From Wikipedia, the free encyclopedia
Jump to: navigation, search
Illustration of the electromagnetic spectrum. Note the visible spectrum, as well as ultraviolet and infrared regions.
Photochemistry, a sub-discipline of chemistry, is the study of the interactions between atoms, small molecules, and light (or electromagnetic radiation).[1] The pillars of photochemistry are UV/VIS spectroscopy, photochemical reactions in organic chemistry and photosynthesis in biochemistry.
|Contents |
|[hide] |
|1 Scientific background |
|2 Spectral regions |
|3 Applications |
|4 See also |
|5 References |
[pic][edit] Scientific background
Like most scientific disciplines, photochemistry utilizes the SI or metric measurement system. Important units and constants that show up regularly include the meter (and variants such as centimeter, millimeter, micrometer, nanometer, etc.), seconds, hertz, joules, moles, the gas constant R, and the Boltzmann constant. These units and constants are also integral to the field of physical chemistry.
The first law of photochemistry, known as the Grotthuss-Draper law (for chemists Theodor Grotthuss and John W. Draper), states that light must be absorbed by a chemical substance in order for a photochemical reaction to take place.
The second law of photochemistry, the Stark-Einstein law, states that for each photon of light absorbed by a chemical system, only one molecule is activated for a photochemical reaction. This is also known as the photoequivalence law and was derived by Albert Einstein at the time when the quantum (photon) theory of light was being developed.
Photochemistry may also be introduced to laymen as a reaction that proceeds with the absorption of light. Normally a reaction (not just a photochemical reaction) occurs when a molecule gains the necessary activation energy to undergo change. A simple example can be the combustion of gasoline (a hydrocarbon) into carbon dioxide and water. This is a chemical reaction where one or more molecules/chemical species are converted into others. For this reaction to take place activation energy should be supplied. The activation energy is provided in the form of heat or a spark. In case of photochemical reactions light provides the activation energy.
The absorption of a photon of light by a reactant molecule may also permit a reaction to occur not just by bringing the molecule to the necessary activation energy, but also by changing the symmetry of the molecule's electronic configuration, enabling an otherwise inaccessible reaction path, as described by the Woodward-Hoffmann selection rules. A 2+2 cycloaddition reaction is one example of a pericyclic reaction that can be analyzed using these rules or by the related frontier molecular orbital theory.
[edit] Spectral regions
Photochemists typically work in only a few sections of the electromagnetic spectrum. Some of the most widely used sections, and their wavelengths, are the following: • Ultraviolet: 100–400 nm • Visible Light: 400–700 nm • Near infrared: 700–2500 nm • Mid infrared: 2500 - 25000 nm • Far infrared: 25–1000 µm
[edit] Applications
There are important processes based in the photochemistry principles. One case is photosynthesis, which some plants use light to create glucose in their chloroplasts to contribute to cell metabolism. The glucose is used by the plant's mitochondria to produce adenosine triphosphate. Medicine bottles are made with darkened glass to prevent the medicine itself from reacting chemically with light. In fireflies, an enzyme in the abdomen works to produce bioluminescence. The mercaptans or thiols produced by Chevron Phillips Chemical Company are produced by photochemical addition of hydrogen sulfide (H2S) to alfa olefins. Among their many uses as a chemical reagent these mercaptans are used to provide a distinctive odor (an odorant) to otherwise odorless natural gas. Many polymerizations are started by photoinitiatiors which decompose upon absorbing light to produce the necessary free radicals for Radical polymerization.
Photoelectrochemical cells or PECs are solar cells which generate electrical energy from light, including visible light. Each cell consists of a semiconducting photoanode and a metal cathode immersed in an electrolyte.
Some photoelectrochemical cells simply produce electrical energy, while others produce hydrogen in a process similar to the electrolysis of water.
|Contents |
|[hide] |
|1 Photogeneration cell |
|2 Graetzel cell |
|3 History |
|4 See also |
|5 References |
|6 Further reading |
|7 External links |
[pic][edit] Photogeneration cell
In this type of photoelectrochemical cell, electrolysis of water to hydrogen and oxygen gas occurs when the anode is irradiated with electromagnetic radiation. This is also referred to as artificial photosynthesis and has been suggested as a way of storing solar energy in an energy carrier, namely hydrogen. This hydrogen can then be used as fuel.
There are two types of photochemical systems with photocatalysis, one that use semiconductor surfaces as catalysts (the semiconductor surface absorbs solar energy and acts as an electrode for water splitting) the other uses in-solution metal complexes as catalysts (When the dissolved metal complex absorbs energy, it creates an electric charge separation that drives the water-splitting reaction)[1].
The photogeneration cells passed the 10 percent economic efficiency barrier. Lab tests confirmed the efficiency of the process. The main problem is the corrosion of the semiconductors which are in direct contact with water[2]. Research is going on to meet the United States Department of Energy requirement, a service life of 10000 hours.
Photosynthesis
From Wikipedia, the free encyclopedia
Jump to: navigation, search
[pic]
Composite image showing the global distribution of photosynthesis, including both oceanic phytoplankton and terrestrial vegetation.
Photosynthesis[α] is a metabolic pathway that converts carbon dioxide into organic compounds, especially sugars, using the energy from sunlight.[1] Photosynthesis occurs in plants, algae, and many species of Bacteria, but is not known in Archaea. Photosynthetic organisms are called photoautotrophs, but not all organisms that use light as a source of energy carry out photosynthesis, since photoheterotrophs use organic compounds, rather than carbon dioxide, as a source of carbon.[2] In plants, algae and cyanobacteria photosynthesis uses carbon dioxide and water, releasing oxygen as a waste product. Photosynthesis is crucially important, since nearly all life on Earth depends on it as a source of energy and it also maintains the normal level of oxygen in the atmosphere.[2][β]
Although photosynthesis can occur in different ways in different types of organisms, some features are always the same. For example, the process always begins when light is absorbed by proteins containing chlorophyll. In plants these proteins are held inside chloroplasts, while they are found within other cell membranes in bacteria. Some of the light energy gathered by chlorophylls is stored in the form of adenosine triphosphate (ATP). The rest of the energy is used to remove electrons from a substance such water, metal ions, or hydrogen sulfide. These electrons are then used in the reactions that turn carbon dioxide into organic compounds. In plants, algae and cyanobacteria these reactions are called the Calvin cycle, but different sets of reactions can be found in bacteria, such as the reverse Krebs cycle in Chlorobium.
|Contents |
|[hide] |
|1 Overview |
|2 Photosynthetic membranes and organelles |
|3 Light reactions |
|3.1 Z scheme |
|3.2 Water photolysis |
|3.3 Oxygen and photosynthesis |
|4 Light-independent reactions |
|4.1 The Calvin Cycle |
|4.2 C4 and C3 photosynthesis and CAM |
|5 Order and kinetics |
|6 Efficiency |
|7 Evolution |
|7.1 Symbiosis and the origin of chloroplasts |
|7.2 Cyanobacteria and the evolution of photosynthesis |
|8 Discovery |
|9 Factors |
|9.1 Light intensity (irradiance), wavelength and temperature |
|9.2 Carbon dioxide levels and photorespiration |
|10 See also |
|11 Footnotes |
|12 References |
|13 Further reading |
|14 External links |
[pic]Overview
Photosynthesis splits water to liberate O2 and fixes CO2 into sugar
Photosynthetic organisms are photoautotrophs, which means that they are able to synthesize food directly from carbon dioxide using energy from light. In plants, algae and cyanobacteria, photosynthesis releases oxygen, this is called oxygenic photosynthesis. Although there are some differences between oxygenic photosynthesis in plants, algae and cyanobacteria, the overall process is quite similar in these organisms. However, there are some types of bacteria that carry out anoxygenic photosynthesis, which consumes carbon dioxide but does not release oxygen.
Carbon dioxide is converted into sugars in a process called carbon fixation. Carbon fixation is a redox reaction, so photosynthesis needs to supply both a source of energy to drive this process, and also the electrons needed to convert carbon dioxide into carbohydrate, which is a reduction reaction. In general outline, photosynthesis is the opposite of cellular respiration, where glucose and other compounds are oxidized to produce carbon dioxide, water, and release chemical energy. However, the two processes take place through a different sequence of chemical reactions and in different cellular compartments.
The general equation for photosynthesis is therefore: CO2 + 2 H2A + photons → (CH2O)n + H2O + 2A carbon dioxide + electron donor + light energy → carbohydrate + oxygen + oxidized electron donor
Since water is used as the electron donor in oxygenic photosynthesis, the equation for this process is: CO2 + 2 H2O + photons → (CH2O)n + H2O + O2 carbon dioxide + water + light energy → carbohydrate + oxygen + water
Photosynthesis occurs in two stages. In the first stage, light-dependent reactions or light reactions capture the energy of light and use it to make the energy-storage molecules ATP and NADPH. During the second stage, the light-independent reactions use these products to capture and reduce carbon dioxide.
Photosynthetic membranes and organelles
Chloroplast ultrastructure:
1. outer membrane
2. intermembrane space
3. inner membrane (1+2+3: envelope)
4. stroma (aqueous fluid)
5. thylakoid lumen (inside of thylakoid)
6. thylakoid membrane
7. granum (stack of thylakoids)
8. thylakoid (lamella)
9. starch
10. ribosome
11. plastidial DNA
12. plastoglobule (drop of lipids) Main articles: Chloroplast and Thylakoid
The proteins that gather light for photosynthesis are embedded within cell membranes. The simplest way these are arranged is in photosynthetic bacteria, where these proteins are held within the plasma membrane.[3] However, this membrane may be tightly-folded into cylindrical sheets called thylakoids,[4] or bunched up into round vesicles called intracytoplasmic membranes.[5] These structures can fill most of the interior of a cell, producing a large increase in the membrane's surface area and therefore increasing the amount of light that the bacteria can absorb.[4]
In plants and algae, photosynthesis takes place in organelles called chloroplasts. A chloroplast is contained by an envelope that consists of an inner and an outer phospholipid membrane. Between these two layers is the intermembrane space. A typical plant cell contains about 10 to 100 chloroplasts. Within the stroma are stacks of thylakoids, the sub-organelles which are the site of photosynthesis. The thylakoids are arranged in stacks called grana (singular: granum). A thylakoid has a flattened disk shape. Inside it is an empty area called the thylakoid space or lumen. The thylakoid membrane contains many integral and peripheral membrane proteins. The proteins complexes which contain special pigments absorbing light energy are called photosystems.
Plants absorb light primarily using the pigment chlorophyll, which is the reason that most plants have a green color. Besides chlorophyll plants also use pigments such as carotenes and xanthophylls. Algae also use chlorophyll, but various other pigments are present as phycocyanin, carotenes, and xanthophylls in green algae, phycoerythrin in red algae (rhodophytes) and fucoxanthol in brown algae and diatoms resulting in a wide variety of colors.
These pigments are embedded in plants and algae in special antenna-proteins. In such proteins all the pigments are ordered to work well together. Such a protein is also called a light-harvesting complex.
Although all cells in the green parts of a plant have chloroplasts, most of the energy is captured in the leaves. The cells in the interior tissues of a leaf, called the mesophyll, can contain between 450,000 and 800,000 chloroplasts for every square millimeter of leaf. The surface of the leaf is uniformly coated with a water-resistant waxy cuticle that protects the leaf from excessive evaporation of water and decreases the absorption of ultraviolet or blue light to reduce heating. The transparent epidermis layer allows light to pass through to the palisade mesophyll cells where most of the photosynthesis takes place.
Light reactions
Light-dependent reactions of photosynthesis at the thylakoid membrane Main article: Light-dependent reaction
In the light reactions, one molecule of the pigment chlorophyll absorbs one photon and loses one electron. This electron is passed to a modified form of chlorophyll called pheophytin, which passes the electron to a quinone molecule, allowing the start of a flow of electrons down an electron transport chain that leads to the ultimate reduction of NADP to NADPH. In addition, this creates a proton gradient across the chloroplast membrane; its dissipation is used by ATP Synthase for the concomitant synthesis of ATP. The chlorophyll molecule regains the lost electron from a water molecule through a process called photolysis, which releases a dioxygen (O2) molecule. The overall equation for the light-dependent reactions under the conditions of non-cyclic electron flow in green plants is:[6] 2 H2O + 2 NADP+ + 2 ADP + 2 Pi + light → 2 NADPH + 2 H+ + 2 ATP + O2
Not all wavelengths of light can support photosynthesis. The photosynthetic action spectrum depends on the type of accessory pigments present. For example, in green plants, the action spectrum resembles the absorption spectrum for chlorophylls and carotenoids with peaks for violet-blue and red light. In red algae, the action spectrum overlaps with the absorption spectrum of phycobilins for blue-green light, which allows these algae to grow in deeper waters that filter out the longer wavelengths used by green plants. The non-absorbed part of the light spectrum is what gives photosynthetic organisms their color (e.g., green plants, red algae, purple bacteria) and is the least effective for photosynthesis in the respective organisms.
Z scheme
A Photosystem: A light-harvesting cluster of photosynthetic pigments present in the thylakoid membrane of chloroplasts.
The "Z scheme"
In plants, light-dependent reactions occur in the thylakoid membranes of the chloroplasts and use light energy to synthesize ATP and NADPH. The light-dependent reaction has two forms; cyclic and non-cyclic reaction. In the non-cyclic reaction, the photons are captured in the light-harvesting antenna complexes of photosystem II by chlorophyll and other accessory pigments (see diagram at right). When a chlorophyll molecule at the core of the photosystem II reaction center obtains sufficient excitation energy from the adjacent antenna pigments, an electron is transferred to the primary electron-acceptor molecule, Pheophytin, through a process called Photoinduced charge separation. These electrons are shuttled through an electron transport chain, the so called Z-scheme shown in the diagram, that initially functions to generate a chemiosmotic potential across the membrane. An ATP synthase enzyme uses the chemiosmotic potential to make ATP during photophosphorylation, whereas NADPH is a product of the terminal redox reaction in the Z-scheme. The electron enters the Photosystem I molecule. The electron is excited due to the light absorbed by the photosystem. A second electron carrier accepts the electron, which again is passed down lowering energies of electron acceptors. The energy created by the electron acceptors is used to move hydrogen ions across the thylakoid membrane into the lumen. The electron is used to reduce the co-enzyme NADP, which has functions in the light-independent reaction. The cyclic reaction is similar to that of the non-cyclic, but differs in the form that it generates only ATP, and no reduced NADP (NADPH) is created. The cyclic reaction takes place only at photosystem I. Once the electron is displaced from the photosystem, the electron is passed down the electron acceptor molecules and returns back to photosystem I, from where it was emitted, hence the name cyclic reaction.
Water photolysis
Main articles: Photodissociation and Oxygen evolution
The NADPH is the main reducing agent in chloroplasts, providing a source of energetic electrons to other reactions. Its production leaves chlorophyll with a deficit of electrons (oxidized), which must be obtained from some other reducing agent. The excited electrons lost from chlorophyll in photosystem I are replaced from the electron transport chain by plastocyanin. However, since photosystem II includes the first steps of the Z-scheme, an external source of electrons is required to reduce its oxidized chlorophyll a molecules. The source of electrons in green-plant and cyanobacterial photosynthesis is water. Two water molecules are oxidized by four successive charge-separation reactions by photosystem II to yield a molecule of diatomic oxygen and four hydrogen ions; the electron yielded in each step is transferred to a redox-active tyrosine residue that then reduces the photoxidized paired-chlorophyll a species called P680 that serves as the primary (light-driven) electron donor in the photosystem II reaction center. The oxidation of water is catalyzed in photosystem II by a redox-active structure that contains four manganese ions and a calcium ion; this oxygen-evolving complex binds two water molecules and stores the four oxidizing equivalents that are required to drive the water-oxidizing reaction. Photosystem II is the only known biological enzyme that carries out this oxidation of water. The hydrogen ions contribute to the transmembrane chemiosmotic potential that leads to ATP synthesis. Oxygen is a waste product of light-independent reactions, but the majority of organisms on Earth use oxygen for cellular respiration, including photosynthetic organisms.[7][8]
Oxygen and photosynthesis
With respect to oxygen and photosynthesis, there are two important concepts. • Plant and cyanobacterial (blue-green algae) cells also use oxygen for cellular respiration, although they have a net output of oxygen since much more is produced during photosynthesis. • Oxygen is a product of the light-driven water-oxidation reaction catalyzed by photosystem II; it is not generated by the fixation of carbon dioxide. Consequently, the source of oxygen during photosynthesis is water, not carbon dioxide.
The concept that oxygen production is not directly associated with the fixation of carbon dioxide was first proposed by Cornelis Van Niel in the 1930s, who studied photosynthetic bacteria. Aside from the cyanobacteria, bacteria only have one photosystem and use reducing agents other than water. They get electrons from a variety of different inorganic chemicals including sulfide or hydrogen, so for most of these bacteria oxygen is not produced.
Others, such as the halophiles (an Archaea), produced so-called purple membranes where the bacteriorhodopsin could harvest light and produce energy. The purple membranes was one of the first to be used to demonstrate the chemiosmotic theory: light hit the membranes and the pH of the solution that contained the purple membranes dropped as protons were pumping out of the membrane.
Light-independent reactions
The Calvin Cycle
Main articles: Carbon fixation and Light-independent reaction
In the Light-independent or dark reactions the enzyme RuBisCO captures CO2 from the atmosphere and in a process that requires the newly formed NADPH, called the Calvin-Benson Cycle, releases three-carbon sugars, which are later combined to form sucrose and starch. The overall equation for the light-independent reactions in green plants is:[6] 3 CO2 + 9 ATP + 6 NADPH + 6 H+ → C3H6O3-phosphate + 9 ADP + 8 Pi + 6 NADP+ + 3 H2O
Overview of the Calvin cycle and carbon fixation
To be more specific, carbon fixation produces an intermediate product, which is then converted to the final carbohydrate products. The carbon skeletons produced by photosynthesis are then variously used to form other organic compounds, such as the building material cellulose, as precursors for lipid and amino acid biosynthesis, or as a fuel in cellular respiration. The latter occurs not only in plants but also in animals when the energy from plants gets passed through a food chain.
The fixation or reduction of carbon dioxide is a process in which carbon dioxide combines with a five-carbon sugar, ribulose 1,5-bisphosphate (RuBP), to yield two molecules of a three-carbon compound, glycerate 3-phosphate (GP), also known as 3-phosphoglycerate (PGA). GP, in the presence of ATP and NADPH from the light-dependent stages, is reduced to glyceraldehyde 3-phosphate (G3P). This product is also referred to as 3-phosphoglyceraldehyde (PGAL) or even as triose phosphate. Triose is a 3-carbon sugar (see carbohydrates). Most (5 out of 6 molecules) of the G3P produced is used to regenerate RuBP so the process can continue (see Calvin-Benson cycle). The 1 out of 6 molecules of the triose phosphates not "recycled" often condense to form hexose phosphates, which ultimately yield sucrose, starch and cellulose. The sugars produced during carbon metabolism yield carbon skeletons that can be used for other metabolic reactions like the production of amino acids and lipids.
C4 and C3 photosynthesis and CAM
Overview of C4 carbon fixation
In hot and dry conditions, plants will close their stomata to prevent loss of water. Under these conditions, CO2 will decrease, and dioxygen gas, produced by the light reactions of photosynthesis, will increase in the leaves, causing an increase of photorespiration by the oxygenase activity of ribulose-1,5-bisphosphate carboxylase/oxygenase and decrease in carbon fixation. Some plants have evolved mechanisms to increase the CO2 concentration in the leaves under these conditions. Main article: C4 carbon fixation
C4 plants chemically fix carbon dioxide in the cells of the mesophyll by adding it to the three-carbon molecule phosphoenolpyruvate (PEP), a reaction catalyzed by an enzyme called PEP carboxylase and which creates the four-carbon organic acid, oxaloacetic acid. Oxaloacetic acid or malate synthesized by this process is then translocated to specialized bundle sheath cells where the enzyme, rubisco, and other Calvin cyle enzymes are located, and where CO2 released by decarboxylation of the four-carbon acids is then fixed by rubisco activity to the three-carbon sugar 3 phosphoglyceric acids. The physical separation of rubisco from the oxygen-generating light reactions reduces photorespiration and increases CO2 fixation and thus photosynthetic capacity of the leaf. [9] C4 plants can produce more sugar than C3 plants in conditions of high light and temperature. Many important crop plants are C4 plants including maize, sorghum, sugarcane, and millet. Plants lacking PEP-carboxylase are called C3 plants because the primary carboxylation reaction, catalyzed by Rubiso, produces the three-carbon sugar 3 phosphoglyceric acids directly in the Calvin-Benson Cycle. Main article: CAM photosynthesis
Xerophytes such as cacti and most succulents also use PEP carboxylase to capture carbon dioxide in a process called Crassulacean acid metabolism (CAM). In contrast to C4 metabolism, which physically separates the CO2 fixation to PEP from the Calvin cycle, CAM only temporally separates these two processes. CAM plants have a different leaf anatomy than C4 plants, and fix the CO2 at night, when their stomata are open. CAM plants store the CO2 mostly in the form of malic acid via carboxylation of phosphoenolpyruvate to oxaloacetate, which is then reduced to malate. Decarboxylation of malate during the day releases CO2 inside the leaves thus allowing carbon fixation to 3-phosphoglycerate by rubisco.
Order and kinetics
The overall process of photosynthesis takes place in four stages. The first, energy transfer in antenna chlorophyll takes place in the femtosecond [1 femtosecond (fs) = 10,−15 s] to picosecond [1 picosecond (ps) = 10−12 s] time scale. The next phase, the transfer of electrons in photochemical reactions, takes place in the picosecond to nanosecond time scale [1 nanosecond (ns) = 10−9 s]. The third phase, the electron transport chain and ATP synthesis, takes place on the microsecond [1 microsecond (μs) = 10−6 s] to millisecond [1 millisecond (ms) = 10−3 s) time scale. The final phase is carbon fixation and export of stable products and takes place in the millisecond to second time scale. The first three stages occur in the thylakoid membranes.
Efficiency
Plants convert light into chemical energy with a maximum photosynthetic efficiency of approximately 6%.[10] By comparison solar panels convert light into electric energy at a photosynthetic efficiency of approximately 10-20%. Actual plant's photosynthetic efficiency varies with the frequency of the light being converted, light intensity, temperature and proportion of CO2 in atmosphere.
Evolution
[pic]
Plant cells with visible chloroplasts.
Early photosynthetic systems, such as those from green and purple sulfur and green and purple non-sulfur bacteria, are thought to have been anoxygenic, using various molecules as electron donors. Green and purple sulfur bacteria are thought to have used hydrogen and sulfur as an electron donor. Green nonsulfur bacteria used various amino and other organic acids. Purple nonsulfur bacteria used a variety of non-specific organic molecules. The use of these molecules is consistent with the geological evidence that the atmosphere was highly reduced at that time.[citation needed]
Fossils of what are thought to be filamentous photosynthetic organisms have been dated at 3.4 billion years old.[11]
The main source of oxygen in the atmosphere is oxygenic photosynthesis, and its first appearance is sometimes referred to as the oxygen catastrophe. Geological evidence suggests that oxygenic photosynthesis, such as that in cyanobacteria, became important during the Paleoproterozoic era around 2 billion years ago. Modern photosynthesis in plants and most photosynthetic prokaryotes is oxygenic. Oxygenic photosynthesis uses water as an electron donor which is oxidized to molecular dioxygen (O2) in the photosynthetic reaction center.
Symbiosis and the origin of chloroplasts
Several groups of animals have formed symbiotic relationships with photosynthetic algae. These are most common in corals, sponges and sea anemones, possibly due to these animals having particularly simple body plans and large surface areas compared to their volumes.[12] In addition, a few marine molluscs Elysia viridis and Elysia chlorotica also maintain a symbiotic relationship with chloroplasts that they capture from the algae in their diet and then store in their bodies. This allows the molluscs to survive solely by photosynthesis for several months at a time.[13][14] Some of the genes from the plant cell nucleus have even been transferred to the slugs, so that the chloroplasts can be supplied with proteins that they need to survive.[15]
An even closer form of symbiosis may explain the origin of chloroplasts. Chloroplasts have many similarities with photosynthetic bacteria including a circular chromosome, prokaryotic-type ribosomes, and similar proteins in the photosynthetic reaction center.[16][17] The endosymbiotic theory suggests that photosynthetic bacteria were acquired (by endocytosis) by early eukaryotic cells to form the first plant cells. Therefore, chloroplasts may be photosynthetic bacteria that adapted to life inside plant cells. Like mitochondria, chloroplasts still possess their own DNA, separate from the nuclear DNA of their plant host cells and the genes in this chloroplast DNA resemble those in cyanobacteria.[18] DNA in chloroplasts codes for redox proteins such as photosynthetic reaction centers. The CoRR Hypothesis proposes that this Co-location is required for Redox Regulation.
Cyanobacteria and the evolution of photosynthesis
The biochemical capacity to use water as the source for electrons in photosynthesis evolved once, in a common ancestor of extant cyanobacteria. The geological record indicates that this transforming event took place early in Earth's history, at least 2450-2320 million years ago (Ma), and possibly much earlier.[citation needed] Available evidence from geobiological studies of Archean (>2500 Ma) sedimentary rocks indicates that life existed 3500 Ma, but the question of when oxygenic photosynthesis evolved is still unanswered. A clear paleontological window on cyanobacterial evolution opened about 2000 Ma, revealing an already-diverse biota of blue-greens. Cyanobacteria remained principal primary producers throughout the Proterozoic Eon (2500-543 Ma), in part because the redox structure of the oceans favored photoautotrophs capable of nitrogen fixation.[citation needed] Green algae joined blue-greens as major primary producers on continental shelves near the end of the Proterozoic, but only with the Mesozoic (251-65 Ma) radiations of dinoflagellates, coccolithophorids, and diatoms did primary production in marine shelf waters take modern form. Cyanobacteria remain critical to marine ecosystems as primary producers in oceanic gyres, as agents of biological nitrogen fixation, and, in modified form, as the plastids of marine algae.[19]
Discovery
Although some of the steps in photosynthesis are still not completely understood, the overall photosynthetic equation has been known since the 1800s.
Jan van Helmont began the research of the process in the mid-1600s when he carefully measured the mass of the soil used by a plant and the mass of the plant as it grew. After noticing that the soil mass changed very little, he hypothesized that the mass of the growing plant must come from the water, the only substance he added to the potted plant. His hypothesis was partially accurate—much of the gained mass also comes from carbon dioxide as well as water. However, this was a signaling point to the idea that the bulk of a plant's biomass comes from the inputs of photosynthesis, not the soil itself.
Joseph Priestley, a chemist and minister, discovered that when he isolated a volume of air under an inverted jar, and burned a candle in it, the candle would burn out very quickly, much before it ran out of wax. He further discovered that a mouse could similarly "injure" air. He then showed that the air that had been "injured" by the candle and the mouse could be restored by a plant.
In 1778, Jan Ingenhousz, court physician to the Austrian Empress, repeated Priestley's experiments. He discovered that it was the influence of sunlight on the plant that could cause it to rescue a mouse in a matter of hours.
In 1796, Jean Senebier, a Swiss pastor, botanist, and naturalist, demonstrated that green plants consume carbon dioxide and release oxygen under the influence of light. Soon afterwards, Nicolas-Théodore de Saussure showed that the increase in mass of the plant as it grows could not be due only to uptake of CO2, but also to the incorporation of water. Thus the basic reaction by which photosynthesis is used to produce food (such as glucose) was outlined.
Cornelis Van Niel made key discoveries explaining the chemistry of photosynthesis. By studying purple sulfur bacteria and green bacteria he was the first scientist to demonstrate that photosynthesis is a light-dependent redox reaction, in which hydrogen reduces carbon dioxide.
Robert Emerson discovered two light reactions by testing plant productivity using different wavelengths of light. With the red alone, the light reactions were suppressed. When blue and red were combined, the output was much more substantial. Thus, there were two photosystems, one aborbing up to 600 nm wavelengths, the other up to 700. The former is known as PSII, the latter is PSI. PSI contains only chlorophyll a, PSII contains primarily chlorophyll a with most of the available chlorophyll b, among other pigments.[20]
Further experiments to prove that the oxygen developed during the photosynthesis of green plants came from water, were performed by Robert Hill in 1937 and 1939. He showed that isolated chloroplasts give off oxygen in the presence of unnatural reducing agents like iron oxalate, ferricyanide or benzoquinone after exposure to light. The Hill reaction is as follows: 2 H2O + 2 A + (light, chloroplasts) → 2 AH2 + O2 where A is the electron acceptor. Therefore, in light the electron acceptor is reduced and oxygen is evolved. Cyt b6, now known as a plastoquinone, is one electron acceptor.
Samuel Ruben and Martin Kamen used radioactive isotopes to determine that the oxygen liberated in photosynthesis came from the water.
Melvin Calvin and Andrew Benson, along with James Bassham, elucidated the path of carbon assimilation (the photosynthetic carbon reduction cycle) in plants. The carbon reduction cycle is known as the Calvin cycle, which inappropriately ignores the contribution of Bassham and Benson. Many scientists refer to the cycle as the Calvin-Benson Cycle, Benson-Calvin, and some even call it the Calvin-Benson-Bassham (or CBB) Cycle.
A Nobel Prize winning scientist, Rudolph A. Marcus, was able to discover the function and significance of the electron transport chain.
Factors
There are three main factors affecting photosynthesis and several corollary factors. The three main are: • Light irradiance and wavelength • Carbon dioxide concentration • Temperature.
Light intensity (irradiance), wavelength and temperature
In the early 1900s Frederick Frost Blackman along with Gabrielle Matthaei investigated the effects of light intensity (irradiance) and temperature on the rate of carbon assimilation. • At constant temperature, the rate of carbon assimilation varies with irradiance, initially increasing as the irradiance increases. However at higher irradiance this relationship no longer holds and the rate of carbon assimilation reaches a plateau. • At constant irradiance, the rate of carbon assimilation increases as the temperature is increased over a limited range. This effect is only seen at high irradiance levels. At low irradiance, increasing the temperature has little influence on the rate of carbon assimilation.
These two experiments illustrate vital points: firstly, from research it is known that photochemical reactions are not generally affected by temperature. However, these experiments clearly show that temperature affects the rate of carbon assimilation, so there must be two sets of reactions in the full process of carbon assimilation. These are of course the light-dependent 'photochemical' stage and the light-independent, temperature-dependent stage. Second, Blackman's experiments illustrate the concept of limiting factors. Another limiting factor is the wavelength of light. Cyanobacteria, which reside several meters underwater, cannot receive the correct wavelengths required to cause photoinduced charge separation in conventional photosynthetic pigments. To combat this problem, a series of proteins with different pigments surround the reaction center.This unit is called a phycobilisome.
Carbon dioxide levels and photorespiration
As carbon dioxide concentrations rise, the rate at which sugars are made by the light-independent reactions increases until limited by other factors. RuBisCO, the enzyme that captures carbon dioxide in the light-independent reactions, has a binding affinity for both carbon dioxide and oxygen. When the concentration of carbon dioxide is high, RuBisCO will fix carbon dioxide. However, if the oxygen concentration is high, RuBisCO will bind oxygen instead of carbon dioxide. This process, called photorespiration, uses energy, but does not make sugar.
RuBisCO oxygenase activity is disadvantageous to plants for several reasons: 1. One product of oxygenase activity is phosphoglycolate (2 carbon) instead of 3-phosphoglycerate (3 carbon). Phosphoglycolate cannot be metabolized by the Calvin-Benson cycle and represents carbon lost from the cycle. A high oxygenase activity, therefore, drains the sugars that are required to recycle ribulose 5-bisphosphate and for the continuation of the Calvin-Benson cycle. 2. Phosphoglycolate is quickly metabolized to glycolate that is toxic to a plant at a high concentration; it inhibits photosynthesis. 3. Salvaging glycolate is an energetically expensive process that uses the glycolate pathway and only 75% of the carbon is returned to the Calvin-Benson cycle as 3-phosphoglycerate. A highly-simplified summary is: 2 glycolate + ATP → 3-phosphoglycerate + carbon dioxide + ADP +NH3
The salvaging pathway for the products of RuBisCO oxygenase activity is more commonly known as photorespiration, since it is characterized by light-dependent oxygen consumption and the release of carbon dioxide.
Ensemble photochemistry and spectroscopy
In this part of our research, the sample of interest does not consist of just one single molecule, but of rather many (in most cases very many). Knowing the properties of the ensemble helps to understand the properties at the single molecule level and vice versa. In the lab, in most cases „ensemble“ means a solution of the sample of interest in a specific solvent. In other cases, specially prepared surfaces are investigated. Spectroscopy
The general method of (optical) spectroscopy uses the interaction with light (photons) to initiate processes in a sample, which are then monitored in order to gain information. In most cases, again photons are used as a carrier of this information (exception: Photoacoustic spectroscopy). The wavelength distribution of the intensities (spectrum) is recorded as the most obvious data set, however also the polarization state of the electric fields involved and the changes thereof can yield important information. On top, other measurement conditions can be varied systematically. Among others, the temperature, solvent, and concentration of the samples are all used as critical parameters.
When light (photons) interacts with sample matter (electrons), fundamentally three different processes are possible: it can (a) be transmitted, (b) reflected or (c) absorbed. While (a) and (b) leave the sample (largely) unchanged, case (c) will yield an excited state (S1) and a changed ground state S0. The former makes up the starting point of many different possible pathways; most of these are investigated in great detail in the lab and listed below. Steady State Spectroscopy
The S1 state has a limited lifetime; in many cases, the electron will return to the ground state by emitting a fluorescence photon. Thus, this state cannot be investigated with constant light illumination. Doing such an experiment will only yield properties of the changes in the ground state (absorption) and the (steady state) fluorescence. Both these types of measurements are routinely and extensively performed in the lab. Excited State Spectroscopy
In order to investigate excited states in molecules, it is necessary to employ pulsed light sources, which allow for interactions with the sample only at specific times and short durations. As the processes mentioned above go on in very different time domains, they all ask for specific measuring equipment including appropriate pulsed laser and detections systems.
In the lab, times in the range from nano- to microseconds can be investigated using a flash photolysis apparatus built around a Nd:YAG-laser pumped dye laser.
For the time range from ca. 30 ps to ca. 10 ns, two independent single photon timing laser systems are available. Although the time resolution attainable is similar in both, the experiments are slightly different with respect to the usable wavelength range. Both systems measure the time resolved fluorescence from the samples of interest.
Furthermore, for even shorter times, a dual-OPA regeneratively amplified femtosecond laser system is in use. Depending on the specific type of experiments, the time range which can be covered by this equipment stretches from ca. 100 fs to ca. 2 ns.
With this system, various types of experiments are performed, which employ different detection schemes (e.g. Upconversion, polychromatic transient absorption, …). Of course, very often it is useful to perform measurements using various of these schemes after one another to investigate and clarify fast kinetic processes in the samples of interest. Excited State kinetics
As mentioned above, the state generated by the optical excitation is the starting point for many possible pathways. The simplest case is, of course, the return of the electron to the ground state by emission of a fluorescence photon. This process is observed in many samples; however others are – dependent on the sample – seen on top.
Under suitable conditions, in some samples the energy put into the S1 state can be transferred to other parts of the molecule(s). Depending on the conditions, this transfer can appear as dissipative (energy hopping) or directional, both types are investigated extensively in the lab in various different samples.
Under again different specific conditions in a sample, a transfer of an electron from one part within a molecule (donor) to a different part (acceptor) can be initiated. Also this type of kinetics is studied at large within the lab.
You May Also Find These Documents Helpful
-
One of such means termed fluorescence occurs when a substance can be induced into giving off light is through absorption of a photon through light or other means of radiations. During this process, electrons are excited from their standard state. The electrons jump from their highest unoccupied orbital (HUMO) into a certain level of the unoccupied orbital (LUMO). As the electrons loose energy, they fall back to a lower orbital, thus emitting light. 1, 2…
- 2366 Words
- 10 Pages
Good Essays -
Photosynthesis is a process which occurs in plants when light energy needs to be transformed into chemical energy. 1. Oxygenic and anoxygenic photosynthesis are the two process which photosynthesis has. The most…
- 1319 Words
- 6 Pages
Powerful Essays -
The process of photosynthesis occurs when six carbon dioxide molecules (CO2), six water molecules (H2O), and light energy are added together and result in glucose (C6H12O6) and six oxygen (O2) molecules. There are two stages to this process; light reactions and dark reactions. Light reactions start with chloroplast which absorbs the light. Inside the chloroplast are thylakoids that contain pigments which absorb certain wavelengths of light. Each cluster of pigments is called a photosystem. Photosystem I and II obtain some of the light’s energy. Light first enters chlorophyll A in photosystem II and the electrons inside become excited enough to leave it. Some of the electrons, which just left, enter a chain of reactions called the electron transport chain and it produces ATP. The electrons that couldn’t fit into the ETC move onto photosystem I. Those electrons then get excited by light energy and enter the ETC where they add a hydrogen atom to NADP to form NADPH.…
- 411 Words
- 3 Pages
Good Essays -
Second Law of Thermodynamics: States that every exchange of energy increases the entropy of the Universe, is that energy conversions cannot be completely efficient; some energy conversion cannot be completely efficient; some energy conversions cannot be completely efficient; some energy is always lost as heat…
- 611 Words
- 3 Pages
Good Essays -
The name of the section of the EM spectrum we can see is the visible light region.…
- 1261 Words
- 6 Pages
Powerful Essays -
1.2.1 Outline the role of photosynthesis in transforming light energy to chemical energy and recall the raw materials for this process…
- 2016 Words
- 9 Pages
Best Essays -
The procedure of using a spectroscope was practiced with a fluorescent light source. The slit was pointed towards the source, and the spectroscope was shifted until the spectrum was clearly visible.…
- 2168 Words
- 9 Pages
Powerful Essays -
Photosynthesis is the process by which green plants and some other organisms use sunlight to synthesize foods from carbon dioxide and water. Photosynthesis in plants generally involves the green pigment chlorophyll and generates oxygen as a byproduct. It produces sugar and other organic compounds such as lipids and proteins. The sugars are then used to provide energy for the organism. Light reaction is the series of biochemical reactions in photosynthesis that require light energy that is captured by light-absorbing pigments; such as chlorophyll, to be converted into chemical energy in the form of ATP and NADPH. Light reactions occur mostly in the thylakoid stacks of the grana. The light-independent reactions, is a light-independent series of reactions which occur in the stroma of the chloroplasts, when the products of the light reaction, ATP and NADPH, are used to make carbohydrates from carbon dioxide ( Light intensity and Wavelength). The light-dependent reaction, in this case would be the ATP Energy from light is like a forcing of electrons to flow from water to NADP in the chloroplast. The electrons retain energy in the NADPH. Some of the NADPH is used to synthesize ATP. NADPH and ATP are the products of the light reactions of photosynthesis.…
- 456 Words
- 2 Pages
Good Essays -
On February 9, 2011, little Enzo Williams was traveling with his mother, father and his older sister, they had approached a red light and were at a complete stop waiting for the light to turn green, when from out of nowhere a SUV driving at a high rate of speed driven by Sydney Wright smashed into the back of their vehicle. Sydney Wright was texting what was claimed to be a short text message and took the life of this innocent little boy. Enzo’s mother, father, and sister walked away from the wreck as did the driver of the other vehicle Sydney. Enzo suffered a bruised windpipe and a skull fracture; he was transported by ambulance to the nearest hospital where he lived for two short days. He was unable to recover from his injuries, he was 6 months old.…
- 445 Words
- 2 Pages
Good Essays -
Chemistry is the study of chemical reactions as a result of molecular interaction. There are four ways to determine if a chemical reaction has occurred.…
- 8428 Words
- 34 Pages
Powerful Essays -
Background- Photosynthesis is a process used by plants and other organisms to convert light energy, normally from the Sun, into chemical energy that can be later released to fuel the organisms' activities. Photosynthesis is the chemical reaction that takes place in plants. Photosynthesis is also an enzyme controlled reaction. The chemical formula for the process of photosynthesis is:…
- 1242 Words
- 7 Pages
Better Essays -
Photosynthesis is a process that captures energy from sunlight to make sugars that store chemical energy by absorbing visible light and takes place in the chloroplast. In photosynthesis there are two stages, light-dependent reactions and…
- 551 Words
- 3 Pages
Good Essays -
First Law- The law of conservation of energy, which states that energy can be converted from one form to another, but it CANNOT be created or destroyed.…
- 251 Words
- 2 Pages
Satisfactory Essays -
In 1556, the alchemist Fabricius was the first to discover that light can photochemically react with these crystals to change the silver ions (Ag+) to elemental silver (AgO). As the reaction proceeds, the silver atoms grow into clusters, which are large enough to scatter light and produce colors in a pattern identical to that of the original light source. Photography utilizes this chemical principle to record color or black and white images.…
- 1830 Words
- 8 Pages
Powerful Essays -
Observation of properties of materials involved in the reaction is a way to detect a chemical change. Signs like a color change, the formation of a solid within two liquids and the production of gas from solids or liquids are all…
- 686 Words
- 3 Pages
Better Essays