Robert Boyle's chiral crystal chemistry: Computational re‐evaluation of enantioselective adsorption on quartz

Kahr, Bart; Chittenden, Brianne; Rohl, Andrew

doi:10.1002/chir.20229

Cited by 14Chemistry and Stereochemistry StudiesAnalytical Chemistry and ChromatographyCrystallography and molecular interactions

Robert Boyle's chiral crystal chemistry: Computational re‐evaluation of enantioselective adsorption on quartz

Kahr, Bart, Chittenden, Brianne, Rohl, Andrew·2006·Chirality

DOI 10.1002/chir.20229

Open this paper in CoChat — free account

Abstract

While searching for early examples of interactions of organic chromophores with minerals in the context of a systematic study of the process of dyeing crystals, we came across Robert Boyle's description of an experiment that may have been evidence of the enantioselective adsorption of a natural product, carminic acid (7‐β‐d‐glucopyranosyl‐9,10‐dihydro‐3,5,6,8‐tetrahydroxy‐1‐methyl‐9,10‐dioxo‐2‐anthracenecarboxylic acid), to the chiral surfaces of α‐quartz, three centuries before such interactions became the subject of active chemical investigations. In order to determine whether Boyle did indeed observe enantioselective adsorption—albeit unbeknownst to him—we attempted to dye quartz with carminic acid according to his recipe. Quartz adsorbs carminic acid only because on heating it develops a network of microfissures that adsorb dye. This process depends on capillarity, not on specific non‐covalent interactions; there is no evidence of enantioselectivity adsorption to heated crystals or enantioselective epitaxy to unheated crystals. These failures changed the focus of our inquiry: Why have almost all attempts to demonstrate the enantioselective adsorption of additives to quartz crystal surfaces been generally confounding and equivocal? In order to answer this question, we complement our experimental historical re‐investigation with contemporary computational techniques for modeling crystal surface structure and the adsorption of additives. Minimizations of the energies associated with the adsorption of carminic acid to relaxed, hydrated d‐ and l‐quartz {10&1macr;0} surfaces are analyzed in light of quartz's abysmal record as an enantioselective stationary phase. © 2005 Wiley‐Liss, Inc. Chirality 18:127–133, 2006.

Integrity signals

Registry

Crossref · 10.1002/chir.20229

Cites

49 of 49 references verified0 citation errors · 0 not checkable

Statistics

Recomputing p-values needs the paper’s full text.

Claims the paper makes

We couldn’t retrieve this paper’s full text, so its claims and self-check weren’t run. The registry and citation checks still apply.

Claims other papers make about this one

Each is checked against this paper’s own text: does it say what the citing paper says it does?

DFT studies show modest computed differences in adsorption energies of enantiomers on quartz (on the order of 2 kcal mol−1 at best).
“In short, the computed differences in the adsorption energies of the enantiomers are modest (on the order of 2 kcal mol À1 at best) but strongly depend on the nature of amino acids and quartz surfaces.”
From Possible chemical and physical scenarios towards biological homochirality (2022) · cites this paper as [255]

The General Utility Lattice Program ( <scp>GULP</scp> )
Gale, J. D., & Rohl, A. L. (2003) · Molecular Simulation · doi:10.1080/0892702031000104887 · Cited by 2,265 · see citing works
Self-citation
Asymmetric Synthesis
Procter, G. (1996) · doi:10.1093/oso/9780198557265.001.0001 · Cited by 1,138 · see citing works
Formation of chiral morphologies through selective binding of amino acids to calcite surface steps
Orme, C. A., Noy, A., Wierzbicki, A., McBride, M. T., Grantham, M., Teng, H. H., Dove, P. M., & DeYoreo, J. J. (2001) · Nature · doi:10.1038/35081034 · Cited by 700 · see citing works
Chiral selection on inorganic crystalline surfaces
Hazen, R. M., & Sholl, D. S. (2003) · Nature Materials · doi:10.1038/nmat879 · Cited by 488 · see citing works
Bridging hydrodyl groups in zeolitic catalysts: a computer simulation of their structure, vibrational properties and acidity in protonated faujasites (HY zeolites)
Schröder, K.-P., Sauer, J., Leslie, M., Catlow, C. R. A., Catlow, C. R. A., & Thomas, J. M. (1992) · Chemical Physics Letters · doi:10.1016/0009-2614(92)90030-q · Cited by 394 · see citing works
Enantiospecific electrodeposition of a chiral catalyst
Switzer, J. A., Kothari, H. M., Poizot, P., Nakanishi, S., & Bohannan, E. W. (2003) · Nature · doi:10.1038/nature01990 · Cited by 376 · see citing works
Understanding and control of nucleation, growth, habit, dissolution and structure of two- and three-dimensional crystals using `tailor-made' auxiliaries
Weissbuch, I., Popovitz-Biro, R., Lahav, M., & Leiserowitz, L. (1995) · Acta Crystallographica Section B Structural Science · doi:10.1107/s0108768194012061 · Cited by 337 · see citing works
d- and l-Quartz-Promoted Highly Enantioselective Synthesis of a Chiral Organic Compound
Soai, K., Osanai, S., Kadowaki, K., Yonekubo, S., Shibata, T., & Sato, I. (1999) · Journal of the American Chemical Society · doi:10.1021/ja993128t · Cited by 336 · see citing works
Dyeing Crystals
Kahr, B. E., & Gurney, R. W. (2001) · Chemical Reviews · doi:10.1021/cr980088n · Cited by 299 · see citing works
Self-citation
Growth and Dissolution of Organic Crystals with “Tailor‐Made” Inhibitors—Implications in Stereochemistry and Materials Science
Addadi, L., BERKOVITCH‐YELLIN, Z., Weissbuch, I., van Mil, J., Shimon, L. J. W., Lahav, M., & Leiserowitz, L. (1985) · Angewandte Chemie International Edition in English · doi:10.1002/anie.198504661 · Cited by 294 · see citing works
The Stereochemistry of Metal Chelates with Polydentate Ligands. Part I
Sarma, B. D., & Bailar, J. C. (1955) · Journal of the American Chemical Society · doi:10.1021/ja01626a007 · Cited by 186 · see citing works
On Quantifying Chirality
Buda, A. B., der Heyde, T. A., & Mislow, K. (1992) · Angewandte Chemie International Edition in English · doi:10.1002/anie.199209891 · Cited by 185 · see citing works
The Stereochemistry of Complex Inorganic Compounds. XVII. The Stereochemistry of Hexadentate Ethylenediaminetetraacetic Acid Complexes
Busch, D. H., & Bailar, J. C. (1953) · Journal of the American Chemical Society · doi:10.1021/ja01114a054 · Cited by 150 · see citing works
Derivation of interatomic potentials for microporous aluminophosphates from the structure and properties of berlinite
Gale, J. D., & Henson, N. J. (1994) · Journal of the Chemical Society Faraday Transactions · doi:10.1039/ft9949003175 · Cited by 130 · see citing works
GDIS: a visualization program for molecular and periodic systems
Fleming, S. D., & Rohl, A. L. (2005) · Zeitschrift für Kristallographie - Crystalline Materials · doi:10.1524/zkri.220.5.580.65071 · Cited by 125 · see citing works
Self-citation
Highly enantioselective synthesis of organic compound using right- and left-handed helical silica
Sato, I., Kadowaki, K., Urabe, H., Jung, J. H., Ono, Y., Shinkai, S., & Soai, K. (2003) · Tetrahedron Letters · doi:10.1016/s0040-4039(02)02707-7 · Cited by 123 · see citing works
Chiral single crystal surface chemistry
Gellman, A. J., Horvath, J. D., & Buelow, M. T. (2001) · Journal of Molecular Catalysis A Chemical · doi:10.1016/s1381-1169(00)00484-2 · Cited by 109 · see citing works
A Computer Modeling Study of the Inhibiting Effect of Organic Adsorbates on Calcite Crystal Growth
de Leeuw, N. H., & Cooper, T. G. (2003) · Crystal Growth & Design · doi:10.1021/cg0341003 · Cited by 105 · see citing works
Adsorption of amino acid derivatives by d- and l-quartz
Kavasmaneck, P. R., & Bonner, W. A. (1977) · Journal of the American Chemical Society · doi:10.1021/ja00443a011 · Cited by 105 · see citing works
Chiral habit modifications of gypsum from epitaxial-like adsorption of stereospecific growth inhibitors
Cody, A. M., & Cody, R. D. (1991) · Journal of Crystal Growth · doi:10.1016/0022-0248(91)90086-k · Cited by 95 · see citing works
L Amino Acids and D-Glucose Bind Stereospecifically to a Colloidal Clay
Bondy, S. C., & Harrington, M. E. (1979) · Science · doi:10.1126/science.424749 · Cited by 92 · see citing works
The Philosophy of Right and Left
Cleve, J. V., & Frederick, R. E. (1991) · Springer eBooks · doi:10.1007/978-94-011-3736-2 · Cited by 88 · see citing works
Naturally Chiral Surfaces
Horvath, J. D., & Gellman, A. J. (2003) · Topics in Catalysis · doi:10.1023/b:toca.0000003094.07345.d1 · Cited by 85 · see citing works
Topics in Stereochemistry
(1987) · Topics in stereochemistry · doi:10.1002/9780470147269 · Cited by 79 · see citing works
A New Method of Resolving a Racemic Compound
Karagunis, G., & Coumoulos, G. D. (1938) · Nature · doi:10.1038/142162a0 · Cited by 71 · see citing works
Asymmetric adsorption by quartz: A model for the prebiotic origin of optical activity
Bonner, W. A., Kavasmaneck, P. R., Martin, F. S., & Flores, J. J. (1975) · Origins of Life · doi:10.1007/bf01130338 · Cited by 68 · see citing works
Cochineal carmine: an ancient dye with a modern role
Baranyovits, F. (1978) · Endeavour · doi:10.1016/0160-9327(78)90061-3 · Cited by 64 · see citing works
Molecular recognition at the interface between crystals and biology: generation, manifestation and detection of chirality at crystal surfacesThis article is based (partly) on a presentation which will be made at the European Research Conference (EURESCO) on "Molecular Crystal Engineering - EuroConference on Design and Preparation of Molecular Materials" (Acquafredda di Maratea, Italy, 31 May - 5 June 2003) organised by the European Science Foundation and supported by the European Commission, Research DG, Human Potential Programme, High-Level Scientific Conferences, Contract HPCF-CT-2002-00270. This information is the sole responsibility of the author(s) and does not reflect the ESF or Community's opinion. The ESF and the Community are not responsible for any use that might be made of data appearing in this publication.
Addadi, L., & Geva, M. (2003) · CrystEngComm · doi:10.1039/b304061e · Cited by 58 · see citing works
Highly enantioselective asymmetric autocatalysis induced by chiral ionic crystals of sodium chlorate and sodium bromate
Sato, I., Kadowaki, K., Ohgo, Y., & Soai, K. (2004) · Journal of Molecular Catalysis A: Chemical · doi:10.1016/j.molcata.2004.03.010 · Cited by 58 · see citing works
Molecular recognition in adsorption and electro-oxidation at chiral platinum surfaces
Hazzazi, O. A., Attard, G. A., & Wells, P. B. (2004) · Journal of Molecular Catalysis A Chemical · doi:10.1016/j.molcata.2004.03.028 · Cited by 50 · see citing works
Chiral indices of crystalline surfaces as a measure of enantioselective potential
Downs, R. T., & Hazen, R. M. (2004) · Journal of Molecular Catalysis A: Chemical · doi:10.1016/j.molcata.2004.03.026 · Cited by 49 · see citing works
Asymmetric adsorption of DL-alanine hydrochloride by quartz
Bonner, W. A., & Kavasmaneck, P. R. (1976) · The Journal of Organic Chemistry · doi:10.1021/jo00874a039 · Cited by 47 · see citing works
Use of "enantiopolar" directions in centrosymmetric crystals for direct assignment of absolute configuration of chiral molecules: application to the system serine/threonine
Addadi, L., BERKOVITCH‐YELLIN, Z., Weissbuch, I., Lahav, M., Leiserowitz, L., & Weinstein, S. (1982) · Journal of the American Chemical Society · doi:10.1021/ja00371a071 · Cited by 44 · see citing works
Salting Benzenes
Gurney, R. W., Mitchell, C. A., Ham, S., Bastin, L. D., & Kahr, B. E. (2000) · The Journal of Physical Chemistry B · doi:10.1021/jp992424p · Cited by 43 · see citing works
Self-citation
Essais de réactions dissymétriques sur quartz optiquement actif
Amariglio, A., Amariglio, H., & Duval, X. (1968) · Helvetica Chimica Acta · doi:10.1002/hlca.19680510832 · Cited by 36 · see citing works
The progress of logwood extract
Kahr, B. E., Lovell, S., & Subramony, J. A. (1998) · Chirality · doi:10.1002/chir.12 · Cited by 36 · see citing works
Self-citation
The Stereochemistry of Complex Inorganic Compounds. VI. A Study of the Stereoisomers of the Dichloro-diammino-ethylenediamine Cobaltic Ion
Bailar, J. C., & Peppard, D. F. (1940) · Journal of the American Chemical Society · doi:10.1021/ja01858a026 · Cited by 35 · see citing works
THE CONFIGURATION OF CHLOROBISDlMETHYLGLYOXIMOAMMINE-COBALT
Tsuchida, R., Kobayashi, M., & Nakamura, A. (1936) · Bulletin of the Chemical Society of Japan · doi:10.1246/bcsj.11.38 · Cited by 31 · see citing works
The quest for chirality
Bonner, W. A. (1996) · AIP conference proceedings · doi:10.1063/1.51234 · Cited by 31 · see citing works
Can Enantiomorphic Crystals Like Quartz Play a Role in the Origin of Homochirality on Earth?
Klabunovskii, E. I. (2001) · Astrobiology · doi:10.1089/153110701753198891 · Cited by 28 · see citing works
Optical Rotatory and Circular Dichroic Scattering
Kaminsky, W., Geday, M. A., Herreros-Cedrés, J., & Kahr, B. E. (2003) · The Journal of Physical Chemistry A · doi:10.1021/jp026364q · Cited by 24 · see citing works
Self-citation
SYNTHESIS OF THE TRIS-(DIMETHYLGLYOXIMO)-COBALTATE(III)
Nakahara, A., & Tsuchida, R. (1954) · Journal of the American Chemical Society · doi:10.1021/ja01640a093 · Cited by 20 · see citing works
The Stereoisomerism of Complex Inorganic Compounds. XIV. Studies upon the Stereochemistry of Saturated Tervalent Nitrogen Compounds1
Kuebler, J. R., & Bailar, J. C. (1952) · Journal of the American Chemical Society · doi:10.1021/ja01134a023 · Cited by 17 · see citing works
Dispersion of anomalous azimuthal rotation and circular extinction contrast in dyed K2SO4 crystals
Kaminsky, W., Herreros-Cedrés, J., Geday, M. A., & Kahr, B. E. (2004) · Chirality · doi:10.1002/chir.20054 · Cited by 15 · see citing works
Self-citation
Absolute configuration and structure of carminic acid existing as the potassium salt in Dactylopius cacti L.
Ishida, T., Inoue, M., Baba, K., KOZAWA, M., Inoue, K., & Inouye, H. (1987) · Acta Crystallographica Section C Crystal Structure Communications · doi:10.1107/s0108270187091169 · Cited by 8 · see citing works
The weak force and SETH: The search for Extra-Terrestrial Homochirality
MacDermott, A. J. (1996) · AIP conference proceedings · doi:10.1063/1.51244 · Cited by 8 · see citing works
Chirality of quartz. Fibrosis and tumour development in dust inoculated mice
Ebbesen, P. (1991) · European Journal of Cancer Prevention · doi:10.1097/00008469-199110000-00008 · Cited by 7 · see citing works
ChemInform Abstract: A Link Between Macroscopic Phenomena and Molecular Chirality: Crystals as Probes for the Direct Assignment of Absolute Configuration of Chiral Molecules
Addadi, L., BERKOVITCH‐YELLIN, Z., Weissbuch, I., Lahav, M., & Leiserowitz, L. (1987) · ChemInform · doi:10.1002/chin.198737381 · Cited by 7 · see citing works
ASYMMETRIC AUTOCATALYSIS AND HOMOCHIRALITY OF BIOMOLECULES
Soai, K., & Sato, I. (2002) · Cited by 5 · see citing works

Flagged first, then by citations

Sorted by citations

Crystalline Architectures as Templates of Relevance to the Origins of Homochirality
Weissbuch, I., & Lahav, M. (2011) · Chemical Reviews · doi:10.1021/cr1002479 · Cited by 284 · see citing works
Possible chemical and physical scenarios towards biological homochirality
Sallembien, Q., Bouteiller, L., Crassous, J., & Raynal, M. (2022) · Chemical Society Reviews · doi:10.1039/d1cs01179k · Cited by 186 · see citing works
Asymmetric Autocatalysis Induced by Cinnabar: Observation of the Enantioselective Adsorption of a 5‐Pyrimidyl Alkanol on the Crystal Surface
Shindo, H., Shirota, Y., Niki, K., Kawasaki, T., Suzuki, K., Araki, Y., Matsumoto, A., & Soai, K. (2013) · Angewandte Chemie International Edition · doi:10.1002/anie.201304284 · Cited by 59 · see citing works
Chirality in Organic and Mineral Systems: A Review of Reactivity and Alteration Processes Relevant to Prebiotic Chemistry and Life Detection Missions
Lee, C., Weber, J. M., Rodriguez, L. E., Sheppard, R. Y., Barge, L. M., Berger, E. L., & Burton, A. S. (2022) · Symmetry · doi:10.3390/sym14030460 · Cited by 39 · see citing works
Prediction of Soai Reaction Enantioselectivity Induced by Crystals ofN-(2-Thienylcarbonyl)glycine
Carter, D. J., Rohl, A. L., Shtukenberg, A., Bian, S., Hu, C., Baylon, L., Kahr, B., Mineki, H., Abe, K., Kawasaki, T., et al. (2012) · Crystal Growth & Design · doi:10.1021/cg300207d · Cited by 36 · see citing works
Self-citation
Anab initiostudy of adsorption of alanine on the chiral calcite surface
Asthagiri, A., & Hazen, R. M. (2007) · Molecular Simulation · doi:10.1080/08927020601155485 · Cited by 36 · see citing works
Enantiospecific adsorption of amino acids on hydroxylated quartz (1010)
Han, J. W., & Sholl, D. S. (2010) · Physical Chemistry Chemical Physics · doi:10.1039/b926035h · Cited by 33 · see citing works
Circular Dichroism Tensor of a Triarylmethyl Propeller in Sodium Chlorate Crystals
Bing, Y., Selassie, D., Paradise, R. H., Isborn, C. M., Kramer, N., Sadı́lek, M., Kaminsky, W., & Kahr, B. E. (2010) · Journal of the American Chemical Society · doi:10.1021/ja1018892 · Cited by 27 · see citing works
Self-citation
Turinese Stereochemistry: Eligio Perucca's Enantioselectivity and Primo Levi's Asymmetry
Kahr, B. E., Bing, Y., Kaminsky, W., & Viterbo, D. (2009) · Angewandte Chemie International Edition · doi:10.1002/anie.200801840 · Cited by 19 · see citing works
Self-citation
Liquid–liquid crystalline phase separation of filamentous colloids and semiflexible polymers: experiments, theory and simulations
Almohammadi, H., Khadem, S. A., Azzari, P., Yuan, Y., Guerra, A., Rey, A. D., & Mezzenga, R. (2025) · Reports on Progress in Physics · doi:10.1088/1361-6633/adb441 · Cited by 19 · see citing works
Dendritic crystal growth, differential circular scattering, and the origin of biomolecular homochirality
Kahr, B. E., & Freudenthal, J. H. (2008) · Chirality · doi:10.1002/chir.20539 · Cited by 17 · see citing works
Self-citation
Asymmetric Autocatalysis Induced by Cinnabar: Observation of the Enantioselective Adsorption of a 5‐Pyrimidyl Alkanol on the Crystal Surface
Shindo, H., Shirota, Y., Niki, K., Kawasaki, T., Suzuki, K., Araki, Y., Matsumoto, A., & Soai, K. (2013) · Angewandte Chemie · doi:10.1002/ange.201304284 · Cited by 11 · see citing works
Turiner Stereochemie: Eligio Peruccas Enantioselektivität und Primo Levis Asymmetrie
Kahr, B. E., Bing, Y., Kaminsky, W., & Viterbo, D. (2009) · Angewandte Chemie · doi:10.1002/ange.200801840 · Cited by 6 · see citing works
Self-citation
Chirality-Dependent Friction of Bulk Molecular Solids
Yang, D., & Cohen, A. E. (2014) · Langmuir · doi:10.1021/la500699z · Cited by 1 · see citing works

Enantioselective adsorption on rock-forming minerals: A thought experiment
Hazen, R. M. (2014) · Surface Science · doi:10.1016/j.susc.2014.01.004 · Cited by 5 · see citing works
Theoretical investigation of amino-acid adsorption on hydroxylated quartz surfaces: dispersion can determine enantioselectivity
Price, A. J. A., & Johnson, E. R. (2020) · Physical Chemistry Chemical Physics · doi:10.1039/d0cp02827d · Cited by 14 · see citing works
High Enantioselectivity in Adsorption of Chiral Molecules on the Surface of Chiral Terbium Phosphate Nanocrystals
Idrees, A., Reuven, B., & Markovich, G. (2025) · Journal of the American Chemical Society · doi:10.1021/jacs.4c16883 · Cited by 3 · see citing works
ASYMMETRIC ADSORPTION ON MINERALS
Клабуновский, Е. И., Smith, G. V., & Zsigmond, Á. G. (2007) · Springer eBooks · doi:10.1007/978-1-4020-4296-6_1 · Cited by 3 · see citing works
Imprinted chiral molecular recognition in dipeptide crystals immobilized on a quartz-crystal microbalance
Okahata, Y., Yasunaga, K., & Ogura, K. (1994) · Journal of the Chemical Society Chemical Communications · doi:10.1039/c39940000469 · Cited by 17 · see citing works

Authors: Kahr, B., Chittenden, B., & Rohl, A.
Affiliations: University of Washington (US)
Corresponding author: Kahr, Bart
Rohl, Andrew
ORCID: Kahr, Bart
Rohl, Andrew
Venue: Chirality
Publisher: Wiley
Published: 2005-12-30
Volume: 18
Issue: 2
Pages: 127-133
ISSN: 0899-0042 (ISSN-L)
1520-636X
DOI: 10.1002/chir.20229
OpenAlex: W2067554924
Cited by: 14
References: 49
Citations by year: 2025: 1 · 2022: 2 · 2014: 1 · 2013: 2 · 2012: 1
FWCI: 0.40
Type: journal article
Language: en
Open access: closed
Licence: onlinelibrary.wiley.com/termsAndConditions#vor (vor)
Locations: Chirality (publishedVersion)
PubMed (publishedVersion)
eSpace (Curtin University) (submittedVersion)
Funders: National Science Foundation
Topics: Physical Sciences › Chemistry › Organic Chemistry › Chemistry and Stereochemistry Studies
Physical Sciences › Chemistry › Spectroscopy › Analytical Chemistry and Chromatography
Physical Sciences › Chemistry › Physical and Theoretical Chemistry › Crystallography and molecular interactions
Keywords: Robert Boyle, enantioselective adsorption, carminic acid, alpha-quartz, capillarity, crystal surface structure, history of chemistry, chiral stationary phase
MeSH terms: Adsorption, Carmine, Computer Simulation, Crystallization, Coloring Agents, Models, Chemical, Models, Molecular, Quartz, Silicon Dioxide, Stereoisomerism

About these checks

Registry, retraction, Cites and statistics results are computed, not judged, with one exception: a printed reference that no index lists is read once by a model before it counts as a citation error. Claims are extracted by a model and kept only when their quote appears verbatim in the text; each cited source is then checked, with a model’s help, for whether it says what the claim relies on. Those verdicts can be wrong — read the claim’s quote and the cited source before relying on one.

Statistics and arithmetic are recomputed, not judged.

Confidence bands are shown only for fields calibrated on our annotated test set. None is calibrated yet, so no band is shown.

What counts as a claim ›How we measure confidence ›How we check this ›

Are you an author, or do you see a problem with this page? Request a review

Robert Boyle's chiral crystal chemistry: Computational re‐evaluation of enantioselective adsorption on quartz

Abstract

Integrity signals

Claims the paper makes

Claims other papers make about this one

Cites

Cited by

Related

Record

About these checks