Vitamin A

From Wikipedia, the free encyclopedia

Chemical structure of retinol, one of the major forms of vitamin A

Vitamin A is a group of unsaturated nutritional organic compounds, that includes retinol, retinal, retinoic acid, and several provitamin A carotenoids, among which beta-carotene is the most important.^[1] Vitamin A has multiple functions: it is important for growth and development, for the maintenance of the immune system and good vision.^[2] Vitamin A is needed by the retina of the eye in the form of retinal, which combines with protein opsin to form rhodopsin, the light-absorbing molecule^[3] necessary for both low-light (scotopic vision) and color vision.^[4] Vitamin A also functions in a very different role as retinoic acid (an irreversibly oxidized form of retinol), which is an important hormone-like growth factor for epithelial and other cells.^[2][5]

In foods of animal origin, the major form of vitamin A is an ester, primarily retinyl palmitate, which is converted to retinol (chemically an alcohol) in the small intestine. The retinol form functions as a storage form of the vitamin, and can be converted to and from its visually active aldehyde form, retinal.

All forms of vitamin A have a beta-ionone ring to which an isoprenoid chain is attached, called a retinyl group. Both structural features are essential for vitamin activity.^[6] The orange pigment of carrots (beta-carotene) can be represented as two connected retinyl groups, which are used in the body to contribute to vitamin A levels. Alpha-carotene and gamma-carotene also have a single retinyl group, which give them some vitamin activity. None of the other carotenes have vitamin activity. The carotenoid beta-cryptoxanthin possesses an ionone group and has vitamin activity in humans.
Vitamin A can be found in two principal forms in foods:

• Retinol, the form of vitamin A absorbed when eating animal food sources, is a yellow, fat-soluble substance. Since the pure alcohol form is unstable, the vitamin is found in tissues in a form of retinyl ester. It is also commercially produced and administered as esters such as retinyl acetate or palmitate.^[7]

• The carotenes alpha-carotene, beta-carotene, gamma-carotene; and the xanthophyll beta-cryptoxanthin (all of which contain beta-ionone rings), but no other carotenoids, function as provitamin A in herbivores and omnivore animals, which possess the enzyme beta-carotene 15,15'-dioxygenase which cleaves beta-carotene in the intestinal mucosa and converts it to retinol.^[8] In general, carnivores are poor converters of ionone-containing carotenoids, and pure carnivores such as cats and ferrets lack beta-carotene 15,15'-dioxygenase and cannot convert any carotenoids to retinal (resulting in none of the carotenoids being forms of vitamin A for these species).

§History

The discovery of vitamin A may have stemmed from research dating back to 1816, when physiologist François Magendie observed that dogs deprived of nutrition developed corneal ulcers and had a high mortality rate.^[9] In 1912, Frederick Gowland Hopkins demonstrated that unknown accessory factors found in milk, other than carbohydrates, proteins, and fats were necessary for growth in rats. Hopkins received a Nobel Prize for this discovery in 1929.^[9][10] By 1917, one of these substances was independently discovered by Elmer McCollum at the University of Wisconsin–Madison, and Lafayette Mendel and Thomas Burr Osborne at Yale University who studied the role of fats in the diet. The "accessory factors" were termed "fat soluble" in 1918 and later "vitamin A" in 1920. In 1919, Harry Steenbock (University of Wisconsin) proposed a relationship between yellow plant pigments (beta-carotene) and vitamin A. In 1931, Swiss chemist Paul Karrer described the chemical structure of vitamin A.^[9] Vitamin A was first synthesized in 1947 by two Dutch chemists, David Adriaan van Dorp and Jozef Ferdinand Arens.

§Equivalencies of retinoids and carotenoids (IU)

As some carotenoids can be converted into vitamin A, attempts have been made to determine how much of them in the diet is equivalent to a particular amount of retinol, so that comparisons can be made of the benefit of different foods. The situation can be confusing because the accepted equivalences have changed. For many years, a system of equivalencies in which an international unit (IU) was equal to 0.3 μg of retinol, 0.6 μg of β-carotene, or 1.2 μg of other provitamin-A carotenoids was used.^[11] Later, a unit called retinol equivalent (RE) was introduced. Prior to 2001, one RE corresponded to 1 μg retinol, 2 μg β-carotene dissolved in oil (it is only partly dissolved in most supplement pills, due to very poor solubility in any medium), 6 μg β-carotene in normal food (because it is not absorbed as well as when in oils), and 12 μg of either α-carotene, γ-carotene, or β-cryptoxanthin in food.

Newer research has shown that the absorption of provitamin-A carotenoids is only half as much as previously thought. As a result, in 2001 the US Institute of Medicine recommended a new unit, the retinol activity equivalent (RAE). Each μg RAE corresponds to 1 μg retinol, 2 μg of β-carotene in oil, 12 μg of "dietary" beta-carotene, or 24 μg of the three other dietary provitamin-A carotenoids.^[12]

Substance and its chemical environment	Micrograms of retinol equivalent per microgram of the substance
retinol	1
beta-carotene, dissolved in oil	1/2
beta-carotene, common dietary	1/12
alpha-carotene, common dietary	1/24
gamma-carotene, common dietary	1/24
beta-cryptoxanthin, common dietary	1/24

Because the conversion of retinol from provitamin carotenoids by the human body is actively regulated by the amount of retinol available to the body, the conversions apply strictly only for vitamin A-deficient humans. The absorption of provitamins depends greatly on the amount of lipids ingested with the provitamin; lipids increase the uptake of the provitamin.^[13]

The conclusion that can be drawn from the newer research is that fruits and vegetables are not as useful for obtaining vitamin A as was thought; in other words, the IUs that these foods were reported to contain were worth much less than the same number of IUs of fat-dissolved oils and (to some extent) supplements. This is important for vegetarians, as night blindness is prevalent in countries where little meat or vitamin A-fortified foods are available.

A sample vegan diet for one day that provides sufficient vitamin A has been published by the Food and Nutrition Board (page 120^[12]). On the other hand, reference values for retinol or its equivalents, provided by the National Academy of Sciences, have decreased. The RDA (for men) of 1968 was 5000 IU (1500 μg retinol). In 1974, the RDA was set to 1000 RE (1000 μg retinol), whereas now the Dietary Reference Intake is 900 RAE (900 μg or 3000 IU retinol). This is equivalent to 1800 μg of β-carotene supplement (3000 IU) or 10800 μg of β-carotene in food (18000 IU).

§Recommended daily allowance

Vitamin A
Dietary Reference Intake:^[14]

Life stage group	RDA Adequate intakes (AI*) μg/day	Upper limit μg/day
Infants 0–6 months 7–12 months	400* 500*	600 600
Children 1–3 years 4–8 years	300 400	600 900
Males 9–13 years 14–18 years 19 – >70 years	600 900 900	1700 2800 3000
Females 9–13 years 14–18 years 19 – >70 years	600 700 700	1700 2800 3000
Pregnancy <19 br="" years=""> 19 – >50 years	750 770	2800 3000
Lactation <19 br="" years=""> 19 – >50 years	1200 1300	2800 3000

(The limit is for synthetic and natural retinol ester forms of vitamin A. Carotene forms from dietary sources are not toxic.^[15][16])

According to the Institute of Medicine of the National Academies, "RDAs are set to meet the needs of almost all (97 to 98%) individuals in a group. For healthy breastfed infants, the AI is the mean intake. The AI for other life stage and gender groups is believed to cover the needs of all individuals in the group, but lack of data prevents being able to specify with confidence the percentage of individuals covered by this intake."^[17]

§Sources

carrots

Vitamin A is found naturally in many foods:

• cod liver oil (30000 μg)
• liver (turkey) (8058 μg 895%)
• liver (beef, pork, fish) (6500 μg 722%)
• liver (chicken) (3296 μg 366%)
• dandelion greens (5588 IU 112%)^[18]
• sweet potato (961 μg 107%)
• carrot (835 μg 93%)
• broccoli leaf (800 μg 89%) – According to USDA database, broccoli florets have much less.^[19]
• broccoli florets (31 μg 3%)
• butter (684 μg 76%)
• kale (681 μg 76%)
• spinach (469 μg 52%)
• pumpkin (400 μg 41%)
• collard greens (333 μg 37%)
• Cheddar cheese (265 μg 29%)
• cantaloupe melon (169 μg 19%)
• egg (140 μg 16%)
• apricot (96 μg 11%)
• papaya (55 μg 6%)
• mango (38 μg 4%)
• pea (38 μg 4%)
• milk (28 μg 3%)
• tomatoes
• seaweed

Note: Data taken from USDA database.^[20] Bracketed values are retinol activity equivalences (RAEs) and percentage of the adult male RDA, per 100 grams of the foodstuff (average).

Conversion of carotene to retinol varies from person to person and bioavailability of carotene in food varies.^[21][22]

§Metabolic functions

Vitamin A plays a role in a variety of functions throughout the body, such as:

• Vision
• Gene transcription
• Immune function
• Embryonic development and reproduction
• Bone metabolism
• Hematopoiesis
• Skin and cellular health
• Antioxidant activity

§Vision

The role of vitamin A in the visual cycle is specifically related to the retinal form. Within the eye, 11-cis-retinal is bound to protein "opsin" to form rhodopsin in rods^[3] and iodopsin (cones) at conserved lysine residues. As light enters the eye, the 11-cis-retinal is isomerized to the all-"trans" form. The all-"trans" retinal dissociates from the opsin in a series of steps called photo-bleaching. This isomerization induces a nervous signal along the optic nerve to the visual center of the brain.
After separating from opsin, the all-"trans"-retinal is recycled and converted back to the 11-"cis"-retinal form by a series of enzymatic reactions. In addition, some of the all-"trans" retinal may be converted to all-"trans" retinol form and then transported with an interphotoreceptor retinol-binding protein (IRBP) to the pigment epithelial cells. Further esterification into all-"trans" retinyl esters allow for storage of all-trans-retinol within the pigment epithelial cells to be reused when needed.^[23] The final stage is conversion of 11-cis-retinal will rebind to opsin to reform rhodopsin (visual purple) in the retina. Rhodopsin is needed to see in low light (contrast) as well as for night vision. Kühne showed that the regeneration of rhodopsin only occurs when retina is attached to retinal pigmented epithelial (RPE).^[3] It is for this reason that a deficiency in vitamin A will inhibit the reformation of rhodopsin and lead to one of the first symptoms, night blindness.^[24]

§Gene transcription

Vitamin A, in the retinoic acid form, plays an important role in gene transcription. Once retinol has been taken up by a cell, it can be oxidized to retinal (retinaldehyde) by retinol dehydrogenases and then retinaldehyde can be oxidized to retinoic acid by retinaldehyde dehydrogenases.^[25] The conversion of retinaldehyde to retinoic acid is an irreversible step, meaning that the production of retinoic acid is tightly regulated, due to its activity as a ligand for nuclear receptors.^[23] The physiological form of retinoic acid (all-trans-retinoic acid) regulates gene transcription by binding to nuclear receptors known as retinoic acid receptors (RARs) which are bound to DNA as heterodimers with retinoid "X" receptors (RXRs). RAR and RXR must dimerize before they can bind to the DNA. RAR will form a heterodimer with RXR (RAR-RXR), but it does not readily form a homodimer (RAR-RAR). RXR, on the other hand, may form a homodimer (RXR-RXR) and will form heterodimers with many other nuclear receptors as well, including the thyroid hormone receptor (RXR-TR), the Vitamin D₃ receptor (RXR-VDR), the peroxisome proliferator-activated receptor (RXR-PPAR) and the liver "X" receptor (RXR-LXR).^[26] The RAR-RXR heterodimer recognizes retinoic acid response elements (RAREs) on the DNA whereas the RXR-RXR homodimer recognizes retinoid "X" response elements (RXREs) on the DNA; although several RAREs near target genes have been shown to control physiological processes,^[25] this has not been demonstrated for RXREs. The heterodimers of RXR with nuclear receptors other than RAR (i.e. TR, VDR, PPAR, LXR) bind to various distinct response elements on the DNA to control processes not regulated by vitamin A.^[23] Upon binding of retinoic acid to the RAR component of the RAR-RXR heterodimer, the receptors undergo a conformational change that causes co-repressors to dissociate from the receptors. Coactivators can then bind to the receptor complex, which may help to loosen the chromatin structure from the histones or may interact with the transcriptional machinery.^[26] This response can upregulate (or downregulate) the expression of target genes, including Hox genes as well as the genes that encode for the receptors themselves (i.e. RAR-beta in mammals).^[23]

§Dermatology

Vitamin A, and more specifically, retinoic acid, appears to maintain normal skin health by switching on genes and differentiating keratinocytes (immature skin cells) into mature epidermal cells.^[27] Exact mechanisms behind pharmacological retinoid therapy agents in the treatment of dermatological diseases are being researched. For the treatment of acne, the most prescribed retinoid drug is 13-cis retinoic acid (isotretinoin). It reduces the size and secretion of the sebaceous glands. Although it is known that 40 mg of isotretinoin will break down to an equivalent of 10 mg of ATRA — the mechanism of action of the drug (original brand name Accutane) remains unknown and is a matter of some controversy. Isotretinoin reduces bacterial numbers in both the ducts and skin surface. This is thought to be a result of the reduction in sebum, a nutrient source for the bacteria. Isotretinoin reduces inflammation via inhibition of chemotactic responses of monocytes and neutrophils.^[23] Isotretinoin also has been shown to initiate remodeling of the sebaceous glands; triggering changes in gene expression that selectively induce apoptosis.^[28] Isotretinoin is a teratogen with a number of potential side-effects. Consequently, its use requires medical supervision.

§Retinal/retinol versus retinoic acid

Vitamin A deprived rats can be kept in good general health with supplementation of retinoic acid. This reverses the growth-stunting effects of vitamin A deficiency, as well as early stages of xerophthalmia. However, such rats show infertility (in both male and females) and continued degeneration of the retina, showing that these functions require retinal or retinol, which are interconvertible but which cannot be recovered from the oxidized retinoic acid. The requirement of retinol to rescue reproduction in vitamin A deficient rats is now known to be due to a requirement for local synthesis of retinoic acid from retinol in testis and embryos.^[29][30]

§Deficiency

Vitamin A deficiency is estimated to affect approximately one third of children under the age of five around the world.^[31] It is estimated to claim the lives of 670,000 children under five annually.^[32] Approximately 250,000–500,000 children in developing countries become blind each year owing to vitamin A deficiency, with the highest prevalence in Southeast Asia and Africa.^[33]
Vitamin A deficiency can occur as either a primary or a secondary deficiency. A primary vitamin A deficiency occurs among children and adults who do not consume an adequate intake of provitamin A carotenoids from fruits and vegetables or preformed vitamin A from animal and dairy products. Early weaning from breastmilk can also increase the risk of vitamin A deficiency.

Secondary vitamin A deficiency is associated with chronic malabsorption of lipids, impaired bile production and release, and chronic exposure to oxidants, such as cigarette smoke, and chronic alcoholism. Vitamin A is a fat soluble vitamin and depends on micellar solubilization for dispersion into the small intestine, which results in poor use of vitamin A from low-fat diets. Zinc deficiency can also impair absorption, transport, and metabolism of vitamin A because it is essential for the synthesis of the vitamin A transport proteins and as the cofactor in conversion of retinol to retinal. In malnourished populations, common low intakes of vitamin A and zinc increase the severity of vitamin A deficiency and lead physiological signs and symptoms of deficiency.^[23] A study in Burkina Faso showed major reduction of malaria morbidity with combined vitamin A and zinc supplementation in young children.^[34]

Due to the unique function of retinal as a visual chromophore, one of the earliest and specific manifestations of vitamin A deficiency is impaired vision, particularly in reduced light – night blindness. Persistent deficiency gives rise to a series of changes, the most devastating of which occur in the eyes. Some other ocular changes are referred to as xerophthalmia. First there is dryness of the conjunctiva (xerosis) as the normal lacrimal and mucus-secreting epithelium is replaced by a keratinized epithelium. This is followed by the build-up of keratin debris in small opaque plaques (Bitot's spots) and, eventually, erosion of the roughened corneal surface with softening and destruction of the cornea (keratomalacia) and leading to total blindness.^[35] Other changes include impaired immunity (increased risk of ear infections, urinary tract infections, Meningococcal disease), hyperkeratosis (white lumps at hair follicles), keratosis pilaris and squamous metaplasia of the epithelium lining the upper respiratory passages and urinary bladder to a keratinized epithelium. With relations to dentistry, a deficiency in Vitamin A leads to enamel hypoplasia.

Adequate supply, but not excess vitamin A, is especially important for pregnant and breastfeeding women for normal fetal development and in breastmilk. Deficiencies cannot be compensated by postnatal supplementation.^[36][37] Excess vitamin A, which is most common with high dose vitamin supplements, can cause birth defects and therefore should not exceed recommended daily values.^[25]

Vitamin A metabolic inhibition as a result of alcohol consumption during pregnancy is the elucidated mechanism for fetal alcohol syndrome and is characterized by teratogenicity closely matching maternal vitamin A deficiency.^[38]

§Vitamin A supplementation

Global efforts to support national governments in addressing vitamin A deficiency are led by the Global Alliance for Vitamin A (GAVA), which is an informal partnership between A2Z, the Canadian International Development Agency, Helen Keller International, the Micronutrient Initiative, UNICEF, USAID, and the World Bank. Joint GAVA activity is coordinated by the Micronutrient Initiative.

While strategies include intake of vitamin A through a combination of breast feeding and dietary intake, delivery of oral high-dose supplements remain the principal strategy for minimizing deficiency.^[39] A meta-analysis of 43 studies showed that vitamin A supplementation of children under five who are at risk of deficiency reduces mortality by up to 24%.^[40] About 75% of the vitamin A required for supplementation activity by developing countries is supplied by the Micronutrient Initiative with support from the Canadian International Development Agency.^[41] Food fortification approaches are becoming increasingly feasible^[42] but cannot yet ensure coverage levels.^[39]

The World Health Organization estimates that Vitamin A supplementation has averted 1.25 million deaths due to vitamin A deficiency in 40 countries since 1998.^[43] In 2008 it was estimated that an annual investment of US$60 million in vitamin A and zinc supplementation combined would yield benefits of more than US$1 billion per year, with every dollar spent generating benefits of more than US$17.^[44] These combined interventions were ranked by the Copenhagen Consensus 2008 as the world’s best development investment.^[44]

§Toxicity

Since vitamin A is fat-soluble, disposing of any excesses taken in through diet takes much longer than with water-soluble B vitamins and vitamin C. This allows for toxic levels of vitamin A to accumulate.
In general, acute toxicity occurs at doses of 25,000 IU/kg of body weight, with chronic toxicity occurring at 4,000 IU/kg of body weight daily for 6–15 months.^[45] However, liver toxicities can occur at levels as low as 15,000 IU (4500 micrograms) per day to 1.4 million IU per day, with an average daily toxic dose of 120,000 IU, particularly with excessive consumption of alcohol .^{[citation needed]} In people with renal failure, 4000 IU can cause substantial damage. Children can reach toxic levels at 1,500 IU/kg of body weight.^[46]

Excessive vitamin A consumption can lead to nausea, irritability, anorexia (reduced appetite), vomiting, blurry vision, headaches, hair loss, muscle and abdominal pain and weakness, drowsiness, and altered mental status. In chronic cases, hair loss, dry skin, drying of the mucous membranes, fever, insomnia, fatigue, weight loss, bone fractures, anemia, and diarrhea can all be evident on top of the symptoms associated with less serious toxicity.^[47] Some of these symptoms are also common to acne treatment with Isotretinoin. Chronically high doses of vitamin A, and also pharmaceutical retinoids such as 13-cis retinoic acid, can produce the syndrome of pseudotumor cerebri.^[48] This syndrome includes headache, blurring of vision and confusion, associated with increased intracerebral pressure. Symptoms begin to resolve when intake of the offending substance is stopped.^[49]

Chronic intake of 1500 RAE of preformed vitamin A may be associated with osteoporosis and hip fractures because it suppresses bone building while simultaneously stimulating bone breakdown.^[50]

High vitamin A intake has been associated with spontaneous bone fractures in animals. Cell culture studies have linked increased bone resorption and decreased bone formation with high intakes. This interaction may occur because vitamins A and D may compete for the same receptor and then interact with parathyroid hormone, which regulates calcium.^[46] Indeed, a study by Forsmo et al. shows a correlation between low bone mineral density and too high intake of vitamin A.^[51] Sufficiently high levels of vitamin D may be protective against the bone density lowering effects of high vitamin A, while inadequate levels of vitamin D may exacerbate those effects.^{[52][53][54][55]}

Toxic effects of vitamin A have been shown to significantly affect developing fetuses. Therapeutic doses used for acne treatment have been shown to disrupt cephalic neural cell activity. The fetus is particularly sensitive to vitamin A toxicity during the period of organogenesis.^[23] These toxicities only occur with preformed (retinoid) vitamin A (such as from liver). The carotenoid forms (such as beta-carotene as found in carrots), give no such symptoms, except with supplements and chronic alcoholism, but excessive dietary intake of beta-carotene can lead to carotenodermia, which causes orange-yellow discoloration of the skin.^[56][57][58]

Hepatic (liver) injury has been found in human and animal studies where consumption of alcohol is paired with high dose vitamin A and beta-carotene supplementation.

Researchers have succeeded in creating water-soluble forms of vitamin A, which they believed could reduce the potential for toxicity.^[59] However, a 2003 study found water-soluble vitamin A was approximately 10 times as toxic as fat-soluble vitamin.^[60] A 2006 study found children given water-soluble vitamin A and D, which are typically fat-soluble, suffer from asthma twice as much as a control group supplemented with the fat-soluble vitamins.^[61]

In some studies, the use of Vitamin A supplements has been linked to an increased rate of mortality,^[62] but there is minimal evidence to show this.^[63]

§Vitamin A and derivatives in medical use

Retinyl palmitate has been used in skin creams, where it is broken down to retinol and ostensibly metabolised to retinoic acid, which has potent biological activity, as described above.
The retinoids (for example, 13-cis-retinoic acid) constitute a class of chemical compounds chemically related to retinoic acid, and are used in medicine to modulate gene functions in place of this compound. Like retinoic acid, the related compounds do not have full vitamin A activity, but do have powerful effects on gene expression and epithelial cell differentiation.^[64]

Pharmaceutics utilizing mega doses of naturally occurring retinoic acid derivatives are currently in use for cancer, HIV, and dermatological purposes.^[65] At high doses, side-effects are similar to vitamin A toxicity.

Rocket propellant

From Wikipedia, the free encyclopedia

 

Rocket propellant is a material used by a rocket as, or to produce in a chemical reaction, the reaction mass (propulsive mass) that is ejected, typically with very high speed, from a rocket engine to produce thrust, and thus provide spacecraft propulsion. A chemical rocket propellant undergoes exothermic chemical reactions to produce hot gas. There may be a single propellant, or multiple propellants; in the latter case one can distinguish fuel and oxidizer. The gases produced expand and push on a nozzle, which accelerates them until they rush out of the back of the rocket at extremely high speed. For smaller attitude control thrusters, a compressed gas escapes the spacecraft through a propelling nozzle.

In ion propulsion, the propellant is made of electrically charged atoms (ions), which are electromagnetically pushed out of the back of the spacecraft. Magnetically accelerated ion drives are not usually considered to be rockets however, but a similar class of thrusters use electrical heating and magnetic nozzles.

A potential other method is that the propellant is not burned but just heated, as in the proposed nuclear thermal rocket concept. In the proposed pulse propulsion, a heavy, metallic base acquires the force from an explosion behind it, for example from an atomic bomb, and transfers it to a dampening system that reduces the shock to the payload.

§Overview

The Space Shuttle Atlantis during ascent.

Rockets create thrust by expelling mass backwards in a high speed jet (see Newton's Third Law). Chemical rockets, the subject of this article, create thrust by reacting propellants within a combustion chamber into a very hot gas at high pressure, which is then expanded and accelerated by passage through a nozzle at the rear of the rocket. The amount of the resulting forward force, known as thrust, that is produced is the mass flow rate of the propellants multiplied by their exhaust velocity (relative to the rocket), as specified by Newton's third law of motion. Thrust is therefore the equal and opposite reaction that moves the rocket, and not by interaction of the exhaust stream with air around the rocket. Equivalently, one can think of a rocket being accelerated upwards by the pressure of the combusting gases against the combustion chamber and nozzle. This operational principle stands in contrast to the commonly-held assumption that a rocket "pushes" against the air behind or below it. Rockets in fact perform better in outer space (where there is nothing behind or beneath them to push against), because there is a reduction in air pressure on the outside of the engine, and because it is possible to fit a longer nozzle without suffering from flow separation, in addition to the lack of air drag.

The maximum velocity that a rocket can attain in the absence of any external forces is primarily a function of its mass ratio and its exhaust velocity. The relationship is described by the rocket equation.  The mass ratio is just a way to express what proportion of the rocket is propellant (fuel/oxidizer combination) prior to engine ignition. Typically, a single-stage rocket might have a mass fraction of 90% propellant, 10% structure, and hence a mass ratio of 9:1 . The impulse delivered by the motor to the rocket vehicle per weight of fuel consumed is often reported as the rocket propellant's specific impulse. A propellant with a higher specific impulse is said to be more efficient because more thrust is produced while consuming a given amount of propellant.

Lower stages will usually use high-density (low volume) propellants because of their lighter tankage to propellant weight ratios and because higher performance propellants require higher expansion ratios for maximum performance than can be attained in atmosphere. Thus, the Saturn V first stage used kerosene-liquid oxygen rather than the liquid hydrogen-liquid oxygen used on its upper stages. Similarly, the Space Shuttle uses high-thrust, high-density solid rocket boosters for its lift-off with the liquid hydrogen-liquid oxygen Space Shuttle Main Engines used partly for lift-off but primarily for orbital insertion.

§Chemical propellants

There are four main types of chemical rocket propellants: solid, storable liquid, cryogenic liquid and liquid monopropellant. Hybrid solid/liquid bi-propellant rocket engines are starting to see limited use as well.

§Solid propellants

§Description

Solid propellants are either "composites" composed mostly of large, distinct macroscopic particles or single-, double-, or triple-bases (depending on the number of primary ingredients), which are homogeneous mixtures of one or more primary ingredients. Composites typically consist of a mixture of granules of solid oxidizer (examples: ammonium nitrate, ammonium perchlorate, potassium nitrate) in a polymer binder (binding agent) with flakes or powders of: energetic compounds (examples: RDX, HMX), metallic additives (examples: Aluminum, Beryllium), plasticizers, stabilizers, and/or burn rate modifiers (iron oxide, copper oxide). Single-, double-, or triple-bases are mixtures of the fuel, oxidizer, binders, and plasticizers that are macroscopically indistinguishable and often blended as liquids and cured in a single batch. Often, the ingredients of a double-base propellant have multiple roles such as RDX which is both a fuel and oxidizer or nitrocellulose which is a fuel, oxidizer, and plasticizer. Further complicating categorization, there are many propellants that contain elements of double-base and composite propellants, which often contain some amount of energetic additives homogeneously mixed into the binder. In the case of gunpowder (a pressed composite without a polymeric binder) the fuel is charcoal, the oxidizer is potassium nitrate, and sulphur serves as a catalyst. (Note: sulphur is not a true catalyst in gunpowder as it is consumed to a great extent into a variety of reaction products such as K₂S.) During the 1950s and 60s researchers in the United States developed Ammonium Perchlorate Composite Propellant (APCP). This mixture is typically 69-70% finely ground ammonium perchlorate (an oxidizer), combined with 16-20% fine aluminium powder (a fuel), held together in a base of 11-14% polybutadiene acrylonitrile (PBAN) or HTPB (polybutadiene rubber fuel). The mixture is formed as a thickened liquid and then cast into the correct shape and cured into a firm but flexible load-bearing solid. APCP solid propellants are the most widely used in spaceflight launch vehicles and are also used in many military missiles. The military, however, uses a wide variety of different types of solid propellants some of which exceed the performance of APCP. A comparison of the highest specific impulses achieved with the various solid and liquid propellant combinations used in current launch vehicles is given in the article on solid-fuel rockets.^[1]

§Advantages

Solid propellant rockets are much easier to store and handle than liquid propellant rockets. High propellant density makes for compact size as well. These features plus simplicity and low cost make solid propellant rockets ideal for military applications. In the 1970s and 1980s the U.S. switched entirely to solid-fueled ICBMs: the LGM-30 Minuteman and LG-118A Peacekeeper (MX). In the 1980s and 1990s, the USSR/Russia also deployed solid-fueled ICBMs (RT-23, RT-2PM, and RT-2UTTH), but retains two liquid-fueled ICBMs (R-36 and UR-100N). All solid-fueled ICBMs on both sides had three initial solid stages, and those with multiple independently targeted warheads had a precision maneuverable bus used to fine tune the trajectory of the re-entry vehicles. U.S. Minuteman III ICBMs were reduced to a single warhead by 2011 in accordance with the START treaty leaving only the Navy's Trident sub-launched ICBMs with multiple warheads.

Their simplicity also makes solid rockets a good choice whenever large amounts of thrust are needed and cost is an issue. The Space Shuttle and many other orbital launch vehicles use solid-fueled rockets in their boost stages (solid rocket boosters) for this reason.

§Disadvantages

Relative to liquid fuel rockets, solid fuel rockets have lower specific impulse. The propellant mass ratios of solid propellant upper stages is usually in the .91 to .93 range which is as good as or better than that of most liquid propellant upper stages but overall performance is less than for liquid stages because of the solids' lower exhaust velocities. The high mass ratios possible with (unsegmented) solids is a result of high propellant density and very high strength-to-weight ratio filament-wound motor casings. A drawback to solid rockets is that they cannot be throttled in real time, although a programmed thrust schedule can be created by adjusting the interior propellant geometry. Solid rockets can be vented to extinguish combustion or reverse thrust as a means of controlling range or accommodating warhead separation. Casting large amounts of propellant requires consistency and repeatability which is assured by computer control. Casting voids in propellant can adversely affect burn rate so the blending and casting takes place under vacuum and the propellant blend is spread thin and scanned to assure no large gas bubbles are introduced into the motor. Solid fuel rockets are intolerant to cracks and voids and often require post-processing such as x-ray scans to identify faults.
Since the combustion process is dependent on the surface area of the fuel; voids and cracks represent local increases in burning surface area. This increases the local temperature, system pressure and radiative heat flux to the surface. This positive feedback loop further increases burn rate and can easily lead to catastrophic failure typically due to case failure or nozzle system damage.

§Liquid propellants

§Current Types

The most common liquid propellants in use today:

• LOX and kerosene (RP-1). Used for the first stages of the Saturn V, Atlas V and Falcon, the Russian Soyuz, Ukrainian Zenit, and developmental rockets like Angara and Long March 6. Very similar to Robert Goddard's first rocket, this combination is widely regarded as the most practical for boosters that lift off at ground level and therefore must operate at full atmospheric pressure.

• LOX and liquid hydrogen, used in the Space Shuttle orbiter, the Centaur upper stage of the Atlas V, Saturn V upper stages, the newer Delta IV rocket, the H-IIA rocket, and most stages of the European Ariane 5 rocket.

• Nitrogen tetroxide (N₂O₄) and hydrazine (N₂H₄), MMH, or UDMH. Used in military, orbital, and deep space rockets because both liquids are storable for long periods at reasonable temperatures and pressures. N₂O₄/UDMH is the main fuel for the Proton rocket, Long March rockets, PSLV, and Fregat and Briz-M upper stages. This combination is hypergolic, making for attractively simple ignition sequences. The major inconvenience is that these propellants are highly toxic, hence they require careful handling.

• Monopropellants such as hydrogen peroxide, hydrazine, and nitrous oxide are primarily used for attitude control and spacecraft station-keeping where their long-term storability, simplicity of use, and ability to provide the tiny impulses needed, outweighs their lower specific impulse as compared to bipropellants. Hydrogen peroxide is also used to drive the turbopumps on the first stage of the Soyuz launch vehicle.

§Historical propellants

These include propellants such as the letter-coded rocket propellants use by Nazi Germany in World War II used for the Messerschmitt Me 163 Komet's Walter HWK 109-509 motor and the V-2 pioneer SRBM missile, and the Soviet/Russian utilized syntin, which is synthetic cyclopropane, C₁₀H₁₆ which was used on Soyuz U2 until 1995.^{[citation needed]} Syntin develops about 10 seconds greater specific impulse than kerosene.

§Advantages

Liquid-fueled rockets have higher specific impulse than solid rockets and are capable of being throttled, shut down, and restarted. Only the combustion chamber of a liquid-fueled rocket needs to withstand high combustion pressures and temperatures and they can be regeneratively cooled by the liquid propellant. On vehicles employing turbopumps, the propellant tanks are at very much less pressure than the combustion chamber. For these reasons, most orbital launch vehicles use liquid propellants.

The primary performance advantage of liquid propellants is due to the oxidizer. Several practical liquid oxidizers (liquid oxygen, nitrogen tetroxide, and hydrogen peroxide) are available which have better specific impulse than the ammonium perchlorate used in most solid rockets, when paired with comparable fuels. These facts have led to the use of hybrid propellants: a storable oxidizer used with a solid fuel, which retain most virtues of both liquids (high ISP) and solids (simplicity).^{[citation needed]}
(The newest nitramine solid propellants based on CL-20 (HNIW) can match the performance of NTO/UDMH storable liquid propellants, but cannot be controlled as can the storable liquids.)

While liquid propellants are cheaper than solid propellants, for orbital launchers, the cost savings do not, and historically have not mattered; the cost of the propellant is a very small portion of the overall cost of the rocket.^{[citation needed]} Some propellants, notably Oxygen and Nitrogen, may be able to be collected from the upper atmosphere, and transferred up to low-Earth orbit for use in propellant depots at substantially reduced cost.^[2]

§Disadvantages

The main difficulties with liquid propellants are also with the oxidizers. These are generally at least moderately difficult to store and handle due to their high reactivity with common materials, may have extreme toxicity (nitric acids), moderately cryogenic (liquid oxygen), or both (liquid fluorine, FLOX- a fluorine/LOX mix). Several exotic oxidizers have been proposed: liquid ozone (O₃), ClF₃, and ClF₅, all of which are unstable, energetic, and toxic.

Liquid-fueled rockets also require potentially troublesome valves and seals and thermally stressed combustion chambers, which increase the cost of the rocket. Many employ specially designed turbopumps which raise the cost enormously due to difficult fluid flow patterns that exist within the casings.

§Gas propellants

A gas propellant usually involves some sort of compressed gas. However, due to the low density and high weight of the pressure vessel, gases see little current use, but are sometimes used for vernier engines, particularly with inert propellants.

GOX (gaseous oxygen) was used as one of the propellants for the Buran program for the orbital maneuvering system.

§Hybrid propellants

A hybrid rocket usually has a solid fuel and a liquid or gas oxidizer. The fluid oxidizer can make it possible to throttle and restart the motor just like a liquid-fueled rocket. Hybrid rockets can also be environmentally safer than solid rockets since some high-performance solid-phase oxidizers contain chlorine (specifically composites with ammonium perchlorate), versus the more benign liquid oxygen or nitrous oxide often used in hybrids. This is only true for specific hybrid systems. There have been hybrids which have used chlorine or fluorine compounds as oxidizers and hazardous materials such as beryllium compounds mixed into the solid fuel grain. Because just one constituent is a fluid, hybrids can be simpler than liquid rockets depending motive force used to transport the fluid into the combustion chamber. Fewer fluids typically means fewer and smaller piping systems, valves and pumps (if utilized).
Hybrid motors suffer two major drawbacks. The first, shared with solid rocket motors, is that the casing around the fuel grain must be built to withstand full combustion pressure and often extreme temperatures as well. However, modern composite structures handle this problem well, and when used with nitrous oxide and a solid rubber propellant (HTPB), relatively small percentage of fuel is needed anyway, so the combustion chamber is not especially large.

The primary remaining difficulty with hybrids is with mixing the propellants during the combustion process. In solid propellants, the oxidizer and fuel are mixed in a factory in carefully controlled conditions. Liquid propellants are generally mixed by the injector at the top of the combustion chamber, which directs many small swift-moving streams of fuel and oxidizer into one another. Liquid-fueled rocket injector design has been studied at great length and still resists reliable performance prediction. In a hybrid motor, the mixing happens at the melting or evaporating surface of the fuel. The mixing is not a well-controlled process and generally quite a lot of propellant is left unburned,^[3] which limits the efficiency of the motor. The combustion rate of the fuel is largely determined by the oxidizer flux and exposed fuel surface area. This combustion rate is not usually sufficient for high power operations such as boost stages unless the surface area or oxidizer flux is high. Too high of oxidizer flux can lead to flooding and loss of flame holding that locally extinguishes the combustion. Surface area can be increased, typically by longer grains or multiple ports, but this can increase combustion chamber size, reduce grain strength and/or reduce volumetric loading. Additionally, as the burn continues, the hole down the center of the grain (the 'port') widens and the mixture ratio tends to become more oxidizer rich.

There has been much less development of hybrid motors than solid and liquid motors. For military use, ease of handling and maintenance have driven the use of solid rockets. For orbital work, liquid fuels are more efficient than hybrids and most development has concentrated there. There has recently been an increase in hybrid motor development for nonmilitary suborbital work:

• Several universities have recently experimented with hybrid rockets. Brigham Young University, the University of Utah and Utah State University launched a student-designed rocket called Unity IV in 1995 which burned the solid fuel hydroxy-terminated polybutadiene (HTPB) with an oxidizer of gaseous oxygen, and in 2003 launched a larger version which burned HTPB with nitrous oxide.. Stanford University researches nitrous-oxide/paraffin wax hybrid motors.
• The Rochester Institute of Technology was building a HTPB hybrid rocket to launch small payloads into space and to several near Earth objects. Its first launch was scheduled forSummer2007.
• Scaled Composites SpaceShipOne, the first private manned spacecraft, is powered by a hybrid rocket burning HTPB with nitrous oxide. The hybrid rocket engine was manufactured by SpaceDev. SpaceDev partially based its motors on experimental data collected from the testing of AMROC's (American Rocket Company) motors at NASA's Stennis Space Center's E1 test stand.
• The Dream Chaser crewed spaceplane intends to use twin hybrid engines of similar design to SpaceShipOne for orbit raising, deorbiting, and emergency escape system.

§Gel propellant

Some work has been done on gelling liquid propellants to give a propellant with low vapor pressure to reduce the risk of an accidental fireball. Gelled propellant behaves like a solid propellant in storage and like a liquid propellant in use.

§Inert propellants

Some rocket designs have their propellants obtain their energy from non chemical or even external sources. For example water rockets use the compressed gas, typically air, to force the water out of the rocket.
Solar thermal rockets and Nuclear thermal rockets typically propose to use liquid hydrogen for an I_sp (Specific Impulse) of around 600–900 seconds, or in some cases water that is exhausted as steam for an I_sp of about 190 seconds.

Additionally for low performance requirements such as attitude control jets, inert gases such as nitrogen^{[citation needed]}have been employed.

Nuclear thermal rockets pass a propellant over a central reactor, heating the propellant and causing it to expand rapidly out a rocket nozzle, pushing the craft forward. The propellant itself is not directly interacting with the interior of the reactor, so the propellant is not irradiated.

Solar thermal rockets use concentrated sunlight to heat a propellant, rather than using a heavy nuclear reactor.

§Mixture ratio

The theoretical exhaust velocity of a given propellant chemistry is a function of the energy released per unit of propellant mass (specific energy). Unburned fuel or oxidizer drags down the specific energy. However, most rockets run fuel-rich mixtures.^{[citation needed]}

The usual explanation for fuel-rich mixtures is that fuel-rich mixtures have lower molecular weight exhaust, which by reducing M increases the ratio Tc√M which is approximately equal to the theoretical exhaust velocity. Fuel-rich mixtures actually have lower theoretical exhaust velocities, because Tc−−√ decreases as fast or faster than M.^{[citation needed]}

The nozzle of the rocket converts the thermal energy of the propellants into directed kinetic energy. This conversion happens in a short time, on the order of one millisecond. During the conversion, energy must transfer very quickly from the rotational and vibrational states of the exhaust molecules into translation. Molecules with fewer atoms (like CO and H₂) store less energy in vibration and rotation than molecules with more atoms (like CO₂ and H₂O). These smaller molecules transfer more of their rotational and vibrational energy to translation energy than larger molecules, and the resulting improvement in nozzle efficiency is large enough that real rocket engines improve their actual exhaust velocity by running rich mixtures with somewhat lower theoretical exhaust velocities.^{[citation needed]}

The effect of exhaust molecular weight on nozzle efficiency is most important for nozzles operating near sea level. High expansion rockets operating in a vacuum see a much smaller effect, and so are run less rich. The Saturn-II stage (a LOX/LH₂ rocket) varied its mixture ratio during flight to optimize performance.

LOX/hydrocarbon rockets are run only somewhat rich (O/F mass ratio of 3 rather than stoichiometric of 3.4 to 4), because the energy release per unit mass drops off quickly as the mixture ratio deviates from stoichiometric. LOX/LH₂ rockets are run very rich (O/F mass ratio of 4 rather than stoichiometric 8) because hydrogen is so light that the energy release per unit mass of propellant drops very slowly with extra hydrogen. In fact, LOX/LH₂ rockets are generally limited in how rich they run by the performance penalty of the mass of the extra hydrogen tankage, rather than the mass of the hydrogen itself.^{[citation needed]}

Another reason for running rich is that off-stoichiometric mixtures burn cooler than stoichiometric mixtures, which makes engine cooling easier. Because fuel-rich combustion products are less chemically reactive (corrosive) than oxygenated products, vast majority of rocket engines are designed to run fuel-rich, with at least one exception for the Russian RD-180 preburner, which burns LOX and RP-1 at a ratio of 2.72.

Additionally, mixture ratios can be dynamic during launch. This can be exploited with designs that adjust the oxidizer to fuel ratio (along with overall thrust) during the flight to maximize overall system performance. For instance, during lift-off thrust is a premium while specific impulse is less so. As such, the system can be optimized by carefully adjusting the O/F ratio so the engine runs cooler at higher thrust levels. This also allows for the engine to be designed slightly more compactly, improving its overall thrust to weight performance.

§Propellant density

Although liquid hydrogen gives a high I_sp, its low density is a significant disadvantage: hydrogen occupies about 7x more volume per kilogram than dense fuels such as kerosene. This not only penalises the tankage, but also the pipes and fuel pumps leading from the tank, which need to be 7x bigger and heavier. (The oxidiser side of the engine and tankage is of course unaffected.) This makes the vehicle's dry mass much higher, so the use of liquid hydrogen is not as advantageous as might be expected. Indeed, some dense hydrocarbon/LOX propellant combinations have higher performance when the dry mass penalties are included.

Due to lower I_sp, dense propellant launch vehicles have a higher takeoff mass, but this does not mean a proportionately high cost; on the contrary, the vehicle may well end up cheaper. Liquid hydrogen is quite an expensive fuel to produce and store, and causes many practical difficulties with design and manufacture of the vehicle.

Because of the higher overall weight, a dense-fueled launch vehicle necessarily requires higher takeoff thrust, but it carries this thrust capability all the way to orbit. This, in combination with the better thrust/weight ratios, means that dense-fueled vehicles reach orbit earlier, thereby minimizing losses due to gravity drag. Thus, the effective delta-v requirement for these vehicles are reduced.

However, liquid hydrogen does give clear advantages when the overall mass needs to be minimised; for example the Saturn V vehicle used it on the upper stages; this reduced weight meant that the dense-fueled first stage could be made significantly smaller, saving quite a lot of money.

Tripropellant rockets designs often try to use an optimum mix of propellants for launch vehicles. These use mainly dense fuel while at low altitude and switch across to hydrogen at higher altitude. Studies by Robert Salkeld in the 1960s proposed SSTO using this technique.^[4] The Space Shuttle approximated this by using dense solid rocket boosters for the majority of the thrust for the first 120 seconds, the main engines, burning a fuel-rich hydrogen and oxygen mixture operate continuously throughout the launch but only provide the majority of thrust at higher altitudes after SRB burnout.