Breeder reactor

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Assembly of the core of Experimental Breeder Reactor I in Idaho, United States, 1951

A breeder reactor is a nuclear reactor that generates more fissile material than it consumes. These reactors can be fueled with more-commonly available isotopes of uranium and thorium, such as uranium-238 and thorium-232, as opposed to the rare uranium-235 which is used in conventional reactors. These materials are called fertile materials since they can be bred into fuel by these breeder reactors.

Breeder reactors achieve this because their neutron economy is high enough to create more fissile fuel than they use. These extra neutrons are absorbed by the fertile material that is loaded into the reactor along with fissile fuel. This irradiated fertile material in turn transmutes into fissile material which can undergo fission reactions.

Breeders were at first found attractive because they made more complete use of uranium fuel than light-water reactors, but interest declined after the 1960s, as more uranium reserves were found, and new methods of uranium enrichment reduced fuel costs.

Fuel resources

Breeder reactors could, in principle, extract almost all of the energy contained in uranium or thorium, decreasing fuel requirements by a factor of 100 compared to widely used once-through light water reactors, which extract less than 1% of the energy in the actinide metal (uranium or thorium) mined from the earth. The high fuel-efficiency of breeder reactors could greatly reduce concerns about fuel supply, energy used in mining, and storage of radioactive waste. With seawater uranium extraction (currently too expensive to be economical), there is enough fuel for breeder reactors to satisfy the world's energy needs for 5 billion years at 1983's total energy consumption rate, thus making nuclear energy effectively a renewable energy. In addition to seawater the average crustal granite rocks contain significant quantities of uranium and thorium that with breeder reactors can supply abundant energy for the remaining lifespan of the sun on the main sequence of stellar evolution.

Fuel efficiency and types of nuclear waste

Nuclear waste became a greater concern by the 1990s. In broad terms, spent nuclear fuel has three main components. The first consists of fission products, the leftover fragments of fuel atoms after they have been split to release energy. Fission products come in dozens of elements and hundreds of isotopes, all of them lighter than uranium. The second main component of spent fuel is transuranics (atoms heavier than uranium), which are generated from uranium or heavier atoms in the fuel when they absorb neutrons but do not undergo fission. All transuranic isotopes fall within the actinide series on the periodic table, and so they are frequently referred to as the actinides. The largest component is the remaining Uranium which is around 98.25% Uranium-238, 1.1% Uranium-235, and 0.65% Uranium-236. The U-236 comes from the non-fission capture reaction where U-235 absorbs a neutron but releases only a high energy gamma ray instead of undergoing fission.

The physical behavior of the fission products is markedly different from that of the actinides. In particular, fission products do not themselves undergo fission, and therefore cannot be used as nuclear fuel, either for nuclear weapons or nuclear reactors. Indeed, because fission products are often neutron poisons (absorbing neutrons that could be used to sustain a chain reaction), fission products are viewed as nuclear 'ashes' left over from consuming fissile materials. Furthermore, only seven long-lived fission product isotopes have half-lives longer than a hundred years, which makes their geological storage or disposal less problematic than for transuranic materials.

With increased concerns about nuclear waste, breeding fuel cycles came under renewed interest as they can reduce actinide wastes, particularly plutonium and minor actinides. Breeder reactors are designed to fission the actinide wastes as fuel, and thus convert them to more fission products.

After spent nuclear fuel is removed from a light water reactor, it undergoes a complex decay profile as each nuclide decays at a different rate. Due to a physical oddity referenced below, there is a large gap in the decay half-lives of fission products compared to transuranic isotopes. If the transuranics are left in the spent fuel, after 1,000 to 100,000 years, the slow decay of these transuranics would generate most of the radioactivity in that spent fuel. Thus, removing the transuranics from the waste eliminates much of the long-term radioactivity of spent nuclear fuel.

Fission probabilities of selected actinides, thermal vs. fast neutrons. The percentages of thermal and fast fission indicate the fraction of nuclei fissioned when hit by a respective neutron. The remainder undergoes neutron capture.

Isotope	Thermal fission cross section	Thermal fission %	Fast fission cross section	Fast fission %
Th-232	nil	1 n	0.350 barn	3 n
U-232	76.66 barn	59	2.370 barn	95
U-233	531.2 barn	89	2.450 barn	93
U-235	584.4 barn	81	2.056 barn	80
U-238	11.77 microbarn	1 n	1.136 barn	11
Np-237	0.02249 barn	3 n	2.247 barn	27
Pu-238	17.89 barn	7	2.721 barn	70
Pu-239	747.4 barn	63	2.338 barn	85
Pu-240	58.77 barn	1 n	2.253 barn	55
Pu-241	1012 barn	75	2.298 barn	87
Pu-242	0.002557 barn	1 n	2.027 barn	53
Am-241	600.4 barn	1 n	0.2299 microbarn	21
Am-242m	6409 barn	75	2.550 barn	94
Am-243	0.1161 barn	1 n	2.140 barn	23
Cm-242	5.064 barn	1 n	2.907 barn	10
Cm-243	617.4 barn	78	2.500 barn	94
Cm-244	1.037 barn	4 n	0.08255 microbarn	33
n=non-fissile

Today's commercial light-water reactors do breed some new fissile material, mostly in the form of plutonium. Because commercial reactors were never designed as breeders, they do not convert enough uranium-238 into plutonium to replace the uranium-235 consumed. Nonetheless, at least one-third of the power produced by commercial nuclear reactors comes from fission of plutonium generated within the fuel. Even with this level of plutonium consumption, light water reactors consume only part of the plutonium and minor actinides they produce, and nonfissile isotopes of plutonium build up, along with significant quantities of other minor actinides.

Conversion ratio, break-even, breeding ratio, doubling time, and burnup

One measure of a reactor's performance is the "conversion ratio", defined as the ratio of new fissile atoms produced to fissile atoms consumed. All proposed nuclear reactors except specially designed and operated actinide burners experience some degree of conversion. As long as there is any amount of a fertile material within the neutron flux of the reactor, some new fissile material is always created. When the conversion ratio is greater than 1, it is often called the "breeding ratio".

For example, commonly used light water reactors have a conversion ratio of approximately 0.6. Pressurized heavy-water reactors (PHWR) running on natural uranium have a conversion ratio of 0.8. In a breeder reactor, the conversion ratio is higher than 1. "Break-even" is achieved when the conversion ratio reaches 1.0 and the reactor produces as much fissile material as it uses.

The doubling time is the amount of time it would take for a breeder reactor to produce enough new fissile material to replace the original fuel and additionally produce an equivalent amount of fuel for another nuclear reactor. This was considered an important measure of breeder performance in early years, when uranium was thought to be scarce. However, since uranium is more abundant than thought in the early days of nuclear reactor development, and given the amount of plutonium available in spent reactor fuel, doubling time has become a less important metric in modern breeder-reactor design.

"Burnup" is a measure of how much energy has been extracted from a given mass of heavy metal in fuel, often expressed (for power reactors) in terms of gigawatt-days per ton of heavy metal. Burnup is an important factor in determining the types and abundances of isotopes produced by a fission reactor. Breeder reactors, by design, have extremely high burnup compared to a conventional reactor, as breeder reactors produce much more of their waste in the form of fission products, while most or all of the actinides are meant to be fissioned and destroyed.

In the past, breeder-reactor development focused on reactors with low breeding ratios, from 1.01 for the Shippingport Reactor running on thorium fuel and cooled by conventional light water to over 1.2 for the Soviet BN-350 liquid-metal-cooled reactor. Theoretical models of breeders with liquid sodium coolant flowing through tubes inside fuel elements ("tube-in-shell" construction) suggest breeding ratios of at least 1.8 are possible on an industrial scale. The Soviet BR-1 test reactor achieved a breeding ratio of 2.5 under non-commercial conditions.

Types of breeder reactor

Production of heavy transuranic actinides in current thermal-neutron fission reactors through neutron capture and decays. Starting at uranium-238, isotopes of plutonium, americium, and curium are all produced. In a fast neutron-breeder reactor, all these isotopes may be burned as fuel.

Many types of breeder reactor are possible:

A "breeder" is simply a reactor designed for very high neutron economy with an associated conversion rate higher than 1.0. In principle, almost any reactor design could be tweaked to become a breeder. For example, the Light Water Reactor, a very heavily moderated thermal design, evolved into the Super Fast Reactor concept, using light water in an extremely low-density supercritical form to increase the neutron economy enough to allow breeding.

Aside from water-cooled, there are many other types of breeder reactor currently envisioned as possible. These include molten-salt cooled, gas cooled, and liquid-metal cooled designs in many variations. Almost any of these basic design types may be fueled by uranium, plutonium, many minor actinides, or thorium, and they may be designed for many different goals, such as creating more fissile fuel, long-term steady-state operation, or active burning of nuclear wastes.

Extant reactor designs are sometimes divided into two broad categories based upon their neutron spectrum, which generally separates those designed to use primarily uranium and transuranics from those designed to use thorium and avoid transuranics. These designs are:

• Fast breeder reactors (FBR's) which use 'fast' (i.e. unmoderated) neutrons to breed fissile plutonium (and possibly higher transuranics) from fertile uranium-238. The fast spectrum is flexible enough that it can also breed fissile uranium-233 from thorium, if desired.
• Thermal breeder reactors which use 'thermal-spectrum' or 'slow' (i.e. moderated) neutrons to breed fissile uranium-233 from thorium (thorium fuel cycle). Due to the behavior of the various nuclear fuels, a thermal breeder is thought commercially feasible only with thorium fuel, which avoids the buildup of the heavier transuranics.

Reprocessing

Fission of the nuclear fuel in any reactor unavoidably produces neutron-absorbing fission products. One must reprocess the fertile material from a breeder reactor to remove those neutron poisons. This step is required to fully utilize the ability to breed as much or more fuel than is consumed. All reprocessing can present a proliferation concern, since it can extract weapons-usable material from spent fuel. The most common reprocessing technique, PUREX, presents a particular concern, since it was expressly designed to separate pure plutonium. Early proposals for the breeder-reactor fuel cycle posed an even greater proliferation concern because they would use PUREX to separate plutonium in a highly attractive isotopic form for use in nuclear weapons.

Several countries are developing reprocessing methods that do not separate the plutonium from the other actinides. For instance, the non-water-based pyrometallurgical electrowinning process, when used to reprocess fuel from an integral fast reactor, leaves large amounts of radioactive actinides in the reactor fuel. More conventional water-based reprocessing systems include SANEX, UNEX, DIAMEX, COEX, and TRUEX, and proposals to combine PUREX with those and other co-processes.

All these systems have moderately better proliferation resistance than PUREX, though their adoption rate is low.

In the thorium cycle, thorium-232 breeds by converting first to protactinium-233, which then decays to uranium-233. If the protactinium remains in the reactor, small amounts of uranium-232 are also produced, which has the strong gamma emitter thallium-208 in its decay chain. Similar to uranium-fueled designs, the longer the fuel and fertile material remain in the reactor, the more of these undesirable elements build up. In the envisioned commercial thorium reactors, high levels of uranium-232 would be allowed to accumulate, leading to extremely high gamma-radiation doses from any uranium derived from thorium. These gamma rays complicate the safe handling of a weapon and the design of its electronics; this explains why uranium-233 has never been pursued for weapons beyond proof-of-concept demonstrations.

While the thorium cycle may be proliferation-resistant with regard to uranium-233 extraction from fuel (because of the presence of uranium-232), it poses a proliferation risk from an alternate route of uranium-233 extraction, which involves chemically extracting protactinium-233 and allowing it to decay to pure uranium-233 outside of the reactor. This process is an obvious chemical operation which is not required for normal operation of these reactor designs, but it could feasibly happen beyond the oversight of organizations such as the International Atomic Energy Agency (IAEA), and thus must be safeguarded against.

Waste reduction

Actinides and fission products by half-life
Actinides by decay chain				Half-life range (a)	Fission products of 235U by yield
4n	4n + 1	4n + 2	4n + 3		4.5–7%	0.04–1.25%	<0.001%
228Ra№				4–6 a		155Euþ
244Cmƒ	241Puƒ	250Cf	227Ac№	10–29 a	90Sr	85Kr	113mCdþ
232Uƒ		238Puƒ	243Cmƒ	29–97 a	137Cs	151Smþ	121mSn
248Bk[38]	249Cfƒ	242mAmƒ		141–351 a	No fission products have a half-life in the range of 100 a–210 ka ...
	241Amƒ		251Cfƒ	430–900 a
		226Ra№	247Bk	1.3–1.6 ka
240Pu	229Th	246Cmƒ	243Amƒ	4.7–7.4 ka
	245Cmƒ	250Cm		8.3–8.5 ka
			239Puƒ	24.1 ka
		230Th№	231Pa№	32–76 ka
236Npƒ	233Uƒ	234U№		150–250 ka	99Tc₡	126Sn
248Cm		242Pu		327–375 ka		79Se₡
				1.53 Ma	93Zr
	237Npƒ			2.1–6.5 Ma	135Cs₡	107Pd
236U			247Cmƒ	15–24 Ma		129I₡
244Pu				80 Ma	... nor beyond 15.7 Ma
232Th№		238U№	235Uƒ№	0.7–14.1 Ga
₡,  has thermal neutron capture cross section in the range of 8–50 barns ƒ,  fissile №,  primarily a naturally occurring radioactive material (NORM) þ,  neutron poison (thermal neutron capture cross section greater than 3k barns)

Nuclear waste became a greater concern by the 1990s. Breeding fuel cycles attracted renewed interest because of their potential to reduce actinide wastes, particularly various isotopes of plutonium and the minor actinides (neptunium, americium, curium, etc.). Since breeder reactors on a closed fuel cycle would use nearly all of the isotopes of these actinides fed into them as fuel, their fuel requirements would be reduced by a factor of about 100. The volume of waste they generate would be reduced by a factor of about 100 as well. While there is a huge reduction in the volume of waste from a breeder reactor, the activity of the waste is about the same as that produced by a light-water reactor.

In addition, the waste from a breeder reactor has a different decay behavior, because it is made up of different materials. Breeder reactor waste is mostly fission products, while light-water reactor waste is mostly un-used uranium isotopes and a large quantity of transuranics. After spent nuclear fuel has been removed from a light-water reactor for longer than 100,000 years, the transuranics would be the main source of radioactivity. Eliminating them would eliminate much of the long-term radioactivity from the spent fuel.

In principle, breeder fuel cycles can recycle and consume all actinides, leaving only fission products. As the graphic in this section indicates, fission products have a peculiar "gap" in their aggregate half-lives, such that no fission products have a half-life between 91 years and two hundred thousand years. As a result of this physical oddity, after several hundred years in storage, the activity of the radioactive waste from a Fast Breeder Reactor would quickly drop to the low level of the long-lived fission products. However, to obtain this benefit requires the highly efficient separation of transuranics from spent fuel. If the fuel reprocessing methods used leave a large fraction of the transuranics in the final waste stream, this advantage would be greatly reduced.

Both types of breeding cycles can reduce actinide wastes:

• The fast breeder reactor's fast neutrons can fission actinide nuclei with even numbers of both protons and neutrons. Such nuclei usually lack the low-speed "thermal neutron" resonances of fissile fuels used in LWRs.
• The thorium fuel cycle inherently produces lower levels of heavy actinides. The fertile material in the thorium fuel cycle has an atomic weight of 232, while the fertile material in the uranium fuel cycle has an atomic weight of 238. That mass difference means that thorium-232 requires six more neutron capture events per nucleus before the transuranic elements can be produced. In addition to this simple mass difference, the reactor gets two chances to fission the nuclei as the mass increases: First as the effective fuel nuclei U233, and as it absorbs two more neutrons, again as the fuel nuclei U235.

A reactor whose main purpose is to destroy actinides, rather than increasing fissile fuel-stocks, is sometimes known as a burner reactor. Both breeding and burning depend on good neutron economy, and many designs can do either. Breeding designs surround the core by a breeding blanket of fertile material. Waste burners surround the core with non-fertile wastes to be destroyed. Some designs add neutron reflectors or absorbers.

Breeder reactor concepts

There are several concepts for breeder reactors; the two main ones are:

• Reactors with a fast neutron spectrum are called fast breeder reactors (FBR's) – these typically utilize uranium-238 as fuel.
• Reactors with a thermal neutron spectrum are called thermal breeder reactors – these typically utilize thorium-232 as fuel.

Fast breeder reactor

Schematic diagram showing the difference between the Loop and Pool types of LMFBR

In 2006 all large-scale fast breeder reactor (FBR) power stations were liquid metal fast breeder reactors (LMFBR) cooled by liquid sodium. These have been of one of two designs:

• Loop type, in which the primary coolant is circulated through primary heat exchangers outside the reactor tank (but inside the biological shield due to radioactive ²⁴
  Na in the primary coolant)

Experimental Breeder Reactor II, which served as the prototype for the Integral Fast Reactor

• Pool type, in which the primary heat exchangers and pumps are immersed in the reactor tank

All current fast neutron reactor designs use liquid metal as the primary coolant, to transfer heat from the core to steam used to power the electricity generating turbines. FBRs have been built cooled by liquid metals other than sodium—some early FBRs used mercury, other experimental reactors have used a sodium-potassium alloy called NaK. Both have the advantage that they are liquids at room temperature, which is convenient for experimental rigs but less important for pilot or full-scale power stations. Lead and lead-bismuth alloy have also been used.

Three of the proposed generation IV reactor types are FBRs:

• Gas-cooled fast reactor (GFR) cooled by helium.
• Sodium-cooled fast reactor (SFR) based on the existing liquid-metal FBR (LMFBR) and integral fast reactor designs.
• Lead-cooled fast reactor (LFR) based on Soviet naval propulsion units.

FBRs usually use a mixed oxide fuel core of up to 20% plutonium dioxide (PuO₂) and at least 80% uranium dioxide (UO₂). Another fuel option is metal alloys, typically a blend of uranium, plutonium, and zirconium (used because it is "transparent" to neutrons). Enriched uranium can also be used on its own.

Many designs surround the core in a blanket of tubes that contain non-fissile uranium-238, which, by capturing fast neutrons from the reaction in the core, converts to fissile plutonium-239 (as is some of the uranium in the core), which is then reprocessed and used as nuclear fuel. Other FBR designs rely on the geometry of the fuel itself (which also contains uranium-238), arranged to attain sufficient fast neutron capture. The plutonium-239 (or the fissile uranium-235) fission cross-section is much smaller in a fast spectrum than in a thermal spectrum, as is the ratio between the ²³⁹Pu/²³⁵U fission cross-section and the ²³⁸U absorption cross-section. This increases the concentration of ²³⁹Pu/²³⁵U needed to sustain a chain reaction, as well as the ratio of breeding to fission. On the other hand, a fast reactor needs no moderator to slow down the neutrons at all, taking advantage of the fast neutrons producing a greater number of neutrons per fission than slow neutrons. For this reason ordinary liquid water, being a moderator and neutron absorber, is an undesirable primary coolant for fast reactors. Because large amounts of water in the core are required to cool the reactor, the yield of neutrons and therefore breeding of ²³⁹Pu are strongly affected. Theoretical work has been done on reduced moderation water reactors, which may have a sufficiently fast spectrum to provide a breeding ratio slightly over 1. This would likely result in an unacceptable power derating and high costs in a liquid-water-cooled reactor, but the supercritical water coolant of the supercritical water reactor (SCWR) has sufficient heat capacity to allow adequate cooling with less water, making a fast-spectrum water-cooled reactor a practical possibility.  The type of coolants, temperatures, and fast neutron spectrum puts the fuel cladding material (normally austenitic stainless or ferritic-martensitic steels) under extreme conditions. The understanding of the radiation damage, coolant interactions, stresses, and temperatures are necessary for the safe operation of any reactor core. All materials used to date in sodium-cooled fast reactors have known limits, as explored in ONR-RRR-088 review. Oxide Dispersion Strengthened (ODS) steel is viewed as the long-term radiation resistant fuel-cladding material that overcome the shortcomings of today's material choices.

There are only two commercially operating breeder reactors as of 2017: the BN-600 reactor, at 560 MWe, and the BN-800 reactor, at 880 MWe. Both are Russian sodium-cooled reactors.

Integral fast reactor

Main article: Integral Fast Reactor

One design of fast neutron reactor, specifically conceived to address the waste disposal and plutonium issues, was the integral fast reactor (IFR, also known as an integral fast breeder reactor, although the original reactor was designed to not breed a net surplus of fissile material).

To solve the waste disposal problem, the IFR had an on-site electrowinning fuel-reprocessing unit that recycled the uranium and all the transuranics (not just plutonium) via electroplating, leaving just short-half-life fission products in the waste. Some of these fission products could later be separated for industrial or medical uses and the rest sent to a waste repository. The IFR pyroprocessing system uses molten cadmium cathodes and electrorefiners to reprocess metallic fuel directly on-site at the reactor. Such systems not only co-mingle all the minor actinides with both uranium and plutonium, they are compact and self-contained, so that no plutonium-containing material needs to be transported away from the site of the breeder reactor. Breeder reactors incorporating such technology would most likely be designed with breeding ratios very close to 1.00, so that after an initial loading of enriched uranium and/or plutonium fuel, the reactor would then be refueled only with small deliveries of natural uranium metal. A quantity of natural uranium metal equivalent to a block about the size of a milk crate delivered once per month would be all the fuel such a 1 gigawatt reactor would need. Such self-contained breeders are currently envisioned as the final self-contained and self-supporting ultimate goal of nuclear reactor designers. The project was canceled in 1994 by United States Secretary of Energy Hazel O'Leary.

Other fast reactors

The graphite core of the Molten Salt Reactor Experiment

Another proposed fast reactor is a fast molten salt reactor, in which the molten salt's moderating properties are insignificant. This is typically achieved by replacing the light metal fluorides (e.g. LiF, BeF₂) in the salt carrier with heavier metal chlorides (e.g., KCl, RbCl, ZrCl₄).

Several prototype FBRs have been built, ranging in electrical output from a few light bulbs' equivalent (EBR-I, 1951) to over 1,000 MWe. As of 2006, the technology is not economically competitive to thermal reactor technology, but India, Japan, China, South Korea, and Russia are all committing substantial research funds to further development of fast breeder reactors, anticipating that rising uranium prices will change this in the long term. Germany, in contrast, abandoned the technology due to safety concerns. The SNR-300 fast breeder reactor was finished after 19 years despite cost overruns summing up to a total of €3.6 billion, only to then be abandoned.

India is also developing FBR technology using both uranium and thorium feedstocks.

Thermal breeder reactor

The Shippingport Reactor, used as a prototype light water breeder for five years beginning in August 1977

The advanced heavy water reactor (AHWR) is one of the few proposed large-scale uses of thorium. India is developing this technology, motivated by substantial thorium reserves; almost a third of the world's thorium reserves are in India, which lacks significant uranium reserves.

The third and final core of the Shippingport Atomic Power Station 60 MWe reactor was a light water thorium breeder, which began operating in 1977. It used pellets made of thorium dioxide and uranium-233 oxide; initially, the U-233 content of the pellets was 5–6% in the seed region, 1.5–3% in the blanket region, and none in the reflector region. It operated at 236 MWt, generating 60 MWe, and ultimately produced over 2.1 billion kilowatt hours of electricity. After five years, the core was removed and found to contain nearly 1.4% more fissile material than when it was installed, demonstrating that breeding from thorium had occurred.

The liquid fluoride thorium reactor (LFTR) is also planned as a thorium thermal breeder. Liquid-fluoride reactors may have attractive features, such as inherent safety, no need to manufacture fuel rods and possibly simpler reprocessing of the liquid fuel. This concept was first investigated at the Oak Ridge National Laboratory Molten-Salt Reactor Experiment in the 1960s. From 2012 it became the subject of renewed interest worldwide. Japan, India, China, the UK, and private US, Czech, and Australian companies have expressed intent to develop and commercialize the technology.

Discussion

Like many aspects of nuclear power, fast breeder reactors have been subject to much controversy over the years. In 2010 the International Panel on Fissile Materials said "After six decades and the expenditure of the equivalent of tens of billions of dollars, the promise of breeder reactors remains largely unfulfilled and efforts to commercialize them have been steadily cut back in most countries". In Germany, the United Kingdom, and the United States, breeder reactor development programs have been abandoned. The rationale for pursuing breeder reactors—sometimes explicit and sometimes implicit—was based on the following key assumptions:

• It was expected that uranium would be scarce and high-grade deposits would quickly become depleted if fission power were deployed on a large scale; the reality, however, is that since the end of the cold war, uranium has been much cheaper and more abundant than early designers expected.
• It was expected that breeder reactors would quickly become economically competitive with the light-water reactors that dominate nuclear power today, but the reality is that capital costs are at least 25% more than water-cooled reactors.
• It was thought that breeder reactors could be as safe and reliable as light-water reactors, but safety issues are cited as a concern with fast reactors that use a sodium coolant, where a leak could lead to a sodium fire.
• It was expected that the proliferation risks posed by breeders and their "closed" fuel cycle, in which plutonium would be recycled, could be managed. But since plutonium-breeding reactors produce plutonium from U238, and thorium reactors produce fissile U233 from thorium, all breeding cycles could theoretically pose proliferation risks. However U-232, which is always present in U-233 produced in breeder reactors, is a strong gamma-emitter via its daughter products, and would make weapon handling extremely hazardous and the weapon easy to detect.

Some past anti-nuclear advocates have become pro-nuclear power as a clean source of electricity since breeder reactors effectively recycle most of their waste. This solves one of the most-important negative issues of nuclear power. In the documentary Pandora's Promise, a case is made for breeder reactors because they provide a real high-kW alternative to fossil fuel energy. According to the movie, one pound of uranium provides as much energy as 5,000 barrels of oil.

FBRs have been built and operated in the United States, the United Kingdom, France, the former USSR, India, and Japan. The experimental FBR SNR-300 was built in Germany but never operated and eventually shut down amid political controversy following the Chernobyl disaster. As of 2019, two FBRs are being operated for power generation in Russia. Several reactors are planned, many for research related to the Generation IV reactor initiative.

Development and notable breeder reactors

Notable breeder reactors

Reactor	Country when built	Started	Shut down	Design MWe	Final MWe	Thermal Power MWt	Capacity factor	Number of coolant leaks	Neutron temperature	Coolant	Reactor class
DFR	UK	1962	1977	14	11	65	34%	7	Fast	NaK	Test
China Experimental Fast Reactor	China	2012	operating	20	22	65	40%	8	Fast	Sodium	Test
CFR-600	China	2017	commissioning/2023	642	682	1882	34%	27	Fast	Sodium	Commercial
BN-350	Soviet Union	1973	1999	350	52	750	43%	15	Fast	Sodium	Prototype
Rapsodie	France	1967	1983	0	–	40	–	2	Fast	Sodium	Test
Phénix	France	1975	2010	233	130	563	40.5%	31	Fast	Sodium	Prototype
PFR	UK	1976	1994	234	234	650	26.9%	20	Fast	Sodium	Prototype
KNK II	Germany	1977	1991	18	17	58	17.1%	21	Fast	Sodium	Research/Test
SNR-300	Germany	1985	1991	327	–	–	non-nuclear tests only	–	Fast	Sodium	Prototype/Commercial
BN-600	Soviet Union	1981	operating	560	560	1470	74.2%	27	Fast	Sodium	Prototype/Commercial (Gen2)
FFTF	US	1982	1993	0	–	400	–	1	Fast	Sodium	Test
Superphénix	France	1985	1998	1200	1200	3000	7.9%	7	Fast	Sodium	Prototype/Commercial (Gen2)
FBTR	India	1985	operating	13	–	40	–	6	Fast	Sodium	Test
PFBR	India	commissioning	commissioning	500	–	1250	–	–	Fast	Sodium	Prototype/Commercial (Gen3)
Jōyō	Japan	1977	2007	0	–	150	–	–	Fast	Sodium	Test
Monju	Japan	1995	2017	246	246	714	trial only	1	Fast	Sodium	Prototype
BN-800	Russia	2015	operating	789	880	2100	73.4%	–	Fast	Sodium	Prototype/Commercial (Gen3)
MSRE	US	1965	1969	0	–	7.4	–	–	Epithermal	Molten salt (FLiBe)	Test
Clementine	US	1946	1952	0	–	0.025	–	–	Fast	Mercury	World's First Fast Reactor
EBR-1	US	1951	1964	0.2	0.2	1.4	–	–	Fast	NaK	World's First Power Reactor
Fermi-1	US	1963	1972	66	66	200	–	–	Fast	Sodium	Prototype
EBR-2	US	1964	1994	19	19	62.5	–	–	Fast	Sodium	Experimental/Test
Shippingport	US	1977 as breeder	1982	60	60	236	–	–	Thermal	Light Water	Experimental-Core3

The Soviet Union (comprising Russia and other countries, dissolved in 1991) constructed a series of fast reactors, the first being mercury-cooled and fueled with plutonium metal, and the later plants sodium-cooled and fueled with plutonium oxide.

BR-1 (1955) was 100W (thermal) was followed by BR-2 at 100 kW and then the 5 MW BR-5.

BOR-60 (first criticality 1969) was 60 MW, with construction started in 1965.

BN-600 (1981), followed by Russia's BN-800 (2016)

Future plants

The Chinese Experimental Fast Reactor is a 65 MW (thermal), 20 MW (electric), sodium-cooled, pool-type reactor with a 30-year design lifetime and a target burnup of 100 MWd/kg.

India has been trying to develop fast breeder reactors for decades but suffered repeated delays. In 2012 an FBR called the Prototype Fast Breeder Reactor was due to be completed and commissioned. The program is intended to use fertile thorium-232 to breed fissile uranium-233. India is also pursuing thorium thermal breeder reactor technology. India's focus on thorium is due to the nation's large reserves, though known worldwide reserves of thorium are four times those of uranium. India's Department of Atomic Energy (DAE) said in 2007 that it would simultaneously construct four more breeder reactors of 500 MWe each including two at Kalpakkam.

BHAVINI, an Indian nuclear power company, was established in 2003 to construct, commission, and operate all stage II fast breeder reactors outlined in India's three stage nuclear power programme. To advance these plans, the Indian FBR-600 is a pool-type sodium-cooled reactor with a rating of 600 MWe.

The China Experimental Fast Reactor (CEFR) is a 25 MW(e) prototype for the planned China Prototype Fast Reactor (CFRP). It started generating power on 21 July 2011.

China also initiated a research and development project in thorium molten-salt thermal breeder-reactor technology (liquid fluoride thorium reactor), formally announced at the Chinese Academy of Sciences (CAS) annual conference in January 2011. Its ultimate target was to investigate and develop a thorium-based molten salt nuclear system over about 20 years.

Kirk Sorensen, former NASA scientist and chief nuclear technologist at Teledyne Brown Engineering, has long been a promoter of thorium fuel cycle and particularly liquid fluoride thorium reactors. In 2011, Sorensen founded Flibe Energy, a company aimed to develop 20–50 MW LFTR reactor designs to power military bases.

South Korea is developing a design for a standardized modular FBR for export, to complement the standardized PWR (pressurized water reactor) and CANDU designs they have already developed and built, but has not yet committed to building a prototype.

A cutaway model of the BN-600 reactor, superseded by the BN-800 reactor family

Construction of the BN-800 reactor

Russia has a plan for increasing its fleet of fast breeder reactors significantly. A BN-800 reactor (800 MWe) at Beloyarsk was completed in 2012, succeeding a smaller BN-600. In June 2014 the BN-800 was started in the minimum power mode. Working at 35% of nominal efficiency, the reactor contributed to the energy network on 10 December 2015. It reached its full power production in August 2016.

Plans for the construction of a larger BN-1200 reactor (1,200 MWe) was scheduled for completion in 2018, with two additional BN-1200 reactors built by the end of 2030. However, in 2015 Rosenergoatom postponed construction indefinitely to allow fuel design to be improved after more experience of operating the BN-800 reactor, and among cost concerns.

An experimental lead-cooled fast reactor, BREST-300 will be built at the Siberian Chemical Combine (SCC) in Seversk. The BREST (Russian: bystry reaktor so svintsovym teplonositelem, English: fast reactor with lead coolant) design is seen as a successor to the BN series and the 300 MWe unit at the SCC could be the forerunner to a 1,200 MWe version for wide deployment as a commercial power generation unit. The development program is as part of an Advanced Nuclear Technologies Federal Program 2010–2020 that seeks to exploit fast reactors for uranium efficiency while 'burning' radioactive substances that would otherwise be disposed of as waste. Its core would measure about 2.3 metres in diameter by 1.1 metres in height and contain 16 tonnes of fuel. The unit would be refuelled every year, with each fuel element spending five years in total within the core. Lead coolant temperature would be around 540 °C, giving a high efficiency of 43%, primary heat production of 700 MWt yielding electrical power of 300 MWe. The operational lifespan of the unit could be 60 years. The design is expected to be completed by NIKIET in 2014 for construction between 2016 and 2020.

On 16 February 2006, the United States, France, and Japan signed an "arrangement" to research and develop sodium-cooled fast reactors in support of the Global Nuclear Energy Partnership.

In April 2007 the Japanese government selected Mitsubishi Heavy Industries (MHI) as the "core company in FBR development in Japan". Shortly thereafter, MHI started a new company, Mitsubishi FBR Systems (MFBR) to develop and eventually sell FBR technology.

The Marcoule Nuclear Site in France, location of the Phénix (on the left)

In September 2010 the French government allocated €651.6 million to the Commissariat à l'énergie atomique to finalize the design of ASTRID (Advanced Sodium Technological Reactor for Industrial Demonstration), a 600 MW fourth-generation reactor design to be finalized in 2020. As of 2013 the UK had shown interest in the PRISM reactor and was working in concert with France to develop ASTRID. In 2019, CEA announced this design would not be built before mid-century.

In October 2010 GE Hitachi Nuclear Energy signed a memorandum of understanding with the operators of the US Department of Energy's Savannah River Site, which should allow the construction of a demonstration plant based on the company's S-PRISM fast breeder reactor prior to the design receiving full Nuclear Regulatory Commission (NRC) licensing approval. In October 2011 The Independent reported that the UK Nuclear Decommissioning Authority (NDA) and senior advisers within the Department for Energy and Climate Change (DECC) had asked for technical and financial details of PRISM, partly as a means of reducing the country's plutonium stockpile.

The traveling wave reactor (TWR) proposed in a patent by Intellectual Ventures is a fast breeder reactor designed to not need fuel reprocessing during the decades-long lifetime of the reactor. The breed-burn wave in the TWR design does not move from one end of the reactor to the other but gradually from the inside out. Moreover, as the fuel's composition changes through nuclear transmutation, fuel rods are continually reshuffled within the core to optimize the neutron flux and fuel usage at any given point in time. Thus, instead of letting the wave propagate through the fuel, the fuel itself is moved through a largely stationary burn wave. This is contrary to many media reports, which have popularized the concept as a candle-like reactor with a burn region that moves down a stick of fuel. By replacing a static core configuration with an actively managed "standing wave" or "soliton" core, TerraPower's design avoids the problem of cooling a highly variable burn region. Under this scenario, the reconfiguration of fuel rods is accomplished remotely by robotic devices; the containment vessel remains closed during the procedure, and there is no associated downtime.

Steroid

From Wikipedia, the free encyclopedia

https://en.wikipedia.org/wiki/Steroid

Structure of 24-ethyl-lanostane, a prototypical steroid with 32 carbon atoms. Its core ring system (ABCD), composed of 17 carbon atoms, is shown with IUPAC-approved ring lettering and atom numbering.

A steroid is an organic compound with four fused rings (designated A, B, C, and D) arranged in a specific molecular configuration.

Steroids have two principal biological functions: as important components of cell membranes that alter membrane fluidity; and as signaling molecules. Examples include the lipid cholesterol, sex hormones estradiol and testosterone, anabolic steroids, and the anti-inflammatory corticosteroid drug dexamethasone. Hundreds of steroids are found in fungi, plants, and animals. All steroids are manufactured in cells from the sterols lanosterol (opisthokonts) or cycloartenol (plants). Lanosterol and cycloartenol are derived from the cyclization of the triterpene squalene.

Steroids are named after the steroid cholesterol which was first described in gall stones from Ancient Greek chole- 'bile' and stereos 'solid'.

The steroid nucleus (core structure) is called gonane (cyclopentanoperhydrophenanthrene). It is typically composed of seventeen carbon atoms, bonded in four fused rings: three six-member cyclohexane rings (rings A, B and C in the first illustration) and one five-member cyclopentane ring (the D ring). Steroids vary by the functional groups attached to this four-ring core and by the oxidation state of the rings. Sterols are forms of steroids with a hydroxy group at position three and a skeleton derived from cholestane. Steroids can also be more radically modified, such as by changes to the ring structure, for example, cutting one of the rings. Cutting Ring B produces secosteroids one of which is vitamin D₃.

Space-filling representation

 

Ball-and-stick representation

 

5α-dihydroprogesterone (5α-DHP), a steroid. The shape of the four rings of most steroids is illustrated (carbon atoms in black, oxygens in red and hydrogens in grey). The nonpolar "slab" of hydrocarbon in the middle (grey, black) and the polar groups at opposing ends (red) are common features of natural steroids. 5α-DHP is an endogenous steroid hormone and a biosynthetic intermediate.

Nomenclature

Rings and functional groups

See also: Gonane and Sterane

Gonane, the simplest steroid, consisting only of the common steroid nucleus

Steroid 5α and 5β stereoisomers

Gonane, also known as steran or cyclopentanoperhydrophenanthrene, the simplest steroid and the nucleus of all steroids and sterols, is composed of seventeen carbon atoms in carbon-carbon bonds forming four fused rings in a three-dimensional shape. The three cyclohexane rings (A, B, and C in the first illustration) form the skeleton of a perhydro derivative of phenanthrene. The D ring has a cyclopentane structure. When the two methyl groups and eight carbon side chains (at C-17, as shown for cholesterol) are present, the steroid is said to have a cholestane framework. The two common 5α and 5β stereoisomeric forms of steroids exist because of differences in the side of the largely planar ring system where the hydrogen (H) atom at carbon-5 is attached, which results in a change in steroid A-ring conformation. Isomerisation at the C-21 side chain produces a parallel series of compounds, referred to as isosteroids.

Examples of steroid structures are:

• 
  Testosterone, the principal male sex hormone and an anabolic steroid
• 
  Cholic acid, a bile acid, showing the carboxylic acid and additional hydroxyl groups often present
• 
  Dexamethasone, a synthetic corticosteroid drug
• 
  Lanosterol, the biosynthetic precursor to animal steroids. The number of carbons (30) indicates its triterpenoid classification.
• 
  β-Sitosterol, a plant or phytosterol, with a fully branched hydrocarbon side chain at C-17 and an hydroxyl group at C-3

In addition to the ring scissions (cleavages), expansions and contractions (cleavage and reclosing to a larger or smaller rings)—all variations in the carbon-carbon bond framework—steroids can also vary:

• in the bond orders within the rings,
• in the number of methyl groups attached to the ring (and, when present, on the prominent side chain at C17),
• in the functional groups attached to the rings and side chain, and
• in the configuration of groups attached to the rings and chain.^[2]: 2–9

For instance, sterols such as cholesterol and lanosterol have a hydroxyl group attached at position C-3, while testosterone and progesterone have a carbonyl (oxo substituent) at C-3. Among these compounds, only lanosterol has two methyl groups at C-4. Cholesterol which has a C-5 to C-6 double bond, differs from testosterone and progesterone which have a C-4 to C-5 double bond.

Cholesterol, a prototypical animal sterol. This structural lipid and key steroid biosynthetic precursor.

5α-cholestane, a common steroid core

Naming convention

Almost all biologically relevant steroids can be presented as a derivative of a parent cholesterol-like hydrocarbon structure that serves as a skeleton. These parent structures have specific names, such as pregnane, androstane, etc. The derivatives carry various functional groups called suffixes or prefixes after the respective numbers, indicating their position in the steroid nucleus. There are widely used trivial steroid names of natural origin with significant biologic activity, such as progesterone, testosterone or cortisol. Some of these names are defined in The Nomenclature of Steroids. These trivial names can also be used as a base to derive new names, however, by adding prefixes only rather than suffixes, e.g., the steroid 17α-hydroxyprogesterone has a hydroxy group (-OH) at position 17 of the steroid nucleus comparing to progesterone.

The letters α and β denote absolute stereochemistry at chiral centers—a specific nomenclature distinct from the R/S convention of organic chemistry to denote absolute configuration of functional groups, known as Cahn–Ingold–Prelog priority rules. The R/S convention assigns priorities to substituents on a chiral center based on their atomic number. The highest priority group is assigned to the atom with the highest atomic number, and the lowest priority group is assigned to the atom with the lowest atomic number. The molecule is then oriented so that the lowest priority group points away from the viewer, and the remaining three groups are arranged in order of decreasing priority around the chiral center. If this arrangement is clockwise, it is assigned an R configuration; if it is counterclockwise, it is assigned an S configuration. In contrast, steroid nomenclature uses α and β to denote stereochemistry at chiral centers. The α and β designations are based on the orientation of substituents relative to each other in a specific ring system. In general, α refers to a substituent that is oriented towards the plane of the ring system, while β refers to a substituent that is oriented away from the plane of the ring system. In steroids drawn from the standard perspective used in this paper, α-bonds are depicted on figures as dashed wedges and β-bonds as solid wedges.

The name "11-deoxycortisol" is an example of a derived name that uses cortisol as a parent structure without an oxygen atom (hence "deoxy") attached to position 11 (as a part of a hydroxy group). The numbering of positions of carbon atoms in the steroid nucleus is set in a template found in the Nomenclature of Steroids that is used regardless of whether an atom is present in the steroid in question.

Unsaturated carbons (generally, ones that are part of a double bond) in the steroid nucleus are indicated by changing -ane to -ene. This change was traditionally done in the parent name, adding a prefix to denote the position, with or without Δ (Greek capital delta) which designates unsaturation, for example, 4-pregnene-11β,17α-diol-3,20-dione (also Δ⁴-pregnene-11β,17α-diol-3,20-dione) or 4-androstene-3,11,17-trione (also Δ⁴-androstene-3,11,17-trione). However, the Nomenclature of Steroids recommends the locant of a double bond to be always adjacent to the syllable designating the unsaturation, therefore, having it as a suffix rather than a prefix, and without the use of the Δ character, i.e. pregn-4-ene-11β,17α-diol-3,20-dione or androst-4-ene-3,11,17-trione. The double bond is designated by the lower-numbered carbon atom, i.e. "Δ⁴-" or "4-ene" means the double bond between positions 4 and 5. The saturation of carbons of a parent steroid can be done by adding "dihydro-" prefix, i.e., a saturation of carbons 4 and 5 of testosterone with two hydrogen atoms is 4,5α-dihydrotestosterone or 4,5β-dihydrotestosterone. Generally, when there is no ambiguity, one number of a hydrogen position from a steroid with a saturated bond may be omitted, leaving only the position of the second hydrogen atom, e.g., 5α-dihydrotestosterone or 5β-dihydrotestosterone. The Δ⁵-steroids are those with a double bond between carbons 5 and 6 and the Δ⁴ steroids are those with a double bond between carbons 4 and 5.

The abbreviations like "P4" for progesterone and "A4" for androstenedione for refer to Δ⁴-steroids, while "P5" for pregnenolone and "A5" for androstenediol refer to Δ⁵-steroids.

The suffix -ol denotes a hydroxy group, while the suffix -one denotes an oxo group. When two or three identical groups are attached to the base structure at different positions, the suffix is indicated as -diol or -triol for hydroxy, and -dione or -trione for oxo groups, respectively. For example, 5α-pregnane-3α,17α-diol-20-one has a hydrogen atom at the 5α position (hence the "5α-" prefix), two hydroxy groups (-OH) at the 3α and 17α positions (hence "3α,17α-diol" suffix) and an oxo group (=O) at the position 20 (hence the "20-one" suffix). However, erroneous use of suffixes can be found, e.g., "5α-pregnan-17α-diol-3,11,20-trione" [sic] — since it has just one hydroxy group (at 17α) rather than two, then the suffix should be -ol, rather than -diol, so that the correct name to be "5α-pregnan-17α-ol-3,11,20-trione".

According to the rule set in the Nomenclature of Steroids, the terminal "e" in the parent structure name should be elided before the vowel (the presence or absence of a number does not affect such elision). This means, for instance, that if the suffix immediately appended to the parent structure name begins with a vowel, the trailing "e" is removed from that name. An example of such removal is "5α-pregnan-17α-ol-3,20-dione", where the last "e" of "pregnane" is dropped due to the vowel ("o") at the beginning of the suffix -ol. Some authors incorrectly use this rule, eliding the terminal "e" where it should be kept, or vice versa.

The term "11-oxygenated" refers to the presence of an oxygen atom as an oxo (=O) or hydroxy (-OH) substituent at carbon 11. "Oxygenated" is consistently used within the chemistry of the steroids since the 1950s. Some studies use the term "11-oxyandrogens" as an abbreviation for 11-oxygenated androgens, to emphasize that they all have an oxygen atom attached to carbon at position 11. However, in chemical nomenclature, the prefix "oxy" is associated with ether functional groups, i.e., a compound with an oxygen atom connected to two alkyl or aryl groups (R-O-R), therefore, using "oxy" within the name of a steroid class may be misleading. One can find clear examples of "oxygenated" to refer to a broad class of organic molecules containing a variety of oxygen containing functional groups in other domains of organic chemistry, and it is appropriate to use this convention.

Even though "keto" is a standard prefix in organic chemistry, the 1989 recommendations of the Joint Commission on Biochemical Nomenclature discourage the application of the prefix "keto" for steroid names, and favor the prefix "oxo" (e.g., 11-oxo steroids rather than 11-keto steroids), because "keto" includes the carbon that is part of the steroid nucleus and the same carbon atom should not be specified twice.

Species distribution

Steroids are found in all domains of life including bacteria, archaea, and eukaryotes. In eukaryotes, steroids are found in fungi, plants, and animals.

Prokaryotic

This section is missing information about non-eukaryotic type sterol framework – see PMID 27446030, fig 4/5, group 1 oxidosqualene cyclase. Please expand the section to include this information. Further details may exist on the talk page. (November 2021)

In prokaryotes, biosynthetic pathways exist for the tetracyclic steroid framework (e.g. in myxobacteria) – where its origin from eukaryotes is conjectured – and the more-common pentacyclic triterpinoid hopanoid framework.

Fungal

Fungal steroids include the ergosterols, which are involved in maintaining the integrity of the fungal cellular membrane. Various antifungal drugs, such as amphotericin B and azole antifungals, utilize this information to kill pathogenic fungi. Fungi can alter their ergosterol content (e.g. through loss of function mutations in the enzymes ERG3 or ERG6, inducing depletion of ergosterol, or mutations that decrease the ergosterol content) to develop resistance to drugs that target ergosterol.

Ergosterol is analogous to the cholesterol found in the cellular membranes of animals (including humans), or the phytosterols found in the cellular membranes of plants. All mushrooms contain large quantities of ergosterol, in the range of tens to hundreds of milligrams per 100 grams of dry weight. Oxygen is necessary for the synthesis of ergosterol in fungi.

Ergosterol is responsible for the vitamin D content found in mushrooms; ergosterol is chemically converted into provitamin D2 by exposure to ultraviolet light. Provitamin D2 spontaneously forms vitamin D2. However, not all fungi utilize ergosterol in their cellular membranes; for example, the pathogenic fungal species Pneumocystis jirovecii does not, which has important clinical implications (given the mechanism of action of many antifungal drugs). Using the fungus Saccharomyces cerevisiae as an example, other major steroids include ergosta‐5,7,22,24(28)‐tetraen‐3β‐ol, zymosterol, and lanosterol. S. cerevisiae utilizes 5,6‐dihydroergosterol in place of ergosterol in its cell membrane.

Plant

Plant steroids include steroidal alkaloids found in Solanaceae and Melanthiaceae (specially the genus Veratrum), cardiac glycosides, the phytosterols and the brassinosteroids (which include several plant hormones).

Animal

Animal steroids include compounds of vertebrate and insect origin, the latter including ecdysteroids such as ecdysterone (controlling molting in some species). Vertebrate examples include the steroid hormones and cholesterol; the latter is a structural component of cell membranes that helps determine the fluidity of cell membranes and is a principal constituent of plaque (implicated in atherosclerosis). Steroid hormones include:

• Sex hormones, which influence sex differences and support reproduction. These include androgens, estrogens, and progestogens.
• Corticosteroids, including most synthetic steroid drugs, with natural product classes the glucocorticoids (which regulate many aspects of metabolism and immune function) and the mineralocorticoids (which help maintain blood volume and control renal excretion of electrolytes)
• Anabolic steroids, natural and synthetic, which interact with androgen receptors to increase muscle and bone synthesis. In popular use, the term "steroids" often refers to anabolic steroids.

Types

By function

The major classes of steroid hormones, with prominent members and examples of related functions, are:

• Corticosteroids:
  • Glucocorticoids:
    • Cortisol, a glucocorticoid whose functions include immunosuppression
  • Mineralocorticoids:
    • Aldosterone, a mineralocorticoid that helps regulate blood pressure through water and electrolyte balance
• Sex steroids:
  • Progestogens:
    • Progesterone, which regulates cyclical changes in the endometrium of the uterus and maintains a pregnancy
  • Androgens:
    • Testosterone, which contributes to the development and maintenance of male secondary sex characteristics
  • Estrogens:
    • Estradiol, which contributes to the development and maintenance of female secondary sex characteristics

Additional classes of steroids include:

• Neurosteroids such as DHEATooltip dehydroepiandrosterone and allopregnanolone
• Bile acids such as taurocholic acid
• Aminosteroid neuromuscular blocking agents (mainly synthetic) such as pancuronium bromide
• Steroidal antiandrogens (mainly synthetic) such as cyproterone acetate
• Steroidogenesis inhibitors (mainly exogenous) such as alfatradiol
• Membrane sterols such as cholesterol, ergosterol, and various phytosterols
• Toxins such as steroidal saponins and cardenolides/cardiac glycosides

As well as the following class of secosteroids (open-ring steroids):

• Vitamin D forms such as ergocalciferol, cholecalciferol, and calcitriol

By structure

Intact ring system

Steroids can be classified based on their chemical composition. One example of how MeSH performs this classification is available at the Wikipedia MeSH catalog. Examples of this classification include:

Cholecalciferol (vitamin D₃), an example of a 9,10-secosteroid

Cyclopamine, an example of a complex C-nor-D-homosteroid

Class	Example	Number of carbon atoms
Cholestanes	Cholesterol	27
Cholanes	Cholic acid	24
Pregnanes	Progesterone	21
Androstanes	Testosterone	19
Estranes	Estradiol	18

In biology, it is common to name the above steroid classes by the number of carbon atoms present when referring to hormones: C₁₈-steroids for the estranes (mostly estrogens), C₁₉-steroids for the androstanes (mostly androgens), and C₂₁-steroids for the pregnanes (mostly corticosteroids). The classification "17-ketosteroid" is also important in medicine.

The gonane (steroid nucleus) is the parent 17-carbon tetracyclic hydrocarbon molecule with no alkyl sidechains.

Cleaved, contracted, and expanded rings

Secosteroids (Latin seco, "to cut") are a subclass of steroidal compounds resulting, biosynthetically or conceptually, from scission (cleavage) of parent steroid rings (generally one of the four). Major secosteroid subclasses are defined by the steroid carbon atoms where this scission has taken place. For instance, the prototypical secosteroid cholecalciferol, vitamin D₃ (shown), is in the 9,10-secosteroid subclass and derives from the cleavage of carbon atoms C-9 and C-10 of the steroid B-ring; 5,6-secosteroids and 13,14-steroids are similar.

Norsteroids (nor-, L. norma; "normal" in chemistry, indicating carbon removal) and homosteroids (homo-, Greek homos; "same", indicating carbon addition) are structural subclasses of steroids formed from biosynthetic steps. The former involves enzymic ring expansion-contraction reactions, and the latter is accomplished (biomimetically) or (more frequently) through ring closures of acyclic precursors with more (or fewer) ring atoms than the parent steroid framework.

Combinations of these ring alterations are known in nature. For instance, ewes who graze on corn lily ingest cyclopamine (shown) and veratramine, two of a sub-family of steroids where the C- and D-rings are contracted and expanded respectively via a biosynthetic migration of the original C-13 atom. Ingestion of these C-nor-D-homosteroids results in birth defects in lambs: cyclopia from cyclopamine and leg deformity from veratramine. A further C-nor-D-homosteroid (nakiterpiosin) is excreted by Okinawan cyanobacteriosponges. e.g., Terpios hoshinota, leading to coral mortality from black coral disease. Nakiterpiosin-type steroids are active against the signaling pathway involving the smoothened and hedgehog proteins, a pathway which is hyperactive in a number of cancers.

Biological significance

Steroids and their metabolites often function as signalling molecules (the most notable examples are steroid hormones), and steroids and phospholipids are components of cell membranes. Steroids such as cholesterol decrease membrane fluidity. Similar to lipids, steroids are highly concentrated energy stores. However, they are not typically sources of energy; in mammals, they are normally metabolized and excreted.

Steroids play critical roles in a number of disorders, including malignancies like prostate cancer, where steroid production inside and outside the tumour promotes cancer cell aggressiveness.

Biosynthesis and metabolism

Simplification of the end of the steroid synthesis pathway, where the intermediates isopentenyl pyrophosphate (PP or IPP) and dimethylallyl pyrophosphate (DMAPP) form geranyl pyrophosphate (GPP), squalene and lanosterol (the first steroid in the pathway)

The hundreds of steroids found in animals, fungi, and plants are made from lanosterol (in animals and fungi; see examples above) or cycloartenol (in other eukaryotes). Both lanosterol and cycloartenol derive from cyclization of the triterpenoid squalene. Lanosterol and cycloartenol are sometimes called protosterols because they serve as the starting compounds for all other steroids.

Steroid biosynthesis is an anabolic pathway which produces steroids from simple precursors. A unique biosynthetic pathway is followed in animals (compared to many other organisms), making the pathway a common target for antibiotics and other anti-infection drugs. Steroid metabolism in humans is also the target of cholesterol-lowering drugs, such as statins. In humans and other animals the biosynthesis of steroids follows the mevalonate pathway, which uses acetyl-CoA as building blocks for dimethylallyl diphosphate (DMAPP) and isopentenyl diphosphate (IPP).

In subsequent steps DMAPP and IPP conjugate to form farnesyl diphosphate (FPP), which further conjugates with each other to form the linear triterpenoid squalene. Squalene biosynthesis is catalyzed by squalene synthase, which belongs to the squalene/phytoene synthase family. Subsequent epoxidation and cyclization of squalene generate lanosterol, which is the starting point for additional modifications into other steroids (steroidogenesis). In other eukaryotes, the cyclization product of epoxidized squalene (oxidosqualene) is cycloartenol.

Mevalonate pathway

Mevalonate pathway

Main article: Mevalonate pathway

The mevalonate pathway (also called HMG-CoA reductase pathway) begins with acetyl-CoA and ends with dimethylallyl diphosphate (DMAPP) and isopentenyl diphosphate (IPP).

DMAPP and IPP donate isoprene units, which are assembled and modified to form terpenes and isoprenoids (a large class of lipids, which include the carotenoids and form the largest class of plant natural products). Here, the isoprene units are joined to make squalene and folded into a set of rings to make lanosterol. Lanosterol can then be converted into other steroids, such as cholesterol and ergosterol.

Two classes of drugs target the mevalonate pathway: statins (like rosuvastatin), which are used to reduce elevated cholesterol levels, and bisphosphonates (like zoledronate), which are used to treat a number of bone-degenerative diseases.

Steroidogenesis

Human steroidogenesis, with the major classes of steroid hormones, individual steroids and enzymatic pathways. Changes in molecular structure from a precursor are highlighted in white.

See also: Steroidogenic enzyme

Steroidogenesis is the biological process by which steroids are generated from cholesterol and changed into other steroids. The pathways of steroidogenesis differ among species. The major classes of steroid hormones, as noted above (with their prominent members and functions), are the progestogens, corticosteroids (corticoids), androgens, and estrogens. Human steroidogenesis of these classes occurs in a number of locations:

• Progestogens are the precursors of all other human steroids, and all human tissues which produce steroids must first convert cholesterol to pregnenolone. This conversion is the rate-limiting step of steroid synthesis, which occurs inside the mitochondrion of the respective tissue.
• Cortisol, corticosterone, aldosterone are produced in the adrenal cortex.
• Estradiol, estrone and progesterone are made primarily in the ovary, estriol in placenta during pregnancy, and testosterone primarily in the testes some testosterone may also be produced in the adrenal cortex).
• Estradiol is converted from testosterone directly (in males), or via the primary pathway DHEA – androstenedione – estrone and secondarily via testosterone (in females).
• Stromal cells have been shown to produce steroids in response to signaling produced by androgen-starved prostate cancer cells.
• Some neurons and glia in the central nervous system (CNS) express the enzymes required for the local synthesis of pregnenolone, progesterone, DHEA and DHEAS, de novo or from peripheral sources.

Alternative pathways

In plants and bacteria, the non-mevalonate pathway (MEP pathway) uses pyruvate and glyceraldehyde 3-phosphate as substrates to produce IPP and DMAPP.

During diseases pathways otherwise not significant in healthy humans can become utilized. For example, in one form of congenital adrenal hyperplasia a deficiency in the 21-hydroxylase enzymatic pathway leads to an excess of 17α-Hydroxyprogesterone (17-OHP) – this pathological excess of 17-OHP in turn may be converted to dihydrotestosterone (DHT, a potent androgen) through among others 17,20 Lyase (a member of the cytochrome P450 family of enzymes), 5α-Reductase and 3α-Hydroxysteroid dehydrogenase.

Catabolism and excretion

Steroids are primarily oxidized by cytochrome P450 oxidase enzymes, such as CYP3A4. These reactions introduce oxygen into the steroid ring, allowing the cholesterol to be broken up by other enzymes into bile acids. These acids can then be eliminated by secretion from the liver in bile. The expression of the oxidase gene can be upregulated by the steroid sensor PXR when there is a high blood concentration of steroids. Steroid hormones, lacking the side chain of cholesterol and bile acids, are typically hydroxylated at various ring positions or oxidized at the 17 position, conjugated with sulfate or glucuronic acid and excreted in the urine.

Isolation, structure determination, and methods of analysis

Steroid isolation, depending on context, is the isolation of chemical matter required for chemical structure elucidation, derivitzation or degradation chemistry, biological testing, and other research needs (generally milligrams to grams, but often more or the isolation of "analytical quantities" of the substance of interest (where the focus is on identifying and quantifying the substance (for example, in biological tissue or fluid). The amount isolated depends on the analytical method, but is generally less than one microgram.

The methods of isolation to achieve the two scales of product are distinct, but include extraction, precipitation, adsorption, chromatography, and crystallization. In both cases, the isolated substance is purified to chemical homogeneity; combined separation and analytical methods, such as LC-MS, are chosen to be "orthogonal"—achieving their separations based on distinct modes of interaction between substance and isolating matrix—to detect a single species in the pure sample.

Structure determination refers to the methods to determine the chemical structure of an isolated pure steroid, using an evolving array of chemical and physical methods which have included NMR and small-molecule crystallography. Methods of analysis overlap both of the above areas, emphasizing analytical methods to determining if a steroid is present in a mixture and determining its quantity.

Chemical synthesis

Microbial catabolism of phytosterol side chains yields C-19 steroids, C-22 steroids, and 17-ketosteroids (i.e. precursors to adrenocortical hormones and contraceptives). The addition and modification of functional groups is key when producing the wide variety of medications available within this chemical classification. These modifications are performed using conventional organic synthesis and/or biotransformation techniques.

Precursors

Semisynthesis

The semisynthesis of steroids often begins from precursors such as cholesterol, phytosterols, or sapogenins. The efforts of Syntex, a company involved in the Mexican barbasco trade, used Dioscorea mexicana to produce the sapogenin diosgenin in the early days of the synthetic steroid pharmaceutical industry.

Total synthesis

Some steroidal hormones are economically obtained only by total synthesis from petrochemicals (e.g. 13-alkyl steroids). For example, the pharmaceutical Norgestrel begins from methoxy-1-tetralone, a petrochemical derived from phenol.

Research awards

A number of Nobel Prizes have been awarded for steroid research, including:

• 1927 (Chemistry) Heinrich Otto Wieland — Constitution of bile acids and sterols and their connection to vitamins
• 1928 (Chemistry) Adolf Otto Reinhold Windaus — Constitution of sterols and their connection to vitamins
• 1939 (Chemistry) Adolf Butenandt and Leopold Ružička — Isolation and structural studies of steroid sex hormones, and related studies on higher terpenes
• 1950 (Physiology or Medicine) Edward Calvin Kendall, Tadeus Reichstein, and Philip Hench — Structure and biological effects of adrenal hormones
• 1965 (Chemistry) Robert Burns Woodward — In part, for the synthesis of cholesterol, cortisone, and lanosterol
• 1969 (Chemistry) Derek Barton and Odd Hassel — Development of the concept of conformation in chemistry, emphasizing the steroid nucleus
• 1975 (Chemistry) Vladimir Prelog — In part, for developing methods to determine the stereochemical course of cholesterol biosynthesis from mevalonic acid via squalene