An optimized approach for in vivo Met- and Leu-Enk measurement.
A. Timeline of in vivo sample collection on day 1 and methionine oxidation reaction overnight, sample processing on day 2, and data acquisition on the LC-MS, days 3-5. The microdialysis probe is implanted via stereotaxic surgery in the Nucleus Accumbens Shell. The mouse is allowed to recover before being connected to the microdialysis lines. Samples are then collected at a rate of 0.8 μL/min for 13 minutes each. After collection is completed, the samples are oxidized overnight. On day 2 the samples undergo solid phase extraction (SPE) and are then dehydrated and reconstituted using formic acid (HCOOH) before being acquired on the LC-MS. B. Custom microdialysis probe specifications including membrane size and inner and outer diameters (ID and OD respectively) compared to fiber photometry probe specifications including OD of optic fiber and numerical aperture (NA). C. Before the methionine oxidation at reaction (Rxn) time 0, Met-Enk exists in three different forms with varying intensities, unoxidized (multi-peak), singly oxidized (multi-peak), and doubly oxidized (single peak). After the reaction completes (Rxn time 1), most of the detected signal is in the doubly oxidized form and shows a single peak (>99% signal intensity). D. (Left) Forward calibration curve of Leu-Enk and Met-Enk showing the peak area ratios as the light standard levels are varied. (Right) Reverse calibration curve of Leu-Enk showing the relationship between the heavy standard concentration applied and the measured concentration based on the instrument. E. Same setup as D but for Met-Enk. F. Violin plots showing that high K+ ringer’s solution increases the release of both Leu-Enk and Met-Enk compared to baseline levels in artificial cerebrospinal fluid (aCSF) (Leu-Enk n=9, Met-Enk n=18). The dashed center line indicates the median. G. The evoked concentrations of Met-Enk to Leu-Enk in the same samples show that Met-Enk is consistently released at a higher level than Leu-Enk (n=9). H. Met-Enk is released at a factor of 2.97 that of Leu-Enk as shown by linear regression analysis of the data in f, suggesting a linear relationship between the two peptides. Data in F, G, and H are transformed to a log scale. In F, 2-way ANOVA analysis shows a main effect of peptide, solution, and interaction. The p-values reported were calculated using a Sidak’s multiple comparisons test.