関: At

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a highly unstable radioactive element (the heaviest of the halogen series); a decay product of uranium and thorium (同)At, atomic number 85

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アスタチン(放射性元素の一つ;化学記号は『At』)
astatineの化学記号

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出典(authority):フリー百科事典『ウィキペディア（Wikipedia）』「2016/09/28 23:39:33」(JST)

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アスタチン（英: astatine）は原子番号85の元素。元素記号は At。ハロゲン元素の一つ。約30の同位体が存在するが、安定同位体は存在せず半減期も短いため、詳しく分っていない部分が多い。

歴史

アスタチンはメンデレーエフによって「エカヨウ素」として予言された^[1]。1932年、アラバマ工科大学のフレッド・アリソンがモナザイトから85番元素を発見したと発表し、アラバミン（元素記号 Ab）と命名したが後に否定された。1940年、アメリカのカリフォルニア大学バークレー校でセグレ等によりビスマス209にアルファ粒子を当てて、アスタチン211が初めて作られた。半減期が短いため、ギリシア語の不安定という astatos が語源。

特徴

アスタチンは壊変系列中の短寿命生成物として存在する元素で半減期が短いのが特徴である。したがって、実験している最中にどんどん崩壊して他の元素に変わっていくため、その詳しい化学的、物理的性質は分かっていない部分が多い。融点は302 °C、沸点は337 °C（アスタチン210のものと思われる）である。

昇華性があり、水に溶け、ヨウ素に似た化学的性質を持つが、ビスマスやポロニウムのように金属と非金属の中間的性質を持つ。アスタチンはヨウ素のように甲状腺に蓄積すると思われている。また色は黒もしくは銀色と推測されている。

また、常温では揮発するが、水溶液は安定しており、四塩化炭素によって水溶液からの抽出も可能である。

自然界にはアスタチン215、アスタチン217、アスタチン218、アスタチン219の存在が知られており、それ以外の同位体は人工放射性同位体である。アスタチンの人工放射性同位体の中で最も普通に作られるのはアスタチン210、アスタチン211である。

用途

アスタチンは強い放射能と短い半減期（アスタチン210でも8.1時間しかない）のため、研究用以外に用途はない。

しかし、アスタチン211は細胞殺傷性の高エネルギーのα線を放出するため、癌の治療という用途に期待されている。現在はアスタチン211の運び屋となる比較的長い半減期を持つ放射性同位体が研究されている。

同位体

詳細は「アスタチンの同位体」を参照

アスタチンは約30の同位体の存在が確認されている。しかし前文で記入したとおり安定同位体は存在せず半減期も短い（アスタチン210でも8.1時間しかない）。それらの質量数の範囲はアスタチン191からアスタチン223までの存在が確認されており、さらに23の核異性体が存在する。その中で一番長い半減期を持つのがアスタチン210（半減期8.1時間）で、一番短い半減期を持つのはアスタチン213（半減期125ナノ秒）である。

アスタチン211

アスタチン211は7.2時間の半減期を持つ同位体である。セグレ等によりビスマス209に亜鉛70のα粒子を当ててアスタチン211が作られた。現在は用途はないが、将来は放射線治療に使われると思われる。

自然界での発生

アスタチンは壊変系列中の短寿命生成物として存在するため、鉱物の主成分とはならず、自然界では非常に稀な元素である。そして、アスタチンはすべての元素の中で地殻含有量が最も少ない元素で、ウラン100万個の原子の中にはアスタチンの原子は数個しか存在しない。地殻中に存在するアスタチンの全量は28g（約1オンス）といわれている^[2]。

アスタチンはウラン系列の崩壊ではウラン238（α崩壊）→トリウム234（β崩壊）→プロトアクチニウム234（β崩壊）→ウラン234（α崩壊）→トリウム230（α崩壊） →ラジウム226（α崩壊）→ラドン222（α崩壊）→ポロニウム218（α崩壊）→鉛214（β崩壊）、アスタチン218（β崩壊）→続

このようにポロニウム218のα崩壊の分岐点でアスタチン218（半減期1.6秒）が生じる。また、アクチニウム系列の崩壊の際に、フランシウム223からアスタチン219（半減期56秒）が生じ、ポロニウム215（β崩壊）からアスタチン215（半減期0.001秒）が生じる。ネプツニウム系列の崩壊の際に、フランシウム221からアスタチン217（半減期0.323秒）が生じる。また、人工ではビスマス209に亜鉛70のアルファ粒子を当ててアスタチン211が作られる。

アスタチンは酸性溶液から硫化水素によって沈殿し、電解によって分離することができる。

アスタチンの化合物

酸化数は7, 5, 3, 1, -1価をとることがわかっている。うち、他のハロゲン同様-1価が最も安定である。

他のハロゲンと同じように水素との化合物を作ることが知られている。知られている化合物の中では、-1価の化合物が最も多い。

アスタチン化水素 (HAt)

性質はヨウ化水素に似ており、刺激臭を持つ有毒な気体と考えられている。

その他にも AtO、AtO₃ などの化合物も確認されている。

脚注

^ 桜井弘『元素111の新知識』講談社、1998年、347頁。ISBN 4-06-257192-7。
^ 地殻中に含まれるフランシウムは20～30gと言われており、アスタチンよりも稀な元素である可能性もある。

Characteristics

Astatine is an extremely radioactive element; all its isotopes have short half-lives of 8.1 hours or less, decaying into bismuth, polonium, radon, or other astatine isotopes. Most of its isotopes are very unstable with half-lives of one second or less. Of the first 101 elements in the periodic table, only francium is less stable.^[7]

The bulk properties of astatine are not known with any certainty.^[8] Research is limited by its short half-life, which prevents the creation of weighable quantities.^[9] A visible piece of astatine would immediately vaporize itself because of the heat generated by its intense radioactivity.^[10] It remains to be seen if, with sufficient cooling, a macroscopic quantity of astatine could be deposited as a thin film.^[2] Astatine is usually classified as either a nonmetal or a metalloid;^[11]^[12] metal formation has also been predicted.^[2]^[13]

Physical

Most of the physical properties of astatine have been estimated (by interpolation or extrapolation), using theoretically or empirically derived methods.^[14] For example, halogens get darker with increasing atomic weight – fluorine is nearly colorless, chlorine is yellow-green, bromine is red-brown, and iodine is dark gray/violet. Astatine is sometimes described as probably being a black solid (assuming it follows this trend), or as having a metallic appearance (if it is a metalloid or a metal).^[15]^[16]^[17] The melting and boiling points of astatine are also expected to follow the trend seen in the halogen series, increasing with atomic number. On this basis they are estimated to be 575 and 610 K (302 and 337 °C; 575 and 638 °F), respectively.^[18] Some experimental evidence suggests astatine may have lower melting and boiling points than those implied by the halogen trend.^[19] Astatine sublimes less readily than does iodine, having a lower vapor pressure.^[9] Even so, half of a given quantity of astatine will vaporize in approximately an hour if put on a clean glass surface at room temperature.^[a] The absorption spectrum of astatine in the middle ultraviolet region has lines at 224.401 and 216.225 nm, suggestive of 6p to 7s transitions.^[21]^[22]

The structure of solid astatine is unknown.^[23] As an analogue of iodine it may have an orthorhombic crystalline structure composed of diatomic astatine molecules, and be a semiconductor (with a band gap of 0.7 eV).^[24] Alternatively, if condensed astatine forms a metallic phase, as has been predicted, it may have a monatomic face-centered cubic structure. Evidence for (or against) the existence of diatomic astatine (At₂) is sparse and inconclusive.^[25]^[26]^[27]^[28]^[29] Some sources state that it does not exist, or at least has never been observed,^[30]^[31] while other sources assert or imply its existence.^[19]^[32]^[33] Despite this controversy, many properties of diatomic astatine have been predicted;^[34] for example, its bond length would be 300 ±10 pm, dissociation energy 83.7 ±12.5 kJ·mol⁻¹,^[35] and heat of vaporization (∆H_vap) 54.39 kJ·mol⁻¹.^[4] The latter figure means that astatine may (at least) be metallic in the liquid state on the basis that elements with a heat of vaporization greater than ~42 kJ·mol⁻¹ are metallic when liquid;^[36] diatomic iodine, with a value of 41.71 kJ·mol⁻¹,^[37] falls just short of the threshold figure.^[b]

Chemical

The chemistry of astatine is "clouded by the extremely low concentrations at which astatine experiments have been conducted, and the possibility of reactions with impurities, walls and filters, or radioactivity by-products, and other unwanted nano-scale interactions."^[24] Many of its apparent chemical properties have been observed using tracer studies on extremely dilute astatine solutions,^[33]^[40] typically less than 10⁻¹⁰ mol·L⁻¹.^[41] Some properties – such as anion formation – align with other halogens.^[9] Astatine has some metallic characteristics as well, such as plating onto a cathode,^[c] coprecipitating with metal sulfides in hydrochloric acid,^[43] and forming a stable monatomic cation in aqueous solution.^[43]^[44] It forms complexes with EDTA, a metal chelating agent,^[45] and is capable of acting as a metal in antibody radiolabeling; in some respects astatine in the +1 state is akin to silver in the same state. Most of the organic chemistry of astatine is, however, analogous to that of iodine.^[46]

Astatine has an electronegativity of 2.2 on the revised Pauling scale – lower than that of iodine (2.66) and the same as hydrogen. In hydrogen astatide (HAt) the negative charge is predicted to be on the hydrogen atom, implying that this compound should instead be referred to as astatine hydride.^[47]^[48]^[49]^[50] That would be consistent with the electronegativity of astatine on the Allred–Rochow scale (1.9) being less than that of hydrogen (2.2).^[51]^[d] The electron affinity of astatine is predicted to be reduced by one-third because of spin-orbit interactions.^[41]

Compounds

Less reactive than iodine, astatine is the least reactive of the halogens,^[53] although its compounds have been synthesized in microscopic amounts and studied as intensively as possible before their radioactive disintegration. The reactions involved have been typically tested with dilute solutions of astatine mixed with larger amounts of iodine. Acting as a carrier, the iodine ensures there is sufficient material for laboratory techniques (such as filtration and precipitation) to work.^[54]^[55]^[e] Like iodine, astatine has been shown to adopt odd-numbered oxidation states ranging from −1 to +7.

Only a few compounds with metals have been reported, in the form of astatides of sodium,^[10] palladium, silver, thallium, and lead.^[58] Some characteristic properties of silver and sodium astatide, and the other hypothetical alkali and alkaline earth astatides, have been estimated by extrapolation from other metal halides.^[59]

Hydrogen astatide space-filling model

The formation of an astatine compound with hydrogen – usually referred to as hydrogen astatide – was noted by the pioneers of astatine chemistry.^[60] As mentioned, there are grounds for instead referring to this compound as astatine hydride. It is easily oxidized; acidification by dilute nitric acid gives the At⁰ or At⁺ forms, and the subsequent addition of silver(I) may only partially, at best, precipitate astatine as silver(I) astatide (AgAt). Iodine, in contrast, is not oxidized, and precipitates readily as silver(I) iodide.^[9]^[61]

Astatine is known to bind to boron,^[62] carbon, and nitrogen.^[63] Various boron cage compounds have been prepared with At–B bonds, these being more stable than At–C bonds.^[64] Carbon tetraastatide (CAt₄) has been synthesized.^[10] Astatine can replace a hydrogen atom in benzene to form astatobenzene C₆H₅At; this may be oxidized to C₆H₅AtCl₂ by chlorine. By treating this compound with an alkaline solution of hypochlorite, C₆H₅AtO₂ can be produced.^[65] In the molecules dipyridine-astatine(I) perchlorate [At(C₅H₅N)₂][ClO₄] and the analogous nitrate, the astatine atom is bonded to each nitrogen atom in the two pyridine rings.^[63]

With oxygen, there is evidence of the species AtO⁻, AtO−
2, and AtO⁺ in aqueous solution, formed by the reaction of astatine with an oxidant such as elemental bromine or (in the last case) by sodium persulfate in a solution of perchloric acid.^[9]^[66] The well characterized AtO−
3 anion can be obtained by, for example, the oxidation of astatine with potassium hypochlorite in a solution of potassium hydroxide.^[65]^[67] Preparation of lanthanum triastatinate La(AtO₃)₃, following the oxidation of astatine by a hot Na₂S₂O₈ solution, has been reported.^[68] Further oxidation of AtO−
3, such as by xenon difluoride (in a hot alkaline solution) or periodate (in a neutral or alkaline solution), yields the perastatate ion AtO−
4; this is only stable in neutral or alkaline solutions.^[69] Astatine is also thought to be capable of forming cations in salts with oxyanions such as iodate or dichromate; this is based on the observation that, in acidic solutions, monovalent or intermediate positive states of astatine coprecipitate with the insoluble salts of metal cations such as silver(I) iodate or thallium(I) dichromate.^[65]^[70]

Astatine may form bonds to the other chalcogens; these include S₇At⁺ and At(CSN)−
2 with sulfur, a coordination selenourea compound with selenium, and an astatine–tellurium colloid with tellurium.^[71]

Structure of astatine monoiodide, one of the astatine interhalogens and the heaviest known diatomic interhalogen.

Astatine is known to react with its lighter homologs iodine, bromine, and chlorine in the vapor state; these reactions produce diatomic interhalogen compounds with formulas AtI, AtBr, and AtCl.^[56] The first two compounds may also be produced in water – astatine reacts with iodine/iodide solution to form AtI, whereas AtBr requires (aside from astatine) an iodine/iodine monobromide/bromide solution. The excess of iodides or bromides may lead to AtBr−
2 and AtI−
2 ions,^[56] or in a chloride solution, they may produce species like AtCl−
2 or AtBrCl−
via equilibrium reactions with the chlorides.^[57] Oxidation of the element with dichromate (in nitric acid solution) showed that adding chloride turned the astatine into a molecule likely to be either AtCl or AtOCl. Similarly, AtOCl−
2 or AtCl−
2 may be produced.^[56] Polyhalides PdAtI₂, CsAtI₂, TlAtI₂,^[72]^[73]^[74] and PbAtI^[75] are known or presumed to have been precipitated. In a plasma ion source mass spectrometer, the ions [AtI]⁺, [AtBr]⁺, and [AtCl]⁺ have been formed by introducing lighter halogen vapors into a helium-filled cell containing astatine, supporting the existence of stable neutral molecules in the plasma ion state.^[56] No astatine fluorides have been discovered yet. Their absence has been speculatively attributed to the extreme reactivity of such compounds, including the reaction of an initially formed fluoride with the walls of the glass container to form a non-volatile product.^[f] Thus, although the synthesis of an astatine fluoride is thought to be possible, it may require a liquid halogen fluoride solvent, as has already been used for the characterization of radon fluoride.^[56]^[69]

History

Mendeleev's table of 1871, with an empty space at the eka-iodine position

In 1869, when Dmitri Mendeleev published his periodic table, the space under iodine was empty; after Niels Bohr established the physical basis of the classification of chemical elements, it was suggested that the fifth halogen belonged there. Before its officially recognized discovery, it was called "eka-iodine" (from Sanskrit eka – "one") to imply it was one space under iodine (in the same manner as eka-silicon, eka-boron, and others).^[79] Scientists tried to find it in nature; given its extreme rarity, these attempts resulted in several false discoveries.^[80]

The first claimed discovery of eka-iodine was made by Fred Allison and his associates at the Alabama Polytechnic Institute (now Auburn University) in 1931. The discoverers named element 85 "alabamine", and assigned it the symbol Ab, designations that were used for a few years.^[81]^[82]^[83] In 1934, H. G. MacPherson of University of California, Berkeley disproved Allison's method and the validity of his discovery.^[84] There was another claim in 1937, by the chemist Rajendralal De. Working in Dacca in British India (now Dhaka in Bangladesh), he chose the name "dakin" for element 85, which he claimed to have isolated as the thorium series equivalent of radium F (polonium-210) in the radium series. The properties he reported for dakin do not correspond to those of astatine; moreover, astatine is not found in the thorium series, and the true identity of dakin is not known.^[85]

In 1936, a team of Romanian physicist Horia Hulubei and French physicist Yvette Cauchois claimed to have discovered element 85 via X-ray analysis. In 1939 they published another paper which supported and extended previous data. In 1944, Hulubei published a summary of data he had obtained up to that time, claiming it was supported by the work of other researchers. He chose the name "dor", presumably from the Romanian for "longing" [for peace], as World War II had started five years earlier. As Hulubei was writing in French, a language which does not accommodate the "ine" suffix, dor would likely have been rendered in English as "dorine", had it been adopted. In 1947, Hulubei's claim was effectively rejected by the Austrian chemist Friedrich Paneth, who would later chair the IUPAC committee responsible for recognition of new elements. Even though Hulubei's samples did contain astatine, his means to detect it were too weak, by current standards, to enable correct identification.^[86] He had also been involved in an earlier false claim as to the discovery of element 87 (francium) and this is thought to have caused other researchers to downplay his work.^[87]

Emilio Segrè, one of the discoverers of astatine

In 1940, the Swiss chemist Walter Minder announced the discovery of element 85 as the beta decay product of radium A (polonium-218), choosing the name "helvetium" (from Helvetia, "Switzerland"). Karlik and Bernert were unsuccessful in reproducing his experiments, and subsequently attributed Minder's results to contamination of his radon stream (radon-222 is the parent isotope of polonium-218).^[88]^[g] In 1942, Minder, in collaboration with the English scientist Alice Leigh-Smith, announced the discovery of another isotope of element 85, presumed to be the product of thorium A (polonium-216) beta decay. They named this substance "anglo-helvetium",^[89] but Karlik and Bernert were again unable to reproduce these results.^[54]

Later in 1940, Dale R. Corson, Kenneth Ross MacKenzie, and Emilio Segrè isolated the element at the University of California, Berkeley. Instead of searching for the element in nature, the scientists created it by bombarding bismuth-209 with alpha particles in a cyclotron (particle accelerator) to produce, after emission of two neutrons, astatine-211.^[1] The discoverers, however, did not immediately suggest a name for the element; this was because an element created synthetically at the moment was not seen as a completely valid one, created in "invisible quantities" and not yet discovered in nature; in addition, chemists were reluctant to recognize radioactive isotopes as legitimately as stable ones.^[90] In 1943, astatine was found as a product of two naturally occurring decay chains by Berta Karlik and Traude Bernert, first in the so-called uranium series, and then in the actinium series.^[91]^[92] (Since then, astatine has been determined in a third decay chain, the neptunium series.^[93]) Friedrich Paneth in 1946 called to finally recognize synthetic elements, quoting, among other reasons, recent confirmation of their natural occurrence, and proposed the discoverers of the newly discovered unnamed elements name these elements. In early 1947, Nature published discoverers' suggestions; a letter from Corson, MacKenzie, and Segrè suggested the name "astatine"^[90] coming from the Greek astatos (αστατος) meaning "unstable", because of its propensity for radioactive decay, with the ending "-ine", found in the names of the four previously discovered halogens.

Corson and his colleagues classified astatine as a metal on the basis of its analytical chemistry.^[94] Subsequent investigators reported iodine-like,^[95]^[96] cationic,^[97]^[98] or amphoteric behavior.^[99]^[100] In a 2003 retrospective, Corson wrote that "some of the properties [of astatine] are similar to iodine … it also exhibits metallic properties, more like its metallic neighbors Po and Bi."^[101]

Isotopes

Alpha decay characteristics for sample astatine isotopes^[h]
Mass number	Mass excess^[7]	Half-life^[7]	Probability of alpha decay^[7]	Alpha decay half-life
207	3011787823767826589♠−13.243 MeV	7003648000000000000♠1.80 h	7000860000000000000♠8.6%	7004752400000000000♠20.9 h
208	3011799872135008830♠−12.491 MeV	7003586800000000000♠1.63 h	6999550000000000000♠0.55%	7006106272000000000♠12.3 d
209	3011793639668474400♠−12.880 MeV	7004194760000000000♠5.41 h	7000410009999999999♠4.1%	7005475200000000000♠5.5 d
210	3011808187430976360♠−11.972 MeV	7004291600000000000♠8.1 h	6999175000000000000♠0.175%	7007166752000000000♠193 d
211	3011813394504559110♠−11.647 MeV	7004259560000000000♠7.21 h	7001418009999900000♠41.8%	7004619200000000000♠17.2 h
212	3011861876365055729♠−8.621 MeV	6999310000000000000♠0.31 s	7001999900000000000♠≈100%	6999310000000000000♠0.31 s
213	3011894592808920269♠−6.579 MeV	6993125000000000000♠125 ns	7002100000000000000♠100%	6993125000000000000♠125 ns
214	3012458464347394000♠−3.380 MeV	6993558000000000000♠558 ns	7002100000000000000♠100%	6993558000000000000♠558 ns
219	6988166578289353390♠10.397 MeV	7001560000000000000♠56 s	7001970000000000000♠97%	7001580000000000000♠58 s
220	6988229912325884500♠14.350 MeV	7002222600000000000♠3.71 min	7000800000000000000♠8%	7003278400000000000♠46.4 min
221^[i]	6988269325867464699♠16.810 MeV	7002138000000000000♠2.3 min	5000000000000000000♠experimentally alpha stable	9000000000000000000♠∞

There are 39 known isotopes of astatine, with atomic masses (mass numbers) of 191–229. Theoretical modeling suggests that 37 more isotopes could exist.^[102] No stable or long-lived astatine isotope has been observed nor is one expected to exist.^[103]

Astatine's alpha decay energies follow the same trend as for other heavy elements.^[103] Lighter astatine isotopes have quite high energies of alpha decay, which become lower as the nuclei become heavier. Astatine-211 has a significantly higher energy than the previous isotope, because it has a nucleus with 126 neutrons, and 126 is a magic number corresponding to a filled neutron shell. Despite having a similar half-life to the previous isotope (8.1 hours for astatine-210 and 7.2 hours for astatine-211), the alpha decay probability is much higher for the latter: 41.81% against only 0.18%.^[7]^[j] The two following isotopes release even more energy, with astatine-213 releasing the most energy. For this reason, it is the shortest-lived astatine isotope.^[103] Even though heavier astatine isotopes release less energy, no long-lived astatine isotope exists, because of the increasing role of beta decay (electron emission).^[103] This decay mode is especially important for astatine; as early as 1950 it was postulated that all isotopes of the element undergo beta decay.^[104] Beta decay modes have been found for all astatine isotopes except astatine-213, -214, -215, and -216m.^[7] Astatine-210 and lighter isotopes exhibit beta plus decay (positron emission), astatine-216 and heavier isotopes exhibit beta (minus) decay, and astatine-212 decays via both modes, while astatine-211 undergoes electron capture.^[7]

The most stable isotope is astatine-210, which has a half-life of 8.1 hours. The primary decay mode is beta plus, to the relatively long-lived (in comparison to astatine isotopes) alpha emitter polonium-210. In total, only five isotopes have half-lives exceeding one hour (astatine-207 to -211). The least stable ground state isotope is astatine-213, with a half-life of 125 nanoseconds. It undergoes alpha decay to the extremely long-lived bismuth-209.^[7]

Astatine has 24 known nuclear isomers, which are nuclei with one or more nucleons (protons or neutrons) in an excited state. A nuclear isomer may also be called a "meta-state", meaning the system has more internal energy than the "ground state" (the state with the lowest possible internal energy), making the former likely to decay into the latter. There may be more than one isomer for each isotope. The most stable of these nuclear isomers is astatine-202m1,^[k] which has a half-life of about 3 minutes, longer than those of all the ground states bar those of isotopes 203–211 and 220. The least stable is astatine-214m1; its half-life of 265 nanoseconds is shorter than those of all ground states except that of astatine-213.^[7]^[102]

Natural occurrence

Neptunium series, showing the decay products, including astatine-217, formed from neptunium-237

Astatine is the rarest naturally occurring element.^[l] The total amount of astatine in the Earth's crust (quoted mass 2.36 × 10²⁵ grams)^[105] is estimated to be less than one gram at any given time.^[9]

Any astatine present at the formation of the Earth has long since disappeared; the four naturally occurring isotopes (astatine-215, -217, -218 and -219)^[106] are instead continuously produced as a result of the decay of radioactive thorium and uranium ores, and trace quantities of neptunium-237. The landmass of North and South America combined, to a depth of 16 kilometers (10 miles), contains only about one trillion astatine-215 atoms at any given time (around 3.5 × 10⁻¹⁰ grams).^[107] Astatine-217 is produced via the radioactive decay of neptunium-237. Primordial remnants of the latter isotope—due to its relatively short half-life of 2.14 million years—are no longer present on Earth. However trace amounts occur naturally as a product of transmutation reactions in uranium ores.^[108] Astatine-218 was the first astatine isotope discovered in nature.^[109] Astatine-219, with a half-life of 56 seconds, is the longest lived of the naturally occurring isotopes.^[7]

Isotopes of astatine are sometimes not listed as naturally occurring because of misconceptions^[99] that there are no such isotopes,^[110] or discrepancies in the literature. Astatine-216 has been counted as a naturally occurring isotope but reports of its observation^[111] (which were described as doubtful) have not been confirmed.^[112]

Synthesis

Formation

Possible reactions after bombarding bismuth-209 with alpha particles
Reaction^[m]	Energy of alpha particle
209 83Bi + 4 2He → 211 85At + 2 1 0	26 MeV^[54]
209 83Bi + 4 2He → 210 85At + 3 1 0	40 MeV^[54]
209 83Bi + 4 2He → 209 85At + 4 1 0	60 MeV^[113]

Astatine was first produced by bombarding bismuth-209 with energetic alpha particles, and this is still the major route used to create the relatively long-lived isotopes astatine-209 through astatine-211. Astatine is only produced in minuscule quantities, with modern techniques allowing production runs of up to 6.6 gigabecquerels^[114] (about 86 nanograms or 2.47 × 10¹⁴ atoms). Synthesis of greater quantities of astatine using this method is constrained by the limited availability of suitable cyclotrons and the prospect of melting the target.^[114]^[115]^[n] Solvent radiolysis due to the cumulative effect of astatine decay^[117] is a related problem. With cryogenic technology, microgram quantities of astatine might be able to be generated via proton irradiation of thorium or uranium to yield radon-211, in turn decaying to astatine-211. Contamination with astatine-210 is expected to be a drawback of this method.^[118]

The most important isotope is astatine-211, the only one in commercial use. To produce the bismuth target, the metal is sputtered onto a gold, copper, or aluminium surface at 50 to 100 milligrams per square centimeter. Bismuth oxide can be used instead; this is forcibly fused with a copper plate.^[119] The target is kept under a chemically neutral nitrogen atmosphere,^[120] and is cooled with water to prevent premature astatine vaporization.^[119] In a particle accelerator, such as a cyclotron,^[121] alpha particles are collided with the bismuth. Even though only one bismuth isotope is used (bismuth-209), the reaction may occur in three possible ways, producing astatine-209, astatine-210, or astatine-211. In order to eliminate undesired nuclides, the maximum energy of the particle accelerator is set to a value (optimally 29.17 MeV)^[122] above that for the reaction producing astatine-211 (to produce the desired isotope) and below the one producing astatine-210 (to avoid producing other astatine isotopes).^[119]

Separation methods

Since astatine is the main product of the synthesis, after its formation it must only be separated from the target and any significant contaminants. Several methods are available, "but they generally follow one of two approaches—dry distillation or [wet] acid treatment of the target followed by solvent extraction." The methods summarized below are modern adaptations of older procedures, as reviewed by Kugler and Keller.^[123]^[o] Pre-1985 techniques more often addressed the elimination of co-produced toxic polonium; this requirement is now mitigated by capping the energy of the cyclotron irradiation beam.^[114]

Dry

The astatine-containing cyclotron target is heated to a temperature of around 650 °C. The astatine volatilizes and is condensed in (typically) a cold trap. Higher temperatures of up to around 850 °C may increase the yield, at the risk of bismuth contamination from concurrent volatilization. Redistilling the condensate may be required to minimize the presence of bismuth^[125] (as bismuth can interfere with astatine labeling reactions). The astatine is recovered from the trap using one or more low concentration solvents such as sodium hydroxide, methanol or chloroform. Astatine yields of up to around 80% may be achieved. Dry separation is the method most commonly used to produce a chemically useful form of astatine.^[115]^[126]

Wet

The bismuth (or sometimes bismuth trioxide) target is dissolved in, for example, concentrated nitric or perchloric acid. Astatine is extracted using an organic solvent such as butyl or isopropyl ether, or thiosemicarbazide. A separation yield of 93% using nitric acid has been reported, falling to 72% by the time purification procedures were completed (distillation of nitric acid, purging residual nitrogen oxides, and redissolving bismuth nitrate to enable liquid-liquid extraction).^[127] Wet methods involve "multiple radioactivity handling steps" and are not well suited for isolating larger quantities of astatine. They can enable the production of astatine in a specific oxidation state and may have greater applicability in experimental radiochemistry.^[114]

Uses and precautions

Several ²¹¹At-containing molecules and their experimental uses^[128]
Agent	Applications
[²¹¹At]astatine-tellurium colloids	Compartmental tumors
6-[²¹¹At]astato-2-methyl-1,4-naphtaquinol diphosphate	Adenocarcinomas
²¹¹At-labeled methylene blue	Melanomas
Meta-[²¹¹At]astatobenzyl guanidine	Neuroendocrine tumors
5-[²¹¹At]astato-2'-deoxyuridine	Various
²¹¹At-labeled biotin conjugates	Various pretargeting
²¹¹At-labeled octreotide	Somatostatin receptor
²¹¹At-labeled monoclonal antibodies and fragments	Various
²¹¹At-labeled bisphosphonates	Bone metastases

Newly formed astatine-211 is the subject of ongoing research in nuclear medicine.^[128] It must be used quickly as it decays with a half-life of 7.2 hours; this is long enough to permit multistep labeling strategies. Astatine-211 has potential for targeted alpha particle radiotherapy, since it decays either via emission of an alpha particle (to bismuth-207),^[129] or via electron capture (to an extremely short-lived nuclide, polonium-211, which undergoes further alpha decay). Polonium X-rays emitted as a result of the electron capture branch, in the range of 77–92 keV, enable the tracking of astatine in animals and patients.^[128]

The principal medicinal difference between astatine-211 and iodine-131 (a radioactive iodine isotope also used in medicine) is that iodine-131 emits high energy beta particles, and astatine does not. Beta particles have much greater penetrating power through tissues than do the much heavier alpha particles. An average alpha particle released by astatine-211 can travel up to 70 µm through surrounding tissues; an average energy beta particle emitted by iodine-131 can travel nearly 30 times as far, to about 2 mm.^[119] The short half-life and limited penetrating power of alpha radiation through tissues offers advantages in situations where the "tumor burden is low and/or malignant cell populations are located in close proximity to essential normal tissues."^[114] Significant morbidity in cell culture models of human cancers has been achieved with from one to ten astatine-211 atoms bound per cell.^[130]

Astatine … [is] miserable to make and hell to work with.^[131]

P Durbin, Human Radiation Studies: Remembering the Early Years, 1995

Several obstacles have been encountered in the development of astatine-based radiopharmaceuticals for cancer treatment. World War II delayed research for close to a decade. Results of early experiments indicated that a cancer-selective carrier would need to be developed and it was not until the 1970s that monoclonal antibodies became available for this purpose. Unlike iodine, astatine shows a tendency to dehalogenate from molecular carriers such as these, particularly at sp³ carbon sites^[p] (less so from sp² sites). Given the toxicity of astatine accumulated and retained in the body, this emphasized the need to ensure it remained attached to its host molecule. While astatine carriers that are slowly metabolized can be assessed for their efficacy, more rapidly metabolized carriers remain a significant obstacle to the evaluation of astatine in nuclear medicine. Mitigating the effects of astatine induced radiolysis of labeling chemistry and carrier molecules is another area requiring further development. A practical application for astatine as a cancer treatment would potentially be suitable for a "staggering" number of patients; production of astatine in the quantities that would be required remains an issue.^[118]^[132]^[q]

Animal studies show that astatine, similarly to iodine, although to a lesser extent, is preferentially concentrated in the thyroid gland. Unlike iodine, astatine also shows a tendency to be taken up by the lungs and spleen, possibly because of in body oxidation of At^– to At⁺.^[46] If administered in the form of a radiocolloid it tends to concentrate in the liver. Experiments in rats and monkeys suggest that astatine-211 causes much greater damage to the thyroid gland than does iodine-131, with repetitive injection of the nuclide resulting in necrosis and cell dysplasia within the gland.^[133] Early research suggested that injection of astatine into female rodents caused morphological changes in breast tissue;^[134] this conclusion remained controversial for many years. General agreement was later reached that this was likely caused by the effect of breast tissue irradiation combined with hormonal changes due to irradiation of the ovaries.^[131]

Notes

^ This half-vaporization period grows to 16 hours if it is instead put on a gold or a platinum surface; this may be caused by poorly understood interactions between astatine and these noble metals.^[20]
^ The extrapolated molar refractivity of diatomic astatine is 41.4 cm³, using the method given by Johnson^[38] (simple plot of the values for F, Cl, Br and I vs the cube of their covalent radii). This indicates astatine may be a metal in its condensed state, based on the Goldhammer-Herzfeld criterion, which predicts metallic behavior if the ratio of molar refractivity to molar volume is ≥1.^[39]
^ It is also possible that this is sorption on a cathode.^[42]
^ The algorithm used to generate the Allred-Rochow scale fails in the case of hydrogen, providing a value that is close to that of oxygen (3.5). Hydrogen is instead assigned a value of 2.2. Despite this shortcoming, the Allred-Rochow scale has achieved a relatively high degree of acceptance.^[52]
^ Iodine can act as a carrier despite it reacting with astatine in water because these reactions require iodide (I⁻), not (only) I₂.^[56]^[57]
^ An initial attempt to fluoridate astatine using chlorine trifluoride resulted in formation of a product which became stuck to the glass. Chlorine monofluoride, chlorine, and tetrafluorosilane were formed. The authors called the effect "puzzling", admitting they had expected formation of a volatile fluoride.^[76] Ten years later, the compound was predicted to be non-volatile, out of line with the other halogens but similar to radon fluoride;^[77] by this time, the latter had been shown to be ionic.^[78]
^ In other words, some other substance was undergoing beta decay (to a different end element), not polonium-218.
^ In the table, under the words "mass excess", the energy equivalents are given rather than the real mass excesses; "mass excess daughter" stands for the energy equivalent of the mass excess sum of the daughter of the isotope and the alpha particle; "alpha decay half-life" refers to the half-life if decay modes other than alpha are omitted.
^ The value for mass excess of astatine-221 is calculated rather than measured.
^ This means that, if decay modes other than alpha are omitted, then astatine-210 has an alpha decay half-life of 4,628.6 hours (128.9 days) and astatine-211 has one of only 17.2 hours (0.7 days). Therefore, astatine-211 is very much less stable toward alpha decay than the previous isotope.
^ "m1" means that this state of the isotope is the next possible one above – with an energy greater than – the ground state. "m2" and similar designations refer to further higher energy states. The number may be dropped if there is only one well-established meta state, such as astatine-216m. Other designation techniques are sometimes used.
^ Emsley^[10] states that this title has been lost to berkelium, "a few atoms of which can be produced in very-highly concentrated uranium-bearing deposits"; however, his assertion is not corroborated by any primary source.
^ A nuclide is commonly denoted by a symbol of the chemical element this nuclide belongs to, preceded by a non-spaced superscript mass number and a subscript atomic number of the nuclide located directly under the mass number. (Neutrons may be considered as nuclei with the atomic mass of 1 and the atomic charge of 0, with the symbol being n or omitted at all.) With the atomic number omitted, it is also sometimes used as a designation of an isotope of an element in isotope-related chemistry.
^ See however Nagatsu et al.^[116] who encapsulate the bismuth target in a thin aluminium foil and place it in a niobium holder capable of holding molten bismuth.
^ See also Lavrukhina and Pozdnyakov.^[124]
^ In other words, where carbon's one s atomic orbital and three p orbitals hybridize to give four new orbitals shaped as intermediates between the original s and p orbitals.
^ "Unfortunately, the conundrum confronting the … field is that commercial supply of ²¹¹At awaits the demonstration of clinical efficacy; however, the demonstration of clinical efficacy requires a reliable supply of ²¹¹At."^[114]

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^ Johnson, G. L.; Leininger, R. F.; Segrè, E. (1949). "Chemical Properties of Astatine. I". Journal of Chemical Physics. 17 (1): 1–10. Bibcode:1949JChPh..17....1J. doi:10.1063/1.1747034.
^ Dreyer, I.; Dreyer, R.; Chalkin, V. A. (1979). "Cations of Astatine in Aqueous Solutions; Production and some Characteristics". Radiochemical and Radioanalytical Letters (in German). 36 (6): 389–398.
^ ^a ^b Aten, A. H. W., Jr. (1964). "The Chemistry of Astatine". Advances in Inorganic Chemistry and Radiochemistry. 6: 207–223. doi:10.1016/S0065-2792(08)60227-7.
^ Nefedov, V. D.; Norseev, Yu. V.; Toropova, M. A.; Khalkin, V. A. (1968). "Astatine". Russian Chemical Reviews. 37 (2): 87–98. Bibcode:1968RuCRv..37...87N. doi:10.1070/RC1968v037n02ABEH001603.
^ Corson, D. R. (2003). "Astatine". Chemical & Engineering News. 81 (36).
^ ^a ^b Fry, C.; Thoennessen, M. (2013). "Discovery of the astatine, radon, francium, and radium isotopes". Atomic Data and Nuclear Data Tables. 09: 497–519. Bibcode:2013ADNDT..99..497F. doi:10.1016/j.adt.2012.05.003.
^ ^a ^b ^c ^d Lavrukhina & Pozdnyakov 1970, p. 229.
^ Rankama, K. (1956). Isotope Geology (2nd ed.). Pergamon Press. p. 403. ISBN 978-0-470-70800-2.
^ Lide, D. R., ed. (2004). CRC Handbook of Chemistry and Physics (85th ed.). CRC Press. p. 14-10. ISBN 0-8493-0485-7.
^ Lavrukhina & Pozdnyakov 1970, p. 228–229.
^ Asimov, I. (1957). Only a Trillion. Abelard-Schuman. p. 24.
^ Kolthoff, I. M.; Elving, P. J., eds. (1964). Treatise on Analytical Chemistry. Part II: Analytical Chemistry of the Elements. 4. New York: Interscience Encyclopedia. p. 487.
^ Kugler & Keller 1985, p. 4.
^ Maiti, M.; Lahiri, S. (2011). "Production cross section of At radionuclides from ⁷Li+^natPb and ⁹Be+^natTl reactions". Physical Review C. 84 (6): 07601–07604 (07601). arXiv:1109.6413. Bibcode:2011PhRvC..84f7601M. doi:10.1103/PhysRevC.84.067601. (subscription required (help)).
^ Greenwood & Earnshaw 2002, p. 796.
^ Kugler & Keller 1985, p. 5.
^ Barton, G. W.; Ghiorso, A.; Perlman, I. (1951). "Radioactivity of Astatine Isotopes". Physical Review. 82 (1): 13–19. Bibcode:1951PhRv...82...13B. doi:10.1103/PhysRev.82.13. (subscription required)
^ ^a ^b ^c ^d ^e ^f Zalutsky & Pruszynski 2011.
^ ^a ^b Larsen, R. H.; Wieland, B. W.; Zalutsky, M. R. J. (1996). "Evaluation of an Internal Cyclotron Target for the Production of ²¹¹At via the ²⁰⁹Bi (α,2n)²¹¹At reaction". Applied Radiation and Isotopes. 47 (2): 135–143. doi:10.1016/0969-8043(95)00285-5. (subscription required (help)).
^ Nagatsu, K.; Minegishi, K. H.; Fukada, M.; Suzuki, H.; Hasegawa, S.; Zhang, M. (2014). "Production of ²¹¹At by a vertical beam irradiation method". Applied Radiation and Isotopes. 94: 363–371. doi:10.1016/j.apradiso.2014.09.012.
^ Barbet, J.; Bourgeois, M.; Chatal, J. (2014). "Cyclotron-Based Radiopharmaceuticals for Nuclear Medicine Therapy". In R. P.; Baum. Therapeutic Nuclear Medicine. Springer. pp. 95–104 (99). ISBN 978-3-540-36718-5.
^ ^a ^b Wilbur, D. S. (2001). "Overcoming the Obstacles to Clinical Evaluation of ²¹¹At-Labeled Radiopharmaceuticals". The Journal of Nuclear Medicine. 42 (10): 1516–1518. PMID 11585866.
^ ^a ^b ^c ^d Lavrukhina & Pozdnyakov 1970, p. 233.
^ Gopalan, R. (2009). Inorganic Chemistry for Undergraduates. Universities Press. p. 547. ISBN 978-81-7371-660-7.
^ Stigbrand, T.; Carlsson, J.; Adams, G. P. (2008). Targeted Radionuclide Tumor Therapy: Biological Aspects. Springer. p. 150. ISBN 978-1-4020-8695-3.
^ Gyehong, G.; Chun, K.; Park, S. H.; Kim, B. (2014). "Production of α-particle emitting ²¹¹At using 45 MeV α-beam". Physics in Medicine and Biology. 59 (11): 2849–2860. Bibcode:2014PMB....59.2849K. doi:10.1088/0031-9155/59/11/2849.
^ Kugler & Keller 1985, pp. 95–106, 133–139.
^ Lavrukhina & Pozdnyakov 1970, pp. 243–253.
^ Kugler & Keller 1985, p. 97.
^ Lindegren, S.; Bäck, T.; Jensen, H. J. (2001). "Dry-distillation of Astatine-211 from Irradiated Bismuth Targets: A Time-saving Procedure with High Recovery Yields". Applied Radiation and Isotopes. 55 (2): 157–160. doi:10.1016/S0969-8043(01)00044-6. (subscription required (help)).
^ Yordanov, A. T.; Pozzi, O.; Carlin, S.; Akabani, G. J.; Wieland, B.; Zalutsky, M. R. (2005). "Wet Harvesting of No-carrier-added ²¹¹At from an Irradiated ²⁰⁹Bi Target for Radiopharmaceutical Applications". Journal of Radioanalytical and Nuclear Chemistry. 262 (3): 593–599. doi:10.1007/s10967-005-0481-7. (subscription required (help)).
^ ^a ^b ^c Vértes, Nagy & Klencsár 2003, p. 337.
^ Zalutsky, Michael; Vaidyanathan, Ganesan (1 September 2000). "Astatine-211-Labeled Radiotherapeutics An Emerging Approach to Targeted Alpha-Particle Radiotherapy". Current Pharmaceutical Design. 6 (14): 1433–1455. doi:10.2174/1381612003399275.
^ Vértes, Nagy & Klencsár 2003, p. 338.
^ ^a ^b Fisher, D. (1995). "Oral History of Dr. Patricia Wallace Durbin, Ph.D.". Human Radiation Studies: Remembering the Early Years. United States Department of Energy, Office of Human Radiation Experiments. Retrieved 25 March 2015.
^ Vaidyanathan, G.; Zalutsky, M. R. (2008). "Astatine Radiopharmaceuticals: Prospects and Problems". Current Radiopharmaceuticals. 1 (3): 177–196. doi:10.2174/1874471010801030177. PMC 2818997. PMID 20150978.
^ Lavrukhina & Pozdnyakov 1970, pp. 232–233.
^ Odell, T. T., Jr.; Upton, A. C. (2013) [Softcover reprint of the hardcover 1st edition 1961]. "Late Effects of Internally Deposited Radioisotopes". In Schwiegk, H.; Turba, F. Radioactive Isotopes in Physiology Diagnostics and Therapy [Radioaktive Isotope in Physiologie Diagnostik Und Therapie]. Springer-Verlag. pp. 375–392 (385). ISBN 978-3-642-49477-2.

Bibliography

Corson, D. R.; MacKenzie, K. R.; Segrè, E. (1940). "Artificially Radioactive Element 85". Physical Review. 58 (8): 672–678. Bibcode:1940PhRv...58..672C. doi:10.1103/PhysRev.58.672. (subscription required)
Greenwood, N. N.; Earnshaw, A. (2002). Chemistry of the Elements (2nd ed.). Butterworth-Heinemann. ISBN 0-7506-3365-4.
Kugler, H. K.; Keller, C. (1985). 'At, Astatine', System No. 8a. Gmelin Handbook of Inorganic and Organometallic Chemistry. 8 (8th ed.). Springer-Verlag. ISBN 3-540-93516-9.
Lavrukhina, A. K.; Pozdnyakov, A. A. (1970). Analytical Chemistry of Technetium, Promethium, Astatine, and Francium. Translated by R. Kondor. Ann Arbor–Humphrey Science Publishers. ISBN 0-250-39923-7.
Vértes, A.; Nagy, S.; Klencsár, Z. (2003). Handbook of Nuclear Chemistry. 4. Springer. ISBN 978-1-4020-1316-4.
Zalutsky, M. R.; Pruszynski, M. (2011). "Astatine-211: Production and Availability". Current Radiopharmaceuticals. 4 (3): 177–185. doi:10.2174/1874471011104030177. PMC 3503149. PMID 22201707. (subscription required (help)).
Zuckerman, J. J.; Hagen, A. P. (1989). Inorganic Reactions and Methods, Volume 3, The Formation of Bonds to Halogens (Part 1). John Wiley & Sons. ISBN 978-0-471-18656-4.
Zuckerman, J. J.; Hagen, A. P. (1990). Inorganic Reactions and Methods, Volume 4, The Formation of Bonds to Halogens (Part 2). John Wiley & Sons. ISBN 978-0-471-18657-1.

External links

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Astatine at The Periodic Table of Videos (University of Nottingham)
Astatine: Halogen or Metal?

English Journal

The pre-clinical characterization of an alpha-emitting sigma-2 receptor targeted radiotherapeutic.

Makvandi M1, Lieberman BP2, LeGeyt B2, Hou C2, Mankoff DA2, Mach RH2, Pryma DA3.
Nuclear medicine and biology.Nucl Med Biol.2016 Jan;43(1):35-41. doi: 10.1016/j.nucmedbio.2015.10.001. Epub 2015 Oct 22.
RATIONALE: The sigma-2 receptor is a protein with a Heme binding region and is capable of receptor-mediated endocytosis. It is overexpressed in many cancers making it a potential vector for therapeutic drug delivery. Our objective was to introduce an alpha-emitting radionuclide, astatine-211, into a
PMID 26702785

Preparation and evaluation of an astatine-211-labeled sigma receptor ligand for alpha radionuclide therapy.

Ogawa K1, Mizuno Y2, Washiyama K2, Shiba K3, Takahashi N4, Kozaka T3, Watanabe S5, Shinohara A4, Odani A2.
Nuclear medicine and biology.Nucl Med Biol.2015 Nov;42(11):875-9. doi: 10.1016/j.nucmedbio.2015.07.001. Epub 2015 Jul 7.
INTRODUCTION: Sigma receptors are overexpressed in a variety of human tumors, making them potential targets for radionuclide receptor therapy. We have previously synthesized and evaluated (131)I-labeled (+)-2-[4-(4-iodophenyl)piperidino]cyclohexanol [(+)-[(131)I]pIV], which has a high affinity for s
PMID 26235266

Automated astatination of biomolecules--a stepping stone towards multicenter clinical trials.

Aneheim E1, Albertsson P1, Bäck T1, Jensen H2, Palm S1, Lindegren S1.
Scientific reports.Sci Rep.2015 Jul 14;5:12025. doi: 10.1038/srep12025.
To facilitate multicentre clinical studies on targeted alpha therapy, it is necessary to develop an automated, on-site procedure for conjugating rare, short-lived, alpha-emitting radionuclides to biomolecules. Astatine-211 is one of the few alpha-emitting nuclides with appropriate chemical and physi
PMID 26169786

Quantitative single-particle digital autoradiography with α-particle emitters for targeted radionuclide therapy using the iQID camera.

Miller BW1, Frost SH2, Frayo SL2, Kenoyer AL2, Santos E2, Jones JC2, Green DJ3, Hamlin DK4, Wilbur DS4, Fisher DR5, Orozco JJ2, Press OW3, Pagel JM3, Sandmaier BM3.
Medical physics.Med Phys.2015 Jul;42(7):4094-105. doi: 10.1118/1.4921997.
PURPOSE: Alpha-emitting radionuclides exhibit a potential advantage for cancer treatments because they release large amounts of ionizing energy over a few cell diameters (50-80 μm), causing localized, irreparable double-strand DNA breaks that lead to cell death. Radioimmunotherapy (RIT) approaches
PMID 26133610

Japanese Journal

α-particle therapy for synovial sarcoma in the mouse using an astatine-211-labeled antibody against frizzled homolog 10

Li Huizi Keiko,Sugyo Aya,Tsuji Atsushi B.,Morokoshi Yukie,Minegishi Katsuyuki,Nagatsu Kotaro,Kanda Hiroaki,Harada Yosuke,Nagayama Satoshi,Katagiri Toyomasa,Nakamura Yusuke,Higashi Tatsuya,Hasegawa Sumitaka
Cancer Science 109(7), 2302-2309, 2018-06-27
… We show in a mouse model that radioimmunotherapy (RIT) with an α‐particle emitting anti‐Frizzled homolog 10 (FZD10) antibody, synthesized using the α‐emitter radionuclide astatine‐211 (211At‐OTSA101), suppresses the growth of SS xenografts more efficiently than the corresponding β‐particle emitting anti‐FZD10 antibody conjugated with the β‐emitter yettrium‐90 (90Y‐OTSA101). …
NAID 120006535011

甲状腺癌に対する新しい核医学治療の将来展望

東達也
日本内分泌・甲状腺外科学会雑誌 35(3), 196-199, 2018
核医学治療の分野では近年α線放出核種Ra-223が前立腺癌領域で初めて臨床応用され，その高い治療効果（高LET，高RBE）と安全性から幅広い注目を浴びている。その他のα線放出核種としてI-131と同じハロゲン族元素であるアスタチン211（At-211）の医学利用が期待されている。現時点で臨床応用は少ないが …
NAID 130007518927

アスタチン（At）の核化学

豊嶋厚史,篠原厚
ＲＡＤＩＯＩＳＯＴＯＰＥＳ 67(10), 461-469, 2018
近年，アスタチン-211（211At）を用いたα線内用療法に関する核医学的研究が世界各地で盛んに行われている。本稿では，211Atの製造法や分離精製法など，核医学研究を行うために必要な核・放射化学的な研究手法について説明する。また，最近活発になってきたアスタチンの化学研究について簡単に紹介 …
NAID 130007498107

Related Pictures

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リンク元

「At」

Astatine, ₈₅At
General properties
Name, symbol	astatine, At
Pronunciation	/ˈæstətiːn/ or /ˈæstətɪn/; AS-tə-teen or AS-tə-tin
Appearance	unknown, probably metallic
Astatine in the periodic table
	polonium ← astatine → radon
Atomic number (Z)	85
Group, block	group 17 (halogens), p-block
Period	period 6
Element category	metalloid, sometimes classified as a nonmetal, or a metal
Standard atomic weight (Ar)	(210)
Electron configuration	[Xe] 4f14 5d10 6s2 6p5
per shell	2, 8, 18, 32, 18, 7
Physical properties
Phase	solid
Melting point	575 K (302 °C, 576 °F)
Boiling point	610 K (337 °C, 639 °F)
Density near r.t.	(At2) 6.35±0.15 g/cm3 (predicted)
Molar volume	(At2) 32.94 cm3/mol (predicted)
Heat of vaporization	(At2) 54.39 kJ/mol
Atomic properties
Oxidation states	−1, +1, +3, +5, +7
Electronegativity	Pauling scale: 2.2
Ionization energies	1st: 899.003 kJ/mol
Covalent radius	150 pm
Van der Waals radius	202 pm
Miscellanea
Crystal structure	face-centered cubic (fcc) ; (predicted)
Thermal conductivity	1.7 W/(m·K)
CAS Number	7440-68-8
History
Naming	after Greek astatos (αστατος), meaning "unstable"
Discovery	Dale R. Corson, Kenneth Ross MacKenzie, Emilio Segrè (1940)
Most stable isotopes of astatine
	view; talk; edit; \| references

外見
	黒色固体（推定）
一般特性
名称, 記号, 番号	アスタチン, At, 85
分類	ハロゲン
族, 周期, ブロック	17, 6, p
原子量	(210)
電子配置	[Xe] 4f14 5d10 6s2 6p5
電子殻	2, 8, 18, 32, 18, 7（画像）
物理特性
相	固体
融点	575 K, 302 °C, 576 °F
沸点	610 K, 337 °C, 639 °F
蒸発熱	40 kJ/mol
蒸気圧
原子特性
酸化数	7, 5, 3, 1, -1
電気陰性度	2.2（ポーリングの値）
イオン化エネルギー	1st: 890 ± 40 kJ/mol
共有結合半径	150 pm
ファンデルワールス半径	202 pm
その他
磁性	no data
熱伝導率	(300 K) 1.7 W/(m·K)
CAS登録番号	7440-68-8
最安定同位体
	詳細はアスタチンの同位体を参照
	表示

　　[★] アスタチン

関: astatine

[sakurai-1] 桜井弘『元素111の新知識』講談社、1998年、347頁。ISBN 4-06-257192-7。

[2] 地殻中に含まれるフランシウムは20～30gと言われており、アスタチンよりも稀な元素である可能性もある。

[21] This half-vaporization period grows to 16 hours if it is instead put on a gold or a platinum surface; this may be caused by poorly understood interactions between astatine and these noble metals.^[20]

[41] The extrapolated molar refractivity of diatomic astatine is 41.4 cm³, using the method given by Johnson^[38] (simple plot of the values for F, Cl, Br and I vs the cube of their covalent radii). This indicates astatine may be a metal in its condensed state, based on the Goldhammer-Herzfeld criterion, which predicts metallic behavior if the ratio of molar refractivity to molar volume is ≥1.^[39]

[45] It is also possible that this is sorption on a cathode.^[42]

[56] The algorithm used to generate the Allred-Rochow scale fails in the case of hydrogen, providing a value that is close to that of oxygen (3.5). Hydrogen is instead assigned a value of 2.2. Despite this shortcoming, the Allred-Rochow scale has achieved a relatively high degree of acceptance.^[52]

[62] Iodine can act as a carrier despite it reacting with astatine in water because these reactions require iodide (I⁻), not (only) I₂.^[56]^[57]

[84] An initial attempt to fluoridate astatine using chlorine trifluoride resulted in formation of a product which became stuck to the glass. Chlorine monofluoride, chlorine, and tetrafluorosilane were formed. The authors called the effect "puzzling", admitting they had expected formation of a volatile fluoride.^[76] Ten years later, the compound was predicted to be non-volatile, out of line with the other halogens but similar to radon fluoride;^[77] by this time, the latter had been shown to be ionic.^[78]

[95] In other words, some other substance was undergoing beta decay (to a different end element), not polonium-218.

[109] In the table, under the words "mass excess", the energy equivalents are given rather than the real mass excesses; "mass excess daughter" stands for the energy equivalent of the mass excess sum of the daughter of the isotope and the alpha particle; "alpha decay half-life" refers to the half-life if decay modes other than alpha are omitted.

[110] The value for mass excess of astatine-221 is calculated rather than measured.

[113] This means that, if decay modes other than alpha are omitted, then astatine-210 has an alpha decay half-life of 4,628.6 hours (128.9 days) and astatine-211 has one of only 17.2 hours (0.7 days). Therefore, astatine-211 is very much less stable toward alpha decay than the previous isotope.

[115] "m1" means that this state of the isotope is the next possible one above – with an energy greater than – the ground state. "m2" and similar designations refer to further higher energy states. The number may be dropped if there is only one well-established meta state, such as astatine-216m. Other designation techniques are sometimes used.

[116] Emsley^[10] states that this title has been lost to berkelium, "a few atoms of which can be produced in very-highly concentrated uranium-bearing deposits"; however, his assertion is not corroborated by any primary source.

[125] A nuclide is commonly denoted by a symbol of the chemical element this nuclide belongs to, preceded by a non-spaced superscript mass number and a subscript atomic number of the nuclide located directly under the mass number. (Neutrons may be considered as nuclei with the atomic mass of 1 and the atomic charge of 0, with the symbol being n or omitted at all.) With the atomic number omitted, it is also sometimes used as a designation of an isotope of an element in isotope-related chemistry.

[130] See however Nagatsu et al.^[116] who encapsulate the bismuth target in a thin aluminium foil and place it in a niobium holder capable of holding molten bismuth.

[139] See also Lavrukhina and Pozdnyakov.^[124]

[147] In other words, where carbon's one s atomic orbital and three p orbitals hybridize to give four new orbitals shaped as intermediates between the original s and p orbitals.

[149] "Unfortunately, the conundrum confronting the … field is that commercial supply of ²¹¹At awaits the demonstration of clinical efficacy; however, the demonstration of clinical efficacy requires a reliable supply of ²¹¹At."^[114]

[FOOTNOTECorsonMacKenzieSegr.C3.A81940-1] Corson, MacKenzie & Segrè 1940.

[Hermann-2] Hermann, A.; Hoffmann, R.; Ashcroft, N. W. (2013). "Condensed Astatine: Monatomic and Metallic". Physical Review Letters. 111 (11): 116404–1—116404–5. doi:10.1103/PhysRevLett.111.116404.

[B.26K-3] Bonchev, D.; Kamenska, V. (1981). "Predicting the Properties of the 113–120 Transactinide Elements". The Journal of Physical Chemistry. ACS Publications. 85 (9): 1177–86. doi:10.1021/j150609a021. Retrieved 6 May 2013.

[Glushko-4] Glushko, V. P.; Medvedev, V. A.; Bergma, G. A. (1966). Termicheskie Konstanty Veshchestv (in Russian). 1. Nakua. p. 65.

[FOOTNOTEGreenwoodEarnshaw200228-5] Greenwood & Earnshaw 2002, p. 28.

[6] Rothe, S.; Andreyev, A. N.; Antalic, S.; Borschevsky, A.; Capponi, L.; Cocolios, T. E.; De Witte, H.; Eliav, E.; et al. (2013). "Measurement of the First Ionization Potential of Astatine by Laser Ionization Spectroscopy". Nature Communications. 4: 1–6. doi:10.1038/ncomms2819. PMC 3674244. PMID 23673620.

[Audi2003-7] ^ ^a ^b ^c ^d ^e ^f ^g ^h ⁱ ^j Audi, G.; Wapstra, A.H.; Thibault, C.; Blachot, J.; Bersillon, O. (2003). "The NUBASE evaluation of nuclear and decay properties". Nuclear Physics A. 729: 3–128. Bibcode:2003NuPhA.729....3A. doi:10.1016/j.nuclphysa.2003.11.001. Archived from the original on 2015-04-02.

[FOOTNOTEGreenwoodEarnshaw2002795-8] Greenwood & Earnshaw 2002, p. 795.

[MoreAtIC-9] ^ ^a ^b ^c ^d ^e ^f Wiberg, N., ed. (2001). Holleman-Wiberg: Inorganic Chemistry. Translation of 101st German edition by M. Eagleson and W. D. Brewer, English language editor B. J. Aylett. Academic Press. p. 423. ISBN 978-0-12-352651-9.

[Emsley-10] Emsley, J. (2011). Nature's Building Blocks: An A-Z Guide to the Elements (New ed.). Oxford University Press. pp. 57–58. ISBN 978-0-19-960563-7.

[11] Kotz, J.C.; Treichel, P.M.; Townsend, J. (2011). Chemistry & Chemical Reactivity (8th ed.). Cengage Learning. p. 65. ISBN 978-0-8400-4828-8.

[Jahn2010-12] Jahn, T.P. (2010). MIPS and Their Role in the Exchange of Metalloids. 679. Springer. p. 41. ISBN 978-1-4419-6314-7.

[13] Siekierski, S.; Burgess, J. (2002). Concise Chemistry of the Elements. Horwood. pp. 65, 122. ISBN 978-1-898563-71-6.

[14] Maddock, A. G. (1956). "Astatine". Supplement to Mellor's Comprehensive Treatise on Inorganic and Theoretical Chemistry, Supplement II, Part 1, (F, Cl, Br, I, At). Longmans, Green & Co. (Ltd.). pp. 1064–1079.

[15] Garrett, A.B.; Richardson, J.B.; Kiefer, A.S. (1961). Chemistry: A First Course in Modern Chemistry. Ginn. p. 313.

[16] Seaborg, G.T. (2015). "Transuranium element". Encyclopædia Britannica. Retrieved 24 February 2015.

[17] Oon, H.L. (2007). Chemistry Expression: An Inquiry Approach. John Wiley and Sons. p. 300. ISBN 978-981-271-162-5.

[Hansen2009-18] Hansen, P.F. (2009). Jensen, O.M., ed. The Science of Construction Materials. Springer. p. B.2. ISBN 978-3-540-70897-1.

[boiling_point_chromatography-19] Otozai, K.; Takahashi, N. (1982). "Estimation Chemical Form Boiling Point Elementary Astatine by Radio Gas Chromatography". Radiochimica Acta. 31 (3–4): 201–203. doi:10.1524/ract.1982.31.34.201.

[FOOTNOTELavrukhinaPozdnyakov1970251-20] Lavrukhina & Pozdnyakov 1970, p. 251.

[22] McLaughlin, R. (1964). "Absorption Spectrum of Astatine". Journal of the Optical Society of America. 54 (8): 965–967. doi:10.1364/JOSA.54.000965.

[FOOTNOTELavrukhinaPozdnyakov1970235-23] Lavrukhina & Pozdnyakov 1970, p. 235.

[24] Donohue, J. (1982). The Structures of the Elements. Robert E. Krieger. p. 400. ISBN 978-0-89874-230-5.

[vernon-25] Vernon, R. (2013). "Which Elements are Metalloids?". Journal of Chemical Education. 90 (12): 1703–1707 (1704). Bibcode:2013JChEd..90.1703V. doi:10.1021/ed3008457. (subscription required (help)).

[26] Merinis, J.; Legoux, G.; Bouissières, G. (1972). "Etude de la formation en phase gazeuse de composés interhalogénés d'astate par thermochromatographie" [Study of the gas-phase formation of interhalogen compounds of astatine by thermochromatography]. Radiochemical and Radioanalytical Letters (in French). 11 (1): 59–64.

[27] Takahashi, N.; Otozai, K. (1986). "The Mechanism of the Reaction of Elementary Astatine with Organic Solvents". Journal of Radioanalytical and Nuclear Chemistry. 103: 1–9. doi:10.1007/BF02165358.

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