Dipyrromethenes and azadipyrromethenes as markers for petroleum products

1. A marked petroleum fuel comprising a fuel additive, a mixture of a fluid petroleum fuel and a marker, wherein the marker consists of a single dye, and wherein the dye is selected from the group consisting of halogenated-boron dipyrromethene dyes characterized by the following structure:

where each R is independently selected from the group consisting of hydrogen, an alkyl group, a branched alkyl group, an alkoxy group, a branched alkoxy group, an amino group, an alkylamino group, a dialkylamino group, a thiol group, an alkylthio group, an alkylester group, an alkyl amide group, a halide group, and a nitro group, wherein the dye is characterized by a resistance to solvatochromatic-based shifting of a fluorescence response when mixed with the petroleum fuel comprising a fuel additive and wherein the dye is present in an amount of from about 0.1 ppb to about 10,000 ppb.

2. The marked petroleum fuel of claim 1 , wherein the petroleum fuel is selected from the group consisting of gasoline diesel fuel, biodiesel fuel, kerosene, liquefied petroleum gas, ethanol, and any combination thereof.

3. The marked petroleum fuel of claim 1 , wherein the fuel additive is an oxygenate.

4. A method of detecting a couterfeit or adulterated petroleum product, the method comprising:

spectroscopically analyzing a portion of the petroleum product for the presence of a marker, wherein the marker consists of a single dye, and wherein the single dye is a halogenated-boron dipyrromethene dyes characterized by the following structure:

where each R is independently selected from the group consisting of hydrogen, an alkyl group, a branched alkyl group, an alkoxy group, a branched alkoxy group, an amino group, an alkylamino group, a dialkylamino group, a thiol group, an alkylthio group, an alkylester group, an alkyl amide group, a halide group, and a nitro group;

determining a concentration of the marker present in the portion of the petroleum product; and

identifying the petroleum product as counterfeit, adulterated or authentic as a function of the determined concentration of the marker wherein the petroleum product is a petroleum fuel comprising a fuel additive, wherein the dye is characterized by a resistance to solvatochromatic-based shifting of a fluorescence response when mixed with the petroleum fuel comprising a fuel additive and wherein the dye is present in an amount of from about 0.1 ppb to about 10,000 ppb.

5. The method of claim 4 , wherein the petroleum product comprises an oxygenate.

6. The method of claim 5 , wherein the oxygenate is selected from the group consisting of methanol, ethanol, gasoline grade t-butanol, methyl t-butyl ether, and any combination thereof.

7. The method of claim 4 , wherein the identifying step further comprises comparing the determined concentration with a target concentration of the marker.

8. A method of detecting an adulterated petroleum product comprising spectroscopically analyzing a portion of the petroleum product for a presence of a marker, wherein the marker consists of a single dye, and wherein the single dye is a a halogenated-boron dipyrromethene dyes characterized by the following structure:

where each R is independently selected from the group consisting of hydrogen, an alkyl group, a branched alkyl group, an alkoxy group, a branched alkoxy group, an amino group, an alkylamino group, a dialkylamino group, a thiol group, an alkylthio group, an alkylester group, an alkyl amide group, a halide group, and a nitro group, wherein the presence of a marker is indicative of adulteration of the petroleum product, wherein the petroleum product is a petroleum fuel, wherein the dye is characterized by a resistance to solvatochromatic-based shifting of a fluorescence response when mixed with the petroleum fuel comprising a fuel additive and wherein the dye is present in an amount of from about 0.1 ppb to about 10,000 ppb.

9. The method of claim 8 , further comprising, previous to the spectroscopically analyzing the portion of the petroleum product, mixing the halogenated-boron dipyrromethene dye with the petroleum product.

10. The method of claim 8 , wherein the fuel additive comprises an oxygenate.

11. The method of claim 10 , wherein the oxygenate is selected from the group consisting of methanol, ethanol, gasoline grade t-butanol, methyl t-butyl ether, and any combination thereof, and wherein the marker is characterized by a resistance to solvatochromatic-based shifting of its fluorescent response when mixed with the petroleum fuel comprising the oxygenate.

12. A method comprising adding a covert dye to a petroleum fuel comprising an oxygenate, wherein the covert dye consists of a single dye, and wherein the single dye is a halogenated-boron dipyrromethene dye characterized by the following structure:

where each R is independently selected from a hydrogen, an alkyl group, a branched alkyl group, an alkoxy group, a branched alkoxy group, an amino group, an alkylamino group, a dialkylamino group, a thiol group, an alkylthio group, an alkylester group, an alkyl amide group, a halide group and a nitro group wherein the convert dye is characterized by a resistance to solvatochromatic-based shifting of its fluorescent response when mixed with the petroleum fuel comprising the oxygenate and wherein the dye is present in an amount of from about 0.1 ppb to about 10,000 ppb.

13. The method of claim 12 further comprising identifying the petroleum fuel by spectroscopically analyzing a portion of the petroleum fuel for the presence of the covert dye.

14. The method of claim 12 wherein the oxygenate is selected from the group consisting of methanol, ethanol, gasoline grade t-butanol, methyl t-butyl ether, and any combination thereof.

15. The method of claim 12 further comprising:

determining a concentration of the covert dye present in a portion of the petroleum fuel; and

identifying the petroleum fuel as counterfeit, adulterated or authentic based on the determined concentration of the covert dye.

16. The method of claim 15 wherein the determining the concentration of the covert dye present in the portion of the petroleum fuel spectroscopically analyzes the portion of the petroleum fuel for the presence of the covert dye.

17. The method of claim 4 wherein spectroscopically analyzing a portion of the petroleum product comprises a direct-read measurement.

18. The method of claim 8 wherein spectroscopically analyzing a portion of the petroleum product comprises a direct-read measurement.

19. The method of claim 12 further comprising spectroscopically analyzing a portion of the petroleum fuel utilizing a direct-read measurement.

20. The method of claim 1 wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

21. The method of claim 4 wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

22. The method of claim 8 . wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

23. The method of claim 12 wherein the dye is present in an amount of from about 500 ppb to about 10,000 ppb.

24. The method of claim 1 wherein the dye is present in an amount of from about 0.1 ppb to about 1,000 ppb.

25. The method of claim 4 wherein the dye is present in an amount of from about 0.1 ppb to about 1,000 ppb.

26. The method of claim 1 wherein the dye has an emission wavelength ranging from about 570 nm to about 815 nm.