Notes

Outline

Developing Numeric Databases – The NIST Mass Spec and WebBook Stephen Heller Guest Researcher  NIST/PCPD Gaithersburg, MD 20899-8380

The slides from this presentation can be found at: http://www.hellers.com/steve/pub-talks/ali2004/frame.htm

An expert is someone who knows no more about the subject than anyone else, but is organized and shows slides.

There are three ways to ruin yourself: Gambling, woman, and technology Gambling is the fastest, Woman are the most pleasurable, Technology is the most certain George Pompidou

NIST and others have developed many good, high quality numeric databases, but VERY few are used by someone other than the creator and his/her mother.

Good and useful are two different words with very different meanings.

If databases were perfect, they wouldn’t be. With apologies toYogi Berra

Outline of this talk Part 1 – Mass Spec Database Part 2 – NIST WebBook

The NIST Mass Spectrometry Data Program

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MS Library History 1971 – EPA/NIH Collection of Collections 1978 – First Distribution – Tape, On-Line, Books 1983 – To EPA, Cincinnati 1988 – To NIST 1990 – Manual Evaluation/Algorithms 1998 – Evaluated Library 2002 – Major Update

New Spectra Focus Areas New Commercially Available Replicates for Important Compounds Derivatives Chemical Weapons Related

New Spectra Quality Up Front Complete With chemical structures Documented Calibrated instruments Upstream filter

Some Sources 14,000 Japan AIST/NIMC Collection: Commercially available common organic compounds 6,976 Russian Academy of Sciences : Institute of Petrochemical Synthesis: Mostly Derivatives (silyl, acyl). 7,182 NIH measurements Synthetic analogues of natural compounds, perspective drugs, drug metabolites, and their intermediates. 1,735 NIST Commercially available common compounds, pesticides, drugs. 1,022 Eastman Chemical Company Commercial and synthetic compounds and silyl derivatives. 406 Verifin (Finland) : Chemical weapons and precursors. 348 HD-Science (UK) : Silyl derivatives of drugs 138 Military Institute of Chemistry and Radiometry (Poland): Chemical weapons related

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When the pear is ripe it falls by itself.

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NIST98 => NIST02 Mainlib: 107,886 => 147,370 spectra 91,856 spectra from old mainlib 1,331 spectra from old replib 54,183 new spectra Replib: 21,250 => 27,844 spectra 14,050 spectra from old replib 7,378 spectra from old mainlib 6,416 new spectra Excluded in the new database: 8,652 spectra from old mainlib 5,869 spectra from old replib

More Statistics 129,136  => 175,214 spectra 90,311    => 134,949 with CAS number 69,061    => 107,105 unique CAS numbers 107,829  => 147,350 structures 255,234  => 440,764 names Peaks per Spectrum 79    => 99 median 96    => 111 average 12% => 5% less than 20 peaks/spectrum 2%   => 0.5% less then 10 peaks/spectrum

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Distributors Instrument Data Systems (15) Agilent, Bruker, ThermoFinnigan, Hitachi, Inficon, JEOL, LECO, Los Gatos,  Micromass, MSS, ONIX/Fisons, Perkin-Elmer, Shimadzu, Shrader, Varian/Bear Software (21) ACD, Aldrich, ARLS, Bio-Rad/Sadtler, Chemical Concepts, ChemSW, ChroMaSoft, CSS, Digital Data Management, Fiveash, Galactic, HD Science, Hiden, JEMS, KORE, Monitor Group, Pro-Lab, Axel Semrau, Spectra Seriea, SIS, Stanton Data (3) ERM, JAICI, Wiley

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The NIST WebBook http://webbook.nist.gov/

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WebBook Motivation Data available Quality of data Data presentation Usage patterns Future directions

Motivation Standard Reference Data Act Provide access to NIST standard reference data over the internet Existing NIST databases Additional data from NIST Data from outside NIST

Data Available (1) Thermodynamic Gas phase Condensed phase Phase change Reaction Ion energetics Ion clustering Fluid property models Group additivity model

Data Available (2) Other IR spectrum Mass spectrum UV / Vis spectrum Vibrational and electronic energy levels Diatomic constants Henry’s law

Thermochemical Properties Many types of thermochemical data Tool for data evaluation Reference to original literature Useful comments provided in many cases Multiple values for many properties Related properties (DfH Û DrH)

Thermochemical Properties (1) DfH° - gas, liq., cr. S° - gas, liq., cr. Cp- gas, liq., cr. DH - phase change DS - phase change Boiling point Melting point

Thermochemical Properties (2) Tc Pc Antoine parameters Heat of combustion DH - reaction DG - reaction DS - reaction

Quality of Data Most data from peer-reviewed literature NIST QA efforts Preserve data in original form (digits, units) Compilers are qualified scientists Inspect multiple determinations Error report tracking system

Data Presentation

Tabular Data

Antoine Equation Parameters

IR Spectrum

Reaction Search

Reaction Search

Reaction Data

Usage Patterns (1) Steadily increasing usage over time Over 20,000 “users” per week in non-holiday months Large numbers of users return to the site Used worldwide

Usage Patterns (2)

Future Directions NIST retention index database (gas chromatography) Links to more NIST data projects and sites Support for the IUPAC Chemical Identifier (INChI) Updates to existing databases

For a talk to be immortal it does not have to be eternal. Muriel Humphrey comment to Vice-President Hubert Humphrey

Acknowledgements Mass Spec Database: Hank Fales (NIH), Bill Milne (NIH), Bill Budde (EPA), Steve Stein (NIST), Jane Klassen (NIST), Anzor Mikaya (NIST) WebBook: Peter Linstrom (NIST), Gary Mallard (NIST)