72433-26-2Relevant articles and documents
Dual-color control of nucleotide polymerization sensed by a fluorescence actuator
Reimao-Pinto, Madalena M.,Cordeiro, Ana,Almeida, Carina,Pinheiro, Andre V.,Moro, Artur,Lima, Joao C.,Baptista, Pedro V.
, p. 751 - 756 (2014/05/06)
Spatial and temporal control of molecular mechanisms can be achieved using photolabile bonds that connect biomolecules to protective caging groups, which can be cleaved upon irradiation of a specific wavelength, releasing the biomolecule ready-to-use. Here we apply and improve a previously reported strategy to tightly control in vitro transcription reactions. The strategy involves two caging molecules that block both ATP and GTP nucleotides. Additionally, we designed a molecular beacon complementary to the synthesized mRNA to infer its presence through a light signal. Upon release of both nucleotides through a specific monochromatic light (390 and 325 nm) we attain a light signal indicative of a successful in vitro transcription reaction. Similarly, in the absence of irradiation, no intense fluorescence signal was obtained. We believe this strategy could further be applied to DNA synthesis or the development of logic gates. This journal is
Photoinitiated release of an aziridinium ion precursor for the temporally controlled alkylation of nucleophiles
McCarron, Stephen T.,Feliciano, Mariel,Johnson, Jeffreys N.,Chambers, James J.
, p. 2395 - 2398 (2013/05/21)
A photo-activatable aziridinium precursor has been developed to investigate the possibility of a photo-initiated traditional nucleophilic reaction. The photolysis of a quaternary amine yields a tertiary amine and has allowed us to temporally control aziridinium formation and subsequent alkylation of a colorimetric nucleophilic reporter molecule. We have also used this photo-initiated reaction to alkylate a sulfhydryl group. This new photo-initiated alkylation strategy is water-soluble and expands the toolkit of photo-activated crosslinkers for protein labeling research.
Coumarin-4-ylmethoxycarbonyls as Phototriggers for Alcohols and Phenols
Suzuki, Akinobu Z.,Watanabe, Takayoshi,Kawamoto, Mika,Nishiyama, Keiko,Yamashita, Hirotaka,Ishii, Megumi,Iwamura, Michiko,Furuta, Toshiaki
, p. 4867 - 4870 (2007/10/03)
(Equation Presented) Caged compounds can be used to regulate the spatial and temporal dynamics of signaling molecules in live cells. Photochemical properties of coumarin-4-ylmethoxy carbonates (1a-d) are investigated to construct caged compounds of hydroxy-containing molecules. All the compounds possess desired properties as phototriggers for alcohols and phenols. The 6-bromo-7-hydroxycoumarin-4-ylmethoxycarbonyl (Bhcmoc) group has the highest photochemical efficiency and is applied to make caged compounds of 1,2-dioctanoylglycerol (diC8), Tyr-OMe, and adenosine.
Synthesis and photoreactivity of caged blockers for glutamate transporters
Takaoka, Kiyo,Tatsu, Yoshiro,Yumoto, Noboru,Nakajima, Terumi,Shimamoto, Keiko
, p. 965 - 970 (2007/10/03)
L-TBOA (L-threo-β-benzyloxyaspartate) is, so far, the most potent non-transportable blocker for glutamate transporters. We synthesized α-CMCM-L-TBOA (1a) possessing [7-(carboxymethoxy)coumarin-4-yl]methyl ester as a caging group. α-CMCM-L-TBOA (1a) is biologically inactive until UV irradiation and the photolysis of 1a immediately released L-TBOA to show glutamate uptake inhibition. The photoreactivity of the coumarin-type caging group was superior to that of the o-nitrobenzyl-type caging group.
Deactivation behavior and excited-state properties of (coumarin-4-yl)methyl derivatives. 2. Photocleavage of selected (coumarin-4-yl)methyl-caged adenosine cyclic 3′,5′-monophosphates with fluorescence enhancement
Eckardt, Torsten,Hagen, Volker,Schade, Bjoern,Schmidt, Reinhardt,Schweitzer, Claude,Bendig, Juergen
, p. 703 - 710 (2007/10/03)
A series of axial and equatorial diastereomers of (coumarin-4-yl)methyl-caged adenosine cyclic 3′,5′-monophosphates (cAMPs), 1-6, having methoxy, dialkylamino, or no substituent in the 6- and/or 7-positions, and their corresponding 4-(hydroxymethyl)coumarin photoproducts 7-12 have been synthesized. The photochemical and UV/vis spectroscopical properties (absorption and fluorescence) of 1-6 and 7-12 have been examined in methanol/aqueous HEPES buffer solution. Donor substitution in the 6-position causes a strong bathochromic shift of the long-wavelength absorption band, whereas substitution in the 7-position leads only to a weak red shift. The photochemical cleavage of the caged cAMPs was investigated, and the photoproducts were analyzed. Photochemical quantum yields, fluorescence quantum yields, and lifetimes of the excited singlet states were determined. The highest values of photochemical quantum yields (photo-SN1 mechanism) were obtained with caged cAMPs having a donor substituent in the 7-position of the coumarin moiety, caused by electronic stabilization of the intermediately formed coumarinylmethyl cation. With donor substitution in the 6-position, the resulting moderate electronic stabilization of the coumarinylmethyl cation is overcompensated by the strong bathochromic shift, reducing the energy gap between the excited-state S1 and the corresponding coumarinylmethyl cation. The rate constant for the ester cleavage and liberation of cAMP is about 109 s-1, estimated for the axial isomer of 6 by analysis of the fluorescence increase of the alcohol 12 formed upon laser pulse photolysis.
Anthraquinon-2-ylmethoxycarbonyl (Aqmoc): A new photochemically removable protecting group for alcohols
Furuta, Toshiaki,Hirayama, Yuuki,Iwamura, Michiko
, p. 1809 - 1812 (2007/10/03)
(formula presented) Synthesis and photochemistry of a new photochemically removable protecting group for alcohols is described. Four carbonates of galactose derivatives (1-4) were synthesized from the corresponding arylmethanols via 4-nitrophenyl carbonate intermediates. Among them, photolysis of anthraquinon-2-ylmethoxycarbonyl (Aqmoc) galactose (1) proceeded with overall photolysis efficiency of 150 (quantum yield 0.10, and molar absorptivity 1500 M-1 cm-1) and rate constant of ～106 s-1. To demonstrate its application to a biologically related molecule, 5′-Aqmoc-adenosine (5) was synthesized and photolyzed to yield adenosine in 91% yield.
Deactivation behavior and excited-state properties of (coumarin-4- yl)methyl derivatives. 1. Photocleavage of (7-methoxycoumarin-4-yl)methyl- caged acids with fluorescence enhancement
Schade, Bjoern,Hagen, Volker,Schmidt, Reinhard,Herbrich, Ralph,Krause, Eberhard,Eckardt, Torsten,Bendig, Juergen
, p. 9109 - 9117 (2007/10/03)
The photochemistry of the (7-methoxycoumarin-4-yl)methyl (MCM) carboxylates 3a-d, the mesylate 4, and the phosphates 5a-e has been examined under near physiological conditions in acetonitrile or methanol/aqueous HEPES buffer solution, respectively. Analysis of photoproducts as well as measurements of photochemical quantum yields, fluorescence quantum yields, and lifetimes for the excited singlet state verified the similar photochemical and photophysical behavior of all the esters studied here. 4- (Hydroxymethyl)-7-methoxycoumarin (2) and the corresponding free acids were obtained as major products upon irradiation. The rates of deactivation of the excited MCM derivatives 3a-5e were found to be dependent on the leaving group ability of the anion concerned as well as on the solvent polarity. The polarity dependence and the exclusive formation of 18O-labeled 2 during irradiation of 5a in 18O-labeled water indicate that photocleavage of the excited singlet state of the MCM caged compounds 3a-5e proceeds via a photo S(N)1 mechanism (solvent-assisted photoheterolysis).
Photochemical Properties of New Photolabile cAMP Derivatives in a Physiological Saline Solution
Furuta, Toshiaki,Torigai, Hiromi,Sugimoto, Masazumi,Iwamura, Michiko
, p. 3953 - 3956 (2007/10/02)
Three new photolabile esters of cAMP (2-anthraquinonyl)methyl (1a), (7-methoxycoumarinyl)methyl (2a), and 2-naphthylmethyl (3a), have been developed.The stability and photochemical properties of these derivatives were compared to the previously reported ones in a physiological saline solution (1percent DMSO in Ringer's solution, pH 7.4).We found that 2a had satisfactory stability (t1/2 > 1000 h) in the dark and was photolyzed to release the parent cAMP on 340 nm irradiation (Φapp = 0.10, Ε340 = 6730) more efficiently than previously reported caged cAMPs.A biological test using the melanophores of the medaka (Oryzias latipes) revealed that 2a penetrated into the melanophores, inactive before irradiation and activated to release cAMP upon irradiation.We have developed a new caged cAMP which can be used in the investigation of biological responses regulated by intracellular cAMP concentrations using living cells.
