Primary photoreactions of the 3′,5′-dimethoxybenzoin cage and determination of the release rate in polar media

被引：16

作者：

Boudebous, Hassen

Kosmrlj, Berta

Sket, Boris

Wirz, Jakob

机构：

[1] Univ Ljubljana, Fac Chem & Chem Technol, SI-1000 Ljubljana, Slovenia

[2] Univ Basel, Dept Chem, CH-4056 Basel, Switzerland

来源：

JOURNAL OF PHYSICAL CHEMISTRY A | 2007年 / 111卷 / 15期

关键词：

PHOTOREMOVABLE PROTECTING GROUPS; REACTION-MECHANISMS; PHOSPHATE-ESTERS; PHOTOLYSIS; DIMETHOXYBENZENE; PHOTOCHEMISTRY; ALCOHOLS; CATION;

D O I：

10.1021/jp071350b

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

3',5'-Dimethoxybenzoin (DMB) is an important photoremovable protecting group. The primary photoreactions of DMB acetate and fluoride following photoexcitation by a subpicosecond laser flash were investigated by pump-probe spectroscopy. The primary photoproduct is identified as a preoxetane biradical intermediate that decays by different pathways depending on solvent polarity. In polar solvents (acetonitrile, water), the biradical decays by releasing acetate or fluoride with a lifetime of about 2 ns. Thus, DMB is an excellent protecting group for the investigation of fast processes such as protein folding.

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页码：2811 / 2813

页数：3

相关论文

共 23 条

[1] NEW PHOTOLABILE PHOSPHATE PROTECTING GROUPS [J].

BALDWIN, JE ;

MCCONNAUGHIE, AW ;

MOLONEY, MG ;

PRATT, AJ ;

SHIM, SB .

TETRAHEDRON, 1990, 46 (19) :6879-6884

[2] DIFFERENT CONFORMATIONS OF ORTHO-DIMETHOXYBENZENE AS STUDIED BY PHOSPHORESCENCE SPECTROSCOPY [J].

BASCHE, T ;

BRAUCHLE, C ;

VOITLANDER, J .

CHEMICAL PHYSICS LETTERS, 1988, 144 (03) :226-230

[3] Designing systems for a multiple use of light signals [J].

Bergamini, G ;

Ceroni, P ;

Balzani, V ;

Vögtle, F ;

Lee, SK .

CHEMPHYSCHEM, 2004, 5 (03) :315-320

[4] Photogeneration of amines from alpha-keto carbamates: Photochemical studies [J].

Cameron, JF ;

Willson, CG ;

Frechet, JMJ .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1996, 118 (51) :12925-12937

[5] Measuring the refolding of β-sheets with different turn sequences on a nanosecond time scale [J].

Chen, RPY ;

Huang, JJT ;

Chen, HL ;

Jan, H ;

Velusamy, M ;

Lee, CT ;

Fann, WS ;

Larsen, RW ;

Chan, SI .

PROCEEDINGS OF THE NATIONAL ACADEMY OF SCIENCES OF THE UNITED STATES OF AMERICA, 2004, 101 (19) :7305-7310

[6] SYNTHETIC, MECHANISTIC AND PHOTOCHEMICAL STUDIES OF PHOSPHATE-ESTERS OF SUBSTITUTED BENZOINS [J].

CORRIE, JET ;

TRENTHAM, DR .

JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 1, 1992, (18) :2409-2417

[7] Photochemical reaction mechanisms of 2-nitrobenzyl compounds:: 2-Nitrobenzyl alcohols form 2-nitroso hydrates by dual proton transfer [J].

Gaplovsky, M ;

Il'ichev, YV ;

Kamdzhilov, Y ;

Kombarova, SV ;

Mac, M ;

Schwörer, MA ;

Wirz, J .

PHOTOCHEMICAL & PHOTOBIOLOGICAL SCIENCES, 2005, 4 (01) :33-42

[8] PHOTOCHEMISTRY OF PHOSPHATE-ESTERS - ALPHA-KETO PHOSPHATES AS A PHOTOPROTECTING GROUP FOR CAGED PHOSPHATE [J].

GIVENS, RS ;

ATHEY, PS ;

MATUSZEWSKI, B ;

KUEPER, LW ;

XUE, JY ;

FISTER, T .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1993, 115 (14) :6001-6012

[9]

Goeldner M, 2005, DYNAMIC STUDIES IN BIOLOGY: PHOTOTRIGGERS, PHOTOSWITCHES AND CAGED BIOMOLECULES, P1, DOI 10.1002/3527605592

[10] 1,3-cyclopentanediyl diradicals: Substituent and temperature dependence of triplet-singlet intersystem crossing [J].

Kita, F ;

Adam, W ;

Jordan, P ;

Nau, WM ;

Wirz, J .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (40) :9265-9275