High-Performance Caged Nitric Oxide:  A New Molecular Design, Synthesis, and Photochemical Reaction

Namiki, Shigeyuki; Arai, Tatsuo; Fujimori, Keiya

doi:10.1021/ja962839d

Cited by 108 publications

(92 citation statements)

References 19 publications

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“…The techniques for caging essentially any biomolecule or second messenger have now been developed, so that protons 60 , inorganic cations, gases 61 , small organic molecules and macromolecules 46 , 62 can be caged. But given the complexity of the syntheses of most caged compounds, commercial availability constrains their use for most laboratories.…”

Section: Caged Mrna and Dnamentioning

confidence: 99%

Caged compounds: photorelease technology for control of cellular chemistry and physiology

2007

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Caged compounds are light-sensitive probes that functionally encapsulate biomolecules in an inactive form. Irradiation liberates the trapped molecule, permitting targeted perturbation of a biological process. Uncaging technology and fluorescence microscopy are 'optically orthogonal': the former allows control, and the latter, observation of cellular function. Used in conjunction with other technologies (for example, patch clamp and/or genetics), the light beam becomes a uniquely powerful tool to stimulate a selected biological target in space or time. Here I describe important examples of widely used caged compounds, their design features and synthesis, as well as practical details of how to use them with living cells.The idea behind the caging technique is that a molecule of interest can be rendered biologically inert (or caged) by chemical modification with a photoremovable protecting group (Fig. 1). Illumination results in a concentration jump of the biologically active molecule that can bind to its cellular receptor, switching on (or off) the targeted process. Virtually every kind of signaling molecule or second messenger, of every size| [mdash]|from protons to proteins| [mdash]|has been caged 1 .Why are caged compounds so useful? A single component of cellular chemistry can control the function of a cell, and such cellular regulation can be temporally or spatially defined, intracellular or extracellular, and amplitude-or frequency-modulated 2 . Photomanipulation of cellular chemistry using caged compounds provides a uniquely powerful means to interact with such cellular dynamics, as it can touch upon any one of the above dimensions. Thus, since light passes through cell membranes, uncaging can rapidly release a biomolecule in an intracellular compartment. This space is not readily accessible to many second messengers (for example, inositol-1,4,5-trisphosphate (IP 3 ), ATP, Ca 2+ , cAMP, cGMP) when they are applied to cells externally, as their charge makes them impermeable to the plasma membrane. Furthermore, uniform illumination results in release throughout the cytosol, or the release can be localized by focusing the uncaging beam on one part of a cell. Likewise, extracellular uncaging of neurotransmitters and hormones is tunable, allowing stimulation of many neurons simultaneously or of single synapses| [mdash]|by global or focused illumination, respectively. Light cannot only be directed, but also modulated in time andCorrespondence should be addressed to Graham C R Ellis-Davies (cagedca@hotmail.com). (Fig. 2) has been widely used to study many Ca 2+ -controlled processes. In particular, secretory processes in neuronal and non-neuronal cells have been extensively studied with caged calcium 22 . Rapid uncaging of glutamate using two-photon photolysis is particularly useful for the rational stimulation of visually identified synapses in complex tissue preparations such as acutely isolated brain slices from the hippocampus 23 (Fig. 2b). Finally, uncaging of mRNA in vivo in zebrafish is an excellen...

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Section: Caged Mrna and Dnamentioning

confidence: 99%

Caged compounds: photorelease technology for control of cellular chemistry and physiology

2007

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“…To confirm in the most direct way that the crucial site of NO action is inside the PC, we perfused PCs with BAPTA plus either of two membrane-impermeant dianionic forms of caged NO, or N,NЈ-dicarboxymethyl-N,NЈ-dinitroso-pphenylenediamine, 2Na (27), then applied 300 flashes of UV at 1 Hz. Although the two molecules are chemically unrelated except for their ability to release NO upon illumination, both induced LTP.…”

Section: No Is Necessary and Sufficient For 1 Hz But Not 4 Hz Ltpmentioning

confidence: 99%

A new form of cerebellar long-term potentiation is postsynaptic and depends on nitric oxide but not cAMP

Lev‐Ram

Wong

Storm

et al. 2002

Proc. Natl. Acad. Sci. U.S.A.

293

238

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Long-term depression (LTD) at cerebellar parallel fiber (PF)-Purkinje cell synapses must be balanced by long-term potentiation (LTP) to prevent saturation and allow reversal of motor learning. The only previously analyzed form of cerebellar LTP is induced by 4 -8 Hz PF stimulation and requires cAMP but not nitric oxide. It is a poor candidate to reverse LTD because it is presynaptically expressed whereas LTD is postsynaptic. We now characterize a new form of LTP induced by 1 Hz PF stimulation for at least 300 s. This LTP is postsynaptically expressed, enhanced by chelating postsynaptic Ca 2؉ , and depends on nitric oxide but not cAMP or cGMP, making it a plausible anti-Hebbian counterpart to Hebbian LTD.T he cerebellar cortex plays a crucial role in a wide variety of behavioral modifications, of which Pavlovian conditioning of eyelid blinking and gain modulation of the vestibuloocular reflex have been the most extensively studied (see refs. 1-4 for reviews). In the cerebellar cortex, the most extensively investigated form of synaptic plasticity has been long-term depression (LTD) of the glutamatergic synapses from parallel fibers (PFs) onto Purkinje cells (PCs). PF-PC LTD is associative (requires concurrent pre-and postsynaptic activity) and fairly synapsespecific (5), requires postsynaptic Ca 2ϩ elevation, and is expressed postsynaptically. Coincidence of the postsynaptic Ca 2ϩ with nitric oxide (NO), normally generated presynaptically and diffusing anterogradely, is necessary and sufficient for a major form of LTD in young adult cerebellar slices; NO acts via cGMP and protein kinase G (6-9). However, the PF-PC synapse also needs long-term potentiation (LTP), driven by presynaptic activity without postsynaptic depolarization, to prevent saturation of LTD, allow extinction of learned associations, and refine the temporal precision of learned responses (10-12). Although a few examples of LTP at the PF-PC synapse had been anecdotally reported in articles focusing on LTD (8, 13-16), the first systematic characterization of LTP was by Salin et al. (17), who stimulated the PFs 120 times at 4-8 Hz and observed a subsequent 40-50% long-term enhancement of excitatory postsynaptic potentials. This work and several subsequent studies have shown that such LTP is induced and expressed presynaptically by means of cAMP signaling (18-21).Although cAMP-mediated presynaptic LTP clearly exists, it remains an unattractive solution to the problem of resetting postsynaptically expressed LTD, because the two processes are expressed in different locations and cannot truly reverse each other (10, 11). Also, presynaptic LTP is independent of the presence or absence of PC activity (17,19). During our studies of associative LTD evoked in young adult slices by coincident increases in Ca 2ϩ , NO, and cGMP during 1-Hz stimulation for 30 s, we sometimes observed small LTP when LTD was blocked by chelation of postsynaptic Ca 2ϩ or inhibition of protein kinase G (6, 7). We now show that such LTP is greatly enhanced by longer stimulation periods...

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“…Because photolabile protecting groups for caging biomolecules are limited, [58][59][60][61][62][63][64][65][66][67][68][69] these results may provide useful information concerning the design and synthesis of sulfonatebased photochemical protecting groups or reagents. Indeed, we have recently reported on the photocleavable biotin linker containing 8-quinolinyl sulfonate moiety for the isolation of dopamine-antibody complex 70) and photolabile liposome.…”

Section: Resultsmentioning

confidence: 99%

Photochemical Cleavage Reactions of 8-Quinolinyl Sulfonates in Aqueous Solution

Kageyama

Ohshima

Sakurama³

et al. 2009

CHEMICAL & PHARMACEUTICAL BULLETIN

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Photochemical cleavage reactions of 8-quinolinyl benzenesulfonate derivatives and related sulfonates in aqueous solutions are reported. The 8-quinolinyl benzenesulfonates undergo photolysis upon photoirradiation at 300-330 nm to give the corresponding 8-quinolinols and benzenesulfonic acids with the production of only negligible amounts of byproducts. The effects of substituent groups of the 8-quinolinyl moiety and the benzene ring on the photolysis reactions were examined. Based on steady-state mechanistic studies using a triplet sensitizer, a triplet quencher, and electron donors, it was suggested that the photolysis proceeds mainly via the homolytic cleavage of S-O bonds in the excited triplet state.

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High-Performance Caged Nitric Oxide: A New Molecular Design, Synthesis, and Photochemical Reaction

Cited by 108 publications

References 19 publications

Caged compounds: photorelease technology for control of cellular chemistry and physiology

Caged compounds: photorelease technology for control of cellular chemistry and physiology

A new form of cerebellar long-term potentiation is postsynaptic and depends on nitric oxide but not cAMP

Photochemical Cleavage Reactions of 8-Quinolinyl Sulfonates in Aqueous Solution

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