New fluorescent perylene bisimide indicators--a platform for broadband pH optodes.
Asymmetric perylene bisimide (PBI) dyes are prepared and are shown to be suitable for the preparation of fluorescence chemosensors for pH. They carry one amino-functional substituent which introduces pH sensitivity via photoinduced electron transfer (PET) while the other one increases solubility. The luminescence quantum yields for the new indicators exceed 75% in the protonated form. The new indicators are non-covalently entrapped in polyurethane hydrogel D4 and poly(hydroxyalkylmethacrylates). Several PET functions including aliphatic and aromatic amino groups were successfully used to tune the dynamic range of the sensor. Because of their virtually identical spectral properties, various PBIs with selected PET functions can easily be integrated into a single sensor with enlarged dynamic range (over 4 pH units). PBIs with two different substitution patterns in the bay position are investigated and possess variable spectral properties. Compared with their tetrachloro analogues, tetra-tert-butyl-substituted PBIs yield more long-wave excitable sensors which feature excellent photostability. Cross-sensitivity to ionic strength was found to be negligible. The practical applicability of the sensors may be compromised by the long response times (especially in case of tetra-tert-butyl-substituted PBIs).
Institute of Analytical Chemistry and Food Chemistry, Graz University of Technology, Graz, Austria.
Daniel
D
Aigner
Sergey M
SM
Borisov
Ingo
I
Klimant
D004579:Electron Transport; D005456:Fluorescent Dyes / Q000138:chemical synthesis / Q000737:chemistry*; D006863:Hydrogen-Ion Concentration; D007094:Imides / Q000138:chemical synthesis / Q000737:chemistry*; D008163:Luminescent Measurements; D015394:Molecular Structure; D010569:Perylene / Q000031:analogs & derivatives* / Q000138:chemical synthesis / Q000737:chemistry; D011789:Quantum Theory; D012995:Solubility; D013237:Stereoisomerism
D005456:Fluorescent Dyes; D007094:Imides; C510697:perylene bisimide; D010569:Perylene
Chemistry. 2007;13(23):6555-61
17614307
Chem Res Toxicol. 2005 Dec;18(12):1814-20
16359171
Biomaterials. 2010 Oct;31(29):7411-22
20619451
Chemistry. 2004 Oct 25;10(21):5297-310
15382203
Spectrochim Acta A Mol Biomol Spectrosc. 2008 Dec 1;71(3):818-22
18343715
Analyst. 2004 Jan;129(1):20-4
14737578
Chemistry. 2008;14(16):4974-92
18418841
Anal Biochem. 1991 May 1;194(2):330-44
1862936
Anal Chim Acta. 2009 Mar 16;636(1):89-94
19231361
Chemistry. 2010 Mar 15;16(11):3372-82
20143362
Analyst. 2010 Jul;135(7):1711-7
20498891
Biomacromolecules. 2005 Jan-Feb;6(1):68-79
15638506
Biotechnol Prog. 2004 Sep-Oct;20(5):1561-6
15458344
Org Biomol Chem. 2008 Dec 7;6(23):4319-22
19005590
J Org Chem. 2003 Jun 27;68(13):5369-76
12816501
Analyst. 2004 Jul;129(7):645-50
15213834
J Org Chem. 2004 Nov 12;69(23):7933-9
15527273
Am J Physiol. 1990 Feb;258(2 Pt 2):F438-43
2309897
Org Lett. 2006 Mar 2;8(5):867-70
16494461
Anal Chem. 2001 Jul 15;73(14):3240-6
11476221
Angew Chem Int Ed Engl. 2000 Mar;39(6):1052-1054
10760919
J Am Chem Soc. 2008 Dec 24;130(51):17242-3
19053419
Org Lett. 2010 Feb 19;12(4):764-7
20092265
J Biomed Mater Res. 1998 Jan;39(1):9-15
9429091