• Research Scientist with Local Roots Headlines Annual Bell’s Event with Inspirational Speech
• Chemistry Historian Presented “How Color Changed the World” at WMU
• Plan to Attend the Great Lakes Regional Meeting in June!
• Note the New Policy for Outreach Volunteers Working with Youth
• Chemistry Reference Books Available
• KACS Calendar

Research Scientist with Local Roots Headlines Annual Bell’s Event with Inspirational Speech

Chemistry Historian Presented “How Color Changed the World” at WMU

Orna proudly donned her ChemEd conference shirt she acquired when she visited Kalamazoo in 2011 for a high school education conference; it was sponsored by the Department of Chemistry and the Mallinson Institute of Science Education (MISE) at WMU. The logo reads “Chemistry grows in Michigan”.

Orna’s interest in the history of color came about when she was asked to develop a new course for art students. The goal was to illustrate the pivotal role of color chemistry in the art world while treading lightly on the physical science content to entice non-chemists. Orna weaved together a wide range of topics that were all related to the intersection of color, chemistry and history. She included powerful examples that highlight how the chemical sciences affected world politics and people’s lives. Topics ranged from natural dyes in the ancient world to natural and synthetic colors in modern times.

Her presentation began with 32,000-year-old cave paintings of a steppe bison by paleolithic artists on the walls of Grotte Chauvet in southern France. Early colors were based on iron(III) oxides that, depending on the degree of hydration, result in various shades of ochre.
Some of the earliest manufactured pigments, such as cinnabar in vermillion which is mercury(II) sulfide, HgS, were toxic. This bright red pigment was commonly used by Roman painters to create Pompeii’s wall paintings. Egyptian Blue is another well-known pigment and was used thousands of years ago, 4613-4494 BP. It is a calcium copper tetrasilicate, CaCuSi4O10, but its exact manufacturing method is still debated. Next up was the role of carmine cochineal. It is a New World pigment-dye, which was considered more precious than silver. It was a real treasure on Spanish galleons. The chemical structure is carminic acid which was extracted from the egg sacs of female scale insects that feed on cactus plants. The parasite dactylopius cocci are gray-reddish scale insects that expressed this acid as a chemical defense ingredient. This phenomenon of deterring predators with colors can be found in many other naturally occurring pigments. Interestingly, “carmine” quickly became a source of contention when Starbucks made headlines like “Beetle coloring bugs vegans”. They had to quickly refrain from using this red-colored dye in their products. An ingredient list may not contain “bugs” as a component but “carmine” instead, which consumers don’t easily recognize as an insect. Carmine is often listed as E120 and had been used in sweets like Skittles. There is no economically viable method to produce carmine other than grinding up many bugs.

Considerable time was spent on the chemistry of indigo and its geopolitical influence. Indigo plants are green but can release the typical blue color when their leaves are crushed together, releasing the enzyme that catalyzes the formation of its oxidized blue form. Indigo is produced on a large scale, 55.000 pounds each year, and 95% of it is used to dye Blue Jeans. A closely related chemical compound, 6,6’-dibromoindigo, was extracted from snails and lead to discussions about how to describe the color of Tyrian, which is Royal Purple. This color could only be worn by the richest people because it took 10,000 snails to obtain 1 g of the precious dye. In religious text this chemistry was hotly debated, whether it was the “color of the sky at dawn” or the “color of the sky at midnight”. During Orna’s Fulbright in Israel she collaborated with Zvi Koren. HPLC analyses proved that the color was specific to each snail, producing varying ratios of indigo (blue) and 6,6’-dibromoindigo (purple). The two bromine atoms in the latter shift the absorption maximum from blue to purple. She marveled that nature came up with the same template by two very different evolutionary pathways, from two very different species, indigo from plants and dibromo indigo from animals.

Scientists eventually caught on to the opportunities of chemically producing dyes in the laboratory when alternative starting material resources were sparse. After all, who wants to milk a python to extract uric acid? The latter was the starting material for Scheele’s and W. Prout’s synthesis of murexide in the 19th century. Synthetic approaches were readily scaled up when unlimited amounts of aniline derivatives from tar could be converted into mauve (W. H. Perkins) and magenta dyes (A. W. von Hofmann).

The chemistry of indigo was the first example with major geopolitical consequences about how color changed the world. The natural dye extraction on Indian plantations was labor-intensive and exploited peasants who spent hours crushing plants. However, once Adolph von Baeyer succeeded at synthesizing indigo from readily available anthranilic acid for a fraction of the cost, 10%, compared to naturally extracted dyes, the ripple effects became obvious. India was no longer a cash cow for the British to exploit leading to the indigo revolt that planted the seeds for India’s fight for independence.

The dye industry made colorful fashion accessible to the masses by replacing costly natural dyes with modern synthetic methods. There was an expansion of the German dye industry, which, in turn, led to an expansion of the German university system to meet the needs of hiring well-trained workers. It would eventually have a world-wide effect by raising the educational level of the masses. However, cottage industries had to give way to board rooms. The dye industry became a powerful lobby to promote favorable politics and instituted a modern patent system to protect their rights. Moreover, research became a big business and allowed Germany to dominate and carry on in two World Wars. The Haber-Bosch process played a pivotal role. It fixed stable N2 in the air into ammonia and gave Germany power and independence. Eventually the knowledge of turning dyes into explosives was converted into using dyes for making drugs in the post-war era.

Biological and biochemical applications of dyes were also addressed. Walther Flemming noticed that certain cell portions would take on dyes and called it chromatin. Wilhelm von Waldeyer-Hartz renamed them as “chromosomes”, linking dyes to genetics. Paul Ehrlich, a chemist and physician, was fascinated with color and developed diagnostic tools to differentiate various tissues. Methylene blue could selectively stain nerve cells. And, of course, chemical substances with a high affinity to diseased tissues would give rise to chemotherapy to eliminate the disease with a “magic bullet”.

Orna pointed out that in an unregulated market, it was possible for bakers to attract children with their colorful creations even though they contained toxic inorganic chemicals such as orpiment, blue vitriol, vermillion, lead white, litharge / massicot, realgar or Paris green. Many food colors were toxic until whistleblowers changed the rules. For example, Frederick Accum published a treatise to combat the use of toxic food colors. It wasn’t until 1906 when Harvey Wiley supported the landmark Pure Food and Drugs Act. Its successor was the USDA and its protective regulations to protect citizens from harmful food additives.

Orna concluded that color chemistry changed many different worlds, that of art, fashion, politics, economies, education, medicine, and, overall, the history of the 19th and 20th centuries. One notable comment in the Q&A session was her response to how she became interested in chemistry. It all began when her younger brother received a chemistry set for Christmas, after which a “hostile takeover” ensued; her passion for chemistry began and the rest is history.

On a personal note, I have known Mary Virginia Orna for some time. My presentations at ACS HIST symposia resulted in my contribution of a book chapter for “Food at the Crossroads: Chemistry’s Role in Sustainability, Past & Present” that she co-edited (ACS Symposium Series, 2020). Throughout the day I observed her embracing every interaction with students, staff and science colleagues. She encouraged everyone to stay in touch with her via email at maryvirginiaorna@gmail.com.

Her visit to Kalamazoo at WMU was preceded by a visit to Eastern Michigan University and followed by a presentation at Grand Valley State University. More background information can be found in our September 2024 issue of The KalChemist News (p. 1), or gleaned from Dr. Mary Virginia Orna’s Wikipedia page (https://en.wikipedia.org/wiki/Mary_Virginia_Orna, retrieved 11/1/2024), or from a full issue of the HIST division’s publication, “Bulletin for the History of Chemistry”, that was dedicated to Dr. Orna’s research (Volume 48, Number 1, 2023).

This event was co-sponsored by the Kalamazoo Section of the American Chemical Society, KACS, www.kalamazooacs.org, and the Department of Chemistry at Western Michigan University (WMU).

Plan to Attend the Great Lakes Regional Meeting in June!

Note the New Policy for Outreach Volunteers Working with Youth

Chemistry Reference Books Available

A generous offer of Chemistry Reference Books available to anyone interested in having any or all of them in his/her library. (If interested please contact Lydia E. M. Hines at lemhwgh@gmail.com and give your name along with reference to the list.)

Organic Functional Group Preparations Vol. 1 Saneller & Kara 1983
Organic Functional Group Preparations Vol. 2 Saneller & Kara 1986
Compendium of Synthetic Organic Methods Vol. 1 Harrison and Harrison 1971
Compendium of Synthetic Organic Methods Vol. 2 Harrison and Harrison 1974
Compendium of Synthetic Organic Methods Vol. 3 Hegedus & Wade 1977
Compendium of Synthetic Organic Methods Vol. 4 Wade 1980
Compendium of Synthetic Organic Methods Vol. 5 Wade 1984
The Chemistry of Amidines and Imidates Patai 1975
The Chemistry of Amides Zabicky 1970
The Chemistry of the Cyano Group Rappoport 1970
The Chemistry of Carboxylic Acids and Esters Patai 1969
The Chemistry of the Azido Group Patai 1971
The Chemistry of the Quinonoid Compounds Vol. 1 Patai 1974
The Chemistry of the Quinonoid Compounds Vol. 2 Patai 1974
Reagents for Organic Synthesis Vol. 1 Fieser and Fieser 1967
Reagents for Organic Synthesis Vol. 2 Fieser and Fieser 1969
Reagents for Organic Synthesis Vol. 3 Fieser and Fieser 1972
Reagents for Organic Synthesis Vol. 4 Fieser and Fieser 1974
Reagents for Organic Synthesis Vol. 5 Fieser and Fieser 1977
Reagents for Organic Synthesis Vol. 6 Fieser and Fieser 1975
Reagents for Organic Synthesis Vol. 7 Fieser and Fieser 1979
Fieser and Fieser’s Reagents for Organic Synthesis Vol. 8 Fieser and Fieser 1980
Fieser’s Reagents for Organic Synthesis Vol. 9 Fieser Danheiser Roush 1981
Fieser’s Reagents for Organic Synthesis Vol. 10 Fieser 1982
Fieser and Fieser’s Reagents for Organic Synthesis Vol. 11 Fieser and Fieser 1984
Fieser and Fieser’s Reagents for Organic Synthesis Vol. 12 Fieser and Fieser 1986
Computer Assisted Structure Elucidation Gray 1986
Infrared Characteristic Group Frequencies G. Socrates 1980
Fourier Transform Infrared Spectroscopy Volume 2 Ferraro & Basile 1979
Fourier Transform Infrared Spectroscopy Volume 3 Ferraro & Basile 1982
Fourier Transform Infrared Spectroscopy Volume 4 Ferraro & Basile 1985
Burger’s Medicinal Chemistry 4 th Edition Part 1 Wolff 1980
Burger’s Medicinal Chemistry 4th Edition Part 2 Wolff 1979
Burger’s Medicinal Chemistry 4th Edition Part 3 Wolff 1981
Organic Synthesis Collective V-1 2nd Edition Gilman & Blatt 1941
Organic Synthesis Collective V-2 Blatt 1943
Organic Synthesis Collective V-3 Horning 1955
Organic Synthesis Collective V-4 Rabjohn 1963
Organic Synthesis Collective V-5 Baumgarten 1973
Organic Synthesis Collective V-1 thru V-6 Cumulative Index Shriner & Shriner 1976
The Sadtler Guide to NMR Spectra W.W. Simons & M. Zanger 1972
Plant & Fungal Toxins Handbook of Natural Toxins V-1 Edited by Richard F Keeler & Anthony T. Tu 1983