Review
doi: 10.1021/cr300177k.
Epub 2012 Dec 21.
Photoremovable protecting groups in chemistry and biology: reaction mechanisms and efficacy
Affiliations
- PMID: 23256727
- PMCID: PMC3557858
- DOI: 10.1021/cr300177k
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Review
Photoremovable protecting groups in chemistry and biology: reaction mechanisms and efficacy
Chem Rev.
.
No abstract available
Figures
UV spectra
of selected chromophores. (a) Benzophenone
(ethanol; solid, red), acetophenone (ethanol;
dashed, blue); (b) 1-acetyl-5-bromo-7-nitroindoline
(acetonitrile; solid, red),
2-nitrotoluene (dashed, blue), (3,4-dimethoxy-6-nitrophenyl)methyl
(nitroveratryl) derivative (acetonitrile, dashed, green); (c) coumarin (acetonitrile, solid, red), p-hydroxyacetophenone (acetonitrile, dashed, blue), and
benzoin (acetonitrile, dotted, black); (d) tris(bipyridyl)ruthenium(II)
chloride (water).
UV–vis
absorption spectra of p-hydroxyphenacyl
diethyl phosphate (24, X = OPO(OEt)2; pHP
DEP; dashed, red) and p-hydroxyphenylacetic acid
(25, R = H; black) in H2O/MeCN (1:1).
Absorption
spectra of pHA (24, X = H; dashed, in red)
in neutral water (λmax = 278 nm), of pHA– in 0.05 M aqueous NaOH (λmax = 325 nm; solid, in
yellow), and of HpHA+ in 70% aqueous HClO4 (λmax = 333 nm; dash–dot, in blue). The triplet excited
state equilibria are shown in Scheme 18. The
pKa of ground state pHA is 7.9 ±
0.1 (the concentration quotient at ionic strength I = 0.1 M, 25 °C). Adapted with permission from ref (89). Copyright 2012 American
Chemical Society.
Picosecond time-resolved resonance Raman spectra of pHP
DEP (24, X = diethyl phosphate) obtained with a 267 nm
pump and
200 nm probe wavelengths in a H2O/CH3CN (1:1)
mixed solvent. The resonance Raman spectrum of an authentic sample
of p-hydroxyphenylacetic acid recorded with 200 nm
excitation is displayed at the top. Reprinted with permission from
ref (96a). Copyright
2005 American Chemical Society.
Pump–probe spectra of pHP DEP (24,
X = diethyl
phosphate) in 87% aqueous CH3CN. The sample was excited
with a pulse from a Ti/Sa–NOPA laser system (266 nm, 150 fs
pulse width, pulse energy 1 μJ). The inset shows the species
spectra of 3pHP DEP and biradical 328 that were determined by global analysis of the spectra taken with
delays of 10–1800 ps using a biexponential fit. Reprinted with
permission from ref (85d). Copyright 2008 American Chemical Society.
Formation of GTP measured as its Mg2+ complex
at 1128
cm–1 from pHP-caged GTP (black) is already complete
at the first data point. Formation of GTP from NPE-caged GTP (green)
takes place more slowly with a rate constant of 2 s–1 because the rate-limiting step is the release from a ground-state
hemiacetal intermediate (section 3.2), an
inherently slow process on the time scale necessary for the kinetic
measurements reported here. Reprinted
with permission from ref (116). Copyright 2007 Wiley and Sons.
(a) Difference spectra
by TR-IR absorption of the intrinsic Ras-catalyzed
GTPase reaction. A single exponential function by global fit analysis
shows the change from Ras GTP to Ras GDP at 1143 cm–1. (b) TR-IR absorbance difference spectra for the GAP-catalyzed GTPase
by Ras. Two intermediates are seen by the fit of three exponential
functions at 1143 and 1114 cm–1. The appearance
of GTP at 1143 cm–1 arises from pHP-caged GTP followed
by GTP hydrolysis. Protein bound Pi appears at 1114 cm–1, which is subsequently released as the rate-limiting
step (Scheme 20). Reprinted with permission
from ref (92a). Copyright
2004 Elsevier B. V.
Comparison of EC50’s for GABAA receptor
activation by rapid photolysis of pHP (24) GABA. Dose–response
curves for 3-CF3O-pHP GABA (blue, n =
7 neurons), 3-CF3-pHP GABA (red, n = 6
neurons), and 3-CH3O-pHP GABA (black, n = 6 neurons) with population data of peak currents normalized to
the maximum peak response. EC50 and Hill’s coefficient
values were as follows: 3-CF3O-pHP GABA, 49.2 μM,
1.8, n = 7 neurons; 3-CH3O-pHP GABA, 93.4
μM, 1.9, n = 6; and 3-CF3-pHP GABA
119.8 μM, 2.73, n = 6. Reprinted with permission
from ref (97b). Copyright
2009 American Chemical Society.
Course of the photolysis of DMB (33) acetate to DMBF
(34) in acetonitrile (Scheme 23); irradiated in a photochemical reactor at 360 nm. Reprinted with
permission from ref (118). Copyright 1971 American Chemical Society.
pH–rate profiles
for the reaction steps 51/51– → 50 (• and
o), 50 → 52 (+ and × ), and 52 → 53 (□) of oNB methyl ether
in aqueous solution. Reprinted with permission from ref (158). Copyright 2004 American
Chemical Society.
References
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