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Are there any experts in organic chemistry? Help SOS
1824, German chemist Willer hydrolyzed cyanide to oxalic acid. 1828, he accidentally heated ammonium cyanate into urea. Cyanide and ammonium cyanate are inorganic compounds, while oxalic acid and urea are organic compounds. Wheeler's experimental results gave the "vitality" theory its first impact. Since then, organic compounds such as acetic acid have been synthesized from carbon, hydrogen and other elements, and the theory of "vitality" has been gradually abandoned by people.
Due to the improvement and development of synthetic methods, more and more organic compounds are synthesized in the laboratory, and most of them are synthesized under completely different conditions from living organisms. The theory of "vitality" was gradually abandoned, but the term "organic chemistry" has been used to this day.
From the beginning of 19 century to 1858, before the concept of valence bond was put forward, organic chemistry was in its infancy. During this period, many organic compounds have been separated and some derivatives have been prepared and qualitatively described.
French chemist lavoisier found that after burning organic compounds, carbon dioxide and water will be produced. His research work laid the foundation for the quantitative analysis of organic compounds. 1830, German chemist Justus von Liebig developed the analysis method of carbon and hydrogen, 1833, French chemist Duma established the analysis method of nitrogen. The establishment of these organic quantitative analysis methods enables chemists to obtain the experimental formula of a compound.
At that time, great difficulties were encountered in solving the problem of how to arrange and combine atoms in organic compounds. At first, organic chemistry used binary theory to solve the structural problems of organic compounds. Binary theory holds that molecules of compounds can be divided into positively charged parts and negatively charged parts, which are combined by electrostatic force. According to some chemical reactions, early chemists believed that the molecules of organic compounds were composed of groups that remained unchanged in the reaction and groups that changed in the reaction according to the electrostatic force of opposite charges. But this theory itself has great contradictions.
French chemists Gé rard and Laurent established the type theory. This theory denies that organic compounds are composed of positively charged and negatively charged groups, but thinks that organic compounds are derived from some parent compounds that can be substituted, so they can be classified according to these parent compounds. Typology divides many organic compounds into different types. According to their types, we can not only explain some properties of compounds, but also predict some new compounds. However, the type theory fails to answer the structural questions of organic compounds.
Organic compounds are classified according to different types. According to their types, we can not only explain some properties of compounds, but also predict some new compounds. However, the type theory fails to answer the structural questions of organic compounds.
The period of classical organic chemistry is from the establishment of 1858 valence bond theory to the introduction of 19 16 valence bond electron theory.
1858, German chemist Kekule and British chemist Cooper put forward the concept of valence bond, and used the dash "-"to represent "bond" for the first time. They believe that the molecules of organic compounds are formed by the combination of their constituent atoms. Because in all known compounds, one hydrogen atom can only combine with the atom of another element, so hydrogen is chosen as the price unit. The valence of an element is the number of hydrogen atoms that can combine with an atom of this element. Kekule also put forward an important concept, that is, carbon atoms in molecules can be combined with each other.
In 1848, Pasteur separated two kinds of tartaric acid crystals, one is the left semi-crystal and the other is the right semi-crystal. The former can rotate plane polarized light to the left, and the latter can rotate it to the right by the same angle. A similar phenomenon has been encountered in the study of lactic acid. Therefore, in 1874, Lebel, a French chemist, and Vantoff, a Dutch chemist, respectively put forward a new concept, which satisfactorily explained this heterogeneous phenomenon.
They think that the molecule is a three-dimensional entity, the four valence bonds of carbon are symmetrical in space, pointing to the four vertices of a regular tetrahedron, and the carbon atom is located in the center of the regular tetrahedron. When carbon atoms are connected to four different atoms or groups, a pair of isomers are produced, which are the physical objects and mirror images of each other, or the chiral relationship between left and right hands. This pair of compounds is the optical isomers of each other. Lebel and Fantoff's theory is the basis of stereochemistry in organic chemistry.
The first free radical, triphenylmethyl radical, was found in 1900, which is a long-lived free radical. 1929 also confirmed the existence of unstable free radicals.
During this period, great progress has been made in the structural determination, reaction and classification of organic compounds. However, valence bond is just a concept that chemists get from practical experience, and the essence of valence bond has not been solved.
In the period of modern organic chemistry, on the basis of physicists' discovery of electrons and elucidation of atomic structure, American physical chemist Lewis and others put forward the valence bond electron theory in 19 16.
They believe that the interaction of electrons in the outer layer of atoms is the reason why atoms are bound together. If the interacting outer electrons are transferred from one atom to another, an ionic bond is formed; If two atoms use outer electrons, they form a valence bond. Through electron transfer or * * * utilization, the outer electrons of the interacting atoms all obtain the electron configuration of the inert gas. In this way, the dash "-"used to represent the valence bond in the valence bond diagram is actually a pair of electrons used by two atoms.
After 1927, Hai and London used quantum mechanics to solve the problem of molecular structure, established the valence bond theory and put forward the mathematical model of chemical bond. Later, Maliken used molecular orbital theory to deal with molecular structure, and the results obtained were basically consistent with those obtained by valence bond electron theory. Because of the simple calculation, many questions that could not be answered at that time were solved.
Research content of organic chemistry
There is no absolute boundary between organic compounds and inorganic compounds. Organic chemistry has become an independent discipline in chemistry because organic compounds do have their internal relations and characteristics.
Carbon elements in the periodic table usually achieve a stable electronic configuration by using outer electrons and atoms of other elements. This valence bond combination determines the characteristics of organic compounds. Most organic compounds are composed of carbon, hydrogen, nitrogen and oxygen, and a few also contain halogen, sulfur and phosphorus. Therefore, most organic compounds have the properties of low melting point, flammability and easy solubility in organic solvents, which are quite different from inorganic compounds.
In an organic compound molecule containing multiple carbon atoms, carbon atoms combine with each other to form the skeleton of the molecule, and atoms of other elements are connected to the skeleton. In the periodic table of elements, no other element can be firmly combined with each other in many ways like carbon. The molecular skeleton formed by carbon atoms has many forms, such as straight chain, branched chain, cyclic and so on.
In the early stage of the development of organic chemistry, the main raw materials of organic chemistry industry were animals and plants, and organic chemistry mainly studied the separation of organic compounds from animals and plants.
/kloc-from the middle of the 0/9th century to the beginning of the 20th century, the organic chemical industry gradually turned to coal tar as the main raw material. The discovery of synthetic dyes has made the dye and pharmaceutical industries flourish, and promoted the study of aromatic compounds and heterocyclic compounds. After 1930s, organic synthesis with acetylene as raw material rose. Around the 1940s, the raw materials of organic chemical industry gradually changed to oil and natural gas, and the industries of synthetic rubber, synthetic plastics and synthetic fibers developed. With the depletion of petroleum resources, organic chemical industry with coal as raw material will surely develop again. Of course, natural animals, plants and microorganisms are still important research objects.
Natural organic chemistry mainly studies the composition, synthesis, structure and properties of natural organic compounds. From the early 20th century to the 1930s, the structures of monosaccharides, amino acids, nucleotide cholic acid, cholesterol and some terpenoids, as well as the composition of peptides and protein were determined one after another. In 1930s and 1940s, the structures of some vitamins, steroid hormones and polysaccharides were determined, and the structures and synthesis of some steroid hormones and vitamins were studied. In the 1940s and 1950s, some antibiotics, such as penicillin, were discovered, and their structures were determined and synthesized. In 1950s, the total synthesis of some alkaloids such as steroids and morphine, and the synthesis of bioactive peptides such as oxytocin were completed. The chemical structure of insulin was determined, and the spiral structure of protein and the double helix structure of DNA were discovered. In 1960s, the total synthesis of insulin and oligonucleotide was completed. From 1970s to early 1980s, prostaglandins, vitamin B 12 and insect pheromones were all synthesized, and the structures of nucleic acids and maytansinone were determined and their total synthesis was completed.
Organic synthesis mainly studies the synthesis of organic compounds from simple compounds or elements through chemical reactions. Urea was synthesized by 19 in 1930s. Acetic acid was synthesized in the 1940s. Subsequently, a series of organic acids such as gluconic acid, citric acid, succinic acid and malic acid were synthesized one after another. /kloc-a variety of dyes were synthesized in the second half of the 0/9 century; In the 1940s, DDT, organophosphorus pesticides, organosulfur fungicides, herbicides and other pesticides were synthesized. At the beginning of the 20th century, 606 kinds of drugs were synthesized, and in the 1930s and 40s, 1000 kinds of sulfonamides were synthesized, some of which can be used as medicine.
Physical organic chemistry is a subject that quantitatively studies the structure, reactivity and reaction mechanism of organic compounds. It is developed on the basis of valence bond electron theory, and cites the new progress of modern physics, physical chemistry and quantum mechanics theory. From 1920s to 1930s, a new organic chemistry system was established by studying the reaction mechanism. Conformation analysis and Hammett equation in 1950s began to estimate the relationship between reactivity and structure semi-quantitatively. The conservation of molecular orbital symmetry and frontier orbital theory appeared in the 1960s.
Organic analysis is the qualitative and quantitative analysis of organic compounds. The quantitative analysis method of carbon and hydrogen was established in 1930s of 19. Quantitative analysis of nitrogen was established in 1990s. The constant analysis of various elements in organic compounds was basically completed at the end of 19; In the 1920s, a quantitative analysis method of organic trace was established. Automated analytical instruments appeared in the 1970s.
Due to the development of science and technology, organic chemistry and other disciplines have infiltrated each other, forming many branches and marginal disciplines. Such as bioorganic chemistry, physical organic chemistry, quantum organic chemistry and marine organic chemistry.
Research methods of organic chemistry
The development of research methods of organic chemistry has gone through the process from manual operation to automation and computerization, from constant to ultra-trace.
Before1940s, the product was purified by traditional distillation, crystallization and sublimation, and its structure was determined by chemical degradation and derivative preparation.
Later, various chromatographic and electrophoretic techniques, especially the application of high pressure liquid chromatography, changed the face of separation technology. The use of various spectrum and energy spectrum techniques enables organic chemists to study the internal motion of molecules and revolutionizes the means of structure determination.
With the introduction of computer, the separation and analysis methods of organic compounds have taken a big step towards automation and ultramicro-quantification. The combination of nuclear magnetic resonance spectrum and infrared spectrum with Fourier transform technology provides a new means for studying the reaction kinetics and mechanism. These instruments, together with X-ray structure analysis and electron diffraction spectrum analysis, have been able to determine the chemical structure of microgram samples. Some progress has also been made in the research of designing synthetic routes with electronic computers.
The development of organic chemistry in the future is to study the development and utilization of energy and resources first. Up to now, most of the energy and resources we use, such as coal, natural gas, oil, animals and plants and microorganisms, are chemical storage forms of solar energy. The important subject of some disciplines in the future is to use solar energy more directly and effectively.
Further study and effective utilization of photosynthesis is a common subject of plant physiology, biochemistry and organic chemistry. Organic chemistry can generate high-energy organic compounds through photochemical reactions and store them; Use its reverse reaction to release energy if necessary. Another goal of developing resources is to fix carbon dioxide under the action of organometallic compounds and produce endless resources. Organic compounds. Some preliminary results have been achieved in these aspects.
Secondly, new organic catalysts were developed to simulate the high-speed, high-efficiency and mild reaction mode of enzymes. The research in this field has already started, and there will be greater development in the future.
In the late 1960s, the research on computer-aided design of organic synthesis began. In the future, the design of organic synthesis route and the determination of organic compound structure will be more systematic and reasonable.
synthetic chemistry
Synthetic chemistry is one of the most central research and production tasks of chemistry, the main source of new intermediates, new drugs, new materials and new catalysts, the most active and creative field in chemistry and the most active direction of the whole scientific community. Now, chemists all over the world synthesize nearly one million new compounds every year.
Synthetic chemistry can be divided into inorganic synthesis and organic synthesis. Up to now, nearly 25 million substances known to mankind are mostly organic compounds (about 90% or more), of which more than 90% are artificially synthesized. Therefore, organic synthesis naturally becomes the most important content of synthetic chemistry.
1828, Woher synthesized urea (organic matter) from ammonium isocyanate, which started the prelude of organic synthesis and made organic chemistry really become one of the main branches of chemistry.
1965, China organic chemists synthesized protein molecular bovine insulin with full-functional biological activity, which broke the boundary between general organic synthesis and biopolymer synthesis for the first time.
1973, Woodward's synthetic vitamin B 12: 1948 was found in the liver; 1955 confirmed its three-dimensional molecular structure; 1973 was successfully synthesized. 100 More than one organic chemist participated in the synthesis. After 95 steps of chemical reaction, they synthesized 5 12 isomers with as many as 9 chiral carbon atoms. -this is a sign that organic synthesis has reached a high level of development, showing the superb art of human organic synthesis.
From 65438 to 0990, E.J.Corey won the Nobel Prize in Chemistry for his outstanding achievements in the theory and method of organic synthesis. Here, the high unity of theory and practice shows that organic synthetic chemistry has entered the palace of science-art from science.
Modern organic synthesis technology is based on high-tech equipment, including computer programming, biochemical synthesis, electrochemical synthesis, photochemical synthesis, catalytic synthesis and bionic synthesis.
Overview of organometallic
A brief history of organometallic chemistry
Metal organic chemistry and organometallic chemistry are different terms with the same concept. Literally translated into English is the journal of organometallic chemistry (J. Organometal. Chemistry. ), and Chinese is also used to it. Throughout the development history of organometallic chemistry, its characteristics are interesting and useful, and the interesting lies in its diversity and surprise. So some people say that the history of organometallic chemistry is a history full of unexpected discoveries.
The earliest organometallic compounds were synthesized by Danish pharmacist Zeiss in 1827 by the reaction of ethanol and chloroplatinate. It is about 40 years earlier than the periodic table of elements proposed by Russian Mendeleev in 1869, and it is similar to the father of organic synthesis W? Her urea synthesis was almost in the same period (1828) (attached: Justus von Liebig, the father of the development of organic chemistry, Justus von Liebig, the founder, Annalen of Jusius Liebig).
S-bonded metal and alkyl compounds were accidentally synthesized by frankland in 1849 (frankland was the discoverer). He designed an experiment to obtain ethyl radical: C4H 10 was mistaken for ethyl radical in the experiment; But this is an amazing discovery to obtain diethyl zinc. Therefore, people call this experiment "the most fruitful failure". Before Grignard reagent was discovered in 1900, zinc alkyl was an important alkylating reagent.
1890, Mond discovered the synthesis method of nickel carbonyl; Grignard's reagent was discovered in 1900 (19 12 won the Nobel Prize in chemistry). However, the opportunity for the rapid development of organometallic chemistry is still: 195 1 year, Pauson and Miller synthesized the famous "sandwich biscuit"-ferrocene, and at the end of 1953, Ziegler catalyst was discovered by MaxPlank Coal Research Institute in West Germany led by Ziegler. Subsequently, Natta discovered Natta catalyst, collectively known as Ziegler-Natta catalyst. Wilkie Sen, Fischer (1973), Ziegler, Natta (1963) and others won the Nobel Prize in chemistry for these studies. The beginning of 1950 is the beginning of a new era of organometallic chemistry.
1979 H.C.Brown and Wittig, the reactor of organophosphorus Wittig, who studied the hydroboration of olefins, won the Nobel Prize in chemistry. Lipscomb (1976) won the Nobel Prize in chemistry for his theoretical research on the electron-deficient bond of borane.
In 2000, Alan J. Heeger, Allen McDiarmid and Hideki Shirakawa won the Nobel Prize for synthesizing polyacetylene catalyzed by Ziegler-Natta.
Metal organic chemistry is a frontier field with Nobel halo! !
The concept of bimetallic organic compounds
Organometallic compounds are compounds in which metal and organic groups are directly bonded through metal and carbon. Therefore, when oxygen, sulfur, nitrogen and other atoms are separated by metal and carbon, no matter how similar metal compounds are to organic compounds, they cannot be called organometallic compounds.
Even though there are metal-carbon bonds, some compounds are obviously inorganic, such as metal carbides (CaC2, Mg2C3, Al4C3) (carbides) KCN) (cyanide (kcn).
However, the metal compound with carbonyl group (CO) shows the nature of organic matter, so it is included in the organometallic compound. Metal hydride belongs to organometallic compound; Organophosphine (P-C) compounds, such as PPh3, are still metalloid organic compounds.
B or Si-C compound is an organometallic compound. Compounds of As, Sb and Bi below P in the periodic table of elements are usually treated as organometallic compounds. The compounds containing metal nitrogen (M-N) have no organic properties; The newly synthesized N2 complexes, such as CoH(N2)(PPh3)3, which is called "Pearl Harbor Complex" by Americans, belong to organometallic compounds (N2 and Co are isoelectronic) and are similar to carbonyl metal compounds.
Electronegativity is also used as a definition standard. Generally, the compounds in which elements with electronegativity below 2.0 bond with C are called organometallic compounds.
bioorganic chemistry
Since the 1960s, many organic chemists feel that the long-term development direction of organic chemistry is to solve problems in biochemistry by combining life phenomena. Future organic chemists are also biochemists, and biochemists are also organic chemists. Therefore, "bioorganic chemistry" began to become a new branch of organic chemistry.
From 65438 to 0972, bioorganic chemistry magazine was published, which marked that the field of bioorganic chemistry entered an active research stage. Development of organic theory (especially reaction mechanism) and kinetic research in physical organic chemistry. The application of isotope labeling, the analysis of X-ray crystal structure and the establishment of structural determination methods such as spectrum provide excellent background and tools for the development of enzymology and bioorganic chemistry.
Pederson, Cram and Lehn have made outstanding achievements in principal-guess chemistry and supramolecular chemistry, and won the 1987 Nobel Prize in chemistry.
On October 9th, 2002/KLOC-0, the Royal Swedish Academy announced that it would award the Nobel Prize in Chemistry to American scientist john fenn, Japanese scientist Kenichi Tanaka and Swiss scientist Kurt Wüthrich, in recognition of their inventions in identifying and analyzing biological macromolecules. (1) The contribution of Finn and Tanaka is to develop a "soft desorption ionization method" for mass spectrometry analysis of biological macromolecules. (2) Wittrich's contribution is to develop a nuclear magnetic resonance technique to determine the three-dimensional structure of biological macromolecules in solution. These research achievements of the three of them are revolutionary to the research of macromolecules including protein, enabling human beings to deepen their understanding of life process through the detailed analysis of protein, and to develop new drugs in a revolutionary way, which are widely used in food control, early diagnosis of breast cancer and prostate cancer and other fields.
10 year10.8, the Scientific Committee of the Royal Swedish Academy announced that the 2003 Nobel Prize in Chemistry would be awarded to American scientists Peter Agre and roderick mackinnon in recognition of their pioneering contributions to cell membrane channels. (1) Agrell won the prize for his discovery of membrane water channels, and McKinnon's contribution mainly focused on the research on the structure and mechanism of membrane ion channels. Their findings show how salt and water enter and leave the cells that make up life. (2) The Nobel Prize in Science is usually awarded to older scientists, and the award-winning achievements have been tested for decades. But Agrell is only 54 years old, and McKinnon is only 47 years old. Their achievements are relatively new: McKinnon's discovery was five years ago; Agrell's work was completed in 1988. (3) The results of Nobel Prize in Chemistry and Prize in Physiology or Medicine show the trend of interdisciplinary research in contemporary science.
Natural organic chemistry
Natural organic chemistry is a subject that studies the chemical composition of metabolites of animals, plants, insects, marine organisms and microorganisms. It even includes the chemical study of many endogenous components in human and animals. It is an important subject to reveal the mysteries of nature at the molecular level, which is closely related to human survival, health and development. The separation, structural analysis and total synthesis of natural products are the main research directions of natural product chemistry. The discovery of each natural product embodies the sweat and painstaking efforts of chemists for years or even decades. Organic chemistry first began with the study of natural products, and transforming nature is also one of the most important goals of the development of organic chemistry. The development history of natural organic chemistry is an important part of the development history of organic chemistry. It mainly includes the following categories: 1, alkaloids 2, terpenoids 3, steroids 4, hormones and pheromones 5, marine products and others.
I. Alkaloids
Broadly speaking, all organic compounds containing nitrogen in biology can be called alkaloids. But alkaloids generally refer to nitrogen-containing organic compounds in plants (except protein, peptides, amino acids and vitamin B).
The origin of alkaloids-alkaloids are a kind of natural organic compounds with biological activity, which were first studied by scientists. The earliest record in China is/kloc-aconitine (extracted from Aconitum) used in White Ape Classic in the early 7th century. In Europe, in 1806, German scientist Sertürn-er isolated morphine from opium for the first time, which was once called a plant medicine. 18 10 Spanish doctor Gomez isolated cinchona (a mixture of quinine and cinchona) from the bark of cinchona. In 18 19, W.Weissner called alkaline compounds in plants alkaline or alkaloid.
Up to now, more than 3,500 kinds of alkaloids with clear structures have been reported, and their numbers are increasing at the rate of about 100 every year. Because most alkaloids have biological activity and complex structure, alkaloids have always attracted the interest of organic chemists and lasted for a long time. In recent years, the discovery of extremely small amounts of macrocyclic nitrogen compounds with complex structures in plants, such as maymenine, makes the separation, structural analysis and total synthesis of alkaloids still an important research field for natural product organic chemists.
Morphine (morphine) quinine (quinine)
The pure morphine was isolated from 1806, the molecular formula was determined from 1847, and the molecular structure was determined from 1925. White has mercerized needle-like crystals or crystalline powder, odorless, bitter and toxic! Soluble in water, soluble in hot ethanol and glycerol, insoluble in chloroform or ether. Its hydrochloride is commonly used. Opioid receptor agonists. It has analgesic, sedative, antitussive and intestinal peristalsis inhibiting effects, and has a strong inhibitory effect on respiratory center. Used for analgesia. It can be prepared by treating morphine extracted from opium with hydrochloric acid. It can also be synthesized artificially. It is easy to deteriorate when exposed to light, losing crystal water at about 100℃ and decomposing at about 200℃.
Quinine-one of the earliest alkaloids studied after morphine. 1792, crude products were separated in Fourcroy; 18 10 years, Spanish doctor Gomez put KOH into the alcohol solution of cinchona bark to separate out crystalline substances, which are called "cinchona"; 1828, French chemists Pelletti and Caventou separated it from the bark of cinchona. Furthermore, it is white powder with melting point172.8 C and tastes extremely bitter. Soluble in ethanol and chloroform, soluble in benzene and ether, slightly soluble in water. Used to treat and prevent all kinds of malaria (the protagonist of the Long March TV series has a dialogue about quinine). It also excites uterus, inhibits myocardium, and has antipyretic and analgesic effects. Main alkaloids in bark of cinchona. The dried and ground cinchona bark can be treated with lime and sodium hydroxide solution, then repeatedly extracted with petroleum ether, and sulfuric acid is added to the extract to separate sulfate. It can also be synthesized from m-hydroxybenzaldehyde and 2- aminoacetaldehyde. The melting point of trihydrate is 57℃, and it is easy to lose water into monohydrate in air. When heated to 1 10℃, it becomes anhydrous. Crystallization from anhydrous ethanol also becomes anhydrous. Quinine sulfate is a colorless needle-like or rod-like crystal that turns brown when exposed to light. Soluble in hot ethanol, soluble in boiling water, slightly soluble in ether and chloroform.
Maytansine is the first novel anticancer nitrogen-containing macrocyclic compound reported by Kupchan in 1972. It was identified by the single crystal structure of its derivatives. It is the first anti-cancer component with high efficiency and low toxicity extracted from the whole plant of Rhododendron rotundifolia, and the yield is 2? 10-8) (only 200mg can be isolated per ton of plants). The structure has eight chiral centers and a 19 yuan lactam ring. 1980e.j.coery (1990 Nobel Prize winner in chemistry) completed the total synthesis for the first time, which is also a classic example of total synthesis (j.am.chem.soc.,1980,102,66/.
Development Frontiers and Research Hotspots of Organic Chemistry
In the 20th century, organic chemistry has made great progress from experimental methods to basic theories, showing the strong momentum and vitality of vigorous development. About 70% of the nearly one million new compounds synthesized every year in the world are organic compounds. Some of them are used in materials, energy, medicine, life science, agriculture, nutrition, petrochemical industry, transportation, environmental science and other industries closely related to human life, which directly or indirectly provide a large number of daily necessities for human beings. At the same time, people are also facing the impact of a large number of natural and synthetic organic matter on ecology, environment and human body. Looking forward to the future, organic chemistry will enable mankind to optimize the use of organic matter and organic reaction process, and organic chemistry will develop more rapidly.
The rapid development of organic chemistry has produced many branches, including organic synthesis, organometallic, elemental organic, natural organic, physical organic, organic catalysis, organic analysis, organic stereochemistry and so on.
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