text:
Taste bud
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Taste buds
Semidiagrammatic view of a portion of the mucous membrane of the tongue. Two fungiform papillæ are shown. On some of the filiform papillæ the epithelial prolongations stand erect in one they are spread out, and in three they are folded in.
Details
Identifiers
Latin
caliculus gustatererius
MeSH
A03.556.500.885.779
Code
TH H3.04.01.0.02116
TH H3.04.01.0.03013
TA
A15.4.00.002
TH
H3.04.01.0.02116, H3.04.01.0.03013
FMA
54825
Anatomical terminology
[edit on Wikidata]
Taste buds contain the taste receptor cells, which are also known as gustatory cells.[1] The taste receptors are located around the small structures known as papillae found on the upper surface of the tongue, soft palate, upper esophagus, the cheek and epiglottis.[2] These structures are involved in detecting the five elements of taste perception: salty, sour, bitter, sweet and umami; through the combination of these elements we detect "flavors." A popular myth assigns these different tastes to different regions of the tongue; in reality these tastes can be detected by any area of the tongue. Via small openings in the tongue epithelium, called taste pores, parts of the food dissolved in saliva come into contact with the taste receptors.[1] These are located on top of the taste receptor cells that constitute the taste buds. The taste receptor cells send information detected by clusters of various receptors and ion channels to the gustatory areas of the brain via the seventh, ninth and tenth cranial nerves.
On average, the human tongue has 2,000–8,000 taste buds.[3]
Contents
[hide]
1 Types of papillae
2 See also
3 References
4 External links
Types of papillae[edit]
The taste buds on the tongue sit on raised protrusions of the tongue surface called papillae. There are three types of lingual papillae that contain taste buds present on the human tongue:
Fungiform papillae - as the name suggests, these are slightly mushroom-shaped if looked at in longitudinal section. These are present mostly at the dorsal surface of the tongue, as well as at the sides. Innervated by facial nerve.
Foliate papillae - these are ridges and grooves towards the posterior part of the tongue found at the lateral borders. Innervated by facial nerve (anterior papillae) and glossopharyngeal nerve (posterior papillae).
Circumvallate papillae - there are only about 10 to 14 of these papillae on most people, and they are present at the back of the oral part of the tongue. They are arranged in a circular-shaped row just in front of the sulcus terminalis of the tongue. They are associated with ducts of Von Ebner's glands, and are innervated by the glossopharyngeal nerve.
The fourth type of papillae the filiform papillae are the most numerous but do not contain taste buds.[4][5] They are characterized by increased keratinisation and are involved in the mechanical aspect of providing abrasion.
Salt, sweet, sour and umami tastes causes depolarization of the taste cells, although different mechanisms are applied.
Bitter causes an internal release of Ca2+, no external Ca2+ is required.
The bud is formed by two kinds of cells: supporting cells and gustatory cells.
The supporting (sustentacular cells) are mostly arranged like the staves of a cask, and form an outer envelope for the bud. Some, however, are found in the interior of the bud between the gustatory cells.
The gustatory (taste) cells, a chemoreceptor, occupy the central portion of the bud; they are spindle-shaped, and each possesses a large spherical nucleus near the middle of the cell.
The peripheral end of the cell terminates at the gustatory pore in a fine hair filament, the gustatory hair.
The central process passes toward the deep extremity of the bud, and there ends in single or bifurcated varicosities.
The nerve fibrils after losing their medullary sheaths enter the taste bud, and end in fine extremities between the gustatory cells; other nerve fibrils ramify between the supporting cells and terminate in fine extremities; these, however, are believed to be nerves of ordinary sensation and not gustatory.
The average life of a taste bud is 10 days[citation needed] .
See also[edit]
Tongue map
References[edit]
^ Jump up to: a b Shier, David (2016). Hole's Human Anatomy and Physiology. New York: McGraw-Hill Education. pp. 454–455. ISBN 978-0-07-802429-0.
Jump up ^ Discovery News, October 26, 2010
Jump up ^ Encyclopædia Britannica. 2009. Encyclopædia Britannica Online.
Jump up ^ Spacing patterns on tongue surface-gustatory papilla. (2004) Jung HS, Akita K, Kim JY. Int J Dev Biol. 48(2-3):157-61. PMID 15272380
Jump up ^ mcq in anatomy by prof deepthi nanayakkara and prof malkanthi chandrasiri volume 1 head and neck 99th mcq
External links[edit]
Taste Perception: Cracking the Code
Scientists Explore the Workings of Taste Buds from National Public Radio's Talk of the Nation, July 22, 2005
http://kidshealth.org/kid/talk/qa/taste_buds.html For kids about taste buds!
http://www.newser.com/story/103744/your-lungs-have-their-own-taste-buds.html
[show]
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Tabula rasa
From Wikipedia, the free encyclopedia
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"Blank slate" redirects here. For other uses, see Blank slate (disambiguation).
For other uses, see Tabula rasa (disambiguation).
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Roman tabula or wax tablet with stylus.
Tabula rasa (/ˈtæbjələ ˈrɑːsə, -zə, ˈreɪ-/) refers to the epistemological idea that individuals are born without built-in mental content and that therefore all knowledge comes from experience or perception. Proponents of tabula rasa generally disagree with the doctrine of innatism which holds that the mind is born already in possession of certain knowledge. Generally, proponents of the tabula rasa theory also favour the "nurture" side of the nature versus nurture debate when it comes to aspects of one's personality, social and emotional behaviour, knowledge and sapience.
Contents
[hide]
1 History
2 Philosophy
3 Science
3.1 Psychology and neurobiology
3.1.1 Social pre-wiring
3.2 Computer science
4 See also
5 Notes and references
6 Bibliography
7 External links
History[edit]
Tabula rasa is a Latin phrase often translated as "blank slate" in English and originates from the Roman tabula used for notes, which was blanked by heating the wax and then smoothing it.[1] This roughly equates to the English term "blank slate" (or, more literally, "erased slate") which refers to the emptiness of a slate prior to it being written on with chalk. Both may be renewed repeatedly, by melting the wax of the tablet or by erasing the chalk on the slate.
Philosophy[edit]
See also: Empiricism
In Western philosophy, the concept of tabula rasa can be traced back to the writings of Aristotle who writes in his treatise "Περί Ψυχῆς" (De Anima or On the Soul) of the "unscribed tablet." In one of the more well-known passages of this treatise he writes that:
Haven't we already disposed of the difficulty about interaction involving a common element, when we said that mind is in a sense potentially whatever is thinkable, though actually it is nothing until it has thought? What it thinks must be in it just as characters may be said to be on a writing-tablet on which as yet nothing stands written: this is exactly what happens with mind.[2]
This idea was further developed in Ancient Greek philosophy by the Stoic school. Stoic epistemology emphasizes that the mind starts blank, but acquires knowledge as the outside world is impressed upon it.[3] The doxographer Aetius summarizes this view as "When a man is born, the Stoics say, he has the commanding part of his soul like a sheet of paper ready for writing upon."[4] Diogenes Laërtius attributes a similar belief to the Stoic Zeno of Citium when he writes in Lives and Opinions of Eminent Philosophers that:
Perception, again, is an impression produced on the mind, its name being appropriately borrowed from impressions on wax made by a seal; and perception they divide into, comprehensible and incomprehensible: Comprehensible, which they call the criterion of facts, and which is produced by a real object, and is, therefore, at the same time conformable to that object; Incomprehensible, which has no relation to any real object, or else, if it has any such relation, does not correspond to it, being but a vague and indistinct representation.[5]
In the eleventh century, the theory of tabula rasa was developed more clearly by the Persian philosopher Avicenna (Ibn Sina in Arabic). He argued that the "...human intellect at birth resembled a tabula rasa, a pure potentiality that is actualized through education and comes to know," and that knowledge is attained through "...empirical familiarity with objects in this world from which one abstracts universal concepts," which develops through a "...syllogistic method of reasoning; observations lead to propositional statements, which when compounded lead to further abstract concepts." He further argued that the intellect itself "...possesses levels of development from the static/material intellect (al-‘aql al-hayulani), that potentiality can acquire knowledge to the active intellect (al-‘aql al-fa‘il), the state of the human intellect at conjunction with the perfect source of knowledge."[6]
In the twelfth century, the Andalusian-Islamic philosopher and novelist, Ibn Tufail, known as "Abubacer" or "Ebn Tophail" in the West, demonstrated the theory of tabula rasa as a thought experiment through his Arabic philosophical novel, Hayy ibn Yaqzan, in which he depicted the development of the mind of a feral child "from a tabula rasa to that of an adult, in complete isolation from society" on a desert island, through experience alone. The Latin translation of his philosophical novel, entitled Philosophus Autodidactus, published by Edward Pococke the Younger in 1671, had an influence on John Locke's formulation of tabula rasa in An Essay Concerning Human Understanding.[7]
Female Figure (Sibyl with Tabula Rasa) by Diego Velázquez, c. 1648
In the thirteenth century, St. Thomas Aquinas brought the Aristotelian and Avicennian notions to the forefront of Christian thought. These notions sharply contrasted with the previously held Platonic notions of the human mind as an entity that preexisted somewhere in the heavens, before being sent down to join a body here on Earth (see Plato's Phaedo and Apology, as well as others). St. Bonaventure (also thirteenth century) was one of the fiercest intellectual opponents of Aquinas, offering some of the strongest arguments toward the Platonic idea of the mind.
The writings of Avicenna, Ibn Tufail, and Aquinas on the tabula rasa theory stood unprogressed and untested for several centuries.[citation needed] For example, the late medieval English jurist Sir John Fortescue, in his work In Praise of the Laws of England (Chapter VI), takes for granted the notion of tabula rasa, stressing it as the basis of the need for the education of the young in general, and of young princes specifically. "Therefore, Prince, whilst you are young and your mind is as it were a clean slate, impress on it these things, lest in future it be impressed more pleasurably with images of lesser worth." (His igitur, Princeps, dum Adolescens es, et Anima tua velut Tabula rasa, depinge eam, ne in futurum ipsa Figuris minoris Frugi delectabilius depingatur.)
The modern idea of the theory, however, is attributed mostly to John Locke's expression of the idea in Essay Concerning Human Understanding (he uses the term "white paper" in Book II, Chap. I, 2). In Locke's philosophy, tabula rasa was the theory that at birth the (human) mind is a "blank slate" without rules for processing data, and that data is added and rules for processing are formed solely by one's sensory experiences. The notion is central to Lockean empiricism. As understood by Locke, tabula rasa meant that the mind of the individual was born blank, and it also emphasized the freedom of individuals to author their own soul. Individuals are free to define the content of their character—but basic identity as a member of the human species cannot be altered. This presumption of a free, self-authored mind combined with an immutable human nature leads to the Lockean doctrine of "natural" rights. Locke's idea of tabula rasa is frequently compared with Thomas Hobbes's viewpoint of human nature, in which humans are endowed with inherent mental content—particularly with selfishness.[citation needed]
The eighteenth-century Swiss philosopher Jean-Jacques Rousseau used tabula rasa to support his argument that warfare is an advent of society and agriculture, rather than something that occurs from the human state of nature. Since tabula rasa states that humans are born with a "blank-slate", Rousseau uses this to suggest that humans must learn warfare.
Tabula rasa also features in Sigmund Freud's psychoanalysis. Freud depicted personality traits as being formed by family dynamics (see Oedipus complex). Freud's theories imply that humans lack free will, but also that genetic influences on human personality are minimal. In Freudian psychoanalysis, one is largely determined by one's upbringing.[citation needed]
The tabula rasa concept became popular in social sciences during the twentieth century. Early ideas of eugenics posited that human intelligence correlated strongly with social class, but these ideas were rejected, and the idea that genes (or simply "blood") determined a person's character became regarded as racist. By the 1970s, scientists such as John Money had come to see gender identity as socially constructed, rather than rooted in genetics.
Science[edit]
Psychology and neurobiology[edit]
Main article: Nature versus nurture
Psychologists and neurobiologists have shown evidence that initially, the entire cerebral cortex is programmed and organized to process sensory input, control motor actions, regulate emotion, and respond reflexively (under predetermined conditions).[8] These programmed mechanisms in the brain subsequently act to learn and refine the ability of the organism.[9][10] For example, psychologist Steven Pinker showed that—in contrast to written language—the brain is "programmed" to pick up spoken language spontaneously.[11]
There have been claims by a minority in psychology and neurobiology, however, that the brain is tabula rasa only for certain behaviours. For instance, with respect to one's ability to acquire both general and special types of knowledge or skills, Howe argued against the existence of innate talent.[12] There also have been neurological investigations into specific learning and memory functions, such as Karl Lashley's study on mass action and serial interaction mechanisms.
Important evidence against the tabula rasa model of the mind comes from behavioural genetics, especially twin and adoption studies (see below). These indicate strong genetic influences on personal characteristics such as IQ, alcoholism, gender identity, and other traits.[11] Critically, multivariate studies show that the distinct faculties of the mind, such as memory and reason, fractionate along genetic boundaries. Cultural universals such as emotion and the relative resilience of psychological adaptation to accidental biological changes (for instance the David Reimer case of gender reassignment following an accident) also support basic biological mechanisms in the mind.[citation needed]
Social pre-wiring[edit]
Twin studies have resulted in important evidence against the tabula rasa model of the mind, specifically, of social behaviour.
The social pre-wiring hypothesis refers to the ontogeny of social interaction. Also informally referred to as, "wired to be social." The theory questions whether there is a propensity to socially oriented action already present before birth. Research in the theory concludes that newborns are born into the world with a unique genetic wiring to be social[13].
Circumstantial evidence supporting the social pre-wiring hypothesis can be revealed when examining newborns' behaviour. Newborns, not even hours after birth, have been found to display a preparedness for social interaction. This preparedness is expressed in ways such as their imitation of facial gestures. This observed behaviour cannot be contributed to any current form of socialization or social construction. Rather, newborns most likely inherit to some extent social behaviour and identity through genetics[13].
Principal evidence of this theory is uncovered by examining twin pregnancies. The main argument is, if there are social behaviours that are inherited and developed before birth, then one should expect twin fetuses to engage in some form of social interaction before they are born. Thus, ten fetuses were analyzed over a period of time using ultrasound techniques. Using kinematic analysis, the results of the experiment were that the twin fetuses would interact with each other for longer periods and more often as the pregnancies went on. Researchers were able to conclude that the performance of movements between the co-twins were not accidental but specifically aimed[13].
The social pre-wiring hypothesis was proved correct, "The central advance of this study is the demonstration that 'social actions' are already performed in the second trimester of gestation. Starting from the 14th week of gestation twin fetuses plan and execute movements specifically aimed at the co-twin. These findings force us to predate the emergence of social behaviour: when the context enables it, as in the case of twin fetuses, other-directed actions are not only possible but predominant over self-directed actions."[13].
Computer science[edit]
In computer science, tabula rasa refers to the development of autonomous agents with a mechanism to reason and plan toward their goal, but no "built-in" knowledge-base of their environment. Thus they truly are a blank slate.
In reality autonomous agents possess an initial data-set or knowledge-base, but this cannot be immutable or it would hamper autonomy and heuristic ability.[citation needed] Even if the data-set is empty, it usually may be argued that there is a built-in bias in the reasoning and planning mechanisms.[citation needed] Either intentionally or unintentionally placed there by the human designer, it thus negates the true spirit of tabula rasa.[14]
A synthetic (programming) language parser (LR(1), LALR(1) or SLR(1), for example) could be considered a special case of a tabula rasa, as it is designed to accept any of a possibly infinite set of source language programs, within a single programming language, and to output either a good parse of the program, or a good machine language translation of the program, either of which represents a success, or, alternately, a failure, and nothing else. The "initial data-set" is a set of tables which are generally produced mechanically by a parser table generator, usually from a BNF representation of the source language, and represents a "table representation" of that single programming language.
See also[edit]
Innatism
Pu (Daoism)
Veil of ignorance
Notes and references[edit]
Jump up ^ Smith, Sir William (1898). Cornish, F. Warre, ed. A Concise Dictionary of Greek and Roman Antiquities. London: Spottiswoode and Co. pp. 608–9.
Jump up ^ Aristotle, De Anima, 429b29–430a1.
Jump up ^ Bardzell, Jeffrey (June 11, 2014). Speculative Grammar and Stoic Language Theory in Medieval Allegorical Narrative: From Prudentius to Alan of Lille. Routledge. pp. 18–9.
Jump up ^ Diels-Kranz 4.11 translated by Long, A.A.; Sedley, D.N. (1987). The Hellenistic Philosophers: Vol. 1. Cambridge, Ma: Cambridge. p. 238.
Jump up ^ Diogenes Laërtius, vii. 43-46
Jump up ^ Sajjad H. Rizvi (2006), Avicenna/Ibn Sina (CA. 980–1037), Internet Encyclopedia of Philosophy
Jump up ^ G. A. Russell (1994), The Impact of the Philosophus autodidactus: Pocockes, John Locke and the Society of Friends, in: G. A. Russell (ed.), The 'Arabick' Interest of the Natural Philosophers in Seventeenth-Century England, pp. 224–262, Brill Publishers, ISBN 90-04-09459-8.
Jump up ^ Rakic P. (July 1988). "Specification of cerebral cortical areas". Science. 241 (4862): 170–6. Bibcode:1988Sci...241..170R. doi:10.1126/science.3291116. PMID 3291116.
Jump up ^ Kalisman N, Silberberg G, Markram H; Silberberg; Markram (January 2005). "The neocortical microcircuit as a tabula rasa". Proc. Natl. Acad. Sci. U.S.A. 102 (3): 880–5. Bibcode:2005PNAS..102..880K. doi:10.1073/pnas.0407088102. PMC 545526  . PMID 15630093. CS1 maint: Multiple names: authors list (link)
Jump up ^ Le Bé JV, Markram H; Markram (August 2006). "Spontaneous and evoked synaptic rewiring in the neonatal neocortex". Proc. Natl. Acad. Sci. U.S.A. 103 (35): 13214–9. Bibcode:2006PNAS..10313214L. doi:10.1073/pnas.0604691103. PMC 1559779  . PMID 16924105.
^ Jump up to: a b Pinker, Steven. The Blank Slate. New York: Penguin. 2002.
Jump up ^ M. J. Howe, J. W. Davidson and J. A. Sloboda. (1998). Innate talents: reality or myth? Behav. Brain. Sci., 21, 399–407; discussion 407–42.
^ Jump up to: a b c d https://www.ncbi.nlm.nih.gov/pmc/articles/PMC2951360/ Umberto Castiello, et al: National Institutes of Health
Jump up ^ The Jargon Files: "Sussman attains enlightenment", also see the article section Hacker koan: Uncarved block
Bibliography[edit]
Aristotle, On the Soul (De Anima), W. S. Hett (trans.), pp. 1–203 in Aristotle, Volume 8, Loeb Classical Library, William Heinemann, London, UK, 1936.
Avicenna, De Anima (Fi’l-Nafs), F. Rahman (trans.), London, UK, 1954.
Tufail, Ibn, The Improvement of Human Reason: Exhibited in the Life of Hai Ebn Yokdhan (Hayy ibn Yaqzan), Simon Ockley (trans.), pp. 1–195, Edm. Powell, London, Great Britain, 1708.
Aquinas, Thomas, Summa Theologica, Fathers of the English Dominican Province (trans.), Daniel J. Sullivan (ed.), vols. 19–20 in Robert Maynard Hutchins (ed.), Great Books of the Western World, Encyclopædia Britannica, Inc., Chicago, IL, 1952.
Locke, John, An Essay Concerning Human Understanding, Kenneth P. Winkler (ed.), pp. xix (Editor's Introduction) and 33–36 (Book II, Chap. I, 1–9), Hackett Publishing Company, Indianapolis, IN, 1996 [1689].
Baird, Forrest E.; Kaufmann, Walter (2008). From Plato to Derrida. Upper Saddle River, New Jersey: Pearson Prentice Hall. ISBN 0-13-158591-6.
External links[edit]
The dictionary definition of tabula rasa at Wiktionary
Works related to Book II, Chapter I of Locke's Essay Concerning Human Understanding at Wikisource
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Believe Me, if All Those Endearing Young Charms
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"Believe Me, if All Those Endearing Young Charms" is a popular song written in 1808 by Irish poet Thomas Moore using a traditional Irish air. Moore’s young[citation needed] wife had been stricken with an illness and worried that she would lose her looks. He wrote the words to reassure her.
Contents
[hide]
1 Origins of the melody
2 Lyrics
3 Other uses of the melody
4 References
5 External links
Origins of the melody[edit]
The tune to which Moore set his words is a traditional Irish air, first printed in a London songbook in 1775.[1] It is occasionally wrongly credited to Sir William Davenant, whose older collection of tunes may have been the source for later publishers, including a collection titled General Collection of Ancient Irish Music, compiled by Edward Bunting in 1796. Sir John Andrew Stevenson has been credited as responsible for the music for Moore's setting.[2]
It is thought that after Moore's wife, Elizabeth, was badly scarred by smallpox, she refused to leave her room, believing herself ugly and unlovable. To convince her his love was unwavering, Moore composed the ‘Endearing’ poem which he set to an old Irish melody and sang outside her bedroom door. He later wrote that this restored her confidence and re-kindled their love.[citation needed]
Lyrics[edit]
The lyrics, as originally published in 1808 in A Selection of Irish Melodies, are as follows:[3]
I.
BELIEVE me, if all those endearing young charms,
Which I gaze on so fondly to-day,
Were to change by to-morrow, and flee from my arms
Like fairy-gifts, fading away!
Thou wouldst still be ador'd as this moment thou art,
Let thy loveliness fade as it will;
And, around the dear ruin, each wish of my heart
Would entwine itself verdantly still!
II.
It is not while beauty and youth are thine own,
And thy cheeks unprofan'd by a tear,
That the fervour and faith of a love can be known,
To which time will but make thee more dear!
No! the heart that has truly lov'd, never forgets,
But as truly loves on to the close;
As the sun-flower turns on her god, when he sets,
The same look which she turn'd when he rose!
Other uses of the melody[edit]
Other than "Believe Me, If All Those Endearing Young Charms", the tune is perhaps best known as the melody to "Fair Harvard", the alma mater of Harvard University. A seventeenth-century folk song, Matthew Locke's "My Lodging is in the Cold, Cold Ground", was set to this tune some time after its original setting to a different, also traditional, air.[4] Simone Mantia, a pioneer of American euphonium music, composed a theme and variations on the melody, which remains a staple of the solo euphonium literature.
The first verse, as originally written, was sung by the character Alfalfa in a 1936 episode of MGM's The Little Rascals entitled Bored of Education. The tune, with the Endearing Young Charms title, also became a staple of Warner Brothers cartoons, appearing first in the 1944 Private Snafu short "Booby Traps". Subsequent uses included the 1951 Merrie Melodies animated cartoon Ballot Box Bunny, 1957 Looney Tunes short Show Biz Bugs (which reappeared in the 1981 package film), 1965 Road Runner cartoon Rushing Roulette, and finally in a new twist on the gag, with Slappy Squirrel's 1993 introductory episode, "Slappy Goes Walnuts", from Animaniacs. Variations were also done in the 1963 Andy Griffith Show episode "Rafe Hollister Sings", and the 2010 South Park episode "Crippled Summer".[5] In its cartoon appearances, the song is often the cue for a classic "bomb gag" wherein the playing of the first line of the song sets off a rigged explosion on the final note. However, the target often misses, forcing the perpetrator to play it themselves and fall for their own trap. The gag is so well known that it is often called "The Xylophone Gag".[6]
Little Virgie (Shirley Temple) sings the song to her father (John Boles) in the 1935 film The Littlest Rebel.
The first line appears in some versions of Dexys Midnight Runners' "Come On Eileen" as an introduction played by a solo fiddle. A short version of the tune also appears at the end of some versions of the "Come On Eileen".
Roger Quilter's setting of the song was included in the Arnold Book of Old Songs, published in 1950.
Debbie Reynolds and Barbara Ruick sing the first stanza in the 1953 film The Affairs of Dobie Gillis.
Walter Huston plays the melody on harmonica in the film The Treasure of the Sierra Madre.
Bing Crosby included the song in a medley on his album 101 Gang Songs (1961).
The song is performed at a Christmas party of the Adams Family at the beginning of "Chapter VIII: John Quincy Adams, Secretary of State" of The Adams Chronicles (1976).
References[edit]
Jump up ^ Songs of Yale. New Haven: Yale Glee Club, 2006. p. 150. The website http://www.contemplator.com/, used in a later reference in this article, claims its first printing was in 1737.
Jump up ^ William Davenant, 1606-1668. "Archived copy" (PDF). Archived from the original (PDF) on 2010-06-16. Retrieved 2010-02-03. , accessed Feb. 3rd, 2010.
Jump up ^ Moore, Thomas (1808). A Selection of Irish Melodies: Second Number. Dublin: W. Powers. pp. 98–102. Retrieved 7 August 2015.
Jump up ^ My Lodging It Is On the Cold Ground. http://www.contemplator.com/england/lodging.html, accessed Feb. 3rd, 2010.
Jump up ^ http://www.southparkstudios.com/clips/307810/ukulele-solo
Jump up ^ "Xylophone Gag". TV Tropes. Retrieved 13 April 2017.
External links[edit]
Choral Public Domain Library
Piano version
hide
v
t
e
Thomas Moore
Operas
The Gypsy Prince (1801)
M.P. (1811)
Non-fiction
Memoirs of the Life of Richard Brinsley Sheridan (1825)
Novels
The Epicurean (1827)
The Fudge Family in Paris (1818)
The Fudge Family in England (1835)
Poetry
"The Minstrel Boy"
The Last Rose of Summer (1805)
"Believe Me, if All Those Endearing Young Charms" (1808)
Lalla-Rookh (1817)
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text:
Non-covalent interactions
From Wikipedia, the free encyclopedia
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A non-covalent interaction differs from a covalent bond in that it does not involve the sharing of electrons,[1] but rather involves more dispersed variations of electromagnetic interactions between molecules or within a molecule. The chemical energy released in the formation of non-covalent interactions is typically on the order of 1-5 kcal/mol (1000–5000 calories per 6.02 x 10^23 molecules).[2] Non-covalent interactions can be classified into different categories, such as electrostatic, π-effects, van der Waals forces, and hydrophobic effects.[3][2]
Non-covalent interactions[4] are critical in maintaining the three-dimensional structure of large molecules, such as proteins and nucleic acids. In addition, they are also involved in many biological processes in which large molecules bind specifically but transiently to one another (see the properties section of the DNA page). These interactions also heavily influence drug design, crystallinity and design of materials, particularly for self-assembly, and, in general, the synthesis of many organic molecules.[3][5][6][7]
Intermolecular forces are non-covalent interactions that occur between different molecules, rather than between different atoms of the same molecule[3]
Contents
[hide]
1 Electrostatic interactions
1.1 Ionic
1.2 Hydrogen bonding
1.3 Halogen bonding
2 Van der Waals forces
2.1 Dipole-dipole
2.2 Dipole-induced dipole
2.3 London dispersion forces
3 π-effects
3.1 π-π interaction
3.2 Cation-π and anion-π interaction
3.3 Polar-π
4 Hydrophobic effect
5 Examples
5.1 Drug design
5.2 Protein folding and structure
5.3 Boiling points
6 References
Electrostatic interactions[edit]
For a more detailed introduction to electrostatics, see Coulomb's Law
Ionic[edit]
Scheme 1. Process of NaF formation -- example of an electrostatic interaction
Ionic interactions involve the attraction of ions or molecules with full permanent charges of opposite signs. For example, sodium fluoride involves the attraction of the positive charge on sodium (Na+) with the negative charge on fluoride (F−). These bonds are harder to break than covalent bonds because there is a strong electrostatic interaction between oppositely charged ions. However, this particular interaction is easily broken upon addition to water, or other highly polar solvents.
These interactions can also be seen in molecules with a localized charge on a particular atom. For example, the full negative charge associated with ethoxide, the conjugate base of ethanol, is most commonly accompanied by the positive charge of an alkali metal salt such as the sodium cation (Na+).
Hydrogen bonding[edit]
A hydrogen bond (H-bond), is a specific type of interaction that involves dipole-dipole attraction between a partially positive hydrogen atom and a highly electronegative, partially negative oxygen, nitrogen, sulfur, or fluorine atom (not covalently bound to said hydrogen atom). It is not a covalent bond, but instead is classified as a strong non-covalent interaction. It is responsible for why water is a liquid at room temperature and not a gas (given water's low molecular weight). Most commonly, the strength of hydrogen bonds lies between 0 - 4 kcal/mol, but can sometimes be as strong as 40 kcal/mol[3]
Halogen bonding[edit]
Figure 1. Anionic Lewis Base forming a halogen bond with electron-withdrawn bromine (Lewis acid)
Halogen bonding is a type of non-covalent interaction which does not involve the formation nor breaking of actual bonds, but rather is similar to the dipole-dipole interaction known as hydrogen bonding. In halogen bonding, a halogen atom acts as an electrophile, or electron-seeking species, and forms a weak electrostatic interaction with a nucleophile, or electron-rich species. The nucleophilic agent in these interactions tends to be highly electronegative (such as oxygen, nitrogen, or sulfur), or may be anionic, bearing a negative formal charge. As compared to hydrogen bonding, the halogen atom takes the place of the partially positively charged hydrogen as the electrophile.
Halogen bonding should not be confused with halogen-aromatic interactions, as the two are related but differ by definition. Halogen-aromatic interactions involve an electron-rich aromatic π-cloud as a nucleophile; halogen bonding is restricted to monatomic nucleophiles.[5]
Van der Waals forces[edit]
Van der Waals Forces are a subset of electrostatic interactions involving permanent or induced dipoles (or multipoles). These include the following:
permanent dipole-dipole interactions, alternatively called the Keesom force
dipole-induced dipole interactions, or the Debye force
induced dipole-induced dipole interactions, commonly referred to as London dispersion forces
Hydrogen bonding and halogen bonding are typically not classified as Van der Waals forces.
Dipole-dipole[edit]
Figure 2. Dipole-dipole interactions between two acetone molecules, with the partially negative oxygen atom interacting with the partially positive carbon atom in the carbonyl.
Dipole-dipole interactions are electrostatic interactions between permanent dipoles in molecules. These interactions tend to align the molecules to increase attraction (reducing potential energy). Normally, dipoles are associated with electronegative atoms, including oxygen, nitrogen, sulfur, and fluorine.
For example, acetone, the active ingredient in some nail polish removers, has a net dipole associated with the carbonyl (see figure 2). Since oxygen is more electronegative than the carbon that is covalently bonded to it, the electrons associated with that bond will be closer to the oxygen than the carbon, creating a partial negative charge (δ−) on the oxygen, and a partial positive charge (δ+) on the carbon. They are not full charges because the electrons are still shared through a covalent bond between the oxygen and carbon. If the electrons were no longer being shared, then the oxygen-carbon bond would be an electrostatic interaction.
H δ + − Cl δ − ⋯ H δ + − Cl δ − {\displaystyle {\overset {\color {Red}\delta +}{{\ce {H}}}}-{\overset {\color {Red}\delta -}{{\ce {Cl}}}}\cdots {\overset {\color {Red}\delta +}{{\ce {H}}}}-{\overset {\color {Red}\delta -}{{\ce {Cl}}}}}
Often molecules contain dipolar groups, but have no overall dipole moment. This occurs if there is symmetry within the molecule that causes the dipoles to cancel each other out. This occurs in molecules such as tetrachloromethane. Note that the dipole-dipole interaction between two individual atoms is usually zero, since atoms rarely carry a permanent dipole. See atomic dipoles.
Dipole-induced dipole[edit]
A dipole-induced dipole interaction (Debye force) is due to the approach of a molecule with a permanent dipole to another non-polar molecule with no permanent dipole. This approach causes the electrons of the non-polar molecule to be polarized toward or away from the dipole (or "induce" a dipole) of the approaching molecule.[8] Specifically, the dipole can cause electrostatic attraction or repulsion of the electrons from the non-polar molecule, depending on orientation of the incoming dipole.[8] Atoms with larger atomic radii are considered more "polarizable" and therefore experience greater attraction as a result of the Debye force.
London dispersion forces[edit]
London dispersion forces are the weakest type of non-covalent interaction. They are also known as "induced dipole-induced dipole interactions" and present between all molecules, even those which inherently do not have permanent dipoles. They are caused by the temporary repulsion of electrons away from the electrons of a neighboring molecule, leading to a partially positive dipole on one molecule and a partially negative dipole on another molecule.[6] Hexane is a good example of a molecule with no polarity or highly electronegative atoms, yet is a liquid at room temperature due mainly to London dispersion forces. In this example, when one hexane molecule approaches another, a temporary, weak partially negative dipole on the incoming hexane can polarize the electron cloud of another, causing a partially positive dipole on that hexane molecule. While these interactions are short-lived and very weak, they can be responsible for why certain non-polar molecules are liquids at room temperature.
π-effects[edit]
π-effects can be broken down into numerous categories, including π-π interactions, cation-π & anion-π interactions, and polar-π interactions. In general, π-effects are associated with the interactions of molecules with the π-systems of conjugated molecules such as benzene.[3]
π-π interaction[edit]
π-π interactions are associated with the interaction between the π-orbitals of a molecular system.[3] For a simple example, a benzene ring, with its fully conjugated π cloud, will interact in two major ways (and one minor way) with a neighboring benzene ring through a π-π interaction (see figure 3). The two major ways that benzene stacks are edge-to-face, with an enthalpy of ~2 kcal/mol, and displaced (or slip stacked), with an enthalpy of ~2.3 kcal/mol.[3] Interestingly, the sandwich configuration is not nearly as stable of an interaction as the previously two mentioned due to high electrostatic repulsion of the electrons in the π orbitals.[3]
Figure 3. Various ways that benzene can interact intermolecularly. Note, however, that the sandwich configuration is not a favorable interaction compared to displaced or edge-to-face
Cation-π and anion-π interaction[edit]
Figure 4.
Cation-π interactions involve the positive charge of a cation interacting with the electrons in a π-system of a molecule.[3] This interaction is surprisingly strong (as strong or stronger than H-bonding in some contexts),[3] and has many potential applications in chemical sensors.[9] For example, the sodium ion can easily sit atop the π cloud of a benzene molecule, with C6 symmetry (for more on point groups and molecular symmetry, see the Wikipedia page on point groups) (See figure 4).
Anion-π interactions are very similar to cation-π interactions, but reversed. In this case, an anion sits atop an electron-poor π-system, usually established by the placement of electron-withdrawing substituents on the conjugated molecule[10]
Figure 5.
Polar-π[edit]
Polar-π interactions involve molecules with permanent dipoles (such as water) interacting with the quadrupole moment of a π-system (such as that in benzene (see figure 5). While not as strong as a cation-π interaction, these interactions can be quite strong (~1-2 kcal/mol), and are commonly involved in protein folding and crystallinity of solids containing both hydrogen bonding and π-systems.[3] In fact, any molecule with a hydrogen bond donor (hydrogen bound to a highly electronegative atom) will have favorable electrostatic interactions with the electron-rich π-system of a conjugated molecule.
Hydrophobic effect[edit]
The hydrophobic effect is the desire for non-polar molecules to aggregate in aqueous solutions in order to separate from water.[11] This phenomenon leads to minimum exposed surface area of non-polar molecules to the polar water molecules (typically spherical droplets), and is commonly used in biochemistry to study protein folding and other various biological phenomenon.[11] The effect is also commonly seen when mixing various oils (including cooking oil) and water. Over time, oil sitting on top of water will begin to aggregate into large flattened spheres from smaller droplets, eventually leading to a film of all oil sitting atop a pool of water. However the hydrophobic effect is not considered a non-covalent interaction as it is a function of entropy and not a specific interaction between the two molecules.
Examples[edit]
Drug design[edit]
Most pharmaceutical drugs are small molecules which elicit a physiological response by "binding" to enzymes or receptors, causing an increase or decrease in the enzyme's ability to function. The binding of a small molecule to a protein is governed by a combination of steric, or spatial considerations, in addition to various non-covalent interactions, although some drugs do covalently modify an active site (see irreversible inhibitors). Using the "lock and key model" of enzyme binding, a drug (key) must be of roughly the proper dimensions to fit the enzyme's binding site (lock).[12] Using the appropriately sized molecular scaffold, drugs must also interact with the enzyme non-covalently in order to maximize binding affinity binding constant and reduce the ability of the drug to dissociate from the binding site. This is achieved by forming various non-covalent interactions between the small molecule and amino acids in the binding site, including: hydrogen bonding, electrostatic interactions, pi stacking, van der Waals interactions, and dipole-dipole interactions.
Non-covalent metallo drugs have been developed. For example, dinuclear triple-helical compounds in which three ligand strands wrap around two metals, resulting in a roughly cylindrical tetracation have been prepared. These compounds bind to the less-common nucleic acid structures, such as duplex DNA, Y-shaped fork structures and 4-way junctions. [13]
Protein folding and structure[edit]
Figure 7. Illustration of the main driving force behind protein structure formation. In the compact fold (to the right), the hydrophobic amino acids (shown as black spheres) are in general shielded from the solvent.
The folding of most proteins from a primary (linear) sequence of amino acids to a three-dimensional structure is governed by many factors, including non-covalent interactions. The first ~5 milliseconds of folding are primarily dependent on van der Waals forces, whereby the protein folds so as to orient nonpolar amino acids in the interior of the globular protein, while more polar amino acid residues are exposed to aqueous solvent. This phase is known as the hydrophobic collapse, when nonpolar non-covalent interactions exclude water from the interior of the developing 3D protein structure.
After this initial "burst phase," more polar non-covalent interactions take over. Between 5 and 1000 milliseconds after protein folding initiation, three-dimensional structures of proteins, known as secondary and tertiary structures, are stabilized by formation of hydrogen bonds, in addition to disulfide bridges (covalent linkages). Through a series of small conformational changes, spatial orientations are modified so as to arrive at the most energetically minimized orientation achievable. The folding of proteins is often facilitated by enzymes known as molecular chaperones[14] Sterics, bond strain, and angle strain also play major roles in the folding of a protein from its primary sequence to its tertiary structure.
Single tertiary protein structures can also assemble to form protein complexes composed of multiple independently folded subunits. As a whole, this is called a protein's quaternary structure. The quaternary structure is generated by the formation of relatively strong non-covalent interactions, such as hydrogen bonds, between different subunits to generate a functional polymeric enzyme.[15] Some proteins also utilize non-covalent interactions to bind cofactors in the active site during catalysis, however a cofactor can also be covalently attached to an enzyme. Cofactors can be either organic or inorganic molecules which assist in the catalytic mechanism of the active enzyme. The strength with which a cofactor is bound to an enzyme may vary greatly; non-covalently bound cofactors are typically anchored by hydrogen bonds or electrostatic interactions.
Boiling points[edit]
Non-covalent interactions have a significant effect on the boiling point of a liquid. Boiling point is defined as the temperature at which the vapor pressure of a liquid is equal to the pressure surrounding the liquid. More simply, it is the temperature at which a liquid becomes a gas. As one might expect, the stronger the non-covalent interactions present for a substance, the higher its boiling point. For example, consider three compounds of similar chemical composition: sodium n-butoxide (C4H9ONa), diethyl ether (C4H10O), and n-butanol (C4H9OH).
Figure 8.Boiling points of 4-carbon compounds
The predominant non-covalent interactions associated with each species in solution are listed in the above figure. As previously discussed, ionic interactions require considerably more energy to break than hydrogen bonds, which in turn are require more energy than dipole-dipole interactions. The trends observed in their boiling points (figure 8) shows exactly the correlation expected, where sodium n-butoxide requires significantly more heat energy (higher temperature) to boil than n-butanol, which boils at a much higher temperature than diethyl ether. The heat energy required for a compound to change from liquid to gas is associated with the energy required to break the intermolecular forces each molecule experiences in its liquid state.
References[edit]
Jump up ^ Lodish, Harvey; Berk, Arnold; Zipursky, S. Lawrence; Matsudaira, Paul; Baltimore, David; Darnell, James (2000). "Glossary".
^ Jump up to: a b Noncovalent bonds – Molecular Cell Biology (textbook), Lodish, Berk, Zipursky, Matsudaira, Baltimore, Darnell.
^ Jump up to: a b c d e f g h i j k Anslyn, Eric (2004). Modern Physical Organic Chemistry. Sausalito, CA: University Science. ISBN 978-1-891389-31-3.
Jump up ^ Noncovalent bonding in Supramolecular Chemistry - Christoph A. Schalley
^ Jump up to: a b Cockroft, Scott L.; Hunter, Christopher A. (1 January 2007). "Chemical double-mutant cycles: dissecting non-covalent interactions". Chemical Society Reviews. 36 (2): 172. doi:10.1039/b603842p.
^ Jump up to: a b Brown, Theodore; et al. (2009). Chemistry : the central science (11th ed.). Upper Saddle River, NJ: Pearson Prentice Hall. ISBN 978-0-13-600617-6.
Jump up ^ Eisler, Matthew (2010). Encyclopedia of nanoscience and society. Thousand Oaks, Calif.: Sage. ISBN 978-1-4129-7209-3.
^ Jump up to: a b "Induced-Dipole Forces". Retrieved 11 November 2013.
Jump up ^ Sastry, G. N., & Mahadevi, A. S. (2013). Cation-π interaction: Its role and relevevance in chemistry, biology, and material science. Chemical Reviews, 113, 2100
Jump up ^ Quiñonero, David; Garau, Carolina; Rotger, Carmen; Frontera, Antonio; Ballester, Pablo; Costa, Antonio; Deyà, Pere M. (16 September 2002). "Anion–π Interactions: Do They Exist?". Angewandte Chemie International Edition. 41 (18): 3389–3392. doi:10.1002/1521-3773(20020916)41:18<3389::AID-ANIE3389>3.0.CO;2-S.
^ Jump up to: a b IUPAC. "Compendium of Chemical Terminology". Retrieved 11 November 2013.
Jump up ^ "Biomolecules: Enzymes". ChemPages Netorials. University of Wisconsin - Madison. Retrieved 27 October 2013.
Jump up ^ Cardo, Lucia; Hannon, Michael J. (2018). "Chapter 11. Non-covalent Metallo-Drugs: Using Shape to Target DNA and RNA Junctions and Other Nucleic Acid Structures". In Sigel, Astrid; Sigel, Helmut; Freisinger, Eva; Sigel, Roland K. O. Metallo-Drugs: Development and Action of Anticancer Agents. 18. Berlin: de Gruyter GmbH. pp. 303–324. doi:10.1515/9783110470734-017.
Jump up ^ Voet, Donald., & Voet, Judith G. (2010). Biochemistry (4th ed.). Hoboken, NJ: John Wiley & Sons. ISBN 978-0-470-57095-1.
Jump up ^ Silverman, Richard B. (2004). The organic chemistry of drug design and drug action (2. ed.). Amsterdam [u.a.]: Elsevier. ISBN 978-0-12-643732-4.
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Non-Covalent Interactions in the Synthesis and Design of New Compounds. A. M. Maharramov, K.T. Mahmudov, M.N. Kopylovich, A.J.L. Pombeiro, (Eds.), John Wiley & Sons, Inc., Hoboken, New Jersey, 2016. ISBN 978-1-119-10989-1 Mahmudov K.T., Kopylovich M.N., Guedes da Silva M.F.C., Pombeiro A.J.L. Noncovalent Interactions in the Synthesis of Coordination Compounds: Recent Advances. Coordination Chemistry Reviews, doi:10.1016/j.ccr.2016.09.002
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