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David Hinks1, [email protected], Nelson Vinueza-Benitez1, David C Muddiman2, Antony J Williams3. (1) Department of Textile Engineering, Chemistry & Science, North Carolina State University, Raleigh, North Carolina 27695, United States, (2) Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695, United States, (3) Department of eScience, Royal Society of Chemistry, Wake Forest, North Carolina 27587, United States The synthetic organic chemistry industry arguably began with the commercialization of the first synthetic dye, Mauveine, by Sir William Henry Perkin in 1856. Throughout the next 150 years, research and development of dyes exploded in response to the growing demand for high performance colored products for multiple major industries, including textiles, plastics, coatings, cosmetics, and printing. While many thousands of prototype dyes have been designed, synthesized, characterized, and tested, most of the structural and property data have been kept from the open literature even though large segments of the colorant industry have matured and many high volume dyes are now off patent. This is unfortunate considering that dyes are of fundamental importance to a number of growing areas of science and technology, including solar energy capture, medicinal chemistry (e.g. photodynamic therapy for cancer treatment), biomarkers, environmental monitoring, security printing, and camouflage. The ability for all scientists to observe comprehensive dye structure-property relationship data could help advance the theoretical and practical understanding of the role of dyes in various complex systems. NC State University's recently formed Forensic Sciences Institute is building a dye library that will enable establishment of the first comprehensive cheminfomatics system for forensic trace evidence analysis of dyed materials, as well as a broad range of dye discovery projects. As part of this effort, NC State recently secured a remarkable donation of approximately 100,000 dye samples, spectra and performance data that were made by a leading chemical manufacturer over a period of more than 50 years. Significant parts of the library will be made available online for free. The scope and challenges in developing a digitized structural database will be reviewed. Once completed, the new library will provide all scientists with a powerful tool for dye discovery and knowledge.
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Cheminformatics for Dye Chemistry Research: Bringing Online an Unprecedented 100,000 Sample Dye Library
March 19, 2014
D a v i d H i n k s , N e l s o n V i n u e z a , A n t o n y J . W i l l i a m s
D e p a r t m e n t o f Te x t i l e E n g i n e e r i n g , C h e m i s t r y & S c i e n c e
Core Research Competencies
• Share information on a new physical dye library resource– Opportunities and cheminformatics challenges
• Gain feedback on ways to optimize its utility• Make new connections for dye and dye-related research• Springboard for new collaborations / research proposals
TECS Department Core Competencies
Goals of this presentation
Core Research Competencies• 1856 William Henry Perkin
– 18 yr old student of Hoffman’s– Failed quinine synthesis– Produced purple impurity
• All too familiar serendipity result
– First dye synthesis patent
– Father of industrial chemistry
TECS Department Core CompetenciesIn the beginning
http://colour.sdc.org.uk/perkin‐timeline/
Core Research CompetenciesTECS Department Core Competencies
In the beginning“Producing a New Coloring Matter for Dyeing with a Lilac or Purple Color Stuffs of Silk, Cotton, Wool, or other Materials”
Core Research CompetenciesTECS Department Core Competencies
Greenford Green DyeworksFirst chemical factory
http://colour.sdc.org.uk/perkin‐timeline/
Core Research CompetenciesTECS Department Core Competencies
Ubiquitous synthetic dyes
Traditional applications• Textiles• Paper• Plastics• Paints• Cosmetics• Photography• Food
Research needed:- toxicity- life-cycle assessment &environmental impact
- application efficiency
Core Research CompetenciesTECS Department Core Competencies
Functional DyesSafety & visibility
Core Research CompetenciesTECS Department Core CompetenciesDyes to
hide by
Core Research CompetenciesTECS Department Core Competencies
Dyes as pharmaceuticals(photodynamic therapy)
Core Research CompetenciesTECS Department Core CompetenciesGrowing Areas of Research in
Functional Dyes
Dye-Sensitized Solar Cells
Dyes as pharmaceuticals(photodynamic therapy)
Security Inks
Core Research CompetenciesTECS Department Core Competencies
Functional Dyes
Biomedical imaging
http://www.koheras.com/side9489.html
Core Research Competencies
• Formerly Eastman-Kodak• R&D in dye chemistry
– Photographic business– Synthetic fibers– Designed, synthesized, and
tested 1000s of dyes– Unpublished– Exited textile dyes business in
1990s
TECS Department Core CompetenciesEastman Chemical CompanyDyes Research
Max WeaverEastman’s lead dye chemist
Core Research Competencies
• All dye samples from Kingsport, TN research building (0.1- 3 g samples)
• >250,000 dyed fabric and carpet samples• >250,000 test data• 100s of technical reports• Text books• Rare BIOS Reports
TECS Department Core CompetenciesEastman Dye LibraryDonation to NC State
Core Research CompetenciesTECS Department Core CompetenciesLocation
College of Textiles, NC State
Textile Engineering, Chemistry & Science
Faculty31 interdisciplinary
faculty
ChemistsOrganic/ Analytical/ Physical
EngineersChemical/Mechanical/Industrial/ Textile/ Aeronautical
Students~485 undergraduates
• Polymer & Color Chemistry• Textile Engineering• Textile Technology
~50 Master’s students~70 PhD students
• Fiber and Polymer Science• Textile Technology
Management15
Department of Textile Engineering, Chemistry & Science
Core Research CompetenciesTECS Department Core Competencies
Renovation
Core Research CompetenciesTECS Department Core Competencies
Moving
Core Research CompetenciesTECS Department Core Competencies
Installation
Core Research Competencies• Joint US-British investigation• Interrogation of German chemists• 1946-49
TECS Department Core CompetenciesBritish Intelligence Objective Subcommittee (BIOS) Reports
Core Research Competencies• Color fastness on variety of synthetic fabrics• Photostability; sublimation stability
TECS Department Core CompetenciesTest Data
Core Research Competencies• Color fastness on variety of fabrics• Photostability; sublimation stability
TECS Department Core CompetenciesTest Data
File #
Synthesis Notebook #
Varying concentrations
Photostability
Core Research CompetenciesTECS Department Core Competencies
98,000 prototype dyes
Core Research CompetenciesTECS Department Core Competencies
500-600 samples per draw
Core Research CompetenciesTECS Department Core Competencies
All major dye classes
• Many– Azo– Anthraquinone
• Fewer– Methine– Nitrodiphenylamine– Porphyrin/phthalocyanine– NIR dyes & UV absorbers
Core Research CompetenciesTECS Department Core Competencies
Anthraquinone dyes
Core Research CompetenciesTECS Department Core Competencies
Azo dyes
Core Research CompetenciesTECS Department Core Competencies
Unusual dyes
Core Research CompetenciesTECS Department Core Competencies
Unusual polymeric dyes
Core Research CompetenciesTECS Department Core CompetenciesLarge number of structures of potential
interest for multiple applications
• Methines
Core Research CompetenciesTECS Department Core Competencies
The oldest compounds (1940s)
Core Research CompetenciesTECS Department Core Competencies
The oldest compounds (~1940s)
NB# 303A‐2C
Core Research CompetenciesTECS Department Core CompetenciesHow well preserved?
Excellent undergrad training
Even the very old dyes appear to be quite pure
Core Research CompetenciesTECS Department Core Competencies
How well preserved?Many of the more complex structures appear good quality
Core Research CompetenciesTECS Department Core Competencies
How well preserved?
356.1485
[M+H]410 nm
Core Research CompetenciesTECS Department Core Competencies
UV/Vis, Fluorescence
1
0.0E+00
5.0E+05
1.0E+06
1.5E+06
2.0E+06
2.5E+06
0
0.1
0.2
0.3
0.4
0.5
0.6
0.7
0.8
0.9
1
250 350 450 550 650 750
Emission
(CPS)
Absorban
ce
Wavlength (nm)
Dye 1Dye 2Dye 3DYE 1EDYE 2EDYE 3E
Dyes UV‐Vis Absorption Emission
max
(nm) ε (M‐1 cm‐1) em (nm)
NCSU‐MWDL1 289; 493 (*) 3820; 8,390 584NCSU‐MWDL2 283; 464 (*) 3360; 5,730 535 NCSU‐MWDL3 287; 474 (*) 3390; 6,200 545
2
3
Core Research Competencies• Likely that none of the dyes have been characterized
crystallographically
TECS Department Core CompetenciesSingle Crystal X-Ray Crystallography
Core Research Competencies• No standardized database of dyes is available for the
criminal justice community– Fibers analyzed via microscopy, uv/vis
microspectrophotometry, sometimes LC-MS– Method development
• LC• MS• Raman
– Dye identification without destruction of evidence– Statistical validation
TECS Department Core CompetenciesForensic Dye Database
Core Research CompetenciesTECS Department Core CompetenciesDetroit Automotive Fabric
Collection (1955 – present)
Mass Spectra of Disperse Blue 60
39
M+H+
2M+Na+
O
O
NH2
NH2
N
O
OO
CH3
Disperse Blue 60
UV Spectra of Disperse Blue 60 _005
40
Disperse Blue 60 Manufacturer variance
DB 60 – 005Mobay Chemical Corp.
0
5000
10000
15000
20000
25000
30000
35000
40000
45000
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
380.1241
781.2228226.2162
[M+H]+
[2M+Na]+
N
O
O
NH2
NH2
O
O O CH3
05000
100001500020000250003000035000400004500050000
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
394.1393
809.2531320.2557
[M+H]+
[2M+Na]+
N
O
O
NH2
NH2
O
O O
CH3
05000
100001500020000250003000035000400004500050000
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
408.1554
837.2854
257.1510
[M+H]+
[2M+Na]+
N
O
O
NH2
NH2
O
O O
CH3
41
Disperse Blue 60 productionDisperse Blue 60 Manufacturer variance
Year Make Model2006 Dodge Dakota2007 Suburu Tribeca2008 Buick Enclave2009 Mitsubishi Eclipse2009 Nissan Maxima2010 Honda Element2010 Honda Pilot2011 Ford Fusion2011 Mazda 62011 Volkswagen Jetta
42
Ford Fusion Automotive Fibers
2011 Ford Fusion
‐1
‐0.5
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10 12 14
Intensity
Time (min)
4.40
7.69
8.89 10.2511.50
660 nm
43
Ford Fusion Black Fiber
2011 Ford Fusion660 nm
0
10000
20000
30000
40000
50000
60000
70000
80000
90000
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
380.1238
781.2216
324.2144
226.2162
N
O
O
NH2
NH2
O
O O CH3
[M+H]+
[2M+Na]+
C.I. Disperse Blue 60
44
Ford Fusion Black Fiber
2011 Ford Fusion
‐1
‐0.5
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10 12 14
Intensity
Time (min)
4.40
7.69
8.89 10.2511.50
660 nm
45
Ford Fusion Black Fiber
2011 Ford Fusion660 nm
0
5
10
15
20
25
30
35
40
45
50
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
377.1130
867.1765
423.1011
268.0841
[M+H]+O
OO
CH3
NH2
OHNH2
OH
[2M+Na]+
C.I. Disperse Blue 73
46
Ford Fusion Black Fiber
2011 Ford Fusion
‐1
‐0.5
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10 12 14
Intensity
Time (min)
4.40
7.69
8.89 10.2511.50
660 nm
47
Ford Fusion Black Fiber
2011 Ford Fusion660 nm
0
10000
20000
30000
40000
50000
60000
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
377.0771
489.3667
775.1277
228.2321
[M+H]+
[2M+Na]+
O
O
NH
OHOH
N+ O
-O
C.I. Disperse Blue 77
48
Ford Fusion Black Fiber
2011 Ford Fusion: C.I. Disperse Blue 77 vs. C.I. Disperse Blue 73
Disperse Blue 77Disperse Blue 73
‐1
‐0.5
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10 12 14
Intensity
Time (min)
4.40
7.69
8.89 10.2511.50
‐1
‐0.5
0
0.5
1
1.5
2
2.5
0 2 4 6 8 10 12 14
Intensity
Time (min)
4.40
7.69
8.89 10.2511.50
0
5
10
15
20
25
30
35
40
45
50
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
377.1130
867.1765
423.1011
268.0841
[M+H]+
O
OO
CH3
NH2
OHNH2
OH
[2M+Na]+
0
10000
20000
30000
40000
50000
60000
100 200 300 400 500 600 700 800 900
Ion Co
unts
m/z
377.0771
489.3667
775.1277
228.2321
[M+H]+
[2M+Na]+
O
O
NH
OHOH
N+ O
-O
49
Ford Fusion Black Fiber
Time-of-Flight Secondary Ion Mass SpectrometryAnalysis of dyed fibers without extraction
O
O
NH2
HN
SO3H
390 392 394 396 3980
1500
3000
4500
6000
Inte
nsity
(a.u
.)
m/z, Negative Ion
Dyed Nylon Cross Section
Core Research CompetenciesStage 1: Digitize and publish all structures on ChemSpider
Stage 2: Protocols for collaborative projects and funding
Stage 3: Education and Training Program (REU?)
Stage 4: Establish online interest group(s)User-based identification of potential high value compounds
Stage 5: Purify and characterize (MAJOR CHALLENGE)
TECS Department Core CompetenciesDevelopment of CheminformaticsFor Public Use
Stage 1
Stage 2
Stage 3
Stage 4
Stage 5
ForensicsSAR Toxicology/Env
BiomedicalSolar CellsTextiles
Core Research Competencies• Eastman Chemical Company
– Max Weaver and team– Stewart Witzeman– Bob Maleski
• Graduate Students– Min Li– Guan Wang– Xiuzhu Fei– Sha Fu– Nanshan Zhang– Ann Crawford
• Undergraduate Students– Cody Zane– Emily Lichtenberger
TECS Department Core CompetenciesAcknowledgments
• NC State Staff– Maqbool Hussain (Post Doc)– Chuanzhen Zhou (Post Doc)– Roger Sommer (Crystallography)– Dzung Nguyen
• NC State Faculty– David Muddiman– Keith Beck– Dieter Griffis
Thank You! [email protected]
