effective use of the powder diffraction file
TRANSCRIPT
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Tim Fawcett Cyrus Crowder Fangling NeedhamExecutive Director Principal Scientist Senior ScientistICDD ICDD ICDD
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This document was presented at PPXRD -Pharmaceutical Powder X-ray Diffraction Symposium
Sponsored by The International Centre for Diffraction Data
This presentation is provided by the International Centre for Diffraction Data in cooperation with the authors and presenters of the PPXRD symposia for the express purpose of educating the scientific community.
All copyrights for the presentation are retained by the original authors.
The ICDD has received permission from the authors to post this material on our website and make the material available for viewing. Usage is restricted for the purposes of education and scientific research.
ICDD Website - www.icdd.comPPXRD Website – www.icdd.com/ppxrd
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Introduction to PDF databases
Material IdentificationFormulation AnalysisPolymorph AnalysisCrystallite SizeQuantitative Analysis
NanomaterialsStructure AnalysisCluster AnalysesCrystallinityIntegral Index
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1941 – Joint Committee for Powder Diffraction Standards 2006 –General member and customer survey2007 – PDF‐4/Organics customer surveyAnnual input by member technical committees of the ICDD
Phase Identification (95%)
20‐30%Quantitative Analysis – Several MethodsCrystallinityCrystallite SizePolymorph ScreeningPowder Structure Analysis
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PDF-2 Inorganic Material Identification
PDF-4+ Identification and Quantitation
PDF4/Organics Pharmaceutical Identification and Quantitation
PDF4/Minerals Mineral Identification and Quantitation
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Powder Diffraction
File
LPFICSD
NIST
CSDICDD Grants
and Contributes
PDF-2
PDF-4+
PDF-4/Organics
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Release 2009
PDF ‐ 674,139 Unique Entries
For Release 2009, Published 48,658 New Entries
ICDD
ICSD
LPFCCDC
NIST
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1998ICSD
2002CSD
2001NISTM&A
2005LPF
2006JAVAInterface2002
FullRDB 2005
Sybase
2003‐Calc.DigitalPatterns
2008SybaseUpgrade
2006EDEBSD
2007CrystalliteSize
2002‐05SubfileReorg
2007AutoSubfiles
2006AutoDup. Review
Software Dev IntegrationFully automated RIR, RietveldAnd LeBail Fitting
2005Calc. Pat.QualityAnalysis
1998‐2001RDBDevelopment
2006AtomWgt %
2008QualityExp. Pat.
2007AutoCrossRef
Science
Publication
SoftwareDevelopers
2009
2007StatisticsPgm
2008ExpPatterns
Strategic Alliances
2007 Integral Index
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Densities>3000 Zeolites
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Launched in fall 2007Database Tutorials (35)
Launched in April, 2009Knowledge Center ‐ linksDXC, ICDD, AIP, PPXRD
Searches on ~ 2400 articles and abstracts, including PPXRD
ToolsPDF‐4/Organics
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1938
Hanawalt, Rinn and Frevel
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Hanawalt
Card 1, 1941
1941
PDF978 Entries
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Experimental patternPositions and Intensities
Total Pattern Analysis
Reduced data d, I pairs
Rietveld 1967Pawley 1981Toraya 1986LeBail 1988
Hanawalt , Frevel & Rinn1938
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7. (1) 198,402 out of 370,844(1.11 Million d‐spacings)
7.2 (0.1) A 27,559
7.22 (0.01) A 2,839
7.222 (0.001) A 291
7.2222 (0.0001) A 33
7.22222 (0.00001) A 1
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Phase Identification works because of theprecision and accuracy in measuring d‐spacings‐ Both in the experiment and for reference patterns
No calibration 1‐10 parts per thousandWith standard calibration 1‐100 parts per million
Quality with Time205,774 S Entries
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Required of the userGood specimen preparation (particle statistics, preferred orientation)Appropriate particle size for good counting statisticsStandardize and calibrate the instrument (Certified Standards)Internal standard for the most important work Use instrument settings appropriate for what your trying to measure
Done by the ICDD – Effective databaseData are standardizedReference quality is measured and evaluatedA range of tools are available for supplemental analytical observations
(searches, indexes, physical properties, structural classifications)
Done by the vendorRigorous validated methods of Search/MatchBatch processing for high speed, cluster tools for looking at large data setsAvailability of high resolution optics and highly efficient detectorsTools for assisting in calibration and instrument standardization
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MgO and TiO2
Synchrotron Data10 PhasesMultiple Databases
Quantitation of 8Components
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Celebrex – Digital Pattern Comparison
Alpha LactoseMonohydrate02‐063‐2272
Celecoxib02‐075‐7351
Stearate
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New in 2009, data to 60 degrees
Celecoxib
Alpha Lactose Monohydrate
22,389,668 d‐spacingsto
66,275,578 d‐spacings
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SIeve –Goodness of MeritComparison
Celebrex – Match and Identification Process
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13 Case Studies•10 Diffractometer•3 Synchrotron
10 Case Studieswith thePDF‐4/Organics
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SubfilesExcipientsInorganic ‐ Salts !MerckPharmacueticalBioactivityPolymersPigmentsForensicExplosives
5,703Inorganics
18,691 EntriesIn these 5 subfiles
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Pharmaceuticals Vitamins Supplements FertilizersAlka‐Selzer Plus Centrum Performance Saw Palmetto MirAcidTums® EX (Extra Strength) Centrum St. John’s Wort Miracle GrowPepcid® AC Centrum Silver Oyster Calcium Bone MealPromethazine Hydrochloride Centrum Carb Smart EchanaceaGoldenseal Rose BloomBenadryl® Vitapower Red* Melatonin Slow ReleaseKroger Decongestant ® VitapowerYellow* LipoicAcid StarterFertilizerAlavert™ Vitapower Grey* StickRobitussin® Cough Drops Senior Vitae Weight Loss Garden ToneClaritin® Childrens Chewable StackerCelebrex™ Capsules Vitamin E with Fe TrimSpaDonnatal MegaMan CortiSlimEffexor® MegaWoman FireStarter
WomenUltra AnabolXOne‐a‐Day Acclimate
SunTheanine
Five groups of materialsFour year study
Materials fromKroger Supermarket, Happy Harry’s, Ace Hardware, CVS PharmacyGenaurdi’s Supermarket, Argonne and Oak Ridge, GNC
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Calcite
Calcium HydroxyPhosphate
Glucosamine Hydrochloride
Caffeine
TRIMSPA, reduced data d,I pairs
TrimSpa
Intensityon log scale
The Food and Drug Administration (FDA) has notified Trimspa
that it has not demonstrated that claims for their product are scientifically supportable.
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USE SUBFILES !!!!!
1. Eliminates false positives particularlywith complex patterns
2. Greatly assists in the statistics of trace/minor phase analysis
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Tutorialshttp://www.icdd.com/resoures/tutorials
3 Case Studies – Inorganic Materials
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Peaks at 13.56 and 11.90 A,
Use the excipients subfile
2 Unknown peak locations match 2/3 of top 3 peaks of stearic acid with the3rd peak overlapping with Celecoxib
Major phases –Celecoxib and Alpha Lactose Monohydrate
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Cellulose II
Cellulose I beta
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Tablet of Pepcid AC
Same molecule, two different crystalline forms
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Use ICDD software – Its designed for data miningVendor software – designed for high throughput
identification
Data mining is an effective tool for identifying polymorphs
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Molecular Symmetry
Molecular Volume
Molecular Packing
Examine Crystal System, Space Group,Space Group Number, Pearson Symbols
Examine Author Cell, Crystal Cell andReduced Cells, Cell Axis Ratio’s, Cell Volumes
Examine Powder patterns for differencesin interplanar spacing, examine strong lines (d1, d2, d3) and long lines (l1, l2, l3)
Search Fields in PDF‐4/Organics
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908 Glycine and glycine derivatives
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Symmetry vsVolume with inserts of the diffraction patterns forthe points in question
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Plots two parameters (edge vs volume)
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References for Form I alpha,Form I beta and Form II
Pepcid AC
Simulation of microcrystallinestates of cellulose
Via PDF-4+
Scardi, LeoniFaber
PDF 00‐056‐1717 Cell IIPDF 00‐056‐1718 Cell I betaPDF 00‐056‐1719 Cell I alpha
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Tools
Comprehensive Database with common polymorphs(Key polymorph data on cellulose added 2006)
Calculated Digital Patterns(Added in 2003)
Crystallite Size Simulation(Added in 2007)
Tutorials
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48 Searches66 Field DisplayGraphics Interface
Use multiple measurements of symmetry, molecular size, molecular volume, packing and molecular orientation to discover and identify polymorphism
Point and ClickJAVA interface
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Use of the database for multi‐component mixtures
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Identification link to correct phase (especiallyfor polymorphs)
Round Robin example: Acetaminophen, Mannitol, Silicon
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β – D‐Mannitol02‐069‐8458Orthorhombica= 8.6940(70)b= 16.9020(80)c= 5.5490(60)P212121 (19)Z= 4.00V= 815.40
AcetaminophenPolymorph Form I02‐076‐2269Monoclinica= 12.7630(60)b=9.2500(40)c=7.0820(20)β =115.52(3) P21/a (14) Z= 4.00V=754.51
SiliconCubica = 5.431Fd‐3m(227)Z=8V=160.19
12 Choices 15 Choices
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Quality Marks, Status, I/Ic, R‐factors(lack of electron density, (i.e. H’s lowers quality mark !)
02‐069‐8458 β – D‐Mannitol
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Step 1: Phase Identification3) Cross Reference to CSDReference Code DMANT07Rietveld
2) I/Ic = 0.51By RIR
Digital PatternCalculation and ExportPattern Fitting(Cluster Analyses)
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3D Structure
Simulated Electron Pattern
Electron Backscattering Pattern
Calculated Diffraction Pattern
PD3 full digital experimental data overlaid on historic stick pattern
Bond Distances/Angles
ICDD Databases
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Material IdentificationFormulation AnalysisPolymorph AnalysisQuantitative AnalysisStructure Refinement
Case HistoriesTools for AnalysisLinks to TutorialsLinks to More CaseHistories
Database, Tools, Methods
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PPXRD2-PPXRD8
Phase Identification
Formulation Analysis‐Health
Supplements‐ Pharmacueticals
Crystallinity‐Celullose
Cluster Analysis4 Case Studies
RietveldAnalysis
Polymorph Analyses‐ 6 Drug Examples‐Cellulose, Tegafur‐ Bone, Teeth
Nanomaterials
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Low Temp Form
2 Room Temp FormsSubtle polymorphism ‐Molecular visualization (CSD)shows 2 similar configurations that vary inmethyl group rotation and close contacts
Note: The low temperatureform has a molecular configurationchange from room temperatureforms
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Application PDF-4/OrganicsIdentification and QuantitationBy Reference Intensity Ratiousing PDF-4/Organics
9 Phase solution used data from 3 different databasesICDD-powder, ICSD – single crystal, CCDC- single crystalNote: Scale of 240,000 counts for this data set, 119 peaks
Minerals, Vitamins andAmino acids
MegaMen Vitamin
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143
412318
ListedComp*
•Five compounds are46.5 wt % of tabletNormalized to 100%
Quantitation by Reference Intensity Ratio –CentrumPerformance
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Quantitation by Reference Intensity RatioCentrum Silver ‐MultiVitamin
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Advanced Techniques% Crystallinity Crystallite SizePolymorph Analysis
Using Pattern Fitting Techniques
Digital Library ofCrystalline Polymorphs withvaried crystallite sizeand amorphous cellulose
Use digital Library to analyzepolymorphs and crystallinity
Key Reference PatternAmorphous CelluloseNot currently in the PDF
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All calcium phosphate polytypesAZTCarbamazepineCelluloses
SRM 640SRM 660SRM 676 and SRM 1776
Used all reference materials, used combined experimental and reference data,used all experimental data – mix and match
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Human dental enamel, 1999‐OH rich, Ca 9.87, J.C. Elliot
Mineral, R. Young, 1964
An OCP derivative with 16 watersWatanabe et al 1998
OCP, Brown et. al, 1962
Another OCP ??, 1957
Apatites
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Naturally occuringtooth enamels
Synthetics, some D,Na, CO3 doped (B types)
Ca9 – calcium deficient
Low resolution dataDeleted by editors
OCP – Ca8
Ca8‐Ca9
SyntheticsandMineral