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Thursday, April 29, 2021

Herbal medicine

From Wikipedia, the free encyclopedia
An antique selection of herbal medicines

Herbal medicine (also herbalism) is the study of pharmacognosy and the use of medicinal plants, which are a basis of traditional medicine. There is limited scientific evidence for the safety and efficacy of plants used in 21st century herbalism, which generally does not provide standards for purity or dosage. The scope of herbal medicine commonly includes fungal and bee products, as well as minerals, shells and certain animal parts. Herbal medicine is also called phytomedicine or phytotherapy.

Paraherbalism describes alternative and pseudoscientific practices of using unrefined plant or animal extracts as unproven medicines or health-promoting agents. Paraherbalism relies on the belief that preserving various substances from a given source with less processing is safer or more effective than manufactured products, a concept for which there is no evidence.

History

A physician preparing an elixir, from an Arabic version of Dioscorides's pharmacopoeia, 1224

Archaeological evidence indicates that the use of medicinal plants dates back to the Paleolithic age, approximately 60,000 years ago. Written evidence of herbal remedies dates back over 5,000 years to the Sumerians, who compiled lists of plants. Some ancient cultures wrote about plants and their medical uses in books called herbals. In ancient Egypt, herbs are mentioned in Egyptian medical papyri, depicted in tomb illustrations, or on rare occasions found in medical jars containing trace amounts of herbs. In ancient Egypt, the Ebers papyrus dates from about 1550 BC, and covers more than 700 compounds, mainly of plant origin. The earliest known Greek herbals came from Theophrastus of Eresos who, in the 4th century BC, wrote in Greek Historia Plantarum, from Diocles of Carystus who wrote during the 3rd century BC, and from Krateuas who wrote in the 1st century BC. Only a few fragments of these works have survived intact, but from what remains, scholars noted overlap with the Egyptian herbals. Seeds likely used for herbalism were found in archaeological sites of Bronze Age China dating from the Shang Dynasty (c. 1600–1046 BC). Over a hundred of the 224 compounds mentioned in the Huangdi Neijing, an early Chinese medical text, are herbs. Herbs were also commonly used in the traditional medicine of ancient India, where the principal treatment for diseases was diet. De Materia Medica, originally written in Greek by Pedanius Dioscorides (c. 40–90 AD) of Anazarbus, Cilicia, a physician and botanist, is one example of herbal writing used over centuries until the 1600s.

Modern herbal medicine

The World Health Organization (WHO) estimates that 80 percent of the population of some Asian and African countries presently use herbal medicine for some aspect of primary health care.

Some prescription drugs have a basis as herbal remedies, including artemisinin, aspirin, digitalis, and quinine.

Regulatory review

In 2015, the Australian Government's Department of Health published the results of a review of alternative therapies that sought to determine if any were suitable for being covered by health insurance; herbalism was one of 17 topics evaluated for which no clear evidence of effectiveness was found. Establishing guidelines to assess safety and efficacy of herbal products, the European Medicines Agency provided criteria in 2017 for evaluating and grading the quality of clinical research in preparing monographs about herbal products. In the United States, the National Center for Complementary and Integrative Health of the National Institutes of Health funds clinical trials on herbal compounds, provides fact sheets evaluating the safety, potential effectiveness and side effects of many plant sources, and maintains a registry of clinical research conducted on herbal products.

According to Cancer Research UK as of 2015, "there is currently no strong evidence from studies in people that herbal remedies can treat, prevent or cure cancer".

Prevalence of use

The use of herbal remedies is more prevalent in people with chronic diseases, such as cancer, diabetes, asthma and end-stage kidney disease. Multiple factors such as gender, age, ethnicity, education and social class are also shown to have association with prevalence of herbal remedies use.

Herbal preparations

Leaves of Eucalyptus olida being packed into a steam distillation unit to gather its essential oil

There are many forms in which herbs can be administered, the most common of which is a liquid consumed as a herbal tea or a (possibly diluted) plant extract.

Herbal teas, or tisanes, are the resultant liquid of extracting herbs into water, though they are made in a few different ways. Infusions are hot water extracts of herbs, such as chamomile or mint, through steeping. Decoctions are the long-term boiled extracts, usually of harder substances like roots or bark. Maceration is the cold infusion of plants with high mucilage-content, such as sage or thyme. To make macerates, plants are chopped and added to cold water. They are then left to stand for 7 to 12 hours (depending on herb used). For most macerates, 10 hours is used.

Tinctures are alcoholic extracts of herbs, which are generally stronger than herbal teas. Tinctures are usually obtained by combining 100% pure ethanol (or a mixture of 100% ethanol with water) with the herb. A completed tincture has an ethanol percentage of at least 25% (sometimes up to 90%). Non-alcoholic tinctures can be made with glycerin but it is believed to be less absorbed by the body than alcohol based tinctures and has a shorter shelf life. Herbal wine and elixirs are alcoholic extract of herbs, usually with an ethanol percentage of 12–38%. Extracts include liquid extracts, dry extracts, and nebulisates. Liquid extracts are liquids with a lower ethanol percentage than tinctures. They are usually made by vacuum distilling tinctures. Dry extracts are extracts of plant material that are evaporated into a dry mass. They can then be further refined to a capsule or tablet.

The exact composition of an herbal product is influenced by the method of extraction. A tea will be rich in polar components because water is a polar solvent. Oil on the other hand is a non-polar solvent and it will absorb non-polar compounds. Alcohol lies somewhere in between.

Many herbs are applied topically to the skin in a variety of forms. Essential oil extracts can be applied to the skin, usually diluted in a carrier oil. Many essential oils can burn the skin or are simply too high dose used straight; diluting them in olive oil or another food grade oil such as almond oil can allow these to be used safely as a topical. Salves, oils, balms, creams and lotions are other forms of topical delivery mechanisms. Most topical applications are oil extractions of herbs. Taking a food grade oil and soaking herbs in it for anywhere from weeks to months allows certain phytochemicals to be extracted into the oil. This oil can then be made into salves, creams, lotions, or simply used as an oil for topical application. Many massage oils, antibacterial salves, and wound healing compounds are made this way.

Inhalation, as in aromatherapy, can be used as a treatment.

Safety

Datura stramonium has been used in Ayurveda for various treatments, but contains alkaloids, such as atropine and scopolamine, which may cause severe toxicity.

Consumption of herbs may cause adverse effects. Furthermore, "adulteration, inappropriate formulation, or lack of understanding of plant and drug interactions have led to adverse reactions that are sometimes life threatening or lethal." Proper double-blind clinical trials are needed to determine the safety and efficacy of each plant before medical use.

Although many consumers believe that herbal medicines are safe because they are natural, herbal medicines and synthetic drugs may interact, causing toxicity to the consumer. Herbal remedies can also be dangerously contaminated, and herbal medicines without established efficacy, may unknowingly be used to replace prescription medicines.

Standardization of purity and dosage is not mandated in the United States, but even products made to the same specification may differ as a result of biochemical variations within a species of plant. Plants have chemical defense mechanisms against predators that can have adverse or lethal effects on humans. Examples of highly toxic herbs include poison hemlock and nightshade. They are not marketed to the public as herbs, because the risks are well known, partly due to a long and colorful history in Europe, associated with "sorcery", "magic" and intrigue. Although not frequent, adverse reactions have been reported for herbs in widespread use. On occasion serious untoward outcomes have been linked to herb consumption. A case of major potassium depletion has been attributed to chronic licorice ingestion, and consequently professional herbalists avoid the use of licorice where they recognize that this may be a risk. Black cohosh has been implicated in a case of liver failure. Few studies are available on the safety of herbs for pregnant women, and one study found that use of complementary and alternative medicines are associated with a 30% lower ongoing pregnancy and live birth rate during fertility treatment.

Examples of herbal treatments with likely cause-effect relationships with adverse events include aconite, which is often a legally restricted herb, ayurvedic remedies, broom, chaparral, Chinese herb mixtures, comfrey, herbs containing certain flavonoids, germander, guar gum, liquorice root, and pennyroyal. Examples of herbs that may have long-term adverse effects include ginseng, which is unpopular among herbalists for this reason, the endangered herb goldenseal, milk thistle, senna, against which herbalists generally advise and rarely use, aloe vera juice, buckthorn bark and berry, cascara sagrada bark, saw palmetto, valerian, kava, which is banned in the European Union, St. John's wort, khat, betel nut, the restricted herb ephedra, and guarana.

There is also concern with respect to the numerous well-established interactions of herbs and drugs. In consultation with a physician, usage of herbal remedies should be clarified, as some herbal remedies have the potential to cause adverse drug interactions when used in combination with various prescription and over-the-counter pharmaceuticals, just as a patient should inform a herbalist of their consumption of orthodox prescription and other medication.

For example, dangerously low blood pressure may result from the combination of an herbal remedy that lowers blood pressure together with prescription medicine that has the same effect. Some herbs may amplify the effects of anticoagulants. Certain herbs as well as common fruit interfere with cytochrome P450, an enzyme critical to much drug metabolism.

In a 2018 study, FDA identified active pharmaceutical additives in over 700 of analyzed dietary supplements sold as "herbal", "natural" or "traditional". The undisclosed additives included "unapproved antidepressants and designer steroids", as well as prescription drugs, such as sildenafil or sibutramine.

Labeling accuracy

A 2013 study found that one-third of herbal supplements sampled contained no trace of the herb listed on the label. The study found products adulterated with contaminants or fillers not listed on the label, including potential allergens such as soy, wheat, or black walnut. One bottle labeled as St. John's wort was found to actually contain Alexandrian senna, a laxative.

Researchers at the University of Adelaide found in 2014 that almost 20 per cent of herbal remedies surveyed were not registered with the Therapeutic Goods Administration, despite this being a condition for their sale. They also found that nearly 60 per cent of products surveyed had ingredients that did not match what was on the label. Out of 121 products, only 15 had ingredients that matched their TGA listing and packaging.

In 2015, the New York Attorney General issued cease and desist letters to four major U.S. retailers (GNC, Target, Walgreens, and Walmart) who were accused of selling herbal supplements that were mislabeled and potentially dangerous. Twenty-four products were tested by DNA barcoding as part of the investigation, with all but five containing DNA that did not match the product labels.

Practitioners of herbalism

A herbalist gathers the flower heads of Arnica montana.

In some countries, formalized training and minimum education standards exist for herbalists, although these are not necessarily uniform within or between countries. In Australia, for example, the self-regulated status of the profession (as of 2009) resulted in variable standards of training, and numerous loosely-formed associations setting different educational standards. One 2009 review concluded that regulation of herbalists in Australia was needed to reduce the risk of interaction of herbal medicines with prescription drugs, to implement clinical guidelines and prescription of herbal products, and to assure self-regulation for protection of public health and safety. In the United Kingdom, the training of herbalists is done by state-funded universities offering Bachelor of Science degrees in herbal medicine. In the United States, according to the American Herbalist Guild, "there is currently no licensing or certification for herbalists in any state that precludes the rights of anyone to use, dispense, or recommend herbs." However, there are U.S. federal restrictions for marketing herbs as cures for medical conditions, or essentially practicing as an unlicensed physician.

United States herbalism fraud

Over the years 2017-21, the U.S. Food and Drug Administration (FDA) issued warning letters to numerous herbalism companies for illegally marketing products under "conditions that cause them to be drugs under section 201(g)(1) of the Act [21 U.S.C. § 321(g)(1)], because they are intended for use in the diagnosis, cure, mitigation, treatment, or prevention of disease and/or intended to affect the structure or any function of the body" when no such evidence existed. During the COVID-19 pandemic, the FDA and U.S. Federal Trade Commission issued warnings to several hundred American companies for promoting false claims that herbal products could prevent or treat COVID-19 disease.

Government regulations

The World Health Organization (WHO), the specialized agency of the United Nations (UN) that is concerned with international public health, published Quality control methods for medicinal plant materials in 1998 in order to support WHO Member States in establishing quality standards and specifications for herbal materials, within the overall context of quality assurance and control of herbal medicines.

In the European Union (EU), herbal medicines are regulated under the Committee on Herbal Medicinal Products.

In the United States, herbal remedies are regulated dietary supplements by the Food and Drug Administration (FDA) under current good manufacturing practice (cGMP) policy for dietary supplements. Manufacturers of products falling into this category are not required to prove the safety or efficacy of their product so long as they do not make 'medical' claims or imply uses other than as a 'dietary supplement', though the FDA may withdraw a product from sale should it prove harmful.

Canadian regulations are described by the Natural and Non-prescription Health Products Directorate which requires an eight-digit Natural Product Number or Homeopathic Medicine Number on the label of licensed herbal medicines or dietary supplements.

Some herbs, such as cannabis and coca, are outright banned in most countries though coca is legal in most of the South American countries where it is grown. The Cannabis plant is used as an herbal medicine, and as such is legal in some parts of the world. Since 2004, the sales of ephedra as a dietary supplement is prohibited in the United States by the FDA, and subject to Schedule III restrictions in the United Kingdom.

Scientific criticism

Herbalism has been criticized as a potential "minefield" of unreliable product quality, safety hazards, and potential for misleading health advice. Globally, there are no standards across various herbal products to authenticate their contents, safety or efficacy, and there is generally an absence of high-quality scientific research on product composition or effectiveness for anti-disease activity. Presumed claims of therapeutic benefit from herbal products, without rigorous evidence of efficacy and safety, receive skeptical views by scientists.

Unethical practices by some herbalists and manufacturers, which may include false advertising about health benefits on product labels or literature, and contamination or use of fillers during product preparation, may erode consumer confidence about services and products.

Paraherbalism

An example of a herbal medicine resource: the bark of the cinchona tree contains quinine, which today is a widely prescribed treatment for malaria. The unpurified bark is still used by some who can not afford to purchase more expensive antimalarial drugs.

Paraherbalism is the pseudoscientific use of extracts of plant or animal origin as supposed medicines or health-promoting agents. Phytotherapy differs from plant-derived medicines in standard pharmacology because it does not isolate and standardize the compounds from a given plant believed to be biologically active. It relies on the false belief that preserving the complexity of substances from a given plant with less processing is safer and potentially more effective, for which there is no evidence either condition applies.

Phytochemical researcher Varro Eugene Tyler described paraherbalism as "faulty or inferior herbalism based on pseudoscience", using scientific terminology but lacking scientific evidence for safety and efficacy. Tyler listed ten fallacies that distinguished herbalism from paraherbalism, including claims that there is a conspiracy to suppress safe and effective herbs, herbs can not cause harm, that whole herbs are more effective than molecules isolated from the plants, herbs are superior to drugs, the doctrine of signatures (the belief that the shape of the plant indicates its function) is valid, dilution of substances increases their potency (a doctrine of the pseudoscience of homeopathy), astrological alignments are significant, animal testing is not appropriate to indicate human effects, anecdotal evidence is an effective means of proving a substance works and herbs were created by God to cure disease. Tyler suggests that none of these beliefs have any basis in fact.

Traditional systems

Ready to drink macerated medicinal liquor with goji berry, tokay gecko, and ginseng, for sale at a traditional medicine market in Xi'an, China.

Africa

Up to 80% of the population in Africa uses traditional medicine as primary health care.

Americas

Native Americans used about 2,500 of the approximately 20,000 plant species that are native to North America.

China

Some researchers trained in both Western and traditional Chinese medicine have attempted to deconstruct ancient medical texts in the light of modern science. In 1972, Tu Youyou, a pharmaceutical chemist, extracted the anti-malarial drug artemisinin from sweet wormwood, a traditional Chinese treatment for intermittent fevers.

India

A platter of herbal medicines at Goa, India

In India, Ayurvedic medicine has quite complex formulas with 30 or more ingredients, including a sizable number of ingredients that have undergone "alchemical processing", chosen to balance dosha. In Ladakh, Lahul-Spiti and Tibet, the Tibetan Medical System is prevalent, also called the 'Amichi Medical System'. Over 337 species of medicinal plants have been documented by C.P. Kala. Those are used by Amchis, the practitioners of this medical system. The Indian book, Vedas, mentions treatment of diseases with plants.

Indonesia

Different types of Indonesian jamu herbal medicines held in bottles

In Indonesia, especially among the Javanese, the jamu traditional herbal medicine may have originated in the Mataram Kingdom era, some 1300 years ago. The bas-reliefs on Borobudur depict the image of people grinding herbs with stone mortar and pestle, a drink seller, an herbalist, and masseuse treating people. The Madhawapura inscription from Majapahit period mentioned a specific profession of herbs mixer and combiner (herbalist), called Acaraki. The book from Mataram dated from circa 1700 contains 3,000 entries of jamu herbal recipes, while Javanese classical literature Serat Centhini (1814) describes some jamu herbal concoction recipes.

Though possibly influenced by Indian Ayurveda systems, the Indonesia archipelago holds numerous indigenous plants not found in India, including plants similar to those in Australia beyond the Wallace Line. Jamu practices may vary from region to region, and are often not recorded, especially in remote areas of the country. Although primarily herbal, some Jamu materials are acquired from animals, such as honey, royal jelly, milk and ayam kampung eggs.

Beliefs

Herbalists tend to use extracts from parts of plants, such as the roots or leaves, believing that plants are subject to environmental pressures and therefore develop resistance to threats such as radiation, reactive oxygen species and microbial attack in order to survive, providing defensive phytochemicals of use in herbalism.

Use of plants by animals

Indigenous healers often claim to have learned by observing that sick animals change their food preferences to nibble at bitter herbs they would normally reject. Field biologists have provided corroborating evidence based on observation of diverse species, such as chickens, sheep, butterflies, and chimpanzees. The habit of changing diet has been shown to be a physical means of purging intestinal parasites. Sick animals tend to forage plants rich in secondary metabolites, such as tannins and alkaloids.

Gadolinium

From Wikipedia, the free encyclopedia
Gadolinium, 64Gd
Gadolinium-4.jpg
Gadolinium
Pronunciation/ˌɡædəˈlɪniəm/ (GAD-ə-LIN-ee-əm)
Appearancesilvery white
Standard atomic weight Ar, std(Gd)157.25(3)
Gadolinium in the periodic table
Hydrogen
Helium
Lithium Beryllium
Boron Carbon Nitrogen Oxygen Fluorine Neon
Sodium Magnesium
Aluminium Silicon Phosphorus Sulfur Chlorine Argon
Potassium Calcium
Scandium Titanium Vanadium Chromium Manganese Iron Cobalt Nickel Copper Zinc Gallium Germanium Arsenic Selenium Bromine Krypton
Rubidium Strontium

Yttrium Zirconium Niobium Molybdenum Technetium Ruthenium Rhodium Palladium Silver Cadmium Indium Tin Antimony Tellurium Iodine Xenon
Caesium Barium Lanthanum Cerium Praseodymium Neodymium Promethium Samarium Europium Gadolinium Terbium Dysprosium Holmium Erbium Thulium Ytterbium Lutetium Hafnium Tantalum Tungsten Rhenium Osmium Iridium Platinum Gold Mercury (element) Thallium Lead Bismuth Polonium Astatine Radon
Francium Radium Actinium Thorium Protactinium Uranium Neptunium Plutonium Americium Curium Berkelium Californium Einsteinium Fermium Mendelevium Nobelium Lawrencium Rutherfordium Dubnium Seaborgium Bohrium Hassium Meitnerium Darmstadtium Roentgenium Copernicium Nihonium Flerovium Moscovium Livermorium Tennessine Oganesson


Gd

Cm
europiumgadoliniumterbium
Atomic number (Z)64
Groupn/a
Periodperiod 6
Block  f-block
Electron configuration[Xe] 4f7 5d1 6s2
Electrons per shell2, 8, 18, 25, 9, 2
Physical properties
Phase at STPsolid
Melting point1585 K ​(1312 °C, ​2394 °F)
Boiling point3273 K ​(3000 °C, ​5432 °F)
Density (near r.t.)7.90 g/cm3
when liquid (at m.p.)7.4 g/cm3
Heat of fusion10.05 kJ/mol
Heat of vaporization301.3 kJ/mol
Molar heat capacity37.03 J/(mol·K)
Vapor pressure (calculated)
P (Pa) 1 10 100 1 k 10 k 100 k
at T (K) 1836 2028 2267 2573 2976 3535
Atomic properties
Oxidation states0, +1, +2, +3 (a mildly basic oxide)
ElectronegativityPauling scale: 1.20
Ionization energies
  • 1st: 593.4 kJ/mol
  • 2nd: 1170 kJ/mol
  • 3rd: 1990 kJ/mol

Atomic radiusempirical: 180 pm
Covalent radius196±6 pm
Color lines in a spectral range
Spectral lines of gadolinium
Other properties
Natural occurrenceprimordial
Crystal structurehexagonal close-packed (hcp)
Speed of sound thin rod2680 m/s (at 20 °C)
Thermal expansionα poly: 9.4 µm/(m⋅K) (at 100 °C)
Thermal conductivity10.6 W/(m⋅K)
Electrical resistivityα, poly: 1.310 µΩ⋅m
Magnetic orderingferromagneticparamagnetic transition at 293.4 K
Molar magnetic susceptibility+755000.0×10−6 cm3/mol (300.6 K)
Young's modulusα form: 54.8 GPa
Shear modulusα form: 21.8 GPa
Bulk modulusα form: 37.9 GPa
Poisson ratioα form: 0.259
Vickers hardness510–950 MPa
CAS Number7440-54-2
History
Namingafter the mineral Gadolinite (itself named after Johan Gadolin)
DiscoveryJean Charles Galissard de Marignac (1880)
First isolationLecoq de Boisbaudran (1886)
Main isotopes of gadolinium
Iso­tope Abun­dance Half-life (t1/2) Decay mode Pro­duct
148Gd syn 75 y α 144Sm
150Gd syn 1.8×106 y α 146Sm
152Gd 0.20% 1.08×1014 y α 148Sm
154Gd 2.18% stable
155Gd 14.80% stable
156Gd 20.47% stable
157Gd 15.65% stable
158Gd 24.84% stable
160Gd 21.86% stable

Gadolinium is a chemical element with the symbol Gd and atomic number 64. Gadolinium is a silvery-white metal when oxidation is removed. It is only slightly malleable and is a ductile rare-earth element. Gadolinium reacts with atmospheric oxygen or moisture slowly to form a black coating. Gadolinium below its Curie point of 20 °C (68 °F) is ferromagnetic, with an attraction to a magnetic field higher than that of nickel. Above this temperature it is the most paramagnetic element. It is found in nature only in an oxidized form. When separated, it usually has impurities of the other rare-earths because of their similar chemical properties.

Gadolinium was discovered in 1880 by Jean Charles de Marignac, who detected its oxide by using spectroscopy. It is named after the mineral gadolinite, one of the minerals in which gadolinium is found, itself named for the Finnish chemist Johan Gadolin. Pure gadolinium was first isolated by the chemist Paul Emile Lecoq de Boisbaudran around 1886.

Gadolinium possesses unusual metallurgical properties, to the extent that as little as 1% of gadolinium can significantly improve the workability and resistance to oxidation at high temperatures of iron, chromium, and related metals. Gadolinium as a metal or a salt absorbs neutrons and is, therefore, used sometimes for shielding in neutron radiography and in nuclear reactors.

Like most of the rare earths, gadolinium forms trivalent ions with fluorescent properties, and salts of gadolinium(III) are used as phosphors in various applications.

The kinds of gadolinium(III) ions occurring in water-soluble salts are toxic to mammals. However, chelated gadolinium(III) compounds are far less toxic because they carry gadolinium(III) through the kidneys and out of the body before the free ion can be released into the tissues. Because of its paramagnetic properties, solutions of chelated organic gadolinium complexes are used as intravenously administered gadolinium-based MRI contrast agents in medical magnetic resonance imaging.

Characteristics

A sample of gadolinium metal

Physical properties

Gadolinium is a silvery-white, malleable, ductile rare-earth element. It crystallizes in the hexagonal close-packed α-form at room temperature, but, when heated to temperatures above 1,235 °C (2,255 °F), it transforms into its β-form, which has a body-centered cubic structure.

The isotope gadolinium-157 has the highest thermal-neutron capture cross-section among any stable nuclide: about 259,000 barns. Only xenon-135 has a higher capture cross-section, about 2.0 million barns, but this isotope is radioactive.

Gadolinium is believed to be ferromagnetic at temperatures below 20 °C (68 °F) and is strongly paramagnetic above this temperature. There is evidence that gadolinium is a helical antiferromagnetic, rather than a ferromagnetic, below 20 °C (68 °F). Gadolinium demonstrates a magnetocaloric effect whereby its temperature increases when it enters a magnetic field and decreases when it leaves the magnetic field. The temperature is lowered to 5 °C (41 °F) for the gadolinium alloy Gd85Er15, and this effect is considerably stronger for the alloy Gd5(Si2Ge2), but at a much lower temperature (<85 K (−188.2 °C; −306.7 °F)). A significant magnetocaloric effect is observed at higher temperatures, up to about 300 kelvins, in the compounds Gd5(SixGe1−x)4.

Individual gadolinium atoms can be isolated by encapsulating them into fullerene molecules, where they can be visualized with a transmission electron microscope. Individual Gd atoms and small Gd clusters can be incorporated into carbon nanotubes.

Chemical properties

Gadolinium combines with most elements to form Gd(III) derivatives. It also combines with nitrogen, carbon, sulfur, phosphorus, boron, selenium, silicon, and arsenic at elevated temperatures, forming binary compounds.

Unlike the other rare-earth elements, metallic gadolinium is relatively stable in dry air. However, it tarnishes quickly in moist air, forming a loosely-adhering gadolinium(III) oxide (Gd2O3):

4 Gd + 3 O2 → 2 Gd2O3,

which spalls off, exposing more surface to oxidation.

Gadolinium is a strong reducing agent, which reduces oxides of several metals into their elements. Gadolinium is quite electropositive and reacts slowly with cold water and quite quickly with hot water to form gadolinium hydroxide:

2 Gd + 6 H2O → 2 Gd(OH)3 + 3 H2.

Gadolinium metal is attacked readily by dilute sulfuric acid to form solutions containing the colorless Gd(III) ions, which exist as [Gd(H2O)9]3+ complexes:

2 Gd + 3 H2SO4 + 18 H2O → 2 [Gd(H2O)9]3+ + 3 SO2−
4
+ 3 H2.

Gadolinium metal reacts with the halogens (X2) at temperature about 200 °C (392 °F):

2 Gd + 3 X2 → 2 GdX3.

Chemical compounds

In the great majority of its compounds, gadolinium adopts the oxidation state +3. All four trihalides are known. All are white, except for the iodide, which is yellow. Most commonly encountered of the halides is gadolinium(III) chloride (GdCl3). The oxide dissolves in acids to give the salts, such as gadolinium(III) nitrate.

Gadolinium(III), like most lanthanide ions, forms complexes with high coordination numbers. This tendency is illustrated by the use of the chelating agent DOTA, an octadentate ligand. Salts of [Gd(DOTA)] are useful in magnetic resonance imaging. A variety of related chelate complexes have been developed, including gadodiamide.

Reduced gadolinium compounds are known, especially in the solid state. Gadolinium(II) halides are obtained by heating Gd(III) halides in presence of metallic Gd in tantalum containers. Gadolinium also form sesquichloride Gd2Cl3, which can be further reduced to GdCl by annealing at 800 °C (1,470 °F). This gadolinium(I) chloride forms platelets with layered graphite-like structure.

Isotopes

Naturally occurring gadolinium is composed of six stable isotopes, 154Gd, 155Gd, 156Gd, 157Gd, 158Gd and 160Gd, and one radioisotope, 152Gd, with the isotope 158Gd being the most abundant (24.8% natural abundance). The predicted double beta decay of 160Gd has never been observed (an experimental lower limit on its half-life of more than 1.3×1021 years has been measured).

29 radioisotopes of gadolinium have been observed, with the most stable being 152Gd (naturally occurring), with a half-life of about 1.08×1014 years, and 150Gd, with a half-life of 1.79×106 years. All of the remaining radioactive isotopes have half-lives of less than 75 years. The majority of these have half-lives of less than 25 seconds. Gadolinium isotopes have four metastable isomers, with the most stable being 143mGd (t1/2= 110 seconds), 145mGd (t1/2= 85 seconds) and 141mGd (t1/2= 24.5 seconds).

The isotopes with atomic masses lower than the most abundant stable isotope, 158Gd, primarily decay by electron capture to isotopes of europium. At higher atomic masses, the primary decay mode is beta decay, and the primary products are isotopes of terbium.

History

Gadolinium is named after the mineral gadolinite, in turn named after Finnish chemist and geologist Johan Gadolin. This makes it the only element whose name is derived from a Hebrew root (gadol, "great"). In 1880, the Swiss chemist Jean Charles Galissard de Marignac observed the spectroscopic lines from gadolinium in samples of gadolinite (which actually contains relatively little gadolinium, but enough to show a spectrum) and in the separate mineral cerite. The latter mineral proved to contain far more of the element with the new spectral line. De Marignac eventually separated a mineral oxide from cerite, which he realized was the oxide of this new element. He named the oxide "gadolinia". Because he realized that "gadolinia" was the oxide of a new element, he is credited with the discovery of gadolinium. The French chemist Paul Émile Lecoq de Boisbaudran carried out the separation of gadolinium metal from gadolinia in 1886.

Occurrence

Gadolinite

Gadolinium is a constituent in many minerals such as monazite and bastnäsite, which are oxides. The metal is too reactive to exist naturally. Paradoxically, as noted above, the mineral gadolinite actually contains only traces of this element. The abundance in the Earth's crust is about 6.2 mg/kg. The main mining areas are in China, the US, Brazil, Sri Lanka, India, and Australia with reserves expected to exceed one million tonnes. World production of pure gadolinium is about 400 tonnes per year. The only known mineral with essential gadolinium, lepersonnite-(Gd), is very rare.

Production

Gadolinium is produced both from monazite and bastnäsite.

  1. Crushed minerals are extracted with hydrochloric acid or sulfuric acid, which converts the insoluble oxides into soluble chlorides or sulfates.
  2. The acidic filtrates are partially neutralized with caustic soda to pH 3–4. Thorium precipitates as its hydroxide, and is then removed.
  3. The remaining solution is treated with ammonium oxalate to convert rare earths into their insoluble oxalates. The oxalates are converted to oxides by heating.
  4. The oxides are dissolved in nitric acid that excludes one of the main components, cerium, whose oxide is insoluble in HNO3.
  5. The solution is treated with magnesium nitrate to produce a crystallized mixture of double salts of gadolinium, samarium and europium.
  6. The salts are separated by ion exchange chromatography.
  7. The rare-earth ions are then selectively washed out by a suitable complexing agent.

Gadolinium metal is obtained from its oxide or salts by heating it with calcium at 1,450 °C (2,640 °F) in an argon atmosphere. Sponge gadolinium can be produced by reducing molten GdCl3 with an appropriate metal at temperatures below 1,312 °C (2,394 °F) (the melting point of Gd) at reduced pressure.

Applications

Gadolinium has no large-scale applications, but it has a variety of specialized uses.

Because 157Gd has a high neutron cross-section, it is used to target tumors in neutron therapy. This element is effective for use with neutron radiography and in shielding of nuclear reactors. It is used as a secondary, emergency shut-down measure in some nuclear reactors, particularly of the CANDU reactor type. Gadolinium is also used in nuclear marine propulsion systems as a burnable poison.

Gadolinium possesses unusual metallurgic properties, with as little as 1% of gadolinium improving the workability and resistance of iron, chromium, and related alloys to high temperatures and oxidation.

Gadolinium is paramagnetic at room temperature, with a ferromagnetic Curie point of 20 °C (68 °F). Paramagnetic ions, such as gadolinium, enhance nuclear relaxation rates, making gadolinium useful for magnetic resonance imaging (MRI). Solutions of organic gadolinium complexes and gadolinium compounds are used as intravenous MRI contrast agent to enhance images in medical magnetic resonance imaging and magnetic resonance angiography (MRA) procedures. Magnevist is the most widespread example. Nanotubes packed with gadolinium, called "gadonanotubes", are 40 times more effective than the usual gadolinium contrast agent. Once injected, gadolinium-based contrast agents accumulate in abnormal tissues of the brain and body, which provides a greater image contrast between normal and abnormal tissues, facilitating location of abnormal cell growths and tumors.

Gadolinium as a phosphor is also used in other imaging. In X-ray systems gadolinium is contained in the phosphor layer, suspended in a polymer matrix at the detector. Terbium-doped gadolinium oxysulfide (Gd2O2S:Tb) at the phosphor layer converts the X-rays released from the source into light. This material emits green light at 540 nm due to the presence of Tb3+, which is very useful for enhancing the imaging quality. The energy conversion of Gd is up to 20%, which means that 1/5 of the X-ray energy striking the phosphor layer can be converted into visible photons. Gadolinium oxyorthosilicate (Gd2SiO5, GSO; usually doped by 0.1–1.0% of Ce) is a single crystal that is used as a scintillator in medical imaging such as positron emission tomography or for detecting neutrons.

Gadolinium compounds are also used for making green phosphors for color TV tubes.

Gadolinium-153 is produced in a nuclear reactor from elemental europium or enriched gadolinium targets. It has a half-life of 240±10 days and emits gamma radiation with strong peaks at 41 keV and 102 keV. It is used in many quality-assurance applications, such as line sources and calibration phantoms, to ensure that nuclear-medicine imaging systems operate correctly and produce useful images of radioisotope distribution inside the patient. It is also used as a gamma-ray source in X-ray absorption measurements or in bone density gauges for osteoporosis screening, as well as in the Lixiscope portable X-ray imaging system.

Gadolinium is used for making gadolinium yttrium garnet (Gd:Y3Al5O12); it has microwave applications and is used in fabrication of various optical components and as substrate material for magneto-optical films.

Gadolinium gallium garnet (GGG, Gd3Ga5O12) was used for imitation diamonds and for computer bubble memory.

Gadolinium can also serve as an electrolyte in solid oxide fuel cells (SOFCs). Using gadolinium as a dopant for materials like cerium oxide (in the form of gadolinium-doped ceria) creates an electrolyte with both high ionic conductivity and low operating temperatures, which are optimal for cost-effective production of fuel cells.

Research is being conducted on magnetic refrigeration near room temperature, which could provide significant efficiency and environmental advantages over conventional refrigeration methods. Gadolinium-based materials, such as Gd5(SixGe1−x)4, are currently the most promising materials, owing to their high Curie temperature and giant magnetocaloric effect. Pure Gd itself exhibits a large magnetocaloric effect near its Curie temperature of 20 °C (68 °F), and this has sparked great interest into producing Gd alloys with a larger effect and tunable Curie temperature. In Gd5(SixGe1−x)4, Si and Ge compositions can be varied to adjust the Curie temperature. This technology is still very early in development, and significant material improvements still need to be made before it is commercially viable.

Physicists Mark Vagins and John Beacom, of the Japanese Super Kamiokande, theorized that gadolinium may facilitate neutrino detection when it is added to very high-purity water in the tank.

Gadolinium barium copper oxide (GdBCO) has been researched for its superconducting properties with applications in superconducting motors or generators - for example in a wind turbine. It can be manufactured in the same way as the most widely researched cuprate high temperature superconductor, Yttrium barium copper oxide (YBCO) and uses an analogous chemical composition (GdBa2Cu3O7−δ ). Most notably, it was used by the Bulk Superconductivity Group from the University of Cambridge in 2014 to set a new world record for the highest trapped magnetic field in a bulk high temperature superconductor, with a field of 17.6T being trapped within two GdBCO bulks.

Biological role

Gadolinium has no known native biological role, but its compounds are used as research tools in biomedicine. Gd3+ compounds are components of MRI contrast agents. It is used in various ion channel electrophysiology experiments to block sodium leak channels and stretch activated ion channels. Gadolinium has recently been used to measure the distance between two points in a protein via electron paramagnetic resonance, something that gadolinium is especially amenable to thanks to EPR sensitivity at w-band (95 GHz) frequencies.

Safety

Gadolinium
Hazards
GHS pictograms GHS02: Flammable
GHS Signal word Danger
H261
P231+232, P422
NFPA 704 (fire diamond)
0
0
1

As a free ion, gadolinium is reported often to be highly toxic, but MRI contrast agents are chelated compounds and are considered safe enough to be used in most persons. The toxicity of free gadolinium ions in animals is due to interference with a number of calcium-ion channel dependent processes. The 50% lethal dose is about 100–200 mg/kg. Toxicities have not been reported following low dose exposure to gadolinium ions. Toxicity studies in rodents, however show that chelation of gadolinium (which also improves its solubility) decreases its toxicity with regard to the free ion by at least a factor of 100 (i.e., the lethal dose for the Gd-chelate increases by 100 times). It is believed therefore that clinical toxicity of gadolinium-based contrast agents (GBCAs) in humans will depend on the strength of the chelating agent; however this research is still not complete. About a dozen different Gd-chelated agents have been approved as MRI contrast agents around the world.

Anaphylactoid reactions are rare, occurring in approximately 0.03–0.1%.

Although gadolinium agents are useful for patients with renal impairment, in patients with severe kidney failure requiring dialysis, there is a risk of a rare but serious illness called nephrogenic systemic fibrosis (NSF) or nephrogenic fibrosing dermopathy, that is linked to the use of MRI contrast agents containing gadolinium. The disease resembles scleromyxedema and to some extent scleroderma. It may occur months after a contrast agent has been injected. Its association with gadolinium and not the carrier molecule is confirmed by its occurrence with various contrast materials in which gadolinium is carried by very different carrier molecules. Due to this, it is not recommended to use these agents for any individual with end-stage kidney failure as they will require emergent dialysis. Similar but not identical symptoms to NSF may occur in subjects with normal or near-normal renal function within hours to 2 months following the administration of GBCAs; the name "gadolinium deposition disease" (GDD) has been proposed for this condition, which occurs in the absence of pre-existent disease or subsequently developed disease of an alternate known process. A 2016 study reported numerous anecdotal cases of GDD. However, in that study, participants were recruited from online support groups for subjects self-identified as having gadolinium toxicity, and no relevant medical history or data were collected. There have yet to be definitive scientific studies proving the existence of the condition. In addition, gadolinium deposition in neural tissues has solely been demonstrated in patients with inflammatory, infective, or malignant disease, and no healthy volunteer studies have assessed the potential of gadolinium deposition within the brain, skin, or bones.

Included in the current guidelines from the Canadian Association of Radiologists are that dialysis patients should only receive gadolinium agents where essential and that they should receive dialysis after the exam. If a contrast-enhanced MRI must be performed on a dialysis patient, it is recommended that certain high-risk contrast agents be avoided but not that a lower dose be considered. The American College of Radiology recommends that contrast-enhanced MRI examinations be performed as closely before dialysis as possible as a precautionary measure, although this has not been proven to reduce the likelihood of developing NSF. The FDA recommends that potential for gadolinium retention be considered when choosing the type of GBCA used in patients requiring multiple lifetime doses, pregnant women, children, and patients with inflammatory conditions.

Long-term environmental impacts of gadolinium contamination due to human usage is a topic of ongoing research.

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