.

<p>The boxplot of time to progression according to the 5FUDR-based metabolic classes.</p

PFS according to the metabolic classes (p = 0.0029).

<p>PFS according to the metabolic classes (p = 0.0029).</p

Differential Denaturation of Serum Proteome Reveals a Significant Amount of Hidden Information in Complex Mixtures of Proteins

<div><p>Recently developed proteomic technologies allow to profile thousands of proteins within a high-throughput approach towards biomarker discovery, although results are not as satisfactory as expected. In the present study we demonstrate that serum proteome denaturation is a key underestimated feature; in fact, a new differential denaturation protocol better discriminates serum proteins according to their electrophoretic mobility as compared to single-denaturation protocols. Sixty nine different denaturation treatments were tested and the 3 most discriminating ones were selected (TRIDENT analysis) and applied to human sera, showing a significant improvement of serum protein discrimination as confirmed by MALDI-TOF/MS and LC-MS/MS identification, depending on the type of denaturation applied. Thereafter sera from mice and patients carrying cutaneous melanoma were analyzed through TRIDENT. Nine and 8 protein bands were found differentially expressed in mice and human melanoma sera, compared to healthy controls (p<0.05); three of them were found, for the first time, significantly modulated: α2macroglobulin (down-regulated in melanoma, p<0.001), Apolipoprotein-E and Apolipoprotein-A1 (both up-regulated in melanoma, p<0.04), both in mice and humans. The modulation was confirmed by immunological methods. Other less abundant proteins (e.g. gelsolin) were found significantly modulated (p<0.05).</p> <p>Conclusions: i) serum proteome contains a large amount of information, still neglected, related to proteins folding; ii) a careful serum denaturation may significantly improve analytical procedures involving complex protein mixtures; iii) serum differential denaturation protocol highlights interesting proteomic differences between cancer and healthy sera.</p> </div

5-fluorouracil metabolism.

<p>5-fluorouracil metabolism.</p

PFS of patients with normal and altered 5-FU-DR (p = 0.03).

<p>PFS of patients with normal and altered 5-FU-DR (p = 0.03).</p