DPPH

Last updated
DPPH
DPPH.svg
Dpph sample.jpg
Names
Preferred IUPAC name
2,2-Diphenyl-1-(2,4,6-trinitrophenyl)hydrazin-1-yl
Other names
2,2-Diphenyl-1-picrylhydrazyl
1,1-Diphenyl-2-picrylhydrazyl radical
2,2-Diphenyl-1-(2,4,6-trinitrophenyl)hydrazyl
Diphenylpicrylhydrazyl
Identifiers
3D model (JSmol)
AbbreviationsDPPH
ChemSpider
ECHA InfoCard 100.015.993 OOjs UI icon edit-ltr-progressive.svg
PubChem CID
UNII
  • InChI=1S/C18H12N5O6/c24-21(25)15-11-16(22(26)27)18(17(12-15)23(28)29)19-20(13-7-3-1-4-8-13)14-9-5-2-6-10-14/h1-12H Yes check.svgY
    Key: HHEAADYXPMHMCT-UHFFFAOYSA-N Yes check.svgY
  • InChI=1/C18H13N5O6/c24-21(25)15-11-16(22(26)27)18(17(12-15)23(28)29)19-20(13-7-3-1-4-8-13)14-9-5-2-6-10-14/h1-12,19H
    Key: WCBPJVKVIMMEQC-UHFFFAOYAG
  • InChI=1/C18H12N5O6/c24-21(25)15-11-16(22(26)27)18(17(12-15)23(28)29)19-20(13-7-3-1-4-8-13)14-9-5-2-6-10-14/h1-12H
    Key: HHEAADYXPMHMCT-UHFFFAOYAG
  • c1ccc(cc1)N(c2ccccc2)[N]c3c(cc(cc3[N+](=O)[O-])[N+](=O)[O-])[N+](=O)[O-]
Properties
C18H12N5O6
Molar mass 394.32 g/mol
AppearanceBlack to green powder, purple in solution
Density 1.4 g/cm3
Melting point 135 °C (275 °F; 408 K)(decomposes)
insoluble
Solubility in methanol 10 mg/mL
Hazards
NFPA 704 (fire diamond)
0
1
0
Safety data sheet (SDS) MSDS
Except where otherwise noted, data are given for materials in their standard state (at 25 °C [77 °F], 100 kPa).
Yes check.svgY  verify  (what is  Yes check.svgYX mark.svgN ?)
Infobox references

DPPH is a common abbreviation for the organic chemical compound 2,2-diphenyl-1-picrylhydrazyl. It is a dark-colored crystalline powder composed of stable free radical molecules. DPPH has two major applications, both in laboratory research: one is a monitor of chemical reactions involving radicals, most notably it is a common antioxidant assay, [1] and another is a standard of the position and intensity of electron paramagnetic resonance signals.

Properties and applications

DPPH has several crystalline forms which differ by the lattice symmetry and melting point. The commercial powder is a mixture of phases which melts at ~130 °C. DPPH-I (m.p. 106 °C) is orthorhombic, DPPH-II (m.p. 137 °C) is amorphous and DPPH-III (m.p. 128–129 °C) is triclinic. [2]

DPPH is a well-known radical and a trap ("scavenger") for other radicals. Therefore, rate reduction of a chemical reaction upon addition of DPPH is used as an indicator of the radical nature of that reaction. Because of a strong absorption band centered at about 520 nm, the DPPH radical has a deep violet color in solution, and it becomes colorless or pale yellow when neutralized. This property allows visual monitoring of the reaction, and the number of initial radicals can be counted from the change in the optical absorption at 520 nm or in the EPR signal of the DPPH. [3]

DPPHreact.png

Because DPPH is an efficient radical trap, it is also a strong inhibitor of radical-mediated polymerization. [4]

Inhibition of polymer chain, R, by DPPH. Termination - with impurity 2.png
Inhibition of polymer chain, R, by DPPH.

As a stable and well-characterized solid radical source, DPPH is the traditional and perhaps the most popular standard of the position (g-marker) and intensity of electron paramagnetic resonance (EPR) signals – the number of radicals for a freshly prepared sample can be determined by weighing and the EPR splitting factor for DPPH is calibrated at g = 2.0036. DPPH signal is convenient by that it is normally concentrated in a single line, whose intensity increases linearly with the square root of microwave power in the wider power range. The dilute nature of the DPPH radicals (one unpaired spin per 41 atoms) results in a relatively small linewidth (1.5–4.7  G). The linewidth may however increase if solvent molecules remain in the crystal and if measurements are performed with a high-frequency EPR setup (~200 GHz), where the slight g-anisotropy of DPPH becomes detectable. [5] [6]

Whereas DPPH is normally a paramagnetic solid, it transforms into an antiferromagnetic state upon cooling to very low temperatures of the order 0.3 K. This phenomenon was first reported by Alexander Prokhorov in 1963. [7] [8] [9] [10]

Related Research Articles

Dynamic nuclear polarization (DNP) results from transferring spin polarization from electrons to nuclei, thereby aligning the nuclear spins to the extent that electron spins are aligned. Note that the alignment of electron spins at a given magnetic field and temperature is described by the Boltzmann distribution under the thermal equilibrium. It is also possible that those electrons are aligned to a higher degree of order by other preparations of electron spin order such as: chemical reactions, optical pumping and spin injection. DNP is considered one of several techniques for hyperpolarization. DNP can also be induced using unpaired electrons produced by radiation damage in solids.

Dangling bond

In chemistry, a dangling bond is an unsatisfied valence on an immobilized atom. An atom with a dangling bond is also referred to as an immobilized free radical or an immobilized radical, a reference to its structural and chemical similarity to a free radical.

Singlet oxygen Oxygen with all of its electrons spin paired

Singlet oxygen, systematically named dioxygen(singlet) and dioxidene, is a gaseous inorganic chemical with the formula O=O, which is in a quantum state where all electrons are spin paired. It is kinetically unstable at ambient temperature, but the rate of decay is slow.

CIDNP, often pronounced like "kidnip", is an nuclear magnetic resonance (NMR) technique that is used to study chemical reactions that involve radicals. It detects the non-Boltzmann nuclear spin state distribution produced in these reactions as enhanced absorption or emission signals.

Electron paramagnetic resonance Technique to study materials that have unpaired electrons

Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spins excited are those of the electrons instead of the atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes and organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford.

Free-radical polymerization (FRP) is a method of polymerization, by which a polymer forms by the successive addition of free-radical building blocks. Free radicals can be formed by a number of different mechanisms, usually involving separate initiator molecules. Following its generation, the initiating free radical adds (nonradical) monomer units, thereby growing the polymer chain.

Frémys salt Chemical compound

Frémy's salt is a chemical compound with the formula (K4[ON(SO3)2]2), sometimes written as (K2[NO(SO3)2]). It a bright yellowish-brown solid, but its aqueous solutions are bright violet. The related sodium salt, disodium nitrosodisulfonate (NDS, Na2ON(SO3)2, CAS 29554-37-8) is also referred to as Frémy's salt.

Oxygen radical absorbance capacity (ORAC) was a method of measuring antioxidant capacities in biological samples in vitro. Because no physiological proof in vivo existed in support of the free-radical theory or that ORAC provided information relevant to biological antioxidant potential, it was withdrawn in 2012.

Ferromagnetic resonance, or FMR, is coupling between an electromagnetic wave and the magnetization of a medium through which it passes. This coupling induces a significant loss of power of the wave. The power is absorbed by the precessing magnetization of the material and lost as heat. For this coupling to occur, the frequency of the incident wave must be equal to the precession frequency of the magnetization and the polarization of the wave must match the orientation of the magnetization.

Spin trapping

Spin trapping is an analytical technique employed in chemistry and biology for the detection and identification of short-lived free radicals through the use of electron paramagnetic resonance (EPR) spectroscopy. EPR spectroscopy detects paramagnetic species such as the unpaired electrons of free radicals. However, when the half-life of radicals is too short to detect with EPR, compounds known as spin traps are used to react covalently with the radical products and form more stable adduct that will also have paramagnetic resonance spectra detectable by EPR spectroscopy. The use of radical-addition reactions to detect short-lived radicals was developed by several independent groups by 1968.

Physical organic chemistry, a term coined by Louis Hammett in 1940, refers to a discipline of organic chemistry that focuses on the relationship between chemical structures and reactivity, in particular, applying experimental tools of physical chemistry to the study of organic molecules. Specific focal points of study include the rates of organic reactions, the relative chemical stabilities of the starting materials, reactive intermediates, transition states, and products of chemical reactions, and non-covalent aspects of solvation and molecular interactions that influence chemical reactivity. Such studies provide theoretical and practical frameworks to understand how changes in structure in solution or solid-state contexts impact reaction mechanism and rate for each organic reaction of interest.

Radical (chemistry) Atom, molecule, or ion that has an unpaired valence electron; typically highly reactive

In chemistry, a free radical is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes.

Electron nuclear double resonance (ENDOR) is a magnetic resonance technique for elucidating the molecular and electronic structure of paramagnetic species. The technique was first introduced to resolve interactions in electron paramagnetic resonance (EPR) spectra. It is currently practiced in a variety of modalities, mainly in the areas of biophysics and heterogeneous catalysis.

The amino radical,
NH
2
, also known as the aminyl radical or azanyl radical, is the neutral form of the amide ion (NH
2
). Aminyl are highly reactive and consequently short lived like most radicals; however, they form an important part of nitrogen chemistry. In sufficiently high concentration, amino radicals dimerise to form hydrazine. While NH2 as a functional group is common in nature, forming a part of many compounds (e.g. the phenethylamines), the radical cannot be isolated in its free form.

Sandra Eaton is an American chemist and Professor at the University of Denver, known for her work on electron paramagnetic resonance.

Wolfgang Lubitz

Wolfgang Lubitz is a German chemist and biophysicist. He is currently a director emeritus at the Max Planck Institute for Chemical Energy Conversion. He is well known for his work on bacterial photosynthetic reaction centres, hydrogenase enzymes, and the oxygen-evolving complex using a variety of biophysical techniques. He has been recognized by a Festschrift for his contributions to electron paramagnetic resonance (EPR) and its applications to chemical and biological systems.

Spectroelectrochemistry

Spectroelectrochemistry (SEC) is a set of multi-response analytical techniques in which complementary chemical information is obtained in a single experiment. Spectroelectrochemistry provides a whole vision of the phenomena that take place in the electrode process. The first spectroelectrochemical experiment was carried out by Theodore Kuwana, PhD, in 1964.

David Collison is a British chemist and a Professor in the Department of Chemistry at The University of Manchester. His research in general is based on inorganic chemistry and magnetochemistry, specifically on coordination chemistry, electron paramagnetic resonance spectroscopy and f-block chemistry.

R. David Britt is the Winston Ko Chair and Distinguished Professor of Chemistry at the University of California, Davis. Britt uses electron paramagnetic resonance (EPR) spectroscopy to study metalloenzymes and enzymes containing organic radicals in their active sites. Britt is the recipient of multiple awards for his research, including the Bioinorganic Chemistry Award in 2019 and the Bruker Prize in 2015 from the Royal Society of Chemistry. He has received a Gold Medal from the International EPR Society (2014), and the Zavoisky Award from the Kazan Scientific Center of the Russian Academy of Sciences (2018). He is a Fellow of the American Association for the Advancement of Science and of the Royal Society of Chemistry.

Electron resonance imaging (ERI) is a preclinical imaging method, together with positron emission tomography (PET), computed tomography scan, magnetic resonance imaging (MRI), and other techniques. ERI is dedicated to imaging small laboratory animals and its unique feature is the ability to detect free radicals. This technique could also be used for other purposes such as material science, quality of food, etc.

References

  1. Sharma, Om P.; Bhat, Tej K. (15 April 2009). "DPPH antioxidant assay revisited". Journal of Food Chemistry. 113 (4): 1202–1205. doi:10.1016/j.foodchem.2008.08.008.
  2. Kiers, C. T.; De Boer, J. L.; Olthof, R.; Spek, A. L. (1976). "The crystal structure of a 2,2-diphenyl-1-picrylhydrazyl (DPPH) modification". Acta Crystallographica Section B. 32 (8): 2297. doi:10.1107/S0567740876007632.
  3. Alger, Mark S. M. (1997). Polymer science dictionary. Springer. p. 152. ISBN   0-412-60870-7.
  4. Cowie, J. M. G.; Arrighi, Valeria (2008). Polymers: Chemistry and Physics of Modern Materials (3rd ed.). Scotland: CRC Press. ISBN   978-0-8493-9813-1.
  5. M.J. Davies (2000). Electron Paramagnetic Resonance. Royal Society of Chemistry. p. 178. ISBN   0-85404-310-1.
  6. Charles P. Poole (1996). Electron spin resonance: a comprehensive treatise on experimental techniques. Courier Dover Publications. p. 443. ISBN   0-486-69444-5.
  7. A. M. Prokhorov and V.B. Fedorov, Soviet Phys. JETP 16 (1963) 1489.
  8. Fujito, Teruaki (1981). "Magnetic Interaction in Solvent-free DPPH and DPPH–Solvent Complexes". Bulletin of the Chemical Society of Japan. 54 (10): 3110. doi: 10.1246/bcsj.54.3110 .
  9. Lundqvist, Stig (1998). "A. M. Prokhorov". Nobel Lectures in Physics, 1963–1970. World Scientific. p. 118. ISBN   981-02-3404-X.
  10. Aleksandr M. Prokhorov, The Nobel Prize in Physics 1964