Early work in the development of liquid-liquid separation techniques was undertaken by Cornish et al. with a process called "systematic fractional distribution" as well as Randall and Longtin, however, the central figure is certainly Lyman C. Craig. Lyman Craig's development of countercurrent distribution began with studying the distribution of a pharmaceutical, mepacrine (atabrine), between the two layers of an ethylene dichloride, methanol, and aqueous buffer biphasic solvent system. The distribution coefficient (Kc which coincides with partition coefficient) of atabrine varied by the composition of the solvent system and the pH of the buffer. In the next article, Craig was inspired by the work of Martin and Synge with partition chromatography to develop an apparatus that would separate compounds based on their distribution constant (K which coincides with partition coefficient). It was shown that a solvent system composed of benzene, n-hexane, methanol and water would separate mixtures of organic acids. It is remarkable that the mathematical theory developed hand-in-hand with the progression of applications. Craig continued to pursue this method of separation by testing different compounds, formulating biphasic solvent systems, and most importantly developing a commercially viable instrument.
Moore, Stanford (1978). "Lyman Creighton Craig 1906-1974". National Academy of Sciences Biographical Memoirs: 49–77. Retrieved 2016-02-26. http://www.nasonline.org/member-directory/deceased-members/20000680.html
Joseph-Nathan, P. (1967). "Liquid-liquid extraction". Journal of Chemical Education. 44 (3): 176. Bibcode:1967JChEd..44..176J. doi:10.1021/ed044p176. /wiki/Bibcode_(identifier)
"Countercurrent Separations". 2 December 2013. https://chem.libretexts.org/Core/Analytical_Chemistry/Instrumental_Analysis/Countercurrent_Separations
Cornish, R. E.; Archibald, R. C.; Murphy, Elizabeth A.; Evans, H. M. (1934). "Purification of Vitamins - Fractional Distribution between Immiscible Solvents". Industrial & Engineering Chemistry. 26 (4): 397–406. doi:10.1021/ie50292a010. /wiki/Doi_(identifier)
Randall, Merle; Longtin, Bruce (1938). "Separation Processes: General Method of Analysis". Industrial & Engineering Chemistry. 30 (9): 1063–1067. doi:10.1021/ie50345a028. /wiki/Doi_(identifier)
Lyman C. Craig (1943). "Identification of Small Amounts of Organic Compounds by Distribution Studies. Application to Atabrine". Journal of Biological Chemistry. 150: 33–45. doi:10.1016/S0021-9258(18)51248-5. https://doi.org/10.1016%2FS0021-9258%2818%2951248-5
Lyman C. Craig (1944). "Identification of Small Amounts of Organic Compounds by Distribution Studies. II. Separation by Counter-current Distribution". Journal of Biological Chemistry. 155: 535–546.
Williamson, Byron; Craig, Calvin (1947). "Identification of Small Amounts of Organic Compounds by Distribution Studies. V. Calculation of Theoretical Curves". Journal of Biological Chemistry. 168 (2): 687–697. doi:10.1016/S0021-9258(17)30926-2. PMID 20238623. https://doi.org/10.1016%2FS0021-9258%2817%2930926-2
Craig, L. C. (1950). "Partition Chromatography and Countercurrent Distribution". Analytical Chemistry. 22 (11): 1346–1352. doi:10.1021/ac60047a003. /wiki/Doi_(identifier)
Sato, Yoshio; Barry, Guy T.; Craig, Lyman C. (1947). "Identification of Small Amounts of Organic Compounds by Distribution Studies. VII. Separation and Estimation of Normal Fatty Acids". Journal of Biological Chemistry. 170 (2): 501–507. doi:10.1016/S0021-9258(17)30832-3. https://doi.org/10.1016%2FS0021-9258%2817%2930832-3
Craig, Lyman C.; Golumbic, Calvin; Mighton, Harold; Titus, Elwood (1945). "Identification of Small Amounts of Organic Compounds by Distribution Studies. III. The Use of Buffers in Counter-current Distribution". Journal of Biological Chemistry. 161: 321–332. doi:10.1016/S0021-9258(17)41546-8. PMID 21005739. https://doi.org/10.1016%2FS0021-9258%2817%2941546-8
Craig, L. C.; Post, Otto (1949). "Apparatus for Countercurrent Distribution". Analytical Chemistry. 21 (4): 500–504. doi:10.1021/ac60028a013. /wiki/Doi_(identifier)
Craig, L. C.; Hausmann, Werner; Ahrens, E. H.; Harfenist, E. J. (1951). "Automatic Countercurrent Distribution Equipment". Analytical Chemistry. 23 (9): 1236–1244. doi:10.1021/ac60057a009. /wiki/Doi_(identifier)
Craig, Lyman C.; Hogeboom, George H.; Carpenter, Frederick H.; Vigneaud, Vincent du (1947). "Separation and Characterization of Some Penicillins by the Method of Counter-Current Distribution". Journal of Biological Chemistry. 168 (2): 665–686. doi:10.1016/S0021-9258(17)30925-0. PMID 20238622. https://doi.org/10.1016%2FS0021-9258%2817%2930925-0
Golumbic, Calvin. (1950). "Separation and Analysis of Polynuclear Compounds by Countercurrent Distribution". Analytical Chemistry. 22 (4): 579–582. doi:10.1021/ac60040a023. /wiki/Doi_(identifier)
Harfenist, Elizabeth J.; Craig, Lyman C. (1951). "Countercurrent Distribution of Insulin". Journal of the American Chemical Society. 73 (2): 877–878. doi:10.1021/ja01146a538. /wiki/Doi_(identifier)
Ahrens, Jr., Edward H.; Craig, Lyman C. (1952). "The Extraction and Separation of Bile Acids". Journal of Biological Chemistry. 195 (2): 763–778. doi:10.1016/S0021-9258(18)55787-2. PMID 14946188. https://doi.org/10.1016%2FS0021-9258%2818%2955787-2
Kirby, K.S. (1960). "Fractionation of ribonucleic acids by countercurrent distribution". Biochimica et Biophysica Acta. 41 (2): 338–340. doi:10.1016/0006-3002(60)90018-4. PMID 14409277. /wiki/Doi_(identifier)
Wani, Mansukh C.; Horwitz, Susan Band (2014). "Nature as a remarkable chemist: a personal story of the discovery and development of Taxol". Anti-Cancer Drugs. 25 (5): 482–487. doi:10.1097/CAD.0000000000000063. PMC 3980006. PMID 24413390. https://www.ncbi.nlm.nih.gov/pmc/articles/PMC3980006
Swart, E. Augustus. (1949). "The Use of Counter-Current Distribution for the Characterization of Streptomyces Antibiotics". Journal of the American Chemical Society. 71 (8): 2942–2944. doi:10.1021/ja01176a524. /wiki/Doi_(identifier)
Craig, Lyman C.; Sogn, John (1975). "Isolation of antibiotics by countercurrent distribution". Methods in Enzymology. Vol. 43. Elsevier. pp. 320–346. doi:10.1016/0076-6879(75)43092-0. ISBN 978-0-12-181943-9. PMID 1134363. 978-0-12-181943-9