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PREP Calibration Mix DIOS Low i. Introduction Pre-packaged PREP Calibration Mixtures eliminate the need to purchase and store large quantities of the component calibration reagents, simplifying sample preparation for TOF mass spectrometry. In addition to calibration, the mixtures are also useful for diagnostic tests and relative comparisons between different instruments. The calibration mixtures are packaged as lyophilized solids in glass vials. The vials are vacuum-sealed in foil pouches to ensure protection from light and air. Contents I. introduction II. Recommended Usage of PREP Calibration Mix DIOS Low III. Preparation of PREP Calibration Mix DIOS Low a. Procedure b. Notes IV. storage and stability V. Peak List for PREP Calibration Mix DIOS Low Prep Calibration Mix- DIOS Low 1

II. Recommended Usage of PREP Calibration Mix DIOS Low Waters PREP Calibration Mix DIOS Low is intended for calibration of a MALDI TOF MS instrument used for small molecule detection between m/z 1 and 1500 in reflectron mode. i The mix contains polyethylene glycol (PEG) 200, 600, and 1000 with sodium iodide, rubidium iodide and cesium iodide (NaI, RbI and CsI). This mixture has not been optimized for use in electrospray systems. The following spectrum of the PREP Calibration Mix DIOS Low was processed by baseline subtraction, smoothing, and centroiding in preparation for calibration. Data was obtained on a Waters MALDI micro MX. Figure 1. spectrum of PREP Calibration Mix DIOS Low obtained on a Waters MALDI TOF mass spectrometer (MALDI micro MX TM ). Data presented was background subtracted, smoothed and centered in preparation for calibration. i Waters provides DIOS-target Plates for small molecule detection (see part numbers on the next page). DIOS stands for desorption/ionization on silicon. III. Preparation of PREP Calibration Mix DIOS Low The following methods are provided as a general guideline for preparation on DIOStarget Plates. The described method only serves as a starting point. Depending on the application, one may consider using other solvents and/or methods. For optimum performance, solvents of the highest purity commercially available are recommended. The following solvents were found to be satisfactory. CH 3 CN: Acetonitrile (J. T. Baker Cat. No.: 9017-03) H 2 O: High purity (18 M) water 3. Vortex the vial for several seconds to ensure that the solid is completely dissolved. 4. Apply 1 μl of the mixture onto a clean DIOS-target Plate. 5. Dry at room temperature before LDI (laser desorption/ionization) analysis. 6. Note that the PREP Calibration Mix is relatively concentrated and tends to leave a visible, shiny residue on the surface. Adjust your instrument laser power so that the signal does not saturate the detector. b. Notes i. Optimization for specific applications is recommended. Other relative ratios and solvents may be used for reconstitution. a. Procedure 1. For a dilution solution, make a 1:1 mixture of CH 3 CN and H 2 O. i 2. Add at least 250 μl of the dilution solution ii to the glass vial containing the lyophilized calibration mixture. ii. In some cases further dilutions of this solution may yield better spectra depending on the instrument and substrate used. The solution for the calibration spectrum shown previously was made by taking 50 µl of the calibration made in #2 and adding 450 µl of dilution solvent mix. Prep Calibration Mix- DIOS Low 2

iv. Storage and Stability It is recommended that PREP Calibration Mixtures remain in the foil pouch (in the dark) at room temperature until use. Once reconstituted in appropriate solvents, the PREP Calibration Mix solution can be used for at least 1 year when stored in the dark at 4 C. v. Peak List for PREP Calibration Mix DIOS Low The following reference file contains the masses of selected low mass clusters formed by the mixture of sodium, rubidium, and cesium iodide as well as the sodium (and some rubidium) adducts of polyethylene glycol oligomers with chemical formula HO[C 2 H 4 O]nH + Na (where n = 1,2,3,...) between 200 and 1500 Da. es were calculated using the following values (where M (x) indicates the mass, M, of the chemical species, x, within the parentheses): M(C) = 12.000000000 M(H) = 1.007825040 M(N) = 14.003074000 M(O) = 15.994914630 M(Na) = 22.989768 M(K) = 38.9637069 M(Rb) = 84.911792 M(I) = 126.90446 M(Cs) = 132.905429 Below m/z 150 the sodium, rubidium, and cesium ions provide the more dominant peaks. Above m/z 200 the sodiated PEG peaks provide the more dominant peaks. Table 1: Calculated masses of selected low mass clusters formed by the mixture of sodium, rubidium, and cesium iodide with polyethylene glycol (PEG) oligomers Identity Comment 22.989768 Na sometimes weak 84.911792 Rb - primary primary peak 86.909185 Rb - isotope 132.905429 Cs primary peak 217.1051919 PEG + Na very weak 261.1314067 PEG + Na weak 279.0272159 PEG + Rb weak 305.1576215 PEG + Na main 323.0534307 PEG + Rb main 349.1838362 PEG + Na primary peak 367.0796455 PEG + Rb 393.210051 PEG + Na primary peak 411.1058602 PEG + Rb 437.2362658 PEG + Na primary peak 455.132075 PEG + Rb 481.2624806 PEG + Na primary peak 499.1582898 PEG + Rb 525.2886954 PEG + Na primary peak 543.1845046 PEG + Rb 569.3149102 PEG + Na primary peak 587.2107194 PEG + Rb 613.341125 PEG + Na primary peak 631.2369342 PEG + Rb 657.3673398 PEG + Na primary peak 675.263149 PEG + Rb 701.3935546 PEG + N a primary peak 719.2893638 PEG + Rb 745.4197694 PEG + Na primary peak 763.3155786 PEG + Rb 789.4459841 PEG + Na primary peak 807.3417934 PEG + Rb 833.4721989 PEG + Na primary peak 851.3680081 PEG + Rb 877.4984137 PEG + Na primary peak 895.3942229 PEG + Rb 921.5246285 PEG + Na primary peak Prep Calibration Mix- DIOS Low 3

Table 1. Calculated masses of selected low mass clusters formed by the mixture of sodium, rubidium, and cesium iodide with polyethylene glycol (PEG) oligomers (continued) Identity Comment 939.4204377 PEG + Rb 965.5508433 PEG + Na primary peak 983.4466525 PEG + Rb 1009.577058 PEG + Na primary peak 1027.472867 PEG + Rb 1053.603273 PEG + Na primary peak 1071.499082 PEG + Rb 1097.629488 PEG + Na primary peak 1115.525297 PEG + Rb 1141.655702 PEG + Na primary peak 1159.551512 PEG + Rb 1185.681917 PEG + Na primary peak 1203.577726 PEG + Rb 1229.708132 PEG + Na primary peak 1247.603941 PEG + Rb 1273.734347 PEG + Na primary peak 1291.630156 PEG + Rb 1317.760562 PEG + Na primary peak 1335.656371 PEG + Rb 1361.786776 PEG + Na primary peak 1379.682586 PEG + Rb 1405.812991 PEG + Na primary peak 1423.7088 PEG + Rb 1449.839206 PEG + Na primary peak 1467.735015 PEG + Rb 1493.865421 PEG + Na primary peak 1511.76123 PEG + Rb Prep Calibration Mix- DIOS Low 4

Sales Offices: Austria and European Export (Central South Eastern Europe, CIS and Middle East) 431 877 18 07 Australia 2 9933 1777 Belgium 32 2 726 1000 Brazil 55 11 5094 3788 Canada 800 252 4752 China 8621 6495 6999 CIS/Russia +7 495 3367000 Czech Republic 42 02 617 11384 Denmark 45 46 59 8080 Finland +358 9 5659 6288 France (33) 1 30 48 72 00 Germany 49 6196 400600 Hong Kong 852 29 64 1800 Hungary 36 1 350 5086 India and India Subcontinent 91 80 2 837 1900 Ireland 353 1 448 1500 Italy 39 02 274 211 Japan (81) 3 3471 7191 Korea (82) 2 820 2700 Mexico 5255 5200 1860 The Netherlands +31 (0)76-50 87 200 Norway 47 63 84 60 50 Poland (48) 22 833 4400 Puerto Rico 787 747 8445 Singapore 65 6273 1221 Spain 34 93 600 93 00 Sweden 46 8 555 11500 Switzerland 41 62 889 2030 Taiwan 886 2 2543 1898 United Kingdom 44 208 238 6100 2007 Waters Corporation,, The Science of What s Possible, Waters, MALDI micro MX TM and PREP are trademarks of Waters Corporation. September 2007 715001478 Rev B VW-PDF Waters Corporation 34 Maple Street Milford, MA 01757 U.S.A. T: 1 508 478 2000 F: 1 508 872 1990 www.waters.com Prep Calibration Mix- DIOS Low 5