Singlet oxygen

From Wikipedia, the free encyclopedia
Jump to: navigation, search
Singlet oxygen
Identifiers
ChEBI CHEBI:26689
Gmelin Reference 491
Jmol-3D images Image 1
Properties
Molecular formula O2
Molar mass 32.00 g mol−1
Solubility in water Reacts
Except where noted otherwise, data are given for materials in their standard state (at 25 °C (77 °F), 100 kPa)
Infobox references

Singlet oxygen (systematically named dioxidene and dioxygen) is an inorganic chemical in an excited state, with the chemical formula O
2
(a1Δg) (also written O
2
*). Singlet oxygen is the common name used for an electronically excited state of molecular oxygen (O2), which is less stable than the normal triplet oxygen. Because of its unusual properties, singlet oxygen can persist for over an hour at room temperature, in isolation. Because of differences in their electron shells, singlet and triplet oxygen differ in their chemical properties. Singlet oxygen is highly reactive.

Singlet oxygen is usually generated with a photosensitizer pigment. The damaging effects of sunlight on many organic materials (polymers, etc.) are often attributed to the effects of singlet oxygen. In photodynamic therapy, singlet oxygen is produced to kill cancer cells.[1]

The blue color of liquid and solid O2 is actually due to the simultaneous excitation by a single photon of two O2 molecules from their ground states to their excited states, in which the associated energy absorbed corresponds to absorption of light in the red to green region of the visible part of the spectrum, thus the reflected color of liquid and solid O2 appears blue.[2]

Production[edit]

Various methods for the production of singlet oxygen exist. A photochemical method involves the irradiation of normal oxygen gas in the presence of an organic dye as a sensitizer, such as rose bengal, methylene blue or porphyrins.[3] Singlet oxygen can also be produced chemically. One of the chemical methods is by the decomposition of hydrogen trioxide, or to react hydrogen peroxide with sodium hypochlorite, which is convenient in school laboratories for demonstrative purposes:

H2O2 + NaOCl → O2(a1Δg) + NaCl + H2O

Another method is via phosphite ozonides, which in turn is generated in situ. The phosphite ozonide is then catalytically decomposed by pyridine at low temperature to give singlet oxygen:

Scheme for preparing singlet oxygen via phosphite ozonides.png

The advantage of this method is that the reaction can be cyclic, which the resulting phosphate ester is reduced to the phosphite ester for further production of singlet oxygen.[2]

Organic chemistry[edit]

The chemistry of singlet oxygen is different from that of ground state oxygen. For example, singlet oxygen can participate in Diels-Alder [4+2] and [2+2] cycloaddition reactions, ene reactions, and heteroatom (S, Se, P, N) and organometallic complex oxidation reactions.[4][5] Singlet oxygen reacts with an alkene -CH=CH-CH2- by abstraction of the allylic proton in an ene reaction type reaction[6] to the allyl hydroperoxide HO-O-R (R = alkyl), which can then be reduced to the allyl alcohol. (This reaction is not actually a true ene reaction, because it isn't concerted: singlet oxygen forms an exciplex that can be called an "epoxide oxide", which then abstracts the hydrogen.) An example is an oxygenation of citronellol:[7][note 1]

Singlet Oxygenation Citronellol

With some substrates 1,2-dioxetanes are formed and cyclic dienes such as 1,3-cyclohexadiene form [4+2]cycloaddition adducts.[8] With water trioxidane, an unusual molecule with three consecutive linked oxygen atoms, is formed.

Biochemistry[edit]

In photosynthesis, singlet oxygen can be produced from the light-harvesting chlorophyll molecules. One of the roles of carotenoids in photosynthetic systems is to prevent damage caused by produced singlet oxygen by either removing excess light energy from chlorophyll molecules or quenching the singlet oxygen molecules directly.

In mammalian biology, singlet oxygen is one of the reactive oxygen species, which is linked to oxidation of LDL cholesterol and resultant cardiovascular effects. Polyphenol antioxidants can scavenge and reduce concentrations of reactive oxygen species and may prevent such deleterious oxidative effects.[9]

Ingestion of pigments capable of producing singlet oxygen with activation by light can produce severe photosensitivity of skin (see phototoxicity, photosensitivity in humans, photodermatitis, phytophotodermatitis). This is especially a concern in herbivorous animals (see Photosensitivity in animals).

Singlet oxygen is the active species in photodynamic therapy.

Orbital states[edit]

Molecular orbital theory predicts two low-lying excited singlet states O2(a¹Δg) and O2(b¹Σg+) (for nomenclature see article on Molecular term symbol). These electronic states differ only in the spin and the occupancy of oxygen's two degenerate antibonding πg-orbitals (see degenerate energy level). The O2(b¹Σg+)-state is very short lived and relaxes quickly to the lowest lying excited state, O2(a¹Δg). Thus, the O2(a¹Δg)-state is commonly referred to as singlet oxygen. The energy difference between the lowest energy of O2 in the singlet state and the lowest energy in the triplet state is about 11340 kelvin (Te (a¹Δg <- X³Σg-) = 7882 cm−1, 94.3 kJ/mol, 0.98 eV)[3] Molecular oxygen differs from most molecules in having an open-shell triplet ground state, O2(X³Σg-). Although the three lowest energy states of oxygen can be described by the simple scheme in the figure below, this is a simplification. The excited states of oxygen are made up of combinations of electronic states. The electrons paired in the same orbital, while the first excited state involves states with the electrons in separate degenerate orbitals, as might be expected from Hund's rule.[10]

Chemistry[edit]

Molecular orbital scheme or the three electronic configurations of molecular oxygen, O2. Shown from left to right are: The singlet oxygen a¹Δg excited state, the singlet oxygen b¹Σg+ excited state, and the triplet ground state X³Σg-. The 1s molecular orbital is omitted for simplicity. Note that the states only differ in the spin and the occupancy of oxygen's two degenerate antibonding πg-orbitals.

The energy difference between ground state and singlet oxygen is 94.3 kJ/mol and corresponds to a transition in the near-infrared at ~1270 nm. In the isolated molecule, the transition is strictly forbidden by spin, symmetry and parity selection rules, making it one of nature's most forbidden transitions. In other words, direct excitation of ground state oxygen by light to form singlet oxygen is very improbable. As a consequence, singlet oxygen in the gas phase is extremely long lived (72 minutes). Interaction with solvents, however, reduces the lifetime to microseconds or even nanoseconds.[11]

Direct detection of singlet oxygen is possible using sensitive laser spectroscopy [12] or through its extremely weak phosphorescence at 1270 nm, which is not visible. However, at high singlet oxygen concentrations, the fluorescence of the so-called singlet oxygen dimol (simultaneous emission from two singlet oxygen molecules upon collision) can be observed as a red glow at 634 nm.[13]

External links[edit]

Notes[edit]

  1. ^ reagent: hydrogen peroxide, catalyst: sodium molybdate, reducing agent: sodium sulfite

References[edit]

  1. ^ http://www.telegraph.co.uk/health/10294405/How-a-light-beam-cured-my-cancer.html
  2. ^ a b .Catherine E. Housecroft; Alan G. Sharpe (2008). "Chapter 16: The group 16 elements". Inorganic Chemistry, 3rd Edition. Pearson. p. 496. ISBN 978-0-13-175553-6. 
  3. ^ a b C. Schweitzer, R. Schmidt (2003). "Physical Mechanisms of Generation and Deactivation of Singlet Oxygen". Chemical Reviews 103 (5): 1685–1757. doi:10.1021/cr010371d. PMID 12744692. 
  4. ^ Clennan, EL; Pace, A (2005). "Advances in singlet oxygen chemistry". Tetrahedron 61 (28): 6665–6691. doi:10.1016/j.tet.2005.04.017. 
  5. ^ Ogilby, PR (2010). "Singlet oxygen: there is indeed something new under the sun". Chemical Society Reviews 39 (8): 3181–3209. doi:10.1039/B926014P. 
  6. ^ Alberti, MN; Orfanopoulos, M (2010). "Unraveling the Mechanism of the Singlet Oxygen Ene Reaction: Recent Computational and Experimental Approaches". Chemistry - A European Journal 16 (31): 9414–9421. doi:10.1002/chem.201000752. 
  7. ^ Paul L. Alsters, Walther Jary, Veronique Nardello-Rataj, Jean-Marie Aubry (2009). "Dark Singlet Oxygenation of β-Citronellol: A Key Step in the Manufacture of Rose Oxide". Organic Process Research & Development 14: 259–262. doi:10.1021/op900076g. 
  8. ^ Carey, Francis A.; Sundberg, Richard J.; (1984). Advanced Organic Chemistry Part A Structure and Mechanisms (2nd ed.). New York N.Y.: Plenum Press. ISBN 0-306-41198-9.
  9. ^ Cell and Molecular Cell Biology concepts and experiments Fourth Edition. Gerald Karp. Page 223 2005
  10. ^ Frimer, Aryeh A. "Singlet Oxygen Volume I, Physical-Chemical Aspects" CRC press Boca Raton, Fl 1985 pg 4-7
  11. ^ Wilkinson, F., Helman, W. P., and Ross, A. B. (1995). "Rate constants for the decay and reactions of the lowest electronically excited singlet state of molecular oxygen in solution. An expanded and revised compilation", Journal of Physical and Chemical Reference Data, 24(2): 663-677
  12. ^ Földes, T.; Čermák, P.; Macko, M.; Veis, P.; Macko, P. (January 2009). "Cavity ring-down spectroscopy of singlet oxygen generated in microwave plasma". Chemical Physics Letters 467 (4–6): 233–236. Bibcode:2009CPL...467..233F. doi:10.1016/j.cplett.2008.11.040. 
  13. ^ Interpretation of the atmospheric oxygen bands; electronic levels of the oxygen molecule R.S. Mulliken Nature Volume 122, Page 505 1928