private void TestTaxolAdduct(string adductText, double expectedMz, int expectedCharge, HashSet <string> coverage)
{
// See http://fiehnlab.ucdavis.edu/staff/kind/Metabolomics/MS-Adduct-Calculator/
var Taxol = "C47H51NO14"; // M=853.33089 (agrees with chemspider)
var calcMass = BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula(Taxol);
Assert.AreEqual(massTaxol, calcMass, .0001);
var adduct = Adduct.FromStringAssumeProtonated(adductText);
Assert.AreEqual(expectedCharge, adduct.AdductCharge);
var mz = BioMassCalc.CalculateIonMz(calcMass, adduct);
Assert.AreEqual(expectedMz, mz, .001);
var massWithIsotopes = adduct.MassFromMz(mz, MassType.Monoisotopic);
Assert.AreEqual(massTaxol, massWithIsotopes - adduct.GetIsotopesIncrementalMonoisotopicMass() / adduct.GetMassMultiplier(), .0001);
coverage.Add(adduct.AsFormula());
}
public Adduct GetProductAdduct(Adduct precursorAdduct)
{
var totalCharge = TotalCharge;
if (totalCharge == 0)
{
return(precursorAdduct);
}
var newCharge = precursorAdduct.AdductCharge - totalCharge;
if (Math.Sign(newCharge) != Math.Sign(precursorAdduct.AdductCharge))
{
return(null);
}
return(precursorAdduct.ChangeCharge(newCharge));
}
private static void CheckRefSpectra(IList <DbRefSpectra> spectra, string name, string formula, string precursorAdduct, double precursorMz, ushort numPeaks)
{
name = RefinementSettings.TestingConvertedFromProteomicPeptideNameDecorator + name;
for (var i = 0; i < spectra.Count; i++)
{
var spectrum = spectra[i];
if (spectrum.MoleculeName.Equals(name) &&
spectrum.ChemicalFormula.Equals(formula) &&
spectrum.PrecursorCharge.Equals(Adduct.FromStringAssumeProtonated(precursorAdduct).AdductCharge) &&
spectrum.PrecursorAdduct.Equals(precursorAdduct) &&
Math.Abs(spectrum.PrecursorMZ - precursorMz) < 0.001 &&
spectrum.NumPeaks.Equals(numPeaks))
{
spectra.RemoveAt(i);
return;
}
}
Assume.Fail(string.Format("{0}, {1}, precursor charge {2}, precursor m/z {3}, with {4} peaks not found", name, formula, precursorAdduct, precursorMz, numPeaks));
}
private static void VerifySharedDocLibraryAnnotations(string shareDocPath)
{
RunUI(() => SkylineWindow.OpenSharedFile(shareDocPath));
var doc = WaitForDocumentLoaded();
AssertEx.IsDocumentState(doc, null, 1, 4, 4, 4); // int revision, int groups, int peptides, int tranGroups, int transitions
SpectrumPeaksInfo spectrum;
IsotopeLabelType label;
// ReSharper disable PossibleNullReferenceException
doc.Settings.TryLoadSpectrum(doc.Molecules.FirstOrDefault().Target, Adduct.FromStringAssumeChargeOnly("M+NH4"),
null, out label, out spectrum);
Assume.IsTrue(spectrum.Annotations.Count() == 1);
var spectrumPeakAnnotations = (spectrum.Annotations.FirstOrDefault() ?? new SpectrumPeakAnnotation[0]).ToArray();
Assume.IsTrue(spectrumPeakAnnotations.Length == 1);
Assume.IsTrue(spectrumPeakAnnotations.FirstOrDefault().Ion.Name == "GP");
// ReSharper restore PossibleNullReferenceException
}
public static Adduct GetChargeFromIndicator(string text, int min, int max, out int foundAt)
{
foundAt = -1;
if (!MayHaveChargeIndicator(text))
{
return(Adduct.EMPTY);
}
// Handle runs of charge characters no matter how long, because users guess this should work
foundAt = FindChargeSymbolRepeatStart('+', text, min, max);
if (foundAt != -1)
{
return(Adduct.FromChargeProtonated(text.Length - foundAt));
}
foundAt = FindChargeSymbolRepeatStart('-', text, min, max);
if (foundAt != -1)
{
return(Adduct.FromChargeProtonated(foundAt - text.Length));
}
Adduct adduct;
for (int i = max; i >= min; i--)
{
adduct = GetChargeFromIndicator(text, i, out foundAt);
if (!adduct.IsEmpty)
{
return(adduct);
}
adduct = GetChargeFromIndicator(text, -i, out foundAt);
if (!adduct.IsEmpty)
{
return(adduct);
}
}
foundAt = FindAdductDescription(text, out adduct);
if (foundAt != -1)
{
return(adduct);
}
return(Adduct.EMPTY);
}
public Transition(TransitionGroup group, IonType type, int?offset, int?massIndex, Adduct adduct,
int?decoyMassShift, CustomMolecule customMolecule = null)
{
_group = group;
IonType = type;
CleavageOffset = offset ?? 0;
MassIndex = massIndex ?? 0;
Adduct = adduct;
DecoyMassShift = decoyMassShift;
// Small molecule precursor transition should have same custom molecule as parent
if (IsPrecursor(type) && group.IsCustomIon)
{
CustomIon = new CustomIon(group.CustomMolecule, adduct);
}
else if (customMolecule is CustomIon)
{
// As with reporter ions
CustomIon = (CustomIon)customMolecule;
Assume.IsTrue(Equals(adduct.AdductCharge, CustomIon.Adduct.AdductCharge));
Adduct = CustomIon.Adduct; // Ion mass is part of formula, so use charge only adduct
}
else if (customMolecule != null)
{
CustomIon = new CustomIon(customMolecule, adduct);
}
// Derived values
if (!IsCustom(type, group))
{
Peptide peptide = group.Peptide;
Ordinal = OffsetToOrdinal(type, (int)offset, peptide.Length);
AA = (IsNTerminal()
? peptide.Sequence[(int)offset]
: peptide.Sequence[(int)offset + 1]);
}
else
{
// caller may have passed in offset = group.Peptide.Length - 1, which for custom ions gives -1
CleavageOffset = 0;
}
Validate();
}
private static int FindChargeIndicatorPos(string line, int min, int max, CultureInfo cultureInfo)
{
for (int i = max; i >= min; i--)
{
// Handle negative charges
int pos = FindChargeIndicatorPos(line, GetChargeIndicator(Adduct.FromChargeProtonated(-i), cultureInfo));
if (pos != -1)
{
return(pos);
}
// Handle positive charges
pos = FindChargeIndicatorPos(line, GetChargeIndicator(Adduct.FromChargeProtonated(i), cultureInfo));
if (pos != -1)
{
return(pos);
}
}
return(-1);
}
private bool DeriveAdductsForCommonFormula(Peptide peptide)
{
// Try to come up with a set of adducts to common formula that explain the declared mz values
var success = false;
if (_precursorRawDetails.TrueForAll(d => Adduct.IsNullOrEmpty(d._nominalAdduct)))
{
// No explicit adducts, just charges.
// Start with the most common scenario, which is that the user meant (de)protonation
// See if we can arrive at a common formula ( by adding or removing H) that works with all charges as (de)protonations
// N.B. the parent molecule may well be completely unrelated to the children, as users were allowed to enter anything they wanted
var commonFormula = ProposedMolecule.Formula;
var precursorsWithFormulas = _precursorRawDetails.Where(d => !string.IsNullOrEmpty(d._formulaUnlabeled)).ToList();
foreach (var detail in precursorsWithFormulas)
{
var revisedCommonFormula = Molecule.AdjustElementCount(commonFormula, BioMassCalc.H, -detail._declaredCharge);
var adjustedMolecule = new CustomMolecule(revisedCommonFormula, peptide.CustomMolecule.Name);
var mass = adjustedMolecule.MonoisotopicMass;
if (precursorsWithFormulas.TrueForAll(d =>
{
d._proposedAdduct = Adduct.ProtonatedFromFormulaDiff(d._formulaUnlabeled, revisedCommonFormula, d._declaredCharge)
.ChangeIsotopeLabels(d._labels);
return(Math.Abs(d._declaredMz - d._proposedAdduct.MzFromNeutralMass(mass)) <= MzToler);
}))
{
ProposedMolecule = adjustedMolecule;
success = true;
break;
}
}
success &= _precursorRawDetails.All(d => !Adduct.IsNullOrEmpty(d._proposedAdduct));
if (!success)
{
foreach (var d in _precursorRawDetails)
{
d._proposedAdduct = Adduct.EMPTY;
}
}
}
return(success);
}
/// <summary>
/// Calculates the matching charge within a tolerance for a mass, assuming (de)protonation.
/// </summary>
/// <param name="mass">The mass to calculate charge for (actually massH if !IsCustomIon)</param>
/// <param name="mz">The desired m/z value the charge should produce</param>
/// <param name="tolerance">How far off the actual m/z is allowed to be</param>
/// <param name="isCustomIon">Is this a custom ion formula?</param>
/// <param name="minCharge">Minimum charge to consider</param>
/// <param name="maxCharge">Maximum charge to consider</param>
/// <param name="massShifts">Possible mass shifts that may have been applied to decoys</param>
/// <param name="massShiftType"></param>
/// <param name="massShift">Mass shift required to to achieve this charge state or zero</param>
/// <param name="nearestCharge">closest matching charge, useful when return value is null</param>
/// <returns>A matching charge or null, in which case the closest non-matching charge can be found in the nearestCharge value.</returns>
public static Adduct CalcCharge(TypedMass mass, double mz, double tolerance, bool isCustomIon, int minCharge, int maxCharge,
ICollection <int> massShifts, MassShiftType massShiftType, out int massShift, out int nearestCharge)
{
Assume.IsTrue(minCharge <= maxCharge);
massShift = 0;
nearestCharge = 0;
double nearestDelta = double.MaxValue;
for (int i = minCharge; i <= maxCharge; i++)
{
if (i != 0) // Avoid z=0 if we're entertaining negative charge states
{
double delta = mz - (isCustomIon ? Adduct.FromChargeProtonated(i).MzFromNeutralMass(mass) : SequenceMassCalc.GetMZ(mass, i));
double deltaAbs = Math.Abs(delta);
int potentialShift = (int)Math.Round(deltaAbs);
double fractionalDelta = deltaAbs - potentialShift;
if (MatchMz(fractionalDelta, tolerance) && MatchMassShift(potentialShift, massShifts, massShiftType))
{
massShift = potentialShift;
if (delta < 0)
{
massShift = -massShift;
}
var result = i;
nearestCharge = i;
return(Adduct.FromChargeProtonated(result));
}
if (deltaAbs < nearestDelta)
{
nearestDelta = deltaAbs;
nearestCharge = i;
}
}
}
Debug.Assert(nearestCharge != 0); // Could only happen if min > max
return(Adduct.EMPTY);
}
private void LoadPeptides(IEnumerable <DbIonMobilityPeptide> peptides)
{
var dictLibrary = new Dictionary <LibKey, DbIonMobilityPeptide>();
foreach (var pep in peptides)
{
var dict = dictLibrary;
try
{
DbIonMobilityPeptide ignored;
var adduct = pep.GetPrecursorAdduct();
if (adduct.IsEmpty)
{
// Older formats didn't consider charge to be a factor is CCS, so just fake up M+H, M+2H and M+3H
for (int z = 1; z <= 3; z++)
{
var newPep = new DbIonMobilityPeptide(pep.GetNormalizedModifiedSequence(),
Adduct.FromChargeProtonated(z), pep.CollisionalCrossSection, pep.HighEnergyDriftTimeOffsetMsec);
var key = newPep.GetLibKey();
if (!dict.TryGetValue(key, out ignored))
{
dict.Add(key, newPep);
}
}
}
else
{
var key = pep.GetLibKey();
if (!dict.TryGetValue(key, out ignored))
{
dict.Add(key, pep);
}
}
}
catch (ArgumentException)
{
}
}
DictLibrary = dictLibrary;
}
public void WriteXml(XmlWriter writer, Adduct adduct)
{
if (adduct.IsEmpty)
{
writer.WriteAttributeIfString(ATTR.neutral_formula, Formula);
}
else
{
writer.WriteAttributeIfString(ATTR.ion_formula,
(Formula ?? string.Empty) +
(adduct.IsProteomic ? string.Empty : adduct.ToString()));
}
Assume.IsFalse(AverageMass.IsMassH()); // We're going to read these as neutral masses
Assume.IsFalse(MonoisotopicMass.IsMassH());
writer.WriteAttributeNullable(ATTR.neutral_mass_average, AverageMass);
writer.WriteAttributeNullable(ATTR.neutral_mass_monoisotopic, MonoisotopicMass);
if (!string.IsNullOrEmpty(Name))
{
writer.WriteAttribute(ATTR.custom_ion_name, Name);
}
writer.WriteAttributeIfString(ATTR.id, AccessionNumbers.ToSerializableString());
}
// Helper function for PrecursorIonFormula and PrecursorNeutralFormula
private void GetPrecursorFormulaAndAdduct(out Adduct adduct, out string formula)
{
if (IsSmallMolecule())
{
formula = (DocNode.CustomMolecule.Formula ?? string.Empty);
adduct = DocNode.PrecursorAdduct;
}
else
{
PeptideDocNode parent = DataSchema.Document.FindNode(IdentityPath.Parent) as PeptideDocNode;
if (parent == null)
{
adduct = Util.Adduct.EMPTY;
formula = String.Empty;
return;
}
var molecule = RefinementSettings.ConvertToSmallMolecule(
RefinementSettings.ConvertToSmallMoleculesMode.formulas, SrmDocument, parent, out adduct,
DocNode.TransitionGroup.PrecursorAdduct.AdductCharge, DocNode.TransitionGroup.LabelType);
formula = molecule.Formula ?? string.Empty;
}
}
public MockTranPeakData(double[] data,
IonType ionType = IonType.a,
IsotopeLabelType labelType = null,
int?charge = null,
double?massError = null,
double libIntensity = 0,
double?isotopeProportion = null)
{
if (labelType == null)
{
labelType = IsotopeLabelType.light;
}
PeakData = new MockPeakData(data, massError) as TPeak;
var peptide = new Peptide(null, "AVVAVVA", null, null, 0);
charge = charge ?? 2;
var tranGroup = new TransitionGroup(peptide, Adduct.FromChargeProtonated(charge), labelType);
int offset = ionType == IonType.precursor ? 6 : 0;
var isotopeInfo = isotopeProportion == null ? null : new TransitionIsotopeDistInfo(1, (float)isotopeProportion);
NodeTran = new TransitionDocNode(new Transition(tranGroup, ionType, offset, 0, Adduct.FromChargeProtonated(charge), null),
null, TypedMass.ZERO_MONO_MASSH, new TransitionDocNode.TransitionQuantInfo(isotopeInfo, new TransitionLibInfo(1, (float)libIntensity), true));
}
private double?_monoMass; // Our internal value for mass, regardless of whether displaying mass or mz
/// <summary>
/// Reusable control for dealing with chemical formulas and their masses
/// </summary>
/// <param name="isProteomic">if true, don't offer Cl, Br, or heavy P or heavy S in elements popup</param>
/// <param name="labelFormulaText">Label text for the formula textedit control</param>
/// <param name="labelAverageText">Label text for the average mass or m/z textedit control</param>
/// <param name="labelMonoText">Label text for the monoisotopic mass or m/z textedit control</param>
/// <param name="adduct">If non-null, treat the average and monoisotopic textedits as describing m/z instead of mass</param>
/// <param name="mode">Controls editing of the formula and/or adduct edit</param>
/// <param name="suggestOnlyAdductsWithMass">If presenting an adduct dropdown menu, do we include things like "[M+]"?</param>
public FormulaBox(bool isProteomic, string labelFormulaText, string labelAverageText, string labelMonoText, Adduct adduct, EditMode mode = EditMode.formula_only, bool suggestOnlyAdductsWithMass = true)
{
InitializeComponent();
if (isProteomic)
{
// Don't offer exotic atoms or isotopes
p32ToolStripMenuItem.Visible =
s33ToolStripMenuItem.Visible =
s34ToolStripMenuItem.Visible =
h3ToolStripMenuItem.Visible =
clToolStripMenuItem.Visible =
cl37ToolStripMenuItem.Visible =
brToolStripMenuItem.Visible =
br81ToolStripMenuItem.Visible = false;
}
_adduct = adduct;
_editMode = mode;
switch (mode)
{
case EditMode.adduct_only:
case EditMode.formula_and_adduct:
TransitionSettingsUI.AppendAdductMenus(contextFormula, suggestOnlyAdductsWithMass, adductStripMenuItem_Click);
break;
}
toolTip1.SetToolTip(textFormula, _editMode == EditMode.adduct_only ? AdductHelpText : FormulaHelpText); // Explain how formulas work, and ion formula adducts if charge.HasValue
labelFormula.Text = labelFormulaText;
labelAverage.Text = labelAverageText;
labelMono.Text = labelMonoText;
Bitmap bm = Resources.PopupBtn;
bm.MakeTransparent(Color.Fuchsia);
btnFormula.Image = bm;
}
private TransitionDocNode TransitionFromPeakAndAnnotations(LibKey key, TransitionGroupDocNode nodeGroup,
Adduct fragmentCharge, SpectrumPeaksInfo.MI peak, int?rank)
{
var charge = fragmentCharge;
var monoisotopicMass = charge.MassFromMz(peak.Mz, MassType.Monoisotopic);
var averageMass = charge.MassFromMz(peak.Mz, MassType.Average);
// Caution here - library peak (observed) mz may not exactly match (theoretical) mz of the annotation
// In the case of multiple annotations, produce single transition for display in library explorer
var annotations = peak.GetAnnotationsEnumerator().ToArray();
var spectrumPeakAnnotationIon = peak.AnnotationsAggregateDescriptionIon;
var molecule = spectrumPeakAnnotationIon.Adduct.IsEmpty
? new CustomMolecule(monoisotopicMass, averageMass)
: spectrumPeakAnnotationIon;
var note = (annotations.Length > 1) ? TextUtil.LineSeparate(annotations.Select(a => a.ToString())) : null;
var noteIfAnnotationMzDisagrees = NoteIfAnnotationMzDisagrees(key, peak);
if (noteIfAnnotationMzDisagrees != null)
{
if (note == null)
{
note = noteIfAnnotationMzDisagrees;
}
else
{
note = TextUtil.LineSeparate(note, noteIfAnnotationMzDisagrees);
}
}
var transition = new Transition(nodeGroup.TransitionGroup,
spectrumPeakAnnotationIon.Adduct.IsEmpty ? charge : spectrumPeakAnnotationIon.Adduct, 0, molecule);
return(new TransitionDocNode(transition, Annotations.EMPTY.ChangeNote(note), null, monoisotopicMass,
rank.HasValue ?
new TransitionDocNode.TransitionQuantInfo(null,
new TransitionLibInfo(rank.Value, peak.Intensity), true) :
TransitionDocNode.TransitionQuantInfo.DEFAULT, ExplicitTransitionValues.EMPTY, null));
}
public static Adduct GetChargeFromIndicator(string text, int min, int max, out int foundAt)
{
foundAt = -1;
if (!MayHaveChargeIndicator(text))
{
return(Adduct.EMPTY);
}
Adduct adduct;
for (int i = max; i >= min; i--)
{
// Handle negative charges
adduct = Adduct.FromChargeProtonated(-i);
var chargeIndicator = GetChargeIndicator(adduct);
if (text.EndsWith(chargeIndicator))
{
foundAt = text.Length - chargeIndicator.Length;
return(adduct);
}
adduct = Adduct.FromChargeProtonated(i);
chargeIndicator = GetChargeIndicator(adduct);
if (text.EndsWith(chargeIndicator))
{
foundAt = text.Length - chargeIndicator.Length;
return(adduct);
}
}
var adductStart = FindAdductDescription(text, out adduct);
if (adductStart >= 0)
{
foundAt = adductStart;
return(adduct);
}
return(Adduct.EMPTY);
}
protected override void DoTest()
{
var testFilesDir = TestFilesDir;
// Verify our use of explict RT where multiple nodes and multiple chromatograms all have same Q1>Q3
// This data set has three chromatograms with Q1=150 Q3=150 (one in negative ion mode), and
// three transition nodes with that Q1>Q3 but different RTs (one with neg charge)
// Expected alignment:
// function 65/ index 242 : RT 6.95 glutamate
// function 66/ index 243 : RT 7.95 glutamine (peak found at 8.1, but declared explicit RT window is 7.95 +/- .1 so no match)
// function 197/ index 117 (neg ion mode): RT 6.4 alpha_ketogluterate
DoSubTest(testFilesDir, "glutes.sky", new[] { 6.95, 0, 6.4 }, new[] { "090215_033" }, null,
new[] { Adduct.M_PLUS_H, Adduct.M_PLUS_H, Adduct.M_MINUS_H });
// Verify our handling of two Q1>Q3 transitions with no RT overlap - formerly we just ignored one or the other though both are needed
// As in https://skyline.gs.washington.edu/labkey/announcements/home/support/thread.view?entityId=924e3c51-7c00-1033-9ff1-da202582a252&_anchor=24723
DoSubTest(testFilesDir, "lysine.sky", new[] { 13.8, 13.8, 13.8, 13.8 }, new[] { "ESvKprosp_20151120_035", "ESvKprosp_20151120_036" }, .5,
new[] { Adduct.M_PLUS_H, Adduct.FromStringAssumeChargeOnly("[M6C132N15+H]") });
// Verify our use of explict RT in peak picking where the correct peak isn't the largest
// As in https://skyline.gs.washington.edu/labkey/announcements/home/support/thread.view?entityId=273ccc30-8258-1033-9ff1-da202582a252&_anchor=24774
DoSubTest(testFilesDir, "test_b.sky", new[] { 9.1, 9.1, 9.1, 9.1, 9.1, 9.1, 9.1, 9.1 }, new[] { "120315_120", "120315_121", "120315_125", "120315_126" }, null,
new[] { Adduct.M_PLUS_H, Adduct.M_PLUS_H });
}
/// <summary>
/// Get a mass value from the text string, treating the string as m/z info if we have a charge state
/// </summary>
private double?GetMassFromText(string text, MassType massType)
{
try
{
if (String.IsNullOrEmpty(text))
{
return(null);
}
else
{
double parsed = double.Parse(text);
if (!Adduct.IsEmpty)
{
// Convert from m/z to mass
return(Adduct.MassFromMz(parsed, massType));
}
return(parsed);
}
}
catch (Exception)
{
return(null);
}
}
public static string GetChargeIndicator(Adduct adduct, CultureInfo cultureInfo)
{
if (!adduct.IsProteomic && !adduct.IsChargeOnly)
{
return(adduct.AsFormulaOrSignedInt());
}
var charge = adduct.AdductCharge;
if (charge >= 0)
{
const string pluses = "++++";
return(charge <= pluses.Length
? pluses.Substring(0, Math.Min(charge, pluses.Length))
: string.Format(@"{0} +{1}", GetChargeSeparator(cultureInfo), charge));
}
else
{
const string minuses = "--";
charge = -charge;
return(charge <= minuses.Length
? minuses.Substring(0, Math.Min(charge, minuses.Length))
: string.Format(@"{0} -{1}", GetChargeSeparator(cultureInfo), charge));
}
}
public static string GetChargeIndicator(Adduct adduct)
{
if (!adduct.IsProteomic && !adduct.IsChargeOnly)
{
return(adduct.AsFormulaOrSignedInt());
}
var charge = adduct.AdductCharge;
if (charge >= 0)
{
const string pluses = "++++"; // Not L10N
return(charge <= pluses.Length
? pluses.Substring(0, Math.Min(charge, pluses.Length))
: string.Format("{0} +{1}", LocalizationHelper.CurrentCulture.NumberFormat.NumberGroupSeparator, charge)); // Not L10N
}
else
{
const string minuses = "--"; // Not L10N
charge = -charge;
return(charge <= minuses.Length
? minuses.Substring(0, Math.Min(charge, minuses.Length))
: string.Format("{0} -{1}", LocalizationHelper.CurrentCulture.NumberFormat.NumberGroupSeparator, charge)); // Not L10N
}
}
public static bool IsFormulaWithAdduct(string formula, out Molecule molecule, out Adduct adduct, out string neutralFormula)
{
molecule = null;
adduct = Adduct.EMPTY;
neutralFormula = null;
if (string.IsNullOrEmpty(formula))
{
return(false);
}
// Does formula contain an adduct description? If so, pull charge from that.
var parts = formula.Split('[');
if (parts.Length == 2 && parts[1].Count(c => c == ']') == 1)
{
neutralFormula = parts[0];
var adductString = formula.Substring(neutralFormula.Length);
if (Adduct.TryParse(adductString, out adduct))
{
molecule = neutralFormula.Length > 0 ? ApplyAdductToFormula(neutralFormula, adduct) : Molecule.Empty;
return(true);
}
}
return(false);
}
/// <summary>
/// Creates a ComplexFragmentIon representing something which has no amino acids from the parent peptide.
/// </summary>
public static ComplexFragmentIon NewOrphanFragmentIon(TransitionGroup transitionGroup, ExplicitMods explicitMods, Adduct adduct)
{
var transition = new Transition(transitionGroup, IonType.precursor,
transitionGroup.Peptide.Sequence.Length - 1, 0, adduct);
return(new ComplexFragmentIon(transition, null, explicitMods?.Crosslinks, true));
}
private void TestAdductOperators()
{
// Test some underlying formula handling for fanciful user-supplied values
Assert.IsTrue(Molecule.AreEquivalentFormulas("C10H30Si5O5H-CH4", "C9H27O5Si5"));
Assert.AreEqual("C7H27O5Si4", BioMassCalc.MONOISOTOPIC.FindFormulaIntersection(new[] { "C8H30Si5O5H-CH4", "C9H27O5Si4", "C9H27O5Si5Na" }));
Assert.AreEqual("C7H27O5Si4", BioMassCalc.MONOISOTOPIC.FindFormulaIntersectionUnlabeled(new[] { "C7C'H30Si5O5H-CH4", "C9H27O5Si4", "C9H25H'2O5Si5Na" }));
// There is a difference between a proteomic adduct and non proteomic, primarily in how they display
Assert.AreEqual(Adduct.FromStringAssumeChargeOnly("M+H"), Adduct.M_PLUS_H);
Assert.AreEqual(Adduct.FromStringAssumeProtonatedNonProteomic("1"), Adduct.M_PLUS_H);
Assert.AreEqual(Adduct.FromStringAssumeChargeOnly("1"), Adduct.M_PLUS);
Assert.AreEqual(Adduct.FromStringAssumeProtonatedNonProteomic("M+H"), Adduct.M_PLUS_H);
Assert.AreEqual(Adduct.FromStringAssumeProtonated("1"), Adduct.SINGLY_PROTONATED);
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M+H"), Adduct.SINGLY_PROTONATED);
Assert.AreEqual(Adduct.FromStringAssumeChargeOnly("M+H").AsFormula(), Adduct.SINGLY_PROTONATED.AsFormula()); // But the underlying chemistry is the same
Assert.AreEqual(Adduct.FromStringAssumeProtonated("[M+S]+"), Adduct.FromStringAssumeProtonated("M+S").ChangeCharge(1));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M(-1.234)+2Na"), Adduct.FromStringAssumeProtonated("M(-1.234)+3Na").ChangeCharge(2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M1.234+2Na"), Adduct.FromStringAssumeProtonated("M1.234+3Na").ChangeCharge(2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M2Cl37-2Na"), Adduct.FromStringAssumeProtonated("M2Cl37+3Na").ChangeCharge(-2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M1.234-2Na"), Adduct.FromStringAssumeProtonated("M1.234+3Na").ChangeCharge(-2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M(-1.234)-2Na"), Adduct.FromStringAssumeProtonated("M(-1.234)+3Na").ChangeCharge(-2));
Assert.IsFalse(Adduct.M_PLUS_H.IsProteomic);
Assert.IsTrue(Adduct.M_PLUS_H.IsProtonated);
Assert.IsTrue(Adduct.SINGLY_PROTONATED.IsProteomic);
Assert.IsTrue(Adduct.SINGLY_PROTONATED.IsProtonated);
Assert.IsFalse(Adduct.SINGLY_PROTONATED.IsEmpty);
Assert.IsFalse(Adduct.EMPTY.IsProteomic);
Assert.IsTrue(Adduct.EMPTY.IsEmpty);
// Exercise the ability to work with masses and isotope labels
Assert.IsTrue(ReferenceEquals(Adduct.SINGLY_PROTONATED, Adduct.SINGLY_PROTONATED.Unlabeled));
var nolabel = Adduct.FromStringAssumeProtonated("M-2Na");
var label = Adduct.FromStringAssumeProtonated("M2Cl37-2Na");
Assert.AreEqual(nolabel, label.Unlabeled);
Assert.IsTrue(ReferenceEquals(nolabel, nolabel.Unlabeled));
Assert.IsFalse(nolabel.MassFromMz(300.0, MassType.Monoisotopic).IsHeavy());
Assert.IsFalse(label.MassFromMz(300.0, MassType.Monoisotopic).IsHeavy());
Assert.IsTrue(label.MassFromMz(300.0, MassType.MonoisotopicHeavy).IsHeavy());
Assert.IsTrue(label.MassFromMz(300.0, MassType.Monoisotopic).IsMonoIsotopic());
Assert.IsFalse(nolabel.MassFromMz(300.0, MassType.Average).IsHeavy());
Assert.IsFalse(label.MassFromMz(300.0, MassType.Average).IsHeavy());
Assert.IsTrue(label.MassFromMz(300.0, MassType.AverageHeavy).IsHeavy());
Assert.IsTrue(label.MassFromMz(300.0, MassType.Average).IsAverage());
var massHeavy = label.ApplyToMass(new TypedMass(300, MassType.MonoisotopicHeavy)); // Will not have isotope effect added in mz calc, as it's already heavy
var massLight = label.ApplyToMass(new TypedMass(300, MassType.Monoisotopic)); // Will have isotope effect added in mz calc
Assert.AreNotEqual(massHeavy, massLight);
Assert.AreNotEqual(label.MzFromNeutralMass(massHeavy), label.MzFromNeutralMass(massLight));
Assert.IsTrue(Adduct.PossibleAdductDescriptionStart("["));
Assert.IsTrue(Adduct.PossibleAdductDescriptionStart("M"));
Assert.IsTrue(Adduct.PossibleAdductDescriptionStart("[2M+CH3COO]"));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M+2CH3COO"), Adduct.FromStringAssumeProtonated("M+CH3COO").ChangeCharge(-2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M-2CH3COO"), Adduct.FromStringAssumeProtonated("M+CH3COO").ChangeCharge(2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M-2Na"), Adduct.FromStringAssumeProtonated("M+Na").ChangeCharge(-2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M+Na"), Adduct.FromStringAssumeProtonated("M+Na").ChangeCharge(1));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M+2Na"), Adduct.FromStringAssumeProtonated("M+Na").ChangeCharge(2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M+2Na"), Adduct.FromStringAssumeProtonated("M+3Na").ChangeCharge(2));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M2Cl37+2Na"), Adduct.FromStringAssumeProtonated("M2Cl37+3Na").ChangeCharge(2));
AssertEx.ThrowsException <InvalidOperationException>(() => Adduct.FromStringAssumeProtonated("M+2Na-H").ChangeCharge(2)); // Too complex to adjust formula
AssertEx.ThrowsException <InvalidOperationException>(() => Adduct.FromStringAssumeProtonatedNonProteomic("[M2")); // Seen in the wild, wasn't handled well
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M++++").AdductCharge, Adduct.FromChargeNoMass(4).AdductCharge);
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M+4"), Adduct.FromChargeNoMass(4));
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M--").AdductCharge, Adduct.FromChargeNoMass(-2).AdductCharge);
Assert.AreEqual(Adduct.FromStringAssumeProtonated("M-2"), Adduct.FromChargeNoMass(-2));
Assert.IsTrue(ReferenceEquals(Adduct.FromStringAssumeChargeOnly("M-"), Adduct.FromChargeNoMass(-1))); // Both should return Adduct.M_MINUS
Assert.IsTrue(ReferenceEquals(Adduct.FromStringAssumeChargeOnly("M+"), Adduct.FromChargeNoMass(1))); // Both should return Adduct.M_PLUS
Assert.IsTrue(ReferenceEquals(Adduct.FromStringAssumeChargeOnly("[M+]"), Adduct.FromChargeNoMass(1))); // Both should return Adduct.M_PLUS
Assert.IsTrue(ReferenceEquals(Adduct.FromStringAssumeChargeOnly("M-H"), Adduct.M_MINUS_H));
Assert.IsTrue(ReferenceEquals(Adduct.FromStringAssumeChargeOnly("M+H"), Adduct.M_PLUS_H));
var a = Adduct.FromChargeProtonated(-1);
var aa = Adduct.FromStringAssumeProtonated("M+CH3COO");
var b = Adduct.FromChargeProtonated(2);
var bb = Adduct.FromChargeProtonated(2);
var bbb = Adduct.FromChargeProtonated(2);
var bbbb = Adduct.FromChargeProtonated(2);
var c = Adduct.FromChargeProtonated(3);
var cc = Adduct.FromStringAssumeChargeOnly("M+3H");
var ccc = Adduct.FromStringAssumeChargeOnly("[M+3H]");
Assert.AreEqual(a.AdductCharge, aa.AdductCharge);
Assert.IsTrue(b == bb);
Assert.IsTrue(b == bbb);
Assert.IsTrue(ReferenceEquals(bbb, bbbb));
Assert.IsTrue(c.AdductCharge == cc.AdductCharge);
Assert.IsFalse(c == cc);
Assert.IsTrue(c != cc);
Assert.IsTrue(cc == ccc);
Assert.IsTrue(a < aa);
Assert.IsTrue(a < b);
Assert.IsTrue(b > a);
Assert.IsTrue(b != a);
var sorted = new List <Adduct> {
a, aa, b, bb, bbb, bbbb, c, cc, ccc
};
var unsorted = new List <Adduct> {
bb, aa, ccc, b, c, bbb, a, bbbb, cc
};
Assert.IsFalse(sorted.SequenceEqual(unsorted));
unsorted.Sort();
Assert.IsTrue(sorted.SequenceEqual(unsorted));
var ints = new AdductMap <int>();
Assert.AreEqual(0, ints[a]);
ints[a] = 7;
Assert.AreEqual(7, ints[a]);
var adducts = new AdductMap <Adduct>();
Assert.AreEqual(null, adducts[a]);
adducts[a] = b;
Assert.AreEqual(b, adducts[a]);
adducts[a] = c;
Assert.AreEqual(c, adducts[a]);
var d = Adduct.FromStringAssumeProtonated("[2M+3H]");
var dd = Adduct.FromStringAssumeProtonated("[M+3H]");
var ddd = Adduct.FromStringAssumeProtonated("[M-Na]");
Assert.IsTrue(d.ChangeMassMultiplier(1).SameEffect(dd));
Assert.IsTrue(dd.ChangeMassMultiplier(2).SameEffect(d));
Assert.AreEqual(dd.ChangeIonFormula("-Na"), ddd);
Assert.AreEqual(d.ChangeMassMultiplier(1).ChangeIonFormula("-Na"), ddd);
CheckLabel(BioMassCalc.Cl37);
CheckLabel(BioMassCalc.Br81);
CheckLabel(BioMassCalc.S33);
CheckLabel(BioMassCalc.S34);
CheckLabel(BioMassCalc.P32);
CheckLabel(BioMassCalc.C14);
CheckLabel(BioMassCalc.O17);
CheckLabel(BioMassCalc.O18);
var tips = Adduct.Tips;
foreach (var nickname in Adduct.DICT_ADDUCT_NICKNAMES)
{
Assert.IsTrue(tips.Contains(nickname.Key));
}
foreach (var nickname in Adduct.DICT_ADDUCT_ISOTOPE_NICKNAMES)
{
Assert.IsTrue(tips.Contains(nickname.Key));
}
}
public void AdductParserTest()
{
TestAdductOperators();
var coverage = new HashSet <string>();
TestPentaneAdduct("[M+2NH4]", "C5H20N2", 2, coverage); // multiple of a group
TestPentaneAdduct("[M+2(NH4)]", "C5H20N2", 2, coverage); // multiple of a group in parenthesis
TestPentaneAdduct("[M+2H]", "C5H14", 2, coverage);
TestPentaneAdduct("[M2C13+2H]", "C3C'2H14", 2, coverage); // Labeled
TestPentaneAdduct("[2M2C13+2H]", "C6C'4H26", 2, coverage); // Labeled dimer
TestPentaneAdduct("[2M2C14+2H]", "C6C\"4H26", 2, coverage); // Labeled dimer
TestPentaneAdduct("[M2C13]", "C3C'2H12", 0, coverage); // Labeled no charge
TestPentaneAdduct("[2M2C13]", "C6C'4H24", 0, coverage); // Labeled, dimer, no charge
TestPentaneAdduct("[2M]", "C10H24", 0, coverage); // dimer no charge
TestPentaneAdduct("[2M2C13+3]", "C6C'4H24", 3, coverage); // Labeled, dimer, charge only
TestPentaneAdduct("[2M2C13]+3", "C6C'4H24", 3, coverage); // Labeled, dimer, charge only
TestPentaneAdduct("[2M2C13+++]", "C6C'4H24", 3, coverage); // Labeled, dimer, charge only
TestPentaneAdduct("[2M2C13]+++", "C6C'4H24", 3, coverage); // Labeled, dimer, charge only
TestPentaneAdduct("[2M+3]", "C10H24", 3, coverage); // dimer charge only
TestPentaneAdduct("[2M]+3", "C10H24", 3, coverage); // dimer charge only
TestPentaneAdduct("[2M+++]", "C10H24", 3, coverage); // dimer charge only
TestPentaneAdduct("[2M]+++", "C10H24", 3, coverage); // dimer charge only
TestPentaneAdduct("[2M2C13-3]", "C6C'4H24", -3, coverage); // Labeled, dimer, charge only
TestPentaneAdduct("[2M2C13---]", "C6C'4H24", -3, coverage); // Labeled, dimer, charge only
TestPentaneAdduct("[2M-3]", "C10H24", -3, coverage); // dimer charge only
TestPentaneAdduct("[2M---]", "C10H24", -3, coverage); // dimer charge only
TestPentaneAdduct("[2M2C133H2+2H]", "C6C'4H20H'6", 2, coverage); // Labeled with some complexity, multiplied
TestPentaneAdduct("M+H", "C5H13", 1, coverage);
TestPentaneAdduct("M+", PENTANE, 1, coverage);
TestPentaneAdduct("M+2", PENTANE, 2, coverage);
TestPentaneAdduct("M+3", PENTANE, 3, coverage);
TestPentaneAdduct("M-", PENTANE, -1, coverage);
TestPentaneAdduct("M-2", PENTANE, -2, coverage);
TestPentaneAdduct("M-3", PENTANE, -3, coverage);
TestPentaneAdduct("M++", PENTANE, 2, coverage);
TestPentaneAdduct("M--", PENTANE, -2, coverage);
TestPentaneAdduct("M", PENTANE, 0, coverage); // Trivial non-adduct
TestPentaneAdduct("M+CH3COO", "C7H15O2", -1, coverage); // From XCMS
TestPentaneAdduct("[M+H]1+", "C5H13", 1, coverage);
TestPentaneAdduct("[M-H]1-", "C5H11", -1, coverage);
TestPentaneAdduct("[M-2H]", "C5H10", -2, coverage);
TestPentaneAdduct("[M-2H]2-", "C5H10", -2, coverage);
TestPentaneAdduct("[M+2H]++", "C5H14", 2, coverage);
TestPentaneAdduct("[MH2+2H]++", "C5H13H'", 2, coverage); // Isotope
TestPentaneAdduct("[MH3+2H]++", "C5H13H\"", 2, coverage); // Isotope
TestPentaneAdduct("[MD+2H]++", "C5H13H'", 2, coverage); // Isotope
TestPentaneAdduct("[MD+DMSO+2H]++", "C7H19H'OS", 2, coverage); // Check handling of Deuterium and DMSO together
TestPentaneAdduct("[MT+DMSO+2H]++", "C7H19H\"OS", 2, coverage); // Check handling of Tritium
TestPentaneAdduct("[M+DMSO+2H]++", "C7H20OS", 2, coverage);
TestPentaneAdduct("[M+DMSO+2H]2+", "C7H20OS", 2, coverage);
TestPentaneAdduct("[M+MeOH-H]", "C6H15O", -1, coverage); // Methanol "CH3OH"
TestPentaneAdduct("[M+MeOX-H]", "C6H14N", -1, coverage); // Methoxamine "CH3N"
TestPentaneAdduct("[M+TMS-H]", "C8H19Si", -1, coverage); // MSTFA(N-methyl-N-trimethylsilytrifluoroacetamide) "C3H8Si"
TestPentaneAdduct("[M+TMS+MeOX]-", "C9H23NSi", -1, coverage);
TestPentaneAdduct("[M+HCOO]", "C6H13O2", -1, coverage);
TestPentaneAdduct("[M+NOS]5+", "C5H12NOS", 5, coverage); // Not a real adduct, but be ready for adducts we just don't know about
TestPentaneAdduct("[M+NOS]5", "C5H12NOS", 5, coverage); // Not a real adduct, but be ready for adducts we just don't know about
TestPentaneAdduct("[M+NOS]5-", "C5H12NOS", -5, coverage); // Not a real adduct, but be ready for adducts we just don't know about
// See http://fiehnlab.ucdavis.edu/staff/kind/Metabolomics/MS-Adduct-Calculator/
// There you will find an excel spreadsheet from which I pulled these numbers, which as it turns out has several errors in it.
// There is also a table in the web page itself that contains the same values and some unmarked corrections.
// Sadly that faulty spreadsheet is copied all over the internet. I've let the author know what we found. - bspratt
TestTaxolAdduct("M+3H", 285.450928, 3, coverage);
TestTaxolAdduct("M+2H+Na", 292.778220, 3, coverage);
TestTaxolAdduct("M+H+2Na", 300.105557, 3, coverage); // Spreadsheet and table both say 300.209820, but also says adduct "mass" = 15.766190, I get 15.6618987 using their H and Na masses (and this is clearly m/z, not mass)
TestTaxolAdduct("M+3Na", 307.432848, 3, coverage);
TestTaxolAdduct("M+2H", 427.672721, 2, coverage);
TestTaxolAdduct("M+H+NH4", 436.185995, 2, coverage);
TestTaxolAdduct("M+H+Na", 438.663692, 2, coverage);
TestTaxolAdduct("M+H+K", 446.650662, 2, coverage);
TestTaxolAdduct("M+ACN+2H", 448.185995, 2, coverage);
TestTaxolAdduct("M+2Na", 449.654663, 2, coverage);
TestTaxolAdduct("M+2ACN+2H", 468.699268, 2, coverage);
TestTaxolAdduct("M+3ACN+2H", 489.212542, 2, coverage);
TestTaxolAdduct("M+H", 854.338166, 1, coverage);
TestTaxolAdduct("M+NH4", 871.364713, 1, coverage);
TestTaxolAdduct("M+Na", 876.320108, 1, coverage);
TestTaxolAdduct("M+CH3OH+H", 886.364379, 1, coverage);
TestTaxolAdduct("M+K", 892.294048, 1, coverage);
TestTaxolAdduct("M+ACN+H", 895.364713, 1, coverage);
TestTaxolAdduct("M+2Na-H", 898.302050, 1, coverage);
TestTaxolAdduct("M+IsoProp+H", 914.396230, 1, coverage);
TestTaxolAdduct("M+ACN+Na", 917.346655, 1, coverage);
TestTaxolAdduct("M+2K-H", 930.249930, 1, coverage); // Spreadsheet and table disagree - spreadsheet says "M+2K+H" but that's 3+, not 1+, and this fits the mz value
TestTaxolAdduct("M+DMSO+H", 932.352110, 1, coverage);
TestTaxolAdduct("M+2ACN+H", 936.391260, 1, coverage);
TestTaxolAdduct("M+IsoProp+Na+H", 468.692724, 2, coverage); // Spreadsheet and table both say mz=937.386000 z=1 (does Isoprop interact somehow to eliminate half the ionization?)
TestTaxolAdduct("2M+H", 1707.669056, 1, coverage);
TestTaxolAdduct("2M+NH4", 1724.695603, 1, coverage);
TestTaxolAdduct("2M+Na", 1729.650998, 1, coverage);
TestTaxolAdduct("2M+3H2O+2H", 881.354, 2, coverage); // Does not appear in table. Charge agrees but spreadsheet says mz= 1734.684900
TestTaxolAdduct("2M+K", 1745.624938, 1, coverage);
TestTaxolAdduct("2M+ACN+H", 1748.695603, 1, coverage);
TestTaxolAdduct("2M+ACN+Na", 1770.677545, 1, coverage);
TestTaxolAdduct("M-3H", 283.436354, -3, coverage);
TestTaxolAdduct("M-2H", 425.658169, -2, coverage);
TestTaxolAdduct("M-H2O-H", 834.312500, -1, coverage);
TestTaxolAdduct("M+-H2O-H", 834.312500, -1, coverage); // Tolerate empty atom description ("+-")
TestTaxolAdduct("M-H", 852.323614, -1, coverage);
TestTaxolAdduct("M+Na-2H", 874.305556, -1, coverage);
TestTaxolAdduct("M+Cl", 888.300292, -1, coverage);
TestTaxolAdduct("M+K-2H", 890.279496, -1, coverage);
TestTaxolAdduct("M+FA-H", 898.329091, -1, coverage);
TestTaxolAdduct("M+Hac-H", 912.344741, -1, coverage);
TestTaxolAdduct("M+Br", 932.249775, -1, coverage);
TestTaxolAdduct("MT+TFA-H", 968.324767, -1, coverage); // Tritium label + TFA
TestTaxolAdduct("M+TFA-H", 966.316476, -1, coverage);
TestTaxolAdduct("2M-H", 1705.654504, -1, coverage);
TestTaxolAdduct("2M+FA-H", 1751.659981, -1, coverage);
TestTaxolAdduct("2M+Hac-H", 1765.675631, -1, coverage);
TestTaxolAdduct("3M-H", 2558.985394, -1, coverage); // Spreadsheet and table give mz as 2560.999946 -but also gives adduct "mass" as 1.007276, should be -1.007276
// A couple more simple ones we support with statics
TestTaxolAdduct("M+4H", 214.3400149, 4, coverage);
TestTaxolAdduct("M+5H", 171.6734671, 5, coverage);
// And a few of our own to exercise the interaction of multiplier and isotope
var dC13 = BioMassCalc.MONOISOTOPIC.GetMass(BioMassCalc.C13) - BioMassCalc.MONOISOTOPIC.GetMass(BioMassCalc.C);
TestTaxolAdduct("M2C13+3H", 285.450928 + (2 * dC13) / 3.0, 3, coverage);
TestTaxolAdduct("M2C13+2H+Na", 292.778220 + (2 * dC13) / 3.0, 3, coverage);
TestTaxolAdduct("2M2C13+3H", 285.450906 + (massTaxol + 4 * dC13) / 3.0, 3, coverage);
TestTaxolAdduct("2M2C13+2H+Na", 292.778220 + (massTaxol + 4 * dC13) / 3.0, 3, coverage);
var dC14 = BioMassCalc.MONOISOTOPIC.GetMass(BioMassCalc.C14) - BioMassCalc.MONOISOTOPIC.GetMass(BioMassCalc.C);
TestTaxolAdduct("M2C14+3H", 285.450928 + (2 * dC14) / 3.0, 3, coverage);
TestTaxolAdduct("M2C14+2H+Na", 292.778220 + (2 * dC14) / 3.0, 3, coverage);
TestTaxolAdduct("2M2C14+3H", 285.450906 + (massTaxol + 4 * dC14) / 3.0, 3, coverage);
TestTaxolAdduct("2M2C14+2H+Na", 292.778220 + (massTaxol + 4 * dC14) / 3.0, 3, coverage);
// Using example adducts from
// https://gnps.ucsd.edu/ProteoSAFe/gnpslibrary.jsp?library=GNPS-LIBRARY#%7B%22Library_Class_input%22%3A%221%7C%7C2%7C%7C3%7C%7CEXACT%22%7D
var Hectochlorin = "C27H34Cl2N2O9S2";
var massHectochlorin = 664.108276; // http://www.chemspider.com/Chemical-Structure.552449.html?rid=3a7c08af-0886-4e82-9e4f-5211b8efb373
var adduct = Adduct.FromStringAssumeProtonated("M+H");
var mol = IonInfo.ApplyAdductToFormula(Hectochlorin, adduct).ToString();
var mass = BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula(mol);
Assert.AreEqual(massHectochlorin + BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula("H"), mass, 0.00001);
var mz = BioMassCalc.CalculateIonMz(BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula(Hectochlorin), adduct);
Assert.AreEqual(665.11555415, mz, .000001); // GNPS says 665.0 for Hectochlorin M+H
mol = IonInfo.ApplyAdductToFormula(Hectochlorin, Adduct.FromStringAssumeProtonated("MCl37+H")).ToString();
Assert.AreEqual("C27ClCl'H35N2O9S2", mol);
mass = BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula(mol);
Assert.AreEqual(667.11315, mass, .00001);
mol = IonInfo.ApplyAdductToFormula(Hectochlorin, Adduct.FromStringAssumeProtonated("M2Cl37+H")).ToString();
Assert.AreEqual("C27Cl'2H35N2O9S2", mol);
// Test ability to describe isotope label by mass only
var heavy = Adduct.FromStringAssumeProtonated("2M1.2345+H");
mz = BioMassCalc.CalculateIonMz(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
heavy = Adduct.FromStringAssumeProtonated("2M1.2345");
mz = BioMassCalc.CalculateIonMass(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
Assert.AreEqual(2 * (massHectochlorin + 1.23456), mz, .001);
heavy = Adduct.FromStringAssumeProtonated("M1.2345");
mz = BioMassCalc.CalculateIonMass(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
Assert.AreEqual(massHectochlorin + 1.23456, mz, .001);
heavy = Adduct.FromStringAssumeProtonated("2M(-1.2345)+H");
mz = BioMassCalc.CalculateIonMz(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
Assert.AreEqual((2 * (massHectochlorin - 1.23456) + BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula("H")), mz, .001);
heavy = Adduct.FromStringAssumeProtonated("2M(-1.2345)");
mz = BioMassCalc.CalculateIonMass(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
Assert.AreEqual(2 * (massHectochlorin - 1.23456), mz, .001);
heavy = Adduct.FromStringAssumeProtonated("2M(1.2345)+H");
mz = BioMassCalc.CalculateIonMz(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
Assert.AreEqual((2 * (massHectochlorin + 1.23456) + BioMassCalc.MONOISOTOPIC.CalculateMassFromFormula("H")), mz, .001);
heavy = Adduct.FromStringAssumeProtonated("2M(1.2345)");
mz = BioMassCalc.CalculateIonMass(new TypedMass(massHectochlorin, MassType.Monoisotopic), heavy);
Assert.AreEqual(2 * (massHectochlorin + 1.23456), mz, .001);
TestException(Hectochlorin, "M3Cl37+H"); // Trying to label more chlorines than exist in the molecule
TestException(Hectochlorin, "M-3Cl+H"); // Trying to remove more chlorines than exist in the molecule
TestException(PENTANE, "M+foo+H"); // Unknown adduct
TestException(PENTANE, "M2Cl37H+H"); // nonsense label ("2Cl37H2" would make sense, but regular H doesn't belong)
TestException(PENTANE, "M+2H+"); // Trailing sign - we now understand this as a charge state declaration, but this one doesn't match described charge
TestException(PENTANE, "[M-2H]3-"); // Declared charge doesn't match described charge
// Test label stripping
Assert.AreEqual("C5H9NO2S", (new IonInfo("C5H9H'3NO2S[M-3H]")).UnlabeledFormula);
// Peptide representations
Assert.AreEqual("C40H65N11O16", (new SequenceMassCalc(MassType.Average)).GetNeutralFormula("PEPTIDER", null));
// Figuring out adducts from old style skyline doc ion molecules and ion precursors
var adductDiff = Adduct.FromFormulaDiff("C6H27NO2Si2C'5", "C'5H11NO2", 3);
Assert.AreEqual("[M+C6H16Si2]3+", adductDiff.AdductFormula);
Assert.AreEqual(3, adductDiff.AdductCharge);
Assert.AreEqual(Adduct.FromString("[M+C6H16Si2]3+", Adduct.ADDUCT_TYPE.non_proteomic, null), adductDiff);
adductDiff = Adduct.FromFormulaDiff("C6H27NO2", "C6H27NO2", 3);
Assert.AreEqual("[M+3]", adductDiff.AdductFormula);
Assert.AreEqual(3, adductDiff.AdductCharge);
adductDiff = Adduct.ProtonatedFromFormulaDiff("C6H27NO2Si2C'5", "C'5H11NO2", 3);
var expectedFromProtonatedDiff = "[M+C6H13Si2+3H]";
Assert.AreEqual(expectedFromProtonatedDiff, adductDiff.AdductFormula);
Assert.AreEqual(3, adductDiff.AdductCharge);
Assert.AreEqual(Adduct.FromString(expectedFromProtonatedDiff, Adduct.ADDUCT_TYPE.non_proteomic, null), adductDiff);
adductDiff = Adduct.ProtonatedFromFormulaDiff("C6H27NO2", "C6H27NO2", 3);
Assert.AreEqual("[M+3H]", adductDiff.AdductFormula);
Assert.AreEqual(3, adductDiff.AdductCharge);
// Implied positive mode
TestPentaneAdduct("MH", "C5H13", 1, coverage); // implied pos mode seems to be fairly common in the wild
TestPentaneAdduct("MH+", "C5H13", 1, coverage); // implied pos mode seems to be fairly common in the wild
TestPentaneAdduct("MNH4", "C5H16N", 1, coverage); // implied pos mode seems to be fairly common in the wild
TestPentaneAdduct("MNH4+", "C5H16N", 1, coverage); // implied pos mode seems to be fairly common in the wild
TestPentaneAdduct("2MNH4+", "C10H28N", 1, coverage); // implied pos mode seems to be fairly common in the wild
// Explict charge states within the adduct
TestPentaneAdduct("[M+S+]", "C5H12S", 1, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[3M+S+]", "C15H36S", 1, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S++]", "C5H12S", 2, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[MS+]", "C5H12S", 1, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[MS++]", "C5H12S", 2, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S+2]", "C5H12S", 2, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S]2+", "C5H12S", 2, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S-]", "C5H12S", -1, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S--]", "C5H12S", -2, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M-3H-3]", "C5H9", -3, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S-2]", "C5H12S", -2, coverage); // We're trusting the user to declare charge
TestPentaneAdduct("[M+S]2-", "C5H12S", -2, coverage); // We're trusting the user to declare charge
// Did we test all the adducts we claim to support?
foreach (var adducts in new[] {
Adduct.DEFACTO_STANDARD_ADDUCTS,
Adduct.COMMON_CHARGEONLY_ADDUCTS,
Adduct.COMMON_SMALL_MOL_ADDUCTS.Select(a => a.AdductFormula),
Adduct.COMMON_PROTONATED_ADDUCTS.Select(a => a.AdductFormula),
})
{
foreach (var adductText in adducts)
{
if (!coverage.Contains(adductText))
{
Assert.Fail("Need to add a test for adduct {0}", adductText);
}
}
}
}
private string _unlabledFormula; // Chemical formula after adduct application and stripping of labels
/// <summary>
/// Constructs an IonInfo, which holds a neutral formula and adduct, or possibly just a chemical formula if no adduct is included in the description
/// </summary>
public IonInfo(string formulaWithOptionalAdduct, Adduct adduct)
{
Formula = formulaWithOptionalAdduct + adduct.AdductFormula;
}
/// <summary>
/// For test purposes
/// </summary>
public static double CalculateIonMass(TypedMass mass, Adduct adduct)
{
return(adduct.ApplyToMass(mass));
}
/// <summary>
/// For test purposes
/// </summary>
public static double CalculateIonMz(TypedMass mass, Adduct adduct)
{
return(adduct.MzFromNeutralMass(mass));
}
/// <summary>
/// For test purposes
/// </summary>
public double CalculateIonMz(string desc, Adduct adduct)
{
var mass = CalculateMassFromFormula(desc);
return(adduct.MzFromNeutralMass(mass));
}
public IList <int> ShowIonCharges(IEnumerable <Adduct> adductPriority)
{
return(Adduct.OrderedAbsoluteChargeValues(adductPriority).ToList());
}
public void UpdateUI(bool selectionChanged = true)
{
// Only worry about updates, if the graph is visible
// And make sure it is not disposed, since rendering happens on a timer
if (!Visible || IsDisposed)
{
return;
}
// Clear existing data from the graph pane
var graphPane = (MSGraphPane)graphControl.MasterPane[0];
graphPane.CurveList.Clear();
graphPane.GraphObjList.Clear();
GraphItem = null;
GraphHelper.FormatGraphPane(graphControl.GraphPane);
GraphHelper.FormatFontSize(graphControl.GraphPane, Settings.Default.SpectrumFontSize);
// Try to find a tree node with spectral library info associated
// with the current selection.
var nodeTree = _stateProvider.SelectedNode as SrmTreeNode;
var nodeGroupTree = nodeTree as TransitionGroupTreeNode;
var nodeTranTree = nodeTree as TransitionTreeNode;
if (nodeTranTree != null)
{
nodeGroupTree = nodeTranTree.Parent as TransitionGroupTreeNode;
}
var nodeGroup = (nodeGroupTree != null ? nodeGroupTree.DocNode : null);
PeptideTreeNode nodePepTree;
if (nodeGroup == null)
{
nodePepTree = nodeTree as PeptideTreeNode;
if (nodePepTree != null)
{
var listInfoGroups = GetLibraryInfoChargeGroups(nodePepTree);
if (listInfoGroups.Length == 1)
{
nodeGroup = listInfoGroups[0];
}
else if (listInfoGroups.Length > 1)
{
_nodeGroup = null;
toolBar.Visible = false;
_graphHelper.SetErrorGraphItem(new NoDataMSGraphItem(
Resources.GraphSpectrum_UpdateUI_Multiple_charge_states_with_library_spectra));
return;
}
}
}
else
{
nodePepTree = nodeGroupTree.Parent as PeptideTreeNode;
}
// Check for appropriate spectrum to load
SrmSettings settings = DocumentUI.Settings;
PeptideLibraries libraries = settings.PeptideSettings.Libraries;
bool available = false;
if (nodeGroup == null || (!nodeGroup.HasLibInfo && !libraries.HasMidasLibrary))
{
_spectra = null;
}
else
{
TransitionGroup group = nodeGroup.TransitionGroup;
TransitionDocNode transition = (nodeTranTree == null ? null : nodeTranTree.DocNode);
var lookupSequence = group.Peptide.Target;// Sequence or custom ion id
ExplicitMods lookupMods = null;
if (nodePepTree != null)
{
lookupSequence = nodePepTree.DocNode.SourceUnmodifiedTarget;
lookupMods = nodePepTree.DocNode.SourceExplicitMods;
}
try
{
// Try to load a list of spectra matching the criteria for
// the current node group.
if (libraries.HasLibraries && libraries.IsLoaded)
{
if (NodeGroupChanged(nodeGroup))
{
try
{
UpdateSpectra(nodeGroup, lookupSequence, lookupMods);
UpdateToolbar();
}
catch (Exception)
{
_spectra = null;
UpdateToolbar();
throw;
}
_nodeGroup = nodeGroup;
if (settings.TransitionSettings.Instrument.IsDynamicMin)
{
ZoomSpectrumToSettings();
}
}
var spectrum = SelectedSpectrum;
if (spectrum != null)
{
IsotopeLabelType typeInfo = spectrum.LabelType;
var types = _stateProvider.ShowIonTypes(group.IsProteomic);
var adducts = (group.IsProteomic ?
Transition.DEFAULT_PEPTIDE_LIBRARY_CHARGES :
nodeGroup.InUseAdducts).ToArray();
var charges = _stateProvider.ShowIonCharges(adducts);
var rankTypes = group.IsProteomic ? settings.TransitionSettings.Filter.PeptideIonTypes : settings.TransitionSettings.Filter.SmallMoleculeIonTypes;
var rankAdducts = group.IsProteomic ? settings.TransitionSettings.Filter.PeptideProductCharges : settings.TransitionSettings.Filter.SmallMoleculeFragmentAdducts;
var rankCharges = Adduct.OrderedAbsoluteChargeValues(rankAdducts);
// Make sure the types and charges in the settings are at the head
// of these lists to give them top priority, and get rankings correct.
int i = 0;
foreach (IonType type in rankTypes)
{
if (types.Remove(type))
{
types.Insert(i++, type);
}
}
i = 0;
var showAdducts = new List <Adduct>();
foreach (var charge in rankCharges)
{
if (charges.Remove(charge))
{
charges.Insert(i++, charge);
}
// NB for all adducts we just look at abs value of charge
// CONSIDER(bspratt): we may want finer per-adduct control for small molecule use
showAdducts.AddRange(adducts.Where(a => charge == Math.Abs(a.AdductCharge)));
}
showAdducts.AddRange(adducts.Where(a => charges.Contains(Math.Abs(a.AdductCharge)) && !showAdducts.Contains(a)));
SpectrumPeaksInfo spectrumInfo = spectrum.SpectrumPeaksInfo;
var spectrumInfoR = new LibraryRankedSpectrumInfo(spectrumInfo,
typeInfo,
nodeGroup,
settings,
lookupSequence,
lookupMods,
showAdducts,
types,
rankAdducts,
rankTypes);
GraphItem = new SpectrumGraphItem(nodeGroup, transition, spectrumInfoR, spectrum.LibName)
{
ShowTypes = types,
ShowCharges = charges,
ShowRanks = Settings.Default.ShowRanks,
ShowMz = Settings.Default.ShowIonMz,
ShowObservedMz = Settings.Default.ShowObservedMz,
ShowDuplicates = Settings.Default.ShowDuplicateIons,
FontSize = Settings.Default.SpectrumFontSize,
LineWidth = Settings.Default.SpectrumLineWidth
};
LibraryChromGroup chromatogramData = null;
if (Settings.Default.ShowLibraryChromatograms)
{
chromatogramData = spectrum.LoadChromatogramData();
}
if (null == chromatogramData)
{
_graphHelper.ResetForSpectrum(new[] { nodeGroup.TransitionGroup });
_graphHelper.AddSpectrum(GraphItem);
_graphHelper.ZoomSpectrumToSettings(DocumentUI, nodeGroup);
}
else
{
_graphHelper.ResetForChromatograms(new[] { nodeGroup.TransitionGroup });
var displayType = GraphChromatogram.GetDisplayType(DocumentUI, nodeGroup);
IList <TransitionDocNode> displayTransitions =
GraphChromatogram.GetDisplayTransitions(nodeGroup, displayType).ToArray();
int numTrans = displayTransitions.Count;
var allChromDatas =
chromatogramData.ChromDatas.Where(
chromData => DisplayTypeMatches(chromData, displayType)).ToList();
var chromDatas = new List <LibraryChromGroup.ChromData>();
for (int iTran = 0; iTran < numTrans; iTran++)
{
var displayTransition = displayTransitions[iTran];
var indexMatch =
allChromDatas.IndexOf(chromData => IonMatches(displayTransition.Transition, chromData));
if (indexMatch >= 0)
{
chromDatas.Add(allChromDatas[indexMatch]);
allChromDatas.RemoveAt(indexMatch);
}
else
{
chromDatas.Add(null);
}
}
allChromDatas.Sort((chromData1, chromData2) => chromData1.Mz.CompareTo(chromData2.Mz));
chromDatas.AddRange(allChromDatas);
double maxHeight = chromDatas.Max(chromData => null == chromData ? double.MinValue : chromData.Height);
int iChromDataPrimary = chromDatas.IndexOf(chromData => null != chromData && maxHeight == chromData.Height);
int colorOffset = displayType == DisplayTypeChrom.products
? GraphChromatogram.GetDisplayTransitions(nodeGroup,
DisplayTypeChrom.
precursors).Count()
: 0;
for (int iChromData = 0; iChromData < chromDatas.Count; iChromData++)
{
var chromData = chromDatas[iChromData];
if (chromData == null)
{
continue;
}
string label;
var pointAnnotation = GraphItem.AnnotatePoint(new PointPair(chromData.Mz, 1.0));
if (null != pointAnnotation)
{
label = pointAnnotation.Label;
}
else
{
label = chromData.Mz.ToString(@"0.####");
}
TransitionDocNode matchingTransition;
Color color;
if (iChromData < numTrans)
{
matchingTransition = displayTransitions[iChromData];
color =
GraphChromatogram.COLORS_LIBRARY[
(iChromData + colorOffset) % GraphChromatogram.COLORS_LIBRARY.Count];
}
else
{
matchingTransition = null;
color =
GraphChromatogram.COLORS_GROUPS[
iChromData % GraphChromatogram.COLORS_GROUPS.Count];
}
TransitionChromInfo tranPeakInfo;
ChromatogramInfo chromatogramInfo;
MakeChromatogramInfo(nodeGroup.PrecursorMz, chromatogramData, chromData, out chromatogramInfo, out tranPeakInfo);
var graphItem = new ChromGraphItem(nodeGroup, matchingTransition, chromatogramInfo, iChromData == iChromDataPrimary ? tranPeakInfo : null, null,
new[] { iChromData == iChromDataPrimary }, null, 0, false, false, null, 0,
color, Settings.Default.ChromatogramFontSize, 1);
LineItem curve = (LineItem)_graphHelper.AddChromatogram(PaneKey.DEFAULT, graphItem);
if (matchingTransition == null)
{
curve.Label.Text = label;
}
curve.Line.Width = Settings.Default.ChromatogramLineWidth;
if (null != transition)
{
if (IonMatches(transition.Transition, chromData))
{
color = ChromGraphItem.ColorSelected;
}
}
curve.Color = color;
}
graphPane.Title.IsVisible = false;
graphPane.Legend.IsVisible = true;
_graphHelper.FinishedAddingChromatograms(chromatogramData.StartTime, chromatogramData.EndTime, false);
graphControl.Refresh();
}
graphControl.IsEnableVPan = graphControl.IsEnableVZoom =
!Settings.Default.LockYAxis;
available = true;
}
}
}
catch (Exception)
{
_graphHelper.SetErrorGraphItem(new NoDataMSGraphItem(
Resources.GraphSpectrum_UpdateUI_Failure_loading_spectrum__Library_may_be_corrupted));
return;
}
}
// Show unavailable message, if no spectrum loaded
if (!available)
{
UpdateToolbar();
_nodeGroup = null;
_graphHelper.SetErrorGraphItem(new UnavailableMSGraphItem());
}
}