chirality
Chirality is a property of asymmetry important in several branches of science. The word ''chirality'' is derived from the Greek (''kheir''), "hand", a familiar chiral object.
An object or a system is ''chiral'' if it is distinguishable from ...
, or handedness. Objects are chiral when they cannot be superposed on their mirror images. For example, the left and right hands of a human are approximately mirror images of each other but are not their own mirror images, so they are chiral. In
biology
Biology is the scientific study of life. It is a natural science with a broad scope but has several unifying themes that tie it together as a single, coherent field. For instance, all organisms are made up of cells that process hereditary ...
, 19 of the 20 natural
amino acid
Amino acids are organic compounds that contain both amino and carboxylic acid functional groups. Although hundreds of amino acids exist in nature, by far the most important are the alpha-amino acids, which comprise proteins. Only 22 alpha ...
s are homochiral, being L-chiral (left-handed), while
sugar
Sugar is the generic name for sweet-tasting, soluble carbohydrates, many of which are used in food. Simple sugars, also called monosaccharides, include glucose, fructose, and galactose. Compound sugars, also called disaccharides or do ...
s are D-chiral (right-handed). Homochirality can also refer to enantiopure substances in which all the constituents are the same
enantiomer
In chemistry, an enantiomer ( /ɪˈnænti.əmər, ɛ-, -oʊ-/ ''ih-NAN-tee-ə-mər''; from Ancient Greek ἐνάντιος ''(enántios)'' 'opposite', and μέρος ''(méros)'' 'part') – also called optical isomer, antipode, or optical anti ...
(a right-handed or left-handed version of an atom or molecule), but some sources discourage this use of the term.
It is unclear whether homochirality has a purpose; however, it appears to be a form of information storage. One suggestion is that it reduces
entropy
Entropy is a scientific concept, as well as a measurable physical property, that is most commonly associated with a state of disorder, randomness, or uncertainty. The term and the concept are used in diverse fields, from classical thermodyna ...
barriers in the formation of large organized molecules. It has been experimentally verified that amino acids form large aggregates in larger abundance from an enantiopure samples of the amino acid than from
racemic
In chemistry, a racemic mixture, or racemate (), is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates. ...
(enantiomerically mixed) ones.
It is not clear whether homochirality emerged before or after life, and many mechanisms for its origin have been proposed. Some of these models propose three distinct steps: mirror-symmetry breaking creates a minute enantiomeric imbalance,
chiral amplification
In chemistry, an enantiomer ( /ɪˈnænti.əmər, ɛ-, -oʊ-/ ''ih-NAN-tee-ə-mər''; from Ancient Greek ἐνάντιος ''(enántios)'' 'opposite', and μέρος ''(méros)'' 'part') – also called optical isomer, antipode, or optical an ...
builds on this imbalance, and chiral transmission is the transfer of chirality from one set of molecules to another.
In biology
Amino acids are the building blocks of
peptide
Peptides (, ) are short chains of amino acids linked by peptide bonds. Long chains of amino acids are called proteins. Chains of fewer than twenty amino acids are called oligopeptides, and include dipeptides, tripeptides, and tetrapeptides. ...
s and
enzyme
Enzymes () are proteins that act as biological catalysts by accelerating chemical reactions. The molecules upon which enzymes may act are called substrates, and the enzyme converts the substrates into different molecules known as products ...
s while sugar-peptide chains are the backbone of RNA and DNA. In biological organisms, amino acids appear almost exclusively in the left-handed form (L-amino acids) and sugars in the right-handed form (R-sugars). Since the enzymes catalyze reactions, they enforce homochirality on a great variety of other chemicals, including
hormone
A hormone (from the Greek participle , "setting in motion") is a class of signaling molecules in multicellular organisms that are sent to distant organs by complex biological processes to regulate physiology and behavior. Hormones are required ...
s, toxins, fragrances and food flavors.
Glycine
Glycine (symbol Gly or G; ) is an amino acid that has a single hydrogen atom as its side chain. It is the simplest stable amino acid ( carbamic acid is unstable), with the chemical formula NH2‐ CH2‐ COOH. Glycine is one of the proteinog ...
is achiral, as are some other non-
proteinogenic
Proteinogenic amino acids are amino acids that are incorporated biosynthetically into proteins during translation. The word "proteinogenic" means "protein creating". Throughout known life, there are 22 genetically encoded (proteinogenic) amino ...
amino acids that are either achiral (such as dimethylglycine) or of the D enantiomeric form.
Biological organisms easily discriminate between molecules with different chiralities. This can affect physiological reactions such as smell and taste.
Carvone
Carvone is a member of a family of chemicals called terpenoids. Carvone is found naturally in many essential oils, but is most abundant in the oils from seeds of caraway (''Carum carvi''), spearmint (''Mentha spicata''), and dill.
Uses
Both c ...
essential oil
An essential oil is a concentrated hydrophobic liquid containing volatile (easily evaporated at normal temperatures) chemical compounds from plants. Essential oils are also known as volatile oils, ethereal oils, aetheroleum, or simply as the o ...
s, smells like mint in its L-form and caraway in its R-form.
Limonene
Limonene is a colorless liquid aliphatic hydrocarbon classified as a cyclic monoterpene, and is the major component in the oil of citrus fruit peels. The -isomer, occurring more commonly in nature as the fragrance of oranges, is a flavoring a ...
tastes like citrics when right-handed and pine when left-handed.
Homochirality also affects the response to drugs.
Thalidomide
Thalidomide, sold under the brand names Contergan and Thalomid among others, is a medication used to treat a number of cancers (including multiple myeloma), graft-versus-host disease, and a number of skin conditions including complications o ...
, in its left-handed form, cures
morning sickness
Morning sickness, also called nausea and vomiting of pregnancy (NVP), is a symptom of pregnancy that involves nausea or vomiting. Despite the name, nausea or vomiting can occur at any time during the day. Typically the symptoms occur between th ...
; in its right-handed form, it causes birth defects. Unfortunately, even if a pure left-handed version is administered, some of it can convert to the right-handed form in the patient. Many drugs are available as both a
racemic mixture
In chemistry, a racemic mixture, or racemate (), is one that has equal amounts of left- and right-handed enantiomers of a chiral molecule or salt. Racemic mixtures are rare in nature, but many compounds are produced industrially as racemates. ...
(equal amounts of both chiralities) and an enantiopure drug (only one chirality). Depending on the manufacturing process, enantiopure forms can be more expensive to produce than stereochemical mixtures.
Chiral preferences can also be found at a macroscopic level. Snail shells can be right-turning or left-turning helices, but one form or the other is strongly preferred in a given species. In the edible snail ''
Helix pomatia
''Helix pomatia'', common names the Roman snail, Burgundy snail, or escargot, is a species of large, edible, air-breathing land snail, a pulmonate gastropod terrestrial mollusc in the family Helicidae.MolluscaBase eds. (2021). MolluscaBase. ...
'', only one out of 20,000 is left-helical. The coiling of plants can have a preferred chirality and even the chewing motion of cows has a 10% excess in one direction.
Origins
Symmetry breaking
Theories for the origin of homochirality in the molecules of life can be classified as deterministic or based on chance depending on their proposed mechanism. If there is a relationship between cause and effect — that is, a specific chiral field or influence causing the mirror symmetry breaking — the theory is classified as deterministic; otherwise it is classified as a theory based on chance (in the sense of randomness) mechanisms.
Another classification for the different theories of the origin of biological homochirality could be made depending on whether life emerged before the enantiodiscrimination step (biotic theories) or afterwards (abiotic theories). Biotic theories claim that homochirality is simply a result of the natural autoamplification process of life—that either the formation of life as preferring one chirality or the other was a chance rare event which happened to occur with the chiralities we observe, or that all chiralities of life emerged rapidly but due to catastrophic events and strong competition, the other unobserved chiral preferences were wiped out by the preponderance and metabolic, enantiomeric enrichment from the 'winning' chirality choices. If this was the case, remains of the extinct chirality sign should be found. Since this is not the case, nowadays biotic theories are no longer supported.
The emergence of chirality consensus as a natural autoamplification process has also been associated with the
2nd law of thermodynamics
The second law of thermodynamics is a physical law based on universal experience concerning heat and energy interconversions. One simple statement of the law is that heat always moves from hotter objects to colder objects (or "downhill"), unles ...
.
Deterministic theories
Deterministic theories can be divided into two subgroups: if the initial chiral influence took place in a specific space or time location (averaging zero over large enough areas of observation or periods of time), the theory is classified as local deterministic; if the chiral influence is permanent at the time the chiral selection occurred, then it is classified as universal deterministic. The classification groups for local determinist theories and theories based on chance mechanisms can overlap. Even if an external chiral influence produced the initial chiral imbalance in a deterministic way, the outcome sign could be random since the external chiral influence has its enantiomeric counterpart elsewhere.
In deterministic theories, the enantiomeric imbalance is created due to an external chiral field or influence, and the ultimate sign imprinted in biomolecules will be due to it. Deterministic mechanisms for the production of non-racemic mixtures from racemic starting materials include: asymmetric physical laws, such as the electroweak interaction (via cosmic rays) or asymmetric environments, such as those caused by
circularly polarized
In electrodynamics, circular polarization of an electromagnetic wave is a polarization state in which, at each point, the electromagnetic field of the wave has a constant magnitude and is rotating at a constant rate in a plane perpendicular to th ...
light, quartz crystals, or the Earth's rotation, β-Radiolysis or the magnetochiral effect. The most accepted universal deterministic theory is the electroweak interaction. Once established, chirality would be selected for.
One supposition is that the discovery of an enantiomeric imbalance in molecules in the Murchison meteorite supports an extraterrestrial origin of homochirality: there is evidence for the existence of
circularly polarized light
In electrodynamics, circular polarization of an electromagnetic wave is a polarization state in which, at each point, the electromagnetic field of the wave has a constant magnitude and is rotating at a constant rate in a plane perpendicular to t ...
originating from
Mie scattering
The Mie solution to Maxwell's equations (also known as the Lorenz–Mie solution, the Lorenz–Mie–Debye solution or Mie scattering) describes the scattering of an electromagnetic plane wave by a homogeneous sphere. The solution takes the ...
on aligned interstellar dust particles which may trigger the formation of an enantiomeric excess within chiral material in space. Interstellar and near-stellar magnetic fields can align dust particles in this fashion. Another speculation (the Vester-Ulbricht hypothesis) suggests that fundamental chirality of physical processes such as that of the beta decay (see
Parity violation
In physics, a parity transformation (also called parity inversion) is the flip in the sign of ''one'' spatial coordinate. In three dimensions, it can also refer to the simultaneous flip in the sign of all three spatial coordinates (a point ref ...
) leads to slightly different half-lives of biologically relevant molecules.
Chance theories
Chance theories are based on the assumption that "''Absolute asymmetric synthesis, i.e., the formation of enantiomerically enriched products from achiral precursors without the intervention of chiral chemical reagents or catalysts, is in practice unavoidable on statistical grounds alone''".
Consider the racemic state as a macroscopic property described by a binomial distribution; the experiment of tossing a coin, where the two possible outcomes are the two enantiomers is a good analogy. The discrete probability distribution of obtaining n successes out of Bernoulli trials, where the result of each Bernoulli trial occurs with probability and the opposite occurs with probability is given by:
.
The discrete probability distribution of having exactly molecules of one chirality and of the other, is given by:
.
As in the experiment of tossing a coin, in this case, we assume both events ( or ) to be equiprobable, . The probability of having exactly the same amount of both enantiomers is inversely proportional to the square root of the total number of molecules . For one mol of a racemic compound, molecules, this probability becomes . The probability of finding the racemic state is so small that we can consider it negligible.
In this scenario, there is a need to amplify the initial stochastic enantiomeric excess through any efficient mechanism of amplification. The most likely path for this amplification step is by asymmetric autocatalysis. An autocatalytic chemical reaction is that in which the reaction product is itself a reactive, in other words, a chemical reaction is autocatalytic if the reaction product is itself the catalyst of the reaction. In asymmetric autocatalysis, the catalyst is a chiral molecule, which means that a chiral molecule is catalysing its own production. An initial enantiomeric excess, such as can be produced by polarized light, then allows the more abundant enantiomer to outcompete the other.
Amplification
Theory
In 1953,
Charles Frank
Charles Reser Frank (born April 17, 1947) is an American actor noted for playing Bret Maverick's cousin Ben Maverick in the 1978 TV-movie ''The New Maverick'' with James Garner and Jack Kelly, and in the short-lived 1979 television series '' ...
proposed a model to demonstrate that homochirality is a consequence of autocatalysis. In his model the L and D enantiomers of a chiral molecule are autocatalytically produced from an achiral molecule A
:
while suppressing each other through a reaction that he called ''mutual antagonism''
In this model the racemic state is unstable in the sense that the slightest enantiomeric excess will be amplified to a completely homochiral state. This can be shown by computing the reaction rates from the
law of mass action
In chemistry, the law of mass action is the proposition that the rate of the chemical reaction is directly proportional to the product of the activities or concentrations of the reactants. It explains and predicts behaviors of solutions in dy ...
:
:
where is the rate constant for the autocatalytic reactions, is the rate constant for mutual antagonism reaction, and the concentration of A is kept constant for simplicity.
The analytical solutions for are found to be . The ratio