Synthesis, Structural Characterization and Complexation Properties of the First “Crowned” Dipyrrolylquinoxalines

Kirkovits, Gregory J.; Zimmerman, Rebecca S.; Huggins, Michael T.; Lynch, Vincent M.; Sessler, Jonathan L.

doi:10.1002/1099-0690(200211)2002:22<3768::aid-ejoc3768>3.0.co;2-r

Cited by 19 publications

(7 citation statements)

References 7 publications

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“…One such modified crown ether is 18-crown-6-dipyrrolylquinoxaline (1), a potential ditopic receptor that we have recently synthesized [26]. In addition to a crown ether moiety suitable for non-covalent complexation with the N-terminus or the lysine side chain of peptides, it contains a chromogenic dipyrrolylquinoxaline (DPQ) functionality that exhibits high absorptivity at both 355 and 266 nm, the third and fourth harmonics of the Nd:YAG laser that are useful for UVPD [26]. It is thus attractive as a potential non-covalent receptor for peptides because it might promote their photodissociation via a combination of recognition and UV/Vis photoexcitation/ energy transfer.…”

Section: Resultsmentioning

confidence: 99%

“…This makes it a challenge to design chromogenic receptors that not only can bind to various target ions of interest but also can allow energy transfer following photoexcitation. In this report we describe a simple first-generation chromogenic molecule (18-crown-6-dipyrrolylquinoxaline, 1) [26] that binds non-covalently to peptides via hydrogen bonding interactions and allows effective energy-transfer upon UV irradiation of the resulting complex in the gas phase. …”

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confidence: 99%

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Photodissociation of non-covalent peptide-crown ether complexes

Wilson

Kirkovits

Sessler

et al. 2008

J. Am. Soc. Mass Spectrom.

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Highly chromogenic 18-crown-6-dipyrrolylquinoxaline coordinates primary amines of peptides, forming non-covalent complexes that can be transferred to the gas-phase by electrospray ionization. The appended chromogenic crown ether facilitates efficient energy transfer to the peptide upon ultraviolet irradiation in the gas phase, resulting in diagnostic peptide fragmentation. Collisional-activated dissociation and infrared multiphoton dissociation of these non-covalent complexes result only in their disassembly with the charge retained on either the peptide or crown ether, yielding no sequence ions. Upon UV photon absorption the intermolecular energy transfer is facilitated by the fast activation timescale of ultraviolet photodissociation (Ͻ10 ns) and by the collectively strong hydrogen bonding between the crown ether and peptide, thus allowing effective transfer of energy to the peptide moiety before disruption of the intermolecular hydrogen bonds. T he ongoing need for improved methods for characterizing biological molecules is driving efforts to develop new ion activation and dissociation approaches in mass spectrometry (MS) [1,2]. Currently, collisional-activated dissociation (CAD) remains the most popular technique used to produce diagnostic fragment ions [3,4]. However, this MS/MS method is subject to a number of shortcomings such as insufficient or inefficient energy deposition. Accordingly, a number of other techniques, including surface induced dissociation (SID) [5], electron capture dissociation (ECD) [6,7], electron-transfer dissociation (ETD) [8], and photodissociation (PD) [9 -22] have been developed in recent years. Of these, photodissociation appears particularly attractive because it offers the possibility of tuning the level of energy deposition and providing high-energy input without collisional scattering effects; it is also compatible with both time-of-flight and ion trapping platforms [9 -22]. Unfortunately, as currently practiced, photodissociation requires that the ions of interest absorb the specific wavelength to induce fragmentation. This is often problematic because many biological molecules display regions of low absorptivity over much of the UV/Vis spectral range. To overcome this deficiency, efforts have been made to append external chromophores to molecules of interest, and this is an approach that we [23,24] and others are exploring [25]. However, far more appealing and potentially more general is the idea of attaching chromophores via non-covalent interactions as an attractive alternative because of its simplicity and potential versatility. On the other hand, non-covalent interactions are relatively weak. This makes it a challenge to design chromogenic receptors that not only can bind to various target ions of interest but also can allow energy transfer following photoexcitation. In this report we describe a simple first-generation chromogenic molecule (18-crown-6-dipyrrolylquinoxaline, 1) [26] that binds non-covalently to peptides via hydrogen bonding interactions and allows effe...

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Section: Resultsmentioning

confidence: 99%

mentioning

confidence: 99%

Photodissociation of non-covalent peptide-crown ether complexes

Wilson

Kirkovits

Sessler

et al. 2008

J. Am. Soc. Mass Spectrom.

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“…4,5-Dinitrobenzo-18-crown-6 (compound 4 , 400 mg, 1 mmol, synthesized as published previously [21]) was placed into a hydrogenation vessel along with 1 g of platinum on activated carbon (5%) and 100 ml ethanol under argon. The mixture was allowed to react with hydrogen gas at 40 psi with agitation for 18 hours.…”

Section: Methodsmentioning

confidence: 99%

Crown ether functionalized texaphyrin monomers and dimers

Preihs

Magda

Sessler

2011

J. Porphyrins Phthalocyanines

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The synthesis and characterization of two 18-crown-6 functionalized analogues of an extensively studied gadolinium texaphyrin derivative, motexafin gadolinium (1, MGd), are reported. These are the monomeric and dimeric species, compounds 2 and 3, respectively. Both crown ether functionalized species proved to be stable at physiological pH and revealed distinct shifts in the UV spectrum when treated with sodium-, potassium-, ammonium- or zinc(II)-salts. Zinc(II) is believed to play a major role regulating apoptosis mechanisms in cancerous cells. Therefore, cytotoxicity studies of 2 and 3 were carried out using Ramos cell lines in the presence and absence of zinc(II).

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“…[16][17][18] Dipyrrolylquinoxaline (DPQ) derivatives have emerged as a new class of ion receptors that exhibit a remarkable selectivity toward anions, [19][20][21][22][23][24][25] but to the best of our knowledge, few of them have been employed as cation receptors. [26][27][28] Previously, we have reported DPQ-bridged Schiff bases 28 (Fig. 1) as strong fluorescent quenching sensors.…”

Section: Introductionmentioning

confidence: 91%

A novel class of Cd(ii), Hg(ii) turn-on and Cu(ii), Zn(ii) turn-off Schiff base fluorescent probes

et al. 2010

Dalton Trans.

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N,N'-((5,5'-(quinoxaline-2,3-diyl)bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))bis(4-methoxyaniline) 4 and N,N'-((5,5'-(quinoxaline-2,3-diyl)-bis(1H-pyrrole-5,2-diyl))bis(methanylylidene))dianiline 5 have been prepared and structurally characterized. The X-ray crystal structures of compounds 4 and 4a have been determined. These compounds displayed good sensitivity toward transition metal ions with Cd(II), Zn(II) turn-on and Cu(II), Hg(II) turn-off in fluorescence. It is an elegant example of on/off behavior like a lamp. When Cd(II) or Zn(II) is added into compounds 4 or 5, the lamp will switch on, and then when Cu(II) or Hg(II) is added into the mixture, the lamp will switch off. The binding properties of 4 and 5 for cations were examined by fluorescence spectroscopy. The fluorescence data and crystal structure indicate that a 1:1 stoichiometry complex is formed between compound 4 (or 5) and metal ions, and the binding affinity is very high. The recognition mechanism between compound 4 (or 5) and metal ion was discussed based on the their chemical constructions and the CHEF/CHEQ effect when they interacted with each other.

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Synthesis, Structural Characterization and Complexation Properties of the First “Crowned” Dipyrrolylquinoxalines

Cited by 19 publications

References 7 publications

Photodissociation of non-covalent peptide-crown ether complexes

Photodissociation of non-covalent peptide-crown ether complexes

Crown ether functionalized texaphyrin monomers and dimers

A novel class of Cd(ii), Hg(ii) turn-on and Cu(ii), Zn(ii) turn-off Schiff base fluorescent probes

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