Friedel–Crafts alkylation.

Friedel–Crafts alkylation involves the alkylation of an aromatic ring with an alkyl halide using a strong Lewis acid, such as aluminium chloride, ferric chloride, or other MX"" reagent, as catalyst. The general mechanism for tertiary alkyl halides is shown below.  For primary (and possibly secondary) alkyl halides, a carbocation-like complex with the Lewis acid, [R---(X---MX"")] is more likely to be involved, rather than a free carbocation.  This reaction suffers from the disadvantage that the product is more nucleophilic than the reactant because alkyl groups are activators for the Friedel–Crafts reaction. Consequently, overalkylation can occur. Steric hindrance can be exploited to limit the number of alkylations, as in the "t"-butylation of 1,4-dimethoxybenzene.  Furthermore, the reaction is only useful for primary alkyl halides in an intramolecular sense when a 5- or 6-membered ring is formed. For the intermolecular case, the reaction is limited to tertiary alkylating agents, some secondary alkylating agents (ones for which carbocation rearrangement is degenerate), or alkylating agents that yield stabilized carbocations (e.g., benzylic or allylic ones). In the case of primary alkyl halides, the carbocation-like complex (R---X---AlCl) will undergo a carbocation rearrangement reaction to give almost exclusively the rearranged product derived from a secondary or tertiary carbocation.  Alkylations are not limited to alkyl halides: Friedel–Crafts reactions are possible with any carbocationic intermediate such as those derived from alkenes and a protic acid, Lewis acid, enones, and epoxides. An example is the synthesis of neophyl chloride from benzene and methallyl chloride:  In one study the electrophile is a bromonium ion derived from an alkene and NBS: In this reaction samarium(III) triflate is believed to activate the NBS halogen donor in halonium ion formation.

Friedel–Crafts dealkylation.

Friedel–Crafts alkylation has been hypothesized to be reversible. In a retro-Friedel–Crafts reaction or Friedel–Crafts dealkylation, alkyl groups are removed in the presence of protons or other Lewis acid.  For example, in a multiple addition of ethyl bromide to benzene, "ortho" and "para" substitution is expected after the first monosubstitution step because an alkyl group is an activating group. However, the actual reaction product is 1,3,5-triethylbenzene with all alkyl groups as a "meta" substituent. Thermodynamic reaction control makes sure that thermodynamically favored "meta" substitution with steric hindrance minimized takes prevalence over less favorable "ortho" and "para" substitution by chemical equilibration. The ultimate reaction product is thus the result of a series of alkylations and dealkylations.

Friedel–Crafts acylation.

Friedel–Crafts acylation involves the acylation of aromatic rings. Typical acylating agents are acyl chlorides. Typical Lewis acid catalysts are acids and aluminium trichloride. However, because the product ketone forms a rather stable complex with Lewis acids such as AlCl, a stoichiometric amount or more of the "catalyst" must generally be employed, unlike the case of the Friedel–Crafts alkylation, in which the catalyst is constantly regenerated. Friedel–Crafts acylation is also possible with acid anhydrides. Reaction conditions are similar to the Friedel–Crafts alkylation. This reaction has several advantages over the alkylation reaction. Due to the electron-withdrawing effect of the carbonyl group, the ketone product is always less reactive than the original molecule, so multiple acylations do not occur. Also, there are no carbocation rearrangements, as the acylium ion is stabilized by a resonance structure in which the positive charge is on the oxygen.  The viability of the Friedel–Crafts acylation depends on the stability of the acyl chloride reagent. Formyl chloride, for example, is too unstable to be isolated. Thus, synthesis of benzaldehyde through the Friedel–Crafts pathway requires that formyl chloride be synthesized "in situ". This is accomplished by the Gattermann-Koch reaction, accomplished by treating benzene with carbon monoxide and hydrogen chloride under high pressure, catalyzed by a mixture of aluminium chloride and cuprous chloride.

Reaction mechanism.

The reaction proceeds through generation of an acylium center. The reaction is completed by deprotonation of the arenium ion by AlCl, regenerating the AlCl catalyst. However, in contrast to the truly catalytic alkylation reaction, the formed ketone is a moderate Lewis base, which forms a complex with the strong Lewis acid aluminum trichloride. The formation of this complex is typically irreversible under reaction conditions. Thus, a stochiometric quantity of AlCl is needed. The complex is destroyed upon aqueous workup to give the desired ketone. For example, the classical synthesis of deoxybenzoin calls for 1.1 equivalents of AlCl with respect to the limiting reagent, phenylacetyl chloride. In certain cases, generally when the benzene ring is activated, Friedel-Crafts acylation can also be carried out with "catalytic" amounts of a milder Lewis acid (e.g. Zn(II) salts) or a Brønsted acid catalyst using the anhydride or even the carboxylic acid itself as the acylation agent.  If desired, the resulting ketone can be subsequently reduced to the corresponding alkane substituent by either Wolff–Kishner reduction or Clemmensen reduction. The net result is the same as the Friedel–Crafts alkylation except that rearrangement is not possible.

Friedel–Crafts hydroxyalkylation.

Arenes react with certain aldehydes and ketones to form the hydroxyalkylated products, for example in the reaction of the mesityl derivative of glyoxal with benzene:  As usual, the aldehyde group is more reactive electrophile than the phenone.

Scope and variations.

This reaction is related to several classic named reactions:

Dyes.

Friedel–Crafts reactions have been used in the synthesis of several triarylmethane and xanthene dyes. Examples are the synthesis of thymolphthalein (a pH indicator) from two equivalents of thymol and phthalic anhydride:  A reaction of phthalic anhydride with resorcinol in the presence of zinc chloride gives the fluorophore fluorescein. Replacing resorcinol by N,N-diethylaminophenol in this reaction gives rhodamine B:

Haworth reactions.

The Haworth reaction is a classic method for the synthesis of 1-tetralone. In this reaction, benzene is reacted with succinic anhydride, the intermediate product is reduced and a second FC acylation takes place with addition of acid.  In a related reaction, phenanthrene is synthesized from naphthalene and succinic anhydride in a series of steps which begin with FC acylation.

Friedel–Crafts test for aromatic hydrocarbons.

Reaction of chloroform with aromatic compounds using an aluminium chloride catalyst gives triarylmethanes, which are often brightly colored, as is the case in triarylmethane dyes. This is a bench test for aromatic compounds.

The Friedel–Crafts reactions are a set of reactions developed by Charles Friedel and James Crafts in 1877 to attach substituents to an aromatic ring. Friedel–Crafts reactions are of two main types: alkylation reactions and acylation reactions. Both proceed by electrophilic aromatic substitution.


Geography.

Dunaújváros is located in the Transdanubian part of the Great Hungarian Plain (called Mezőföld), south of Budapest on the Danube, Highway 6, Motorways M6, M8 and the electrified Budapest-Pusztaszabolcs-Dunaújváros-Paks railway.

Name.

The city replaced the village of "Dunapentele" ("Pantaleon up on the Danube"), named after Saint Pantaleon. The construction of this new industrial city started in 1949 and the original village was renamed "Sztálinváros" ("Stalin City") in 1951. After the Hungarian revolution of 1956 the new government renamed the city the neutral "Dunaújváros" in 1961, which means "Danube New City" (New City on the Danube).

History.

Dunaújváros is one of the newest cities in the country. It was built in the 1950s during the industrialization of the country under Socialist rule, as a new city next to an already existing village, "Dunapentele".

Dunapentele.

Dunapentele was not built on until the 1950s. The construction started on the Danube's right side. The area has been inhabited since ancient times. When Western Hungary was a Roman province under the name "Pannonia", a military camp and a town called "Intercisa" stood in this place, at the border of the province. The Hungarians conquered the area in the early 10th century. The village of "Pentele", named after the medieval Greek saint, Pantaleon, was founded shortly after.  Between 1541 and 1688 the village was under Ottoman rule, and during the 150-year war it was completely destroyed. During the freedom fight led by Prince Ferenc II Rákóczi of Transylvania, the place was deserted again. In the 18th century the village began to prosper. In 1830 the village was given the right to hold markets days twice a week. In 1831 there was a cholera epidemic and which caused a small scale peasants revolt. In 1833 Pentele was granted town status "(oppidum)" by Ferdinand V. The citizens took part in the freedom fight in 1848–49.  After the Second World War the new, Communist government started a major industrialisation programme, in support of its rearmament efforts. In 1949 "Dunaújváros" was chosen as the site of the largest iron and steel works in the country. Originally they were to be built close to Mohács, but the Hungarian-Yugoslavian relations worsened, and this new site was chosen, farther away from the Yugoslav border. The city was designed to have 25,000 residents.  The construction of the city began on May 2, 1950 near Dunapentele. Within one year more than 1,000 housing units were built and construction on the factory complex began. The city officially took the name of Joseph Stalin on April 4, 1952; its name was "Sztálinváros" 'Stalin City' as a parallel to Stalingrad in the USSR.  The metal works were opened in 1954. The city had a population of 27,772 at this time; 85% of them lived in nice, comfortable apartments, while about 4,200 people still lived in uncomfortable barracks which originally provided "homes" for the construction workers.  In the middle of the 1950s, public transport was organized, with buses carrying 24,000 passengers each day. During the 1950s many cultural and sports facilities were built, the Endre Ságvári Primary School being the largest school in Central Europe in the 1960s. The official and obligatory architectural style and art movement of the communist system was socialist realism. Per definition the style's meaning was communist, its form was national, and its preferred mode of representation was the allegory. There are several public statues and reliefs in the town, which represent the allegoric union of workers, peasants and intellectuals, surrounded by traditional folk motifs. Thanks to the inspiration of Bauhaus the buildings and monuments of this era (1949–56), like the forge, the cinema, the theatre, the hospital and the city's schools where characterized by a structural functionalism, but the ideological function resulted in classicist decorations, like columns, tympanums and arcades, because of which the informal name of the style became ‘Stalin’s Baroque’  In 1956, the construction was hindered by an earthquake and a flood, and in October by the start of the 1956 Hungarian Revolution. During the revolution the city used its historical name "Dunapentele" again. The "Rákóczi" radio station, which was created by the revolutionaries, broadcast from Dunapentele (in fact from a bus that was constantly moving around in the city so that it couldn't be located.) Even though the citizens of Dunapentele tried to defend their city, the Soviet army occupied the city on November 7, 1956. The city came under martial law and soviet tanks were stationed throughout the city.  After the revolution the city was still the "trademark city" of socialism in Hungary, and was presented as such to foreign visitors. Among the visitors were Yuri Gagarin and the Indonesian president Sukarno. The city also provided a scenic backdrop to popular movies.  In 1960, the ten-year-old city already had 31,000 residents who celebrated its anniversary.  On November 26, 1961 the city's name was changed to "Dunaújváros" (Duna|új|város meaning "Danube-new-city"; "New City upon Danube". See also Tiszaújváros) as a consequence of Stalin's death (1953) and the Hungarian Revolution (1956).  In 1990 it became a city with county rights—as one of the then four, (now five) cities in the country that have this status but are not county capitals—in accordance with a new law that granted this status to all cities with a population over 50,000. Even though the population of Dunaújváros has been under 50,000 since 2008, it has kept its status as a city with county rights (along with Hódmezővásárhely, which is in a similar situation).  The DUNAFERR factory complex is still is an important enterprise in the Hungarian steel industry, and a major employer in the area. Today, Dunaújváros is home to many new infrastructures (Pentele Bridge, direct highway link between Budapest and Dunaújváros), the new South Korean Hankook factory, Europe's biggest tire factory of Hankook, and Hamburger Hungaria, one of the largest containerboard manufacturers in Europe. This and other projects make Dunaújváros a new Hungarian boomtown.  Thanks to its formal political and economic importance, the communist urban design, the socialist realist architecture and its unique atmosphere the town is the considerable memento of communism. Many of the half-century old buildings have received the protection of historic monuments, and the town is in the focus of growing touristic interest.

Demographics.

In 2001 Dunaújváros had 55,309 residents (92.5% Hungarian, 0.6% Romani, 0.6% German, 6.3% other). Religions: 38.9% Roman Catholic, 8.3% Calvinist, 2% Lutheran, 37.8% Atheist, 0.2% other, 12.8% no answer.

Politics.

The current mayor of Dunaújváros is Pintér Tamás (Jobbik).  The local Municipal Assembly, elected at the 2019 local government elections, is made up of 15 members (1 Mayor, 10 Individual constituencies MEPs and 4 Compensation List MEPs) divided into this political parties and alliances:

Sport.

The most popular sport is ice hockey, and the city is home to the Steel Bulls. The second most popular sport in the town is football. The town has one team playing in the top level league, the Nemzeti Bajnokság I, the Dunaújváros PASE. However the most well-known team is the defunct Dunaújváros FC which also won the 1999-2000 Nemzeti Bajnokság I season. The women's water polo team of Dunaújvárosi FVE won the 2018 edition of the LEN Trophy.

International relations.

Twin towns — sister cities.

Dunaújváros is twinned with:

Dunaújváros (; formerly known as "Dunapentele" and "Sztálinváros"; ) is an industrial city in Fejér County, Central Hungary. The city is best known for its steelworks, which is the largest in the country.


Background.

Kalniete was born in Togur, Kolpashevsky District, Tomsk Oblast, Siberia, Russia, where her family had been deported from Latvia by the Soviet secret police during the occupation of her country by the Soviet Union, for use as slave labour. Her mother Ligita Kalniete (née Dreifelde, 1926-2006) was first deported together with her mother and father in 1941, after which Ligita returned in 1948, just to be deported again in 1949. Her father Aivars Kalnietis (born 1931) was deported together with his mother in 1949 as well. She only saw her native country when she was five years old, when the family was allowed to return in 1957.  She studied art at the Latvian Academy of Art from 1977 to 1981 and worked as an art historian, publishing a book, "Latvian Textile Art", in 1989. She joined politics in 1988, during Latvia's independence movement, and was a deputy chairwoman and one of the founders of Latvian Popular Front, the main pro-independence political organization. Ms. Kalniete has graduated from the Department of Art History and Art Theory at the Art Academy of Latvia (1981), the Institute for International Studies at the University of Leeds (1992), The Graduate Institute of International Studies at the University of Geneva (1995), and has a Master of Arts from the Art Academy of Latvia (1996).  After Latvia declared independence, Kalniete worked in Latvia's Ministry of Foreign Affairs and served as Latvia's ambassador to the UN (from 1993 to 1997), France (from 1997 to 2000) and UNESCO (from 2000 to 2002).

Political career.

Kalniete became Foreign Minister of Latvia in November 2002 and served in this position until in 2004 when she was appointed the first Latvian Commissioner of the European Union in charge of Agriculture and Fisheries.  A large part of the Latvian society was shocked after she was not re-nominated as Latvia's EU Commissioner. Afterwards, Kalniete stepped aside from politics and refused the low-rank diplomatic positions she was offered.  At the beginning of 2006, Kalniete joined the New Era Party. In October 2006, she was elected to the Latvian parliament. She was the 2007 candidate of the New Era Party for the post of Latvian president, before withdrawing in favor of Aivars Endziņš on 24 May 2007.  Between 2006 and 2007, Kalniete served as member of the Amato Group, a group of high-level European politicians unofficially working on rewriting the Treaty establishing a Constitution for Europe into what became known as the Treaty of Lisbon following its rejection by French and Dutch voters.  In 2008, Kalniete announced she was leaving the New Era Party. She joined the newly founded Civic Union and became the party's leader. In the 2009 European Parliament election she was elected as a Member of the European Parliament and reelected in the 2014 European Parliament election in Latvia. She put herself forward as a potential candidate to succeed Andris Bērziņš as President of Latvia after his decision to step down in 2015.

Human rights activism.

Sandra Kalniete is involved in many human rights causes pertaining to totalitarian crimes. She is the chair of the Reconciliation of European Histories Group, an all-party group in the European Parliament aimed at coming to terms with the totalitarian past in many countries of Europe.  In 2004, she argued that "behind the Iron Curtain the Soviet regime continued to commit genocide against the peoples of Eastern Europe and, indeed, against its own people [...] the two totalitarian regimes—Nazism and Communism—were equally criminal." She elaborated on this in 2006 when she came up with death counts for the two regimes, pointing out that the Soviet Union killed around 94.5 million people.

Publications.

She is an author of three books:  "With Dancing Shoes in Siberian Snows" was published in French as "En escarpins dans les neiges de Sibérie" and was nominated for the "documentary book of the month" by the readers of "Elle" magazine. Since its publishing it has been translated into more than ten languages.

Translations.

The book "Ar balles kurpēm Sibīrijas sniegos", Riga, Latvia: Atēna, 2001 () has been translated into several languages:

Sandra Kalniete (born 22 December 1952) is a Latvian politician, author, diplomat and independence movement leader. She served as Foreign Minister of Latvia 2002–2004 and as European Commissioner for Agriculture, Rural Development and Fisheries in 2004. Since 2009, she has served as Member of the European Parliament (MEP) for the European People's Party.


Background.

In 1903, a group of Sudeten Germans living in the Bohemian crown lands of the Austro-Hungarian Monarchy created the German Workers' Party (DAP). Influenced by the ideas of pan-Germanism and anti-Slavism, they opposed the Czech National Revival movement advocated by the Young Czech Party. The history of this party is centered on the cities of Eger (German for present-day Cheb) and Aussig (Ústí nad Labem), it originated and gave the impetus for Austrian National Socialism.  At the end of World War I, the Austro-Hungarian Empire broke up into several nation states. The DAP was renamed German National Socialist Workers' Party on 5 May 1918 and after the proclamation of Czechoslovakia claimed the right of self-determination in the predominantly German-settled "Sudetenland" and "German Bohemian" territories, demanding affiliation with the newly established Republic of German-Austria. However, the new Czech-dominated government demanded the unity of the Bohemian (or now called Czech) lands, as confirmed by the 1919 Treaty of Saint-Germain-en-Laye, and considered the Pan-German party offensive and dangerous for the existence of the country. The Czechoslovakian DNSAP led by Hans Knirsch together with the conservative German National Party ("Deutsche Nationalpartei", DNP) became the main proponent of so-called "negativism", the general tendency among the Sudeten Germans not to accept the legitimacy of the Czechoslovakian state. Under Knirsch's successor Rudolf Jung, the party increasingly influenced by the rise of the Nazi Party in the German Weimar Republic. In 1933, both the DNSAP and DNP decided to dissolve in order to prevent the imminent ban by the Prague government.

SHF.

The SHF was founded on 1 October 1933. The party entered into an alliance with the Carpatho-German Party (KdP) in the same year.

Konrad Henlein.

The newly established SdP did not see itself as a successor of the DNSAP; in fact, SdP leader Konrad Henlein sharply rejected the idea. At first he advocated the "Ständestaat" concept of the Austrofascist movement according to the ideas of Othmar Spann and would have rather preferred the affiliation with the Federal State of Austria than with Nazi Germany. In his earlier speeches (until 1937), Henlein stressed his distance from German National Socialism, affirming loyalty to the Czechoslovak state and stressing approval of the idea of a cantonal system and individual freedom. He later described his contact to Nazi leaders as merely tactical. In 1935 when Karl Hermann Frank became deputy leader, the SdP gradually adopted the DNSAP tradition and became more radical.  In the parliamentary election of May 1935, the SdP with 1,249,534 (15.2%) of the votes became the strongest of all parties in Czechoslovakia. The party had won about 68% of the German votes, thus surpassing the German Social Democratic Workers Party, the German Christian Social People's Party and the Farmers' League. Meanwhile, the influence exerted by the German Nazi dictatorship became stronger and after 1935 several groups within the party were financed by Germany. In November 1937 Adolf Hitler openly declared - according to the Hossbach Memorandum - his intention to separate the Sudetenland from the Czechoslovak state. The SdP officially coordinated this policy with Nazi leaders in order to integrate the German-speaking parts of Bohemia and Moravia into the German Reich.  After the Austrian "Anschluss" Henlein first met Hitler on 28 March 1938. His policy was the so-called "Grundplanung OA" (Basic planning) of summer 1938 and later in the interior policy of the Protectorate of Bohemia and Moravia. In March 1938 the Farmers League joined the SdP, as well as many Christian Social deputies in the Czechoslovak parliament. At a convention in Carlsbad on 24 April the majority of the party advocated the demand of the Sudeten Germans as an autonomous ethnic group, the separation of a self-governing German settlement area and the freedom to decide for the "Anschluss" to Nazi Germany. At this time the SdP had about 1.35 million members.

Annexation.

In September 1938 the policy of SdP succeeded in the German annexation of Sudetenland according to the Munich Agreement (see: German occupation of Czechoslovakia). On 1 October Henlein was appointed "Reichskommissar" of the incorporated territories, which became the "Reichsgau Sudetenland". After a last convention at Aussig, the organization officially merged into the German Nazi Party at a festive ceremony in Reichenberg (Liberec) on 5 November 1938. However, as many Nazi officials like Reinhard Heydrich were suspicious of the SdP party members, they were not absorbed, but had to apply for admission to the Nazi Party. About 520,000 members were approved, among them Henlein himself who also joined the "SS". He was officially appointed "Gauleiter" in 1939, an office he held until 1945, though largely losing power to Reich Protector Heydrich.  As of October 1938 the SdP/KdP parliamentary club had 52 members from the Chamber of Deputies, and their joint Senate club had 26 members. On 30 October 1938 the parliamenary mandates of 46 deputies and 22 Senators of SdP and KdP were annulled.  The SdP branches in areas that remained in Czechoslovakia after the Sudetenland annexation formed the German People's Group in Czecho-Slovakia ("Deutsche Volksgruppe in der Tschecho-Slowakei").

The Sudeten German Party (, SdP, ) was created by Konrad Henlein under the name "Sudetendeutsche Heimatfront" ("Front of the Sudeten German Homeland") on 1 October 1933, some months after the First Czechoslovak Republic had outlawed the German National Socialist Workers' Party ("Deutsche Nationalsozialistische Arbeiterpartei", DNSAP). In April 1935, the party was renamed "Sudetendeutsche Partei" following a mandatory demand of the Czechoslovak government. The name was officially changed to Sudeten German and Carpathian German Party ("Sudetendeutsche und Karpatendeutsche Partei") in November 1935.


Common names.

Because it is widely known, "Lumbricus" goes under a variety of common names. In Britain, it is primarily called the common earthworm or lob worm (though the name is also applied to a marine polychaete). In North America, the term nightcrawler (or vitalis) is also used. In Canada, it is also called the dew worm, or "Grandaddy Earthworm". In several Germanic languages, it is called variants of "rain worm", for example in German "Gemeiner Regenwurm" ("common rain worm") or in Danish "Stor regnorm" ("large rain worm"). In the rest of the world, many references are just to the scientific name, though with occasional reference to the above names.  Although this is not the most abundant earthworm, even in its native range, it is a very conspicuous and familiar earthworm species in garden and agricultural soils of the temperate zone, and is frequently seen on the surface, unlike most other earthworms. It is also used as the example earthworm for millions of biology students around the world, even in areas where the species does not exist. However, 'earthworm' can be a source of confusion, since in most of the world, other species are more typical. For example, through much of the unirrigated temperate areas of the world, the "common earthworm" is actually "Aporrectodea" (="Allolobophora") "trapezoides", which in those areas is a similar size and dark color to "L. terrestris".

Biology.

"L. terrestris" is an anecic worm. That is, it forms temporary deep burrows and comes to the surface to feed, as opposed to burrowing through the soil for its food as most other earthworms do. An unusual habit of this species is to pull leaves into the mouth of its burrow where they partially decay before being eaten. While they generally feed on plant material, they have been observed feeding on dead insects and feces.  The natural lifespan of "L. terrestris" is unknown, though individuals have lived for six years in captivity.  In parts of Europe, notably the Atlantic fringe of northwestern Europe, it is now locally endangered due to predation by the New Zealand flatworm ("Arthurdendyus triangulatus") and the Australian flatworm ("Australoplana sanguinea"), two predatory flatworms accidentally introduced from New Zealand and Australia. These predators are very efficient earthworm eaters, being able to survive for lengthy periods with no food, so still persist even when their prey has dropped to unsustainably low populations. In some areas, this is having a seriously adverse effect on the soil structure and quality. The soil aeration and organic material mixing previously done by the earthworms has ceased in some areas.

As an invasive species in North America.

"L. terrestris" is considered invasive in the north central United States. It does not do well in tilled fields because of pesticide exposure, physical injuries from farm equipment and a lack of nutrients. It thrives in fence rows and woodlots and can lead to reductions in native herbaceous and tree regrowth.

Lumbricus terrestris is a large, reddish worm species widely distributed around the world (along with several other lumbricids). In some areas where it is an introduced species, some people consider it a serious pest for outcompeting native worms. It has an unusual habit of copulating on the surface at night, which makes it more visible than most other earthworms.


Geography.

Piz Bernina is one of the few isolated Alpine four-thousanders and the most topographically isolated mountain of Switzerland. It is the culminating point of a group of summits slightly lower than 4,000 meters (13,120 feet) mostly lying on the main watershed between Switzerland and Italy (such as Piz Scerscen, Piz Zupò, and Piz Palü). The only other summit higher than is La Spedla (the "Shoulder"), a minor prominence south of the mountain, which is also the highest point on the Italian side of the massif.  The summit itself is located on a perpendicular chain (orientated north–south) starting at La Spedla on the border and finishing at Piz Chalchagn, composed also of Piz Morteratsch and Piz Boval.  Piz Bernina separates two glacial valleys, the Tschierva Glacier on the west and the Morteratsch Glacier on the east. The waters flowing on both side of the mountain end up in the Inn River running northeast through Engadin. South of Piz Bernina the watershed separates the drainage basins of the Danube (Black Sea) and the Po River (Adriatic Sea). The summit of Piz Bernina is the culminating point of the Danube drainage basin. Politically, it is split between the municipalities of Samedan and Pontresina.

Geology.

The rocks composing Piz Bernina are mostly diorites and gabbros. The massif in general is also composed of granites, notable on Piz Corvatsch and Piz Palü. Most of the range belongs to the Austroalpine nappes, a tectonic unit whose rocks come from the Apulian plate, a small continent which broke away from Africa (Gondwana) before the Alpine orogeny. The Austroalpine nappes are common throughout all of the Eastern Alps.

Climbing history.

The first ascent was made via the east ridge in 1850 by the 28-year-old topographer Johann Wilhelm Coaz (1822-1918, from S-Chanf) and his assistants, the brothers Jon and Lorenz Ragut Tscharner. On 13 September 1850, shortly after 6 a.m., they left the Bernina Inn (at ) with their measuring instruments. They traversed the Labyrinth (on the Morteratsch Glacier) and headed to the "Fuorcla Crast'Agüzza", a col between the Crast' Agüzza and Piz Bernina. They reached the summit at around 6 p.m.  Johan Coaz wrote in his diary:  In 1866, the south ridge running from La Spedla was climbed by Francis Fox Tuckett and F. A. Y. Brown with guides Christian Almer and F. Andermatten. They started at midnight from the "Alpe Foppa" on the Italian side, and reached the summit at 11 a.m., descending to Pontresina only a few hours later.  The first attempt to climb the northern ridge, the "Biancograt", was made on 12 August 1876 by Henri Cordier and Thomas Middlemore with guides Johann Jaun and Kaspar Maurer. They successfully reached the top of the ridge, Piz Alv, but when they saw the chasm lying between them and the summit of Piz Bernina, they considered it to be beyond their powers and returned down the Biancograt. Cordier later declared the gap to be "absolutely impossible".  Exactly two years later, Paul Güssfeldt, accompanied by the guides H. Grass and J. Gross, reached the summit via the Biancograt and accomplished the first complete ascent on this route. The first winter ascent was made on 15 March 1929 by C. Colmus with guides C. and U. Grass. To win a bet worth 200 CHF, Hermann Buhl reached the summit of Piz Bernina from the Boval hut in 6 hours; he then descended the north ridge in only 15 minutes, establishing a record.

Tourism.

Piz Bernina is the highest summit of the Engadin region and lies close to the resorts of St. Moritz and Pontresina. The mountain can be seen from different viewpoints with the use of ski-lifts from Diavolezza, Piz Corvatsch or Piz Nair. The Bernina railway connects St. Moritz with the southern Val Poschiavo through the Bernina Pass.

Climbing routes and huts.

The normal route starts from the Rifugio Marco e Rosa, located at above the Fuorcla Crast'Agüzza, and follows the route taken by the first ascentionists.  The north ridge, called the "Biancograt" or "Crast Alva" (both meaning "White Ridge"), is the most well-known and attractive route to the summit, and is much more difficult than the normal route. The route starts from the Tschierva Hut () in Val Roseg, accessible from Pontresina. The Biancograt itself starts at the Fuorcla Prievlusa () and leads to Piz Bianco (). To reach the summit, the Bernina gap – which repulsed Cordier, Middlemore, Jaun and Maurer in 1876 – has to be traversed.  Other huts in the area

Piz Bernina or Pizzo Bernina () is the highest mountain in the Eastern Alps, the highest point of the Bernina Range, and the highest peak in the Rhaetian Alps. It rises 4,048.6 m (13,283 ft) and is located south of Pontresina and near the major Alpine resort of St. Moritz, in the Engadin valley with the massif partially in Italy. It is also the most easterly mountain higher than in the Alps, the highest point of the Swiss canton of Graubünden, and the fifth-most prominent peak in the Alps. The minor summit () known as La Spedla is the highest point in the Italian Lombardy region.


Morphology.

The leaves of the common sundew are arranged in a basal rosette. The narrow, hairy, long petioles support long laminae. The upper surface of the lamina is densely covered with red glandular hairs that secrete a sticky mucilage.  A typical plant has a diameter of around, with a tall inflorescence. The flowers grow on one side of a single slender, hairless stalk that emanates from the centre of the leaf rosette. White or pink in colour, the five-petalled flowers produce, light brown, slender, tapered seeds.  In the winter, "D. rotundifolia" produces a hibernaculum to survive the cold conditions. This consists of a bud of tightly curled leaves at ground level.

Carnivory.

The plant feeds on insects, which are attracted to the glistening drops of mucilage, loaded with a sugary substance, covering its leaves. It has evolved this carnivorous behaviour in response to its habitat, which is usually poor in nutrients or is so acidic that nutrient availability is severely decreased. The plant uses enzymes to dissolve the insects – which become stuck to the glandular tentacles – and extract ammonia (from proteins) and other nutrients from their bodies. The ammonia replaces the nitrogen that other plants absorb from the soil, and plants that are placed in a high-nitrogen environment rely less upon nitrogen from captured insects.  It has been assumed that insects were also attracted to the bright red color of the common sundew, but studies using artificial traps have suggested that color does not affect prey attraction.

Distribution.

In North America, the common sundew is found in all parts of Canada except the Canadian Prairies and the tundra regions, southern Alaska, the Pacific Northwest, and along the Appalachian Mountains south to Georgia and Louisiana.  It is found in much of Europe, including the British Isles, most of France, the Benelux nations, Germany, Denmark, Switzerland, Czech Republic, Poland, Belarus, the Baltic countries, Sweden and Finland, as well as northern portions of Portugal, Spain, Romania, mountain regions of Bulgaria and in Iceland and southern regions of Norway and Greenland. It is infrequent in Austria and Hungary, and some populations are scattered around the Balkans.  In Britain, this is the most common form of sundew and it can be found on Exmoor, Dartmoor, Sedgemoor, the Lake District, Shropshire, Pennines and in Scotland, among other places. It is usually found in bogs, marshes and in hollows or corries on the sides of mountains. It is the county flower of Shropshire.  In Asia, it is found across Siberia and Japan, as well as parts of Turkey, the Caucasus region, the Kamchatka Peninsula and southern parts of Korea. Populations can also be found on the island of New Guinea and Italy.

Habitat.

The common sundew thrives in wetlands such as marshes and fens. It is also found in wet stands of black spruce, "Sphagnum" bogs, silty and boggy shorelines and wet sands. It prefers open, sunny or partly sunny habitats.

Conservation.

The round-leaved sundew is classified as Least Concern in the IUCN red list. In North America, it is considered endangered in the US states of Illinois and Iowa, exploitably vulnerable in New York, and threatened in Tennessee.

Cultivation.

"D. rotundifolia" is one of the temperate species of "Drosera" cultivated by growers interested in carnivorous plants. To be grown successfully, plants of the wild species must be given a substantial period of winter dormancy during which they form hibernacula. The cultivar "D. rotundifolia" 'Charles Darwin' can be grown more successfully without a period of dormancy.

Medicinal properties.

According to D.H. Paper, "et al.", "Drosera rotundifolia" plant extracts show great efficacy as an anti-inflammatory and antispasmodic, more so than "D. madagascariensis", as a result of the flavonoids such as hyperoside, quercetin and isoquercetin, but not the naphthoquinones present in the extracts. The flavonoids are thought to affect the M muscarinic receptors in smooth muscle, causing the antispasmodic effects. Ellagic acid in "D. rotundifolia" extracts has also been shown to have antiangiogenic effects.

Drosera rotundifolia, the round-leaved sundew or common sundew, is a species of sundew, a carnivorous plant often found in bogs, marshes and fens. One of the most widespread sundew species, it has a circumboreal distribution, being found in all of northern Europe, much of Siberia, large parts of northern North America, Korea and Japan but is also found as far south as California, Mississippi and Alabama in the United States of America and on New Guinea.


History.

The sestertius was introduced c. 211 BC as a small silver coin valued at one-quarter of a denarius (and thus one hundredth of an aureus). A silver denarius was supposed to weigh about 4.5 grams, valued at ten grams, with the silver sestertius valued at two and one-half grams. In practice, the coins were usually underweight.  When the denarius was retariffed to sixteen "asses" (due to the gradual reduction in the size of bronze denominations), the sestertius was accordingly revalued to four "asses", still equal to one quarter of a denarius. It was produced sporadically, far less often than the denarius, through 44 BC. In or about 23 BC, with the coinage reform of Augustus, the sestertius was reintroduced as a large brass denomination. While the "as", now made of copper, was worth one quarter of a sestertius. Augustus tariffed the value of the sestertius as one hundredth of the gold aureus. The sestertius was produced as the largest brass denomination until the late 3rd century AD. Most were struck in the mint of Rome but from AD 64 during the reign of Nero (AD 54–68) and Vespasian (AD 69–79), the mint of Lyon ("Lugdunum"), supplemented production. Lyon sestertii can be recognised by a small globe, or legend stop, beneath the bust.  The brass sestertius typically weighs in the region of 25 to 28 grams, is around 32–34 mm in diameter and about 4 mm thick. The distinction between bronze and brass was important to the Romans. Their name for brass was "orichalcum", also spelled "aurichalcum" (echoing the word for a gold coin, aureus), meaning 'gold-copper', because of its shiny, gold-like appearance when the coins were newly struck (see, for example Pliny the Elder in his "Natural History" Book 34.4).  Orichalcum was considered, by weight, to be about double the value of copper. This is why the half-sestertius, the dupondius, was around the same size and weight as the bronze was, but was worth two asses.  Sestertii continued to be struck until the late 3rd century, although there was a marked deterioration in the quality of the metal used and the striking even though portraiture remained strong. Later emperors increasingly relied on melting down older sestertii, a process which led to the zinc component being gradually lost as it burned off in the high temperatures needed to melt copper (zinc melts at 419 °C but boils at 907 °C, copper melts at 1085 °C). The shortfall was made up with bronze and even lead. Later sestertii tend to be darker in appearance as a result and are made from more crudely prepared blanks (see the Hostilian coin on this page).  The gradual impact of inflation caused by debasement of the silver currency meant that the purchasing power of the sestertius and smaller denominations like the dupondius and as was steadily reduced. In the 1st century AD, everyday small change was dominated by the dupondius and "as", but in the 2nd century, as inflation hit, the sestertius became the dominant small change. In the 3rd century silver coinage contained less and less silver, and more and more copper or bronze. By the 260s and 270s the main unit was the double-denarius, the Antoninianus, but by then these small coins were almost all bronze. Although these coins were theoretically worth eight sestertii, the average sestertius was worth far more in plain terms of the metal it contained.  Some of the last sestertii were struck by Aurelian (270–275 AD). During the end of its issue, when sestertii were reduced in size and quality, the double sestertius was issued first by Trajan Decius (249–251 AD) and later in large quantity by the ruler of a breakaway regime in the West, named Postumus (259–268 AD), who often used worn old sestertii to overstrike his image and legends on. The double sestertius was distinguished from the sestertius by the radiate crown worn by the emperor, a device used to distinguish the dupondius from the "as" and the Antoninianus from the denarius.  Eventually, many sestertii were withdrawn by the state and by forgers, to melt down to make the debased Antoninianus, which made inflation worse. In the coinage reforms of the 4th century, the sestertius played no part and passed into history.

Unit of account.

The sestertius was also used as a standard unit of account and was represented on inscriptions with the monogram HS. Large values were recorded in terms of "sestertium milia", thousands of sestertii, with the "milia" often omitted and implied. The wealthy general and politician of the late Roman Republic, Crassus, who fought in the war to defeat Spartacus, was said by Pliny the Elder to have had "estates worth 200 million sesterces".  A loaf of bread cost roughly half a sestertius, and a sextarius (c. 0.5 L) of wine anywhere from less than half to more than one sestertius. One modius (6.67 kg) of wheat in 79 AD Pompeii cost seven sestertii, of rye three sestertii, a bucket two sestertii, a tunic fifteen sestertii, a donkey five hundred sestertii.  According to Tacitus' "Annals", book I, chapter 17.4 and 17.5, soldiers of the Rhine army who rose against Tiberius were paid ten "asses" a day, out of which they had to pay, among other things, for their own uniforms. They demanded to be paid a denarius a day, and they got it.  Records from Pompeii show a slave being sold at auction for 6,252 sestertii. A writing tablet from Londinium (Roman London), dated to c. 75–125 AD, records the sale of a Gallic slave girl called Fortunata for 600 denarii, equal to 2,400 sestertii, to a man called Vegetus. It is difficult to make any comparisons with modern coinage or prices, but for most of the 1st century AD, the ordinary legionary was paid nine hundred sestertii per annum, rising to twelve hundred under Domitian (81–96 AD), the equivalent of 3.3 sestertii per day. Half of it was deducted for living costs, leaving the soldier, if he was lucky enough to get paid, with about 1.65 sestertii per day.

Numismatic value.

Sestertii are highly valued by numismatists, since their large size gave "caelatores" (engravers) a large area in which to produce detailed portraits and reverse types. The most celebrated are those produced for Nero (54–68 AD) between the years 64 and 68 AD, created by some of the most accomplished coin engravers in history. The brutally realistic portraits of this emperor, and the elegant reverse designs, greatly impressed and influenced the artists of the Renaissance. The series issued by Hadrian (117–138 AD), recording his travels around the Roman Empire, depicts the Empire at its height, and included the first representation on a coin of the figure of Britannia; centuries later it was revived by English king Charles II, and continues to feature on the United Kingdom coinage.  As a result of ceasing production and withdrawals from circulation in the 4th century, sestertii are less common as a whole compared to other Roman bronze coins. Fully struck examples with sharp detail often command high premiums at auction.

The sestertius (plural sestertii), or sesterce (plural sesterces), was an ancient Roman coin. During the Roman Republic it was a small, silver coin issued only on rare occasions. During the Roman Empire it was a large brass coin.


History.

Until the 11th century, the Archdeacon of the Roman Church was responsible for the administration of the property of the Church (i.e., the Diocese of Rome), but its numerous ancient privileges and rights had come to make it a frequent hindrance to independent action on the part of the Pope; as a result, when the last Archdeacon Hildebrand was elected to the papacy as Gregory VII in 1073, he suppressed the Archdeaconate and the prelate entrusted with the supervision of the Apostolic Camera ("Camera Apostolica"), i.e., the possessions of the Holy See, became known as the "Camerarius" ("Chamberlain").  Prior to the 18th century, the Camerlengo enjoyed an income of 10,000 to 12,000 scudi a year out of the Apostolic Camera. He had jurisdiction over all suits involving the Apostolic Camera, and could judge separately or in association with the Clerics of the Apostolic Camera; he was not impeded by Consistory. He has appellate jurisdiction over suits decided by the Masters of the Roads. In a narration of the 18th century, the Camerlengo is the chief officer in the Apostolic Camera, the Financial Council of the Pope. In his office are the Governor of Rome (who is Vice-Chancellor), The Treasurer, the Auditor, the President, the Advocate General, the Fiscal Procurator, the Commissary, and twelve Clerks of the Chamber (one with the special title of Prefect of the Grain Supply, another Prefect of Provisions, another Prefect of Prisons, and another Prefect of Roads). Each Clerk of the Chamber received around 8,000 scudi a year, representing 10% of the business that passes through his office.  The powers and functions of the Camerlengo were diminished considerably in the 19th century, first by the reorganisation of the papal government after the election of Pope Pius VII in 1800, then by the reorganization of the papal government after the return of Pope Pius IX from exile in 1850, and then by the loss of the Papal States in 1860 and the City of Rome in 1870. The chief beneficiary of these changes was the Cardinal Secretary of State. Since early in the 20th century, the offices of Secretary of State and Camerlengo were held concurrently by Pietro Gasparri (1916–1930), Eugenio Pacelli (1935–1939), Jean-Marie Villot (1970–1979), and by Tarcisio Bertone (2007–2013). Since then Pope Francis has appointed as Camerlengo prelates who have not been Secretary of State: Jean-Louis Tauran (2014–2018) and Kevin Joseph Farrell (2019–present).

Responsibilities.

The camerlengo is responsible for the formal determination of the death of the reigning pope; the traditional procedure – abandoned centuries ago – was to call his baptismal name (e.g. "Albine, dormisne?", meaning "[name], are you sleeping?"). After the pope is declared dead, the camerlengo takes possession of the Ring of the Fisherman and cuts it with shears in the presence of the cardinals. This act symbolizes the end of the late Pope's authority and prevents its use in forging documents. The camerlengo then notifies the appropriate officers of the Roman Curia and the dean of the College of Cardinals. He participates in the preparations for the conclave and the pope's funeral.  In the past the camerlengo took possession of the pope's last will and took responsibility for revealing its contents. Now the last will of the pope is given to the College of Cardinals and its content is revealed during the first meeting of the College of Cardinals. The only responsibility still in the camerlengo's hands is to safekeep the last will of the pope until the College of Cardinals takes possession of it.  Until a successor Pope can be elected, the camerlengo serves as Vatican City's acting sovereign. He is no longer, however, responsible for the government of the Catholic Church when the papacy is vacant; that task was placed in the hands of the College of Cardinals by "Universi Dominici gregis" (1996). His power is extremely limited, being merely enough to allow Church institutions to continue to operate and perform some basic functions without making any definitive decisions or appointments that are normally reserved to other powers delegated by the pope. Unlike the rest of the Roman Curia, the camerlengo retains his office during the "sede vacante" period and functions as the executive director of the Vatican's operations, answerable to the College of Cardinals. This is primarily to carry out the College's decisions with regard to the funeral of the late pope and the events leading up to the conclave. The only other people who keep their offices during this time are the Major Penitentiary, the Archpriest of St. Peter's Basilica, the Papal Almoner, and the Vicars General for Rome and for the Vatican City State.

List of Camerlengos.

Those who have held the office of Camerlengo are:  Two Camerlengos have been elected Pope: Gioacchino Pecci (Pope Leo XIII) in 1878 and Eugenio Pacelli (Pope Pius XII) in 1939. Two others, Cencio Savelli (elected Pope Honorius III in 1216) and Rinaldo Conti di Segni (elected Pope Alexander IV in 1254) were not Camerlengo at the time of their election to the papacy, Cencio having served from 1188 until 1198 and Rinaldo from 1227 until 1231.

The Camerlengo of the Holy Roman Church is an office of the papal household that administers the property and revenues of the Holy See. Formerly, his responsibilities included the fiscal administration of the Patrimony of Saint Peter. As regulated in the apostolic constitution "Pastor bonus" of 1988, the camerlengo is always a cardinal, though this was not the case prior to the 15th century. His heraldic arms are ornamented with two keysone gold, one silverin saltire, surmounted by an ombrellino, a canopy or umbrella of alternating red and yellow stripes. These also form part of the coat of arms of the Holy See during a papal interregnum ("sede vacante"). The camerlengo has been Kevin Farrell since his appointment by Pope Francis on 14 February 2019. The vice camerlengo has been Archbishop Ilson de Jesus Montanari since 1 May 2020.


Structure, chemistry, and fluorescence.

As with most fluorescent compounds, ethidium bromide is aromatic. Its core heterocyclic moiety is generically known as a phenanthridine, an isomer of which is the fluorescent dye acridine. Absorption maxima of EtBr in aqueous solution are at 210 nm and 285 nm, which correspond to ultraviolet light. As a result of this excitation, EtBr emits orange light with wavelength 605 nm.  Ethidium bromide's intense fluorescence after binding with DNA is probably not due to rigid stabilization of the phenyl moiety, because the phenyl ring has been shown to project outside the intercalated bases. In fact, the phenyl group is found to be almost perpendicular to the plane of the ring system, as it rotates about its single bond to find a position where it will impinge upon the ring system minimally. Instead, the hydrophobic environment found between the base pairs is believed to be responsible. By moving into this hydrophobic environment and away from the solvent, the ethidium cation is forced to shed any water molecules that were associated with it. As water is a highly efficient fluorescence quencher, the removal of these water molecules allows the ethidium to fluoresce.

Applications.

Ethidium bromide is commonly used to detect nucleic acids in molecular biology laboratories. In the case of DNA this is usually double-stranded DNA from PCRs, restriction digests, etc. Single-stranded RNA can also be detected, since it usually folds back onto itself and thus provides local base pairing for the dye to intercalate. Detection typically involves a gel containing nucleic acids placed on or under an ultraviolet lamp. Since ultraviolet light is harmful to eyes and skin, gels stained with ethidium bromide are usually viewed indirectly using an enclosed camera, with the fluorescent images recorded as photographs. Where direct viewing is needed, the viewer's eyes and exposed skin should be protected. In the laboratory the intercalating properties have long been used to minimize chromosomal condensation when a culture is exposed to mitotic arresting agents during harvest. The resulting slide preparations permit a higher degree of resolution, and thus more confidence in determining structural integrity of chromosomes upon microscopic analysis.  Ethidium bromide is also used during DNA fragment separation by agarose gel electrophoresis. It is added to running buffer and binds by intercalating between DNA base pairs. When the agarose gel is illuminated using UV light, DNA bands become visible. Intercalation of EtBr can alter properties of the DNA molecule, such as charge, weight, conformation, and flexibility. Since the mobilities of DNA molecules through the agarose gel are measured relative to a molecular weight standard, the effects of EtBr can be critical to determining the sizes of molecules.  Ethidium bromide has also been used extensively to reduce mitochondrial DNA copy number in proliferating cells. The effect of EtBr on mitochondrial DNA is used in veterinary medicine to treat trypanosomiasis in cattle, as EtBr binds molecules of kinetoplastid DNA and changes their conformation to the Z-DNA form. This form inhibits replication of kinetoplastid DNA, which is lethal for trypanosomes.

Alternatives.

There are alternatives to ethidium bromide which are advertised as being less dangerous and having better performance. For example, several SYBR-based dyes are used by some researchers and there are other emerging stains such as "Novel Juice". SYBR dyes are less mutagenic than EtBr by the Ames test with liver extract. However, SYBR Green I was actually found to be more mutagenic than EtBr to the bacterial cells exposed to UV (which is used to visualize either dye). This may be the case for other "safer" dyes, but while mutagenic and toxicity details are available these have not been published in peer-reviewed journals. The MSDS for SYBR Safe reports an for rats of over 5 g/kg, which is higher than that of EtBr (1.5 g/kg). Many alternative dyes are suspended in DMSO, which has health implications of its own, including increased skin absorption of organic compounds. Despite the performance advantage of using SYBR dyes instead of EtBr for staining purposes, many researchers still prefer EtBr since it is considerably less expensive.

Health risks.

Ethidium bromide is thought to act as a mutagen because it intercalates double-stranded DNA (i.e. inserts itself between the strands), deforming the DNA. This could affect DNA biological processes, like DNA replication and transcription. Ethidium bromide has been shown to be mutagenic to bacteria via the Ames test, but only after treatment with liver homogenate, which simulates the metabolic breakdown of the molecule being tested. The lack of detected mutagenicity without liver homogenate indicates that ethidium bromide is not directly mutagenic, but that its metabolites are; however, the identity of these mutagenic metabolites are unknown. The National Toxicology Program states it is not mutagenic in rats and mice. These conclusions are supported by a subchronic carcinogenicity study in mice, whereby no mutagenic effects were detected. Ethidium bromide (Homidium brand) use in animals to treat trypanosome infection suggests that toxicity and mutagenicity are not high. Studies have been conducted in animals to evaluate EtBr as a potential antitumorigenic chemotherapeutic agent. Its chemotherapeutic use is due to its toxicity to mitochondria. A more recent study shows that EtBr acts as a topoisomerase I poison, just like several anticancer drugs used in humans. The above studies do not support the commonly-held idea that ethidium bromide is a potent mutagen in humans, but they do indicate that it can be toxic at high concentrations. Recent science writers have reported on what is perceived to be disproportionate fear over the toxicity and mutagenicity of the compound.  Most use of ethidium bromide in the laboratory (0.25–1 μg/ml) is below the level required for toxicity, and is 3 orders of magnitude lower than the therapeutic dosages used in cattle. The level is high enough that exposure may interfere with replication of mitochondrial DNA in some human cell lines, although the implications of that are not clear. Testing in humans and longer studies in any mammalian system would be required to fully understand the potential risk ethidium bromide poses to lab workers.  Ethidium bromide can be added to YPD media and used as an inhibitor for cell growth.

Handling and disposal.

Ethidium bromide is not regulated as hazardous waste at low concentrations, but is treated as hazardous waste by many organizations. Material should be handled according to the material safety data sheet (MSDS).  The disposal of laboratory ethidium bromide remains a controversial subject. Ethidium bromide can be degraded chemically, or collected and incinerated. It is common for ethidium bromide waste below a mandated concentration to be disposed of normally (such as pouring it down a drain). A common practice is to treat ethidium bromide with sodium hypochlorite (bleach) before disposal. According to Lunn and Sansone, chemical degradation using bleach yields compounds which are mutagenic by the Ames test. Data are lacking on the mutagenic effects of degradation products. Lunn and Sansone describe more effective methods for degradation. Elsewhere, ethidium bromide removal from solutions with activated charcoal or ion exchange resin is recommended. Various commercial products are available for this use.

Ethidium bromide is an intercalating agent commonly used as a fluorescent tag (nucleic acid stain) in molecular biology laboratories for techniques such as agarose gel electrophoresis. It is commonly abbreviated as EtBr, which is also an abbreviation for bromoethane. To avoid confusion, some laboratories have used the abbreviation EthBr. When exposed to ultraviolet light, it will fluoresce with an orange colour, intensifying almost 20-fold after binding to DNA. Under the name homidium, it has been commonly used since the 1950s in veterinary medicine to treat trypanosomiasis in cattle. The high incidence of antimicrobial resistance makes this treatment impractical in some areas, where the related isometamidium chloride is used instead. Ethidium bromide may be a mutagen, although this depends on the organism exposed and the circumstances of exposure.


Geography.

The Duchy of Brabant (adjective: "Brabantian" or "Brabantine") was historically divided into four parts, each with its own capital. The four capitals were Leuven, Brussels, Antwerp and's-Hertogenbosch. Before's-Hertogenbosch was founded, Tienen was the fourth capital.  Its territory consisted essentially of the three modern-day Belgian provinces of Flemish Brabant, Walloon Brabant and Antwerp; the Brussels-Capital Region; and most of the present-day Dutch province of North Brabant. Its most important cities were Brussels, Antwerp, Leuven, Breda,'s-Hertogenbosch, Lier and Mechelen.

Brabantian lion.

The modern flag of Belgium takes its colors from Brabant's coat of arms: "Sable a lion or armed and langued gules" (a gold lion on a black field with red claws and tongue).  Probably first used by Count Lambert I of Louvain (ruled 1003–1015), the lion is documented in a 1306 town's seal of Kerpen, together with the red lion of Limburg. Up to the present, the Brabantian lion features as the primary heraldic charge on the coats of arms of both Flemish and Walloon Brabant, and of the Dutch province of North Brabant.

History.

The region's name is first recorded as the Carolingian shire "pagus Bracbatensis", located between the rivers Scheldt and Dijle, from "braec" "marshy" and "bant" "region". Upon the 843 Treaty of Verdun it was part of Lotharingia within short-lived Middle Francia, and was ceded to East Francia according to the 880 Treaty of Ribemont.  In earlier Roman times, the Nervii, a Belgic tribe, lived in the same area. They were incorporated into the Roman province of Belgica, and considered to have both Celtic and Germanic cultural links. At the end of the Roman period the region was conquered by the Germanic Franks.

Counts of Leuven.

In 959 the East Frankish king Otto I of Germany elevated Count Godfrey of Jülich to the rank of duke of Lower Lorraine. In 962 the duchy became an integral part of the Holy Roman Empire, where Godfrey's successors of the ducal Ardennes-Verdun dynasty also ruled over the "Gau" of Brabant. Here, the counts of Leuven rose to power, when about 1000 Count Lambert I the Bearded married Gerberga, the daughter of Duke Charles of Lower Lorraine, and acquired the County of Brussels. About 1024 southernmost Brabant fell to Count Reginar V of Mons ("Bergen", later Hainaut), and Imperial lands up to the Schelde river in the west came under the rule of the French Counts Baldwin V of Flanders by 1059. Upon the death of Count Palatine Herman II of Lotharingia in 1085, Emperor Henry IV assigned his fief between the Dender and Zenne rivers as the Landgraviate of Brabant to Count Henry III of Leuven and Brussels.  About one hundred years later, in 1183/1184, Emperor Frederick I Barbarossa formally established the Duchy of Brabant and created the hereditary title of duke of Brabant in favour of Henry I of Brabant, son of Count Godfrey III of Leuven. Although the original county was still quite small - and limited to the territory between the Dender and Zenne rivers, situated to the west of Brussels - from the 13th century onwards its name came to apply to the entire territory under control of the dukes.  In 1190, after the death of Godfrey III, Henry I also became Duke of Lower Lotharingia. By that time the title had lost most of its territorial authority. According to protocol, all his successors were thereafter called Dukes of Brabant and Lower Lotharingia (often called Duke of Lothier).  After the Battle of Worringen in 1288, the dukes of Brabant also acquired the Duchy of Limburg and the lands of Overmaas (trans-Meuse). In 1354 Duke John III of Brabant granted a Joyous Entry (charter of liberty) to the subjects of Brabant.

Burgundian and Habsburg Netherlands.

In 1430 the Duchies of Lower Lotharingia, Brabant and Limburg were inherited by Philip the Good of Burgundy and became part of the Burgundian Netherlands.  In 1477 the Duchy of Brabant became part of the House of Habsburg as part of the dowry of Mary of Burgundy. At that time the Duchy extended from Luttre, south of Nivelles to's Hertogenbosch, with Leuven as the capital city. The subsequent history of Brabant is part of the history of the Habsburg Seventeen Provinces.

Eighty Years War and division of Brabant.

The Eighty Years' War (1568–1648) brought the northern parts (essentially the present Dutch province of North Brabant) under military control of the northern insurgents. After the Treaty of Westphalia in 1648, the United Provinces' independence was confirmed and northern Brabant was formally ceded to the United Provinces as Staats-Brabant, a federally governed territory and part of the Dutch Republic.  The southern part remained in Spanish Habsburg hands as a part of the Southern Netherlands. It was transferred to the Austrian branch of the Habsburg monarchy in 1714. Brabant was included in the unrecognised United States of Belgium, which existed from January to December 1790 during short-lived revolt against Emperor Joseph II, until imperial troops regained the Austrian Netherlands for Leopold II who had succeeded his brother.  The area was overrun during the French Revolution in 1794, and formally annexed by France in 1795. The duchy of Brabant was dissolved and the territory was reorganised in the "départements" of Deux-Nèthes (present province of Antwerp) and Dyle (the later province of Brabant).  After the defeat of Bonaparte in 1815, the United Kingdom of the Netherlands was created at the Congress of Vienna. The three old provinces were restored as North Brabant, Antwerp and South Brabant. The latter two became part of modern Belgium when it was created in 1830, South Brabant becoming simply Brabant province.

Cities of Brabant.

Brabant had fortified walled cities and unwalled cities. The unwalled cities did not have the right to construct walls. Trade was allowed in the walled areas and usually this right resulted in a larger population and the development of major villages and later cities. The unwalled cities also had the right to hold markets, which they held on large market squares. This distinguishes them from surrounding villages that were not allowed to hold markets and did not possess market squares. Being unwalled also meant that some of these places suffered heavily in war and during the Dutch Revolt.

Quarter of Antwerp.

Unwalled cities.

Note: the city of Mechelen formed an independent state along with the Land of Heist-op-den-Berg and Gestel. Willemstad, Geertruidenberg and Klundert were part of the County of Holland.

Quarter of's-Hertogenbosch.

Source:

The Duchy of Brabant was a State of the Holy Roman Empire established in 1183. It developed from the Landgraviate of Brabant and formed the heart of the historic Low Countries, part of the Burgundian Netherlands from 1430 and of the Habsburg Netherlands from 1482, until it was partitioned after the Dutch revolt.


Emperor of Russia.

Ivan was born on 23 August 1740 at Saint Petersburg, the eldest child of Duke Anthony Ulrich of Brunswick-Lüneburg by his wife, Duchess Anna Leopoldovna of Mecklenburg-Schwerin, the only niece of the childless Empress Anna of Russia, and the only granddaughter of Tsar Ivan V. She had lived in Russia almost all her life, and her husband had also made his home in that country, in the expectation that they or their progeny would inherit the throne upon the death of the empress.  This expectation was fulfilled within two months of the birth of their first-born child. On 5 October 1740 the infant Ivan was adopted by his grandaunt (who was on her deathbed) and declared her heir apparent. The empress also declared that her longtime lover and advisor, Ernst Johann von Biron, duke of Courland, would serve as regent until Ivan came of age. Indeed, the desire to ensure that her lover would enjoy power and influence after her death was the primary reason the dying empress chose to name as her heir the infant rather than his mother.  Empress Anna died soon thereafter on 28 October 1740. The following day the infant was proclaimed emperor as Ivan VI, Autocrat of All The Russias, and Biron became regent. However, the idea of Biron wielding power was not acceptable either to Ivan's parents or to most of the nobility. During his years as Anna's lover he had made many enemies, and was tremendously unpopular at court. Within three weeks Ivan's father had engineered Biron's fall. At midnight on 8/19 November 1740 Biron was seized in his bedroom by partisans of the royal couple and banished to Siberia (he was later permitted to reside at Yaroslavl). Ivan's mother, Anna Leopoldovna, was made regent, though the vice-chancellor, Andrei Osterman, effectively ran the government during her brief regency.

Deposition and imprisonment.

Ivan's reign, and his mother's regency, lasted thirteen months, for on December 6, 1741 a coup d'état placed Elizabeth of Russia on the throne, and Ivan and his family were imprisoned in the fortress of Dünamünde (13 December 1742) after a preliminary detention at Riga, from where the new Empress had at first intended to send the unhappy family home to Brunswick. In June 1744, following the Lopukhina Affair, the Empress transferred Ivan to Kholmogory on the White Sea where, isolated from his family and seeing no one other than his jailer, he remained for the next twelve years. When news of his confinement at Kholmogory circulated more widely, young Ivan was secretly transferred to the fortress of Shlisselburg (1756) where he was still more rigorously guarded; not even the commandant of the fortress knowing the true identity of "a certain prisoner". Throughout Elizabeth's reign her predecessor's name was subjected to a damnatio memoriae procedure; all coins, documents, and publications bearing Ivan's name and titles were systematically confiscated and destroyed, and now are of an extraordinary rarity.  Upon the accession of Peter III in 1762, Ivan's situation seemed about to improve, for the new emperor visited and sympathised with his plight, but Peter himself was deposed a few weeks later. New instructions were sent to Ivan’s guardian to place manacles on his charge and even to scourge him should he become unmanageable.

Death.

On the accession of Catherine II, in the summer of 1762, still more stringent orders were sent to the officer in charge of "the nameless one"; if any attempt were made from outside to release him, the prisoner was to be put to death. Under no circumstances was he to be delivered alive into anyone's hands, without an express written order in the Empress' handwriting. By this time twenty years of solitary confinement had disturbed Ivan's mental equilibrium, though he does not seem to have been actually insane. Nevertheless, despite the mystery surrounding him, he was well aware of his imperial origin and always called himself "Gosudar" (Sovereign). Instructions had been given not to educate him, but he had been taught his letters and could read his Bible. Since his presence at Shlisselburg could not remain concealed forever, its eventual discovery was the cause of his demise.  A sub-lieutenant of the garrison, Vasily Mirovich, learned of his identity and formed a plan for freeing and proclaiming him Emperor. At midnight on 5 July 1764, Mirovich won over some of the garrison, arrested the commandant, Berednikov, and demanded the release of Ivan. His jailers, on orders of their commander, an officer surnamed Chekin, immediately murdered Ivan in compliance with the secret instructions already in their possession. Mirovich and his supporters were arrested and executed shortly thereafter. Ivan was buried quietly in the fortress, and his death secured Catherine II's position on the throne until her own son came of age.  Ivan's siblings, who were born in prison, were released into the custody of their aunt, the Danish queen dowager, Juliana Maria of Brunswick-Wolfenbüttel, on 30 June 1780 and settled at Horsens in Jutland. There they lived under house arrest for the rest of their lives under Juliana's guardianship and Catherine's expense. Although they were prisoners, they lived in relative comfort and retained a small "court" of forty to fifty people, all Danes except for the priest.

Ivan VI Antonovich of Russia (Ioann Antonovich; ; – ) was Emperor of Russia in 1740–41. He was only two months old when he was proclaimed emperor and his mother named regent. Scarcely a year later his first cousin twice-removed, Elizabeth, seized the throne in a coup. Ivan and his parents were imprisoned far from the capital and spent the rest of their lives in captivity. After more than twenty years as a prisoner, Ivan was killed by his guards when some army officers (unknown to Ivan) attempted to free him. His surviving siblings, who had been born in prison, were then released into the custody of their aunt, the Queen of Denmark, but none could live normally after a lifetime of confinement.


Life.

Eubulides was a pupil of Euclid of Megara, the founder of the Megarian school. He was a contemporary of Aristotle, against whom he wrote with great bitterness. He taught logic to Demosthenes, and he is also said to have taught Apollonius Cronus, the teacher of Diodorus Cronus, and the historian Euphantus. He may have been the author of a book about Diogenes of Sinope.

Paradoxes of Eubulides.

Eubulides is most famous for inventing the forms of seven famous paradoxes, some of which, however, are also ascribed to Diodorus Cronus:  The first paradox (the Liar) is probably the most famous, and is similar to the famous paradox of Epimenides the Cretan. The second, third and fourth paradoxes are variants of a single paradox and relate to the problem of what it means to "know" something and the identity of objects involved in an affirmation (compare the masked man fallacy). The fifth and sixth paradoxes are also a single paradox and is usually thought to relate to the vagueness of language. The final paradox attacks presumptions involved in a proposition, and is related to the syllogistic fallacy.  These paradoxes were very well known in ancient times, some are alluded to by Eubulides' contemporary Aristotle and even partially by Plato. Aulus Gellius mentions how the discussion of such paradoxes was considered (for him) after-dinner entertainment at the Saturnalia, but Seneca, on the other hand, considered them a waste of time: "Not to know them does no harm, and mastering them does no good."

Eubulides (; fl. 4th century BCE) of Miletus was a philosopher of the Megarian school, and a pupil of Euclid of Megara. He is famous for his paradoxes.


Design and development.

Built to Air Ministry specification O.27/34, it was a low-wing monoplane of all-metal (duralumin) construction, with a retractable undercarriage and enclosed cockpit. It was the Fleet Air Arm's first service monoplane and was a radical departure for a force that was primarily equipped with open-cockpit biplanes such as the Fairey Swordfish.  Performance for the fighter role was compromised by the aircraft's naval requirements for folding wings, large fuel capacity, heavy armament with large ammunition supply, rear gunner and lack of power of contemporary aircooled engines, resulting in a relatively low speed; in common with contemporary marks of Japanese and United States Navy Aircraft Carrier borne fighters along with the Royal Navy's Gloster Sea Gladiator. These naval fighters compared unfavourably with land based fighters such as the Messerschmitt Bf 109 which reached at sea level over the Skua's and the Gloster Sea Gladiator's. The armament of four fixed, forward-firing 0.303 in (7.7 mm) Browning machine guns in the wings and a single flexible, rearward-firing.303 in (7.7 mm) Vickers K machine gun was effective for the time. For the dive-bombing role, a or bomb was carried on a special swinging "trapeze" crutch under the fuselage (somewhat like that of the Junkers Ju 87), which enabled the bomb to clear the propeller arc on release. Four bombs or eight Cooper bombs could also be carried in racks under each wing. It had large Zap-type air brakes/flaps, which helped in dive bombing and landing on aircraft carriers at sea.  Two prototypes were ordered from Blackburn in 1935 and the first, serial number "K5178", first flew on 9 February 1937. Both prototypes were powered by the Bristol Mercury XII radial engine but following trials when a production order for 190 aircraft was placed, they were to have Bristol Perseus XII engines.

Operational history.

The first unit to receive the Skua was 800 Naval Air Squadron in late 1938 at Worth Down. By November the squadron had embarked on and was followed in 1939 by 801 and 803 squadrons. With the start of the Second World War, Skuas were soon in action and on 14 September three took off from Ark Royal to go to the aid of the SS "Fanad Head" which had been attacked by a U-boat. When they arrived, the "Fanad Head" was being shelled by "U-30" and all three dived to attack the submarine, which quickly dived to safety. Two of the Skuas were damaged by the blasts and had to ditch. "U-30" returned to Germany with the crews of the two ditched Skuas, who became the first naval airmen to be prisoners of war in the conflict.  Skuas were originally credited with the first confirmed kill by British aircraft during the Second World War: a Dornier Do 18 flying boat was shot down over the North Sea on 26 September 1939 by three Skuas of 803 Naval Air Squadron, flying from Ark Royal. (An earlier victory by a Fairey Battle on 20 September 1939 over Aachen, was later confirmed by French sources). On 10 April 1940, 16 Skuas of 800 and 803 NAS led by Lieutenant Commander William Lucy, flying from RNAS Hatston in the Orkney Islands, sank the in Bergen harbour during Operation Weserübung, the German invasion of Norway.  "Königsberg" was the first major warship ever sunk in war by air attack and the first major warship ever to be sunk by dive bombing. Lucy later also became a fighter ace flying the Skua. These two mostly-Skua squadrons suffered heavy losses during an attempt to bomb the German battleship Scharnhorst at Trondheim on 13 June 1940; of 15 aircraft in the raid, eight were shot down and the crews killed or taken prisoner. Among the latter were both squadron commanders, Captain R. T. Partridge (RM) and Lieutenant Commander John Casson (RN).  Although it fared reasonably well against Axis bombers over Norway and in the Mediterranean, the Skua suffered heavy losses when confronted with modern fighters, particularly the Bf 109, and they were withdrawn from front line service in 1941. Most Skuas were replaced by another two-seater, the Fairey Fulmar, which doubled the Skua's forward armament and had a speed advantage of. A number of aircraft were converted to target tugs, following withdrawal from front line service. Others were completed as target tugs from the factory and used by the RAF and Fleet Air Arm in this role (Fleet Requirements). They were also used as advanced trainers for the Fleet Air Arm. The last Skua in service was struck off charge in March 1945.  The Blackburn Roc was a very similar aircraft developed as a turret fighter, with all its armament in a dorsal turret. The Roc was expected to fly with the Skua. Rocs were attached to Skua squadrons to protect the fleet anchorage at Scapa Flow in early 1940 and briefly from and "Ark Royal" during the Norwegian Campaign. Skuas and Rocs flew fighter sweeps and bombing sorties over the English Channel during Operation Dynamo and Operation Ariel, the evacuations of Allied forces from Dunkirk and other French ports.

Surviving aircraft.

No intact Skuas survive. In April 2007 the only known nearly complete Blackburn Skua was discovered in Orkdalsfjorden in Norway at depth. Due to an engine failure, the Skua, flown by John Casson, leader of 803 Squadron, had to make an emergency water landing in the fjord. Both crew members survived and spent the next five years as prisoners of war. Despite efforts to raise the aircraft to the surface as gently as possible, the tail broke off. The engine had become detached in the ditching. The fuselage, cockpit and wings were salvaged. The Skua will be restored at Norway's aviation museum in Bodø.  In 1974, L2940 was recovered from Breidalsvatnet lake, near Grotli in Skjåk municipality in Norway. Captain R. T. Partridge (RM) shot down a Heinkel He 111 and then made an emergency landing on the ice-covered lake on 27 April 1940. Survivors from both aeroplanes independently made their way to a mountain lodge, where they encountered each another. This incident serves as the basis for the film "Into the White".

The Blackburn B-24 Skua was a carrier-based low-wing, two-seater, single-radial engine aircraft operated by the British Fleet Air Arm which combined the functions of a dive bomber and fighter. It was designed in the mid-1930s and saw service in the early part of the Second World War. It took its name from the sea bird.


Background.

The ancient Roman and Byzantine empires had well-developed associations, known as "demes", which supported the different factions (or teams) under which competitors in certain sporting events took part; this was particularly true of chariot racing. There were initially four major factional teams of chariot racing, differentiated by the colour of the uniform in which they competed; the colours were also worn by their supporters. These were the Blues, the Greens, the Reds, and the Whites, although by the Byzantine era the only teams with any influence were the Blues and Greens. Emperor Justinian I was a supporter of the Blues.  The team associations had become a focus for various social and political issues for which the general Byzantine population lacked other forms of outlet. They combined aspects of street gangs and political parties, taking positions on current issues, notably theological problems or claimants to the throne. They frequently tried to affect the policy of the emperors by shouting political demands between races. The imperial forces and guards in the city could not keep order without the cooperation of the circus factions which were in turn backed by the aristocratic families of the city; these included some families who believed they had a more rightful claim to the throne than Justinian.  In 531 some members of the Blues and Greens had been arrested for murder in connection with deaths that occurred during rioting after a recent chariot race. Relatively limited riots were not unknown at chariot races, similar to the football hooliganism that occasionally erupts after association football matches in modern times. The murderers were to be executed, and most of them were. But on January 10, 532, two of them, a Blue and a Green, escaped and were taking refuge in the sanctuary of a church surrounded by an angry mob.  Justinian was nervous: he was in the midst of negotiating with the Persians over peace in the east at the end of the Iberian War and now he faced a potential crisis in his city. Facing this, he declared that a chariot race would be held on January 13 and commuted the sentences to imprisonment. The Blues and the Greens responded by demanding that the two men be pardoned entirely.

Causes.

Justinian and two of his leading officials, John the Cappadocian and Tribonian, were extremely unpopular because of the high taxes they levied, the corruption of the latter two and John's cruelty against debtors. John and Justinian had also reduced spending on the civil service and combated the corruption of the civil service. The many nobles who had lost their power and fortune when removed from the smaller, less corrupt civil service joined the ranks of the Greens. Justinian was also reducing the power of both teams, the Greens seeing this as further imperial oppression akin to the reforms in the civil service, while the Blues felt betrayed. The Roman legal code had a popular image as the biggest distinguishing feature of the civilized Romans as compared to "barbarians" (). The law code was also religiously important as the Romans were believed to be "chosen by God", it being a symbol of justice. As such it brought legitimacy with it if an emperor successfully made significant legal reforms but if this process bogged down it showed divine anger. What had taken nine years for the Theodosian code took Justinian just thirteen months.  Just before the Nika riots of January 532, however, the pace of reforms had slowed to a crawl. At the same time Justinian was fighting an unsuccessful war against the Persians; while Byzantine victories at Dara (spring of 530) and Satala (summer of 530) had fostered his legitimacy for a short while, the defeat at Calinicum (531) and negative strategic situation damaged the emperor's reputation. On top of that the legal reforms were unpopular with the aristocracy from the start, as they made it impossible to use obscure laws and jurisprudence to avoid unfavorable verdicts, further angering the aristocracy. On top of this both Justinian and his wife Theodora were of low birth - late Roman and Byzantine society was not as class driven as the feudal-dominated society of the west. The Greens were a Monophysite group and represented the interest of the moneyed non-landowners, Justinian being neither of those. When Justinian refused to pardon the two arrested rioters there was already a deep-seated resentment among the general populace as well as among the aristocracy.

Riots.

On January 13, 532, a tense and angry populace arrived at the Hippodrome for the races. The Hippodrome was next to the palace complex, and thus Justinian could watch from the safety of his box in the palace and preside over the races. From the start, the crowd had been hurling insults at Justinian. By the end of the day, at race 22, the partisan chants had changed from "Blue" or "Green" to a unified (""Nika"", meaning "Win!" "Victory!" or "Conquer!"), and the crowds broke out and began to assault the palace. For the next five days, the palace was under siege. The fires that started during the tumult resulted in the destruction of much of the city, including the city's foremost church, the Hagia Sophia (which Justinian would later rebuild).  Some of the senators saw this as an opportunity to overthrow Justinian, as they were opposed to his new taxes and his lack of support for the nobility. The rioters, now armed and probably controlled by their allies in the Senate, also demanded that Justinian dismiss the prefect John the Cappadocian and the "quaestor" Tribonian. They then declared a new emperor, Hypatius, who was a nephew of former Emperor Anastasius I.  Justinian, in despair, considered fleeing, but his wife Theodora is said to have dissuaded him, saying, "Those who have worn the crown should never survive its loss. Never will I see the day when I am not saluted as empress." She is also credited with adding, "[W]ho is born into the light of day must sooner or later die; and how could an Emperor ever allow himself to be a fugitive." Although an escape route across the sea lay open for the emperor, Theodora insisted that she would stay in the city, quoting an ancient saying, "Royalty is a fine burial shroud," or perhaps, "[the royal color] Purple makes a fine winding sheet."  As Justinian rallied himself, he created a plan that involved Narses, a popular eunuch, as well as the generals Belisarius and Mundus. Carrying a bag of gold given to him by Justinian, the slightly built eunuch entered the Hippodrome alone and unarmed against a murderous mob that had already killed hundreds. Narses went directly to the Blues' section, where he approached the important Blues and reminded them that Emperor Justinian supported them over the Greens. He also reminded them that Hypatius, the man they crowned, was a Green. Then, he distributed the gold. The Blue leaders spoke quietly with each other and then they spoke to their followers. Then, in the middle of Hypatius' coronation, the Blues stormed out of the Hippodrome. The Greens sat, stunned. Then, Imperial troops led by Belisarius and Mundus stormed into the Hippodrome, killing any remaining rebels indiscriminately be they Blues or Greens.  About thirty thousand rioters were reportedly killed. Justinian also had Hypatius executed and exiled the senators who had supported the riot. He then rebuilt Constantinople and the Hagia Sophia and was free to establish his rule.

The Nika riots ( "Stásis toû Níka"), Nika revolt or Nika sedition took place against Emperor Justinian I in Constantinople over the course of a week in 532 CE. They were the most violent riots in the city's history, with nearly half of Constantinople being burned or destroyed and tens of thousands of people killed.


Production.

Acrolein is prepared industrially by oxidation of propene. The process uses air as the source of oxygen and requires metal oxides as heterogeneous catalysts: About 500,000 tons of acrolein are produced in this way annually in North America, Europe, and Japan. Additionally, all acrylic acid is produced via the transient formation of acrolein. The main challenge is in fact the competing overoxidation to this acid. Propane represents a promising but challenging feedstock for the synthesis of acrolein (and acrylic acid).  When glycerol (also called glycerin) is heated to 280 °C, it decomposes into acrolein: This route is attractive when glycerol is co-generated in the production of biodiesel from vegetable oils or animal fats. The dehydration of glycerol has been demonstrated but has not proven competitive with the route from petrochemicals.

Niche or laboratory methods.

The original industrial route to acrolein, developed by Degussa, involves condensation of formaldehyde and acetaldehyde: Acrolein may also be produced on lab scale by the reaction of potassium bisulfate on glycerol (glycerine).

Reactions.

Acrolein is a relatively electrophilic compound and a reactive one, hence its high toxicity. It is a good Michael acceptor, hence its useful reaction with thiols. It forms acetals readily, a prominent one being the spirocycle derived from pentaerythritol, diallylidene pentaerythritol. Acrolein participates in many Diels-Alder reactions, even with itself. Via Diels-Alder reactions, it is a precursor to some commercial fragrances, including lyral, norbornene-2-carboxaldehyde, and myrac aldehyde. The monomer 3,4-epoxycyclohexylmethyl-3’,4’-epoxycyclohexane carboxylate is also produced from acrolein via the intermediacy of tetrahydrobenzaldehyde.

Uses.

Biocide.

Acrolein is mainly used as a contact herbicide to control submersed and floating weeds, as well as algae, in irrigation canals. It is used at a level of 10 ppm in irrigation and recirculating waters. In the oil and gas industry, it is used as a biocide in drilling waters, as well as a scavenger for hydrogen sulfide and mercaptans.

Chemical precursor.

A number of useful compounds are made from acrolein, exploiting its bifunctionality. The amino acid methionine is produced by addition of methanethiol followed by the Strecker synthesis. Acrolein condenses with acetaldehyde and amines to give methylpyridines. It is also thought to be an intermediate in the Skraup synthesis of quinolines, but is rarely used as such due to its instability.  Acrolein will polymerize in the presence of oxygen and in water at concentrations above 22%. The color and texture of the polymer depends on the conditions. Over time, it will polymerize with itself to form a clear, yellow solid. In water, it will form a hard, porous plastic.  Acrolein is sometimes used as a fixative in preparation of biological specimens for electron microscopy.

Health risks.

Acrolein is toxic and is a strong irritant for the skin, eyes, and nasal passages. The main metabolic pathway for acrolein is the alkylation of glutathione. The WHO suggests a "tolerable oral acrolein intake" of 7.5 μg per day per kg of body weight. Although acrolein occurs in French fries, the levels are only a few μg per kg. In response to occupational exposures to acrolein, the US Occupational Safety and Health Administration has set a permissible exposure limit at 0.1 ppm (0.25 mg/m) at an eight-hour time-weighted average. Acrolein acts in an immunosuppressive manner and may promote regulatory cells, thereby preventing the generation of allergy on the one hand, but also increasing the risk of cancer.

Cigarette smoke.

Connections exist between acrolein gas in the smoke from tobacco cigarettes and the risk of lung cancer. In terms of the "noncarcinogenic health quotient" for components in cigarette smoke, acrolein dominates, contributing 40 times more than the next component, hydrogen cyanide. The acrolein content in cigarette smoke depends on the type of cigarette and added glycerin, making up to 220 μg acrolein per cigarette. Importantly, while the concentration of the constituents in mainstream smoke can be reduced by filters, this has no significant effect on the composition of the side-stream smoke where acrolein usually resides, and which is inhaled by passive smoking. E-cigarettes, used normally, only generate "negligible" levels of acrolein (less than 10 μg "per puff").

Chemotherapy metabolite.

Cyclophosphamide and ifosfamide treatment results in the production of acrolein. Acrolein produced during cyclophosphamide treatment collects in the urinary bladder and if untreated can cause hemorrhagic cystitis.

Analytical methods.

The "acrolein test" is for the presence of glycerin or fats. A sample is heated with potassium bisulfate, and acrolein is released if the test is positive. When a fat is heated strongly in the presence of a dehydrating agent such as potassium bisulfate (), the glycerol portion of the molecule is dehydrated to form the unsaturated aldehyde, acrolein (CH=CH–CHO), which has the odor peculiar to burnt cooking grease. More modern methods exist.  In the US, EPA methods 603 and 624.1 are designed to measure acrolein in industrial and municipal wastewater streams.

Acrolein (systematic name: propenal) is the simplest unsaturated aldehyde. It is a colourless liquid with a piercing, acrid smell. The smell of burnt fat (as when cooking oil is heated to its smoke point) is caused by glycerol in the burning fat breaking down into acrolein. It is produced industrially from propylene and mainly used as a biocide and a building block to other chemical compounds, such as the amino acid methionine.


Charles Bonaventure de Longueval, 2nd Count of Bucquoy

Career in the Spanish Army of Flanders.

Bucquoy was born in Arras on 9 January 1571, son of Maximilian de Longueval, 1st Count of Bucquoy. He began serving in Spanish forces in the Low Countries as a teenager, and was a colonel at the age of 26. He fought in the Battle of Nieuwpoort (1600), the Siege of Ostend (1601–1604) and distinguished himself as General of the Artillery in the Frisian campaigns of Ambrosio Spinola. In 1606 he married Maria Maddalena Biglia, daughter of a Milanese nobleman in the entourage of the Archduke Albert and in 1607 they had a son named Charles Albert. In 1610 he was ambassador extraordinary to France, to convey the condolences of Archdukes Albert and Isabella on the murder of Henry IV of France.  In 1613 he became a knight of the Order of the Golden Fleece. As a mark of special favour the commandery in the Order of Calatrava that he had to renounce upon entering the Golden Fleece, was transferred to his son. That year also saw his appointment as Grand Bailiff (or governor) of the County of Hainaut.

Commander of the Imperial Army.

He travelled to Bohemia to represent Archduke Albert at the Diet of Budweis in January 1614. Shortly after his election, Emperor Matthias invited Bucquoy to take charge the Imperial Army and he accepted the post in August 1614. He happened to be on leave in the Habsburg Netherlands when on 23 May 1618 the Second Defenestration of Prague triggered the Bohemian Revolt. Bucquoy returned to Vienna in August and took command of the imperial forces raised to put down the revolt. Short of soldiers, supplies and money, his first campaign came close to disaster more than once. Defeated by Count Jindřich Matyáš Thurn on 9 November in the Battle of Lomnice, he was unable to save the besieged town of Pilsen. While his army encamped in its winter quarters around Budweis, Thurn's surprise march on Vienna was only halted by the severity of winter. After receiving reinforcements provided by Archduke Albert, his campaign of 1619 did much to reverse the fortunes of the war. On 10 June he defeated Ernst von Mansfeld in the Battle of Sablat, thereby forcing the Bohemians to abandon their siege of Budweis.  He also commanded the imperial forces during the Battle of White Mountain on 8 November 1620. As a result of his successes, Emperor Ferdinand II gave him estates at Nové Hrady, Rožmberk and Libějovice. These estates remained in the family until 1945.  Bucquoy was killed during the siege of Érsekújvár (Neuhäusel) (Nové Zámky) on 10 July 1621. One of his commanders, Torquato Conti attempted to retrieve his body from the battlefield but was captured. Conti was later released and replaced Bucquoy as a commander of Imperial forces.  His funeral, with full honours, took place in the Franciscan Church, Vienna, on 31 July 1621.

Charles Bonaventure de Longueval, Count of Bucquoy (,, full name in, ) (Arras, 9 January 1571 – Nové Zámky, 10 July 1621) was a military commander who fought for the Spanish Netherlands during the Eighty Years' War and for the Holy Roman Empire during the Thirty Years' War.