Anthocyanins in Fruit Juices

Lecture Connections

Chapter

Section

Keyword

Explanation

4

4.3

Acids & bases

Determine pH of the samples in the lab

6

6.3

UV-vis spectrum

Uses visible radiation to show pH relationships in the lab

8

8.2

Ions & Ionic bonds

Effect acid & base conditions

Chemistry at Work (p342) Molecular orbital theory Light can excite an electron from a filled molecular orbital to an empty one at higher energy. Because the MOs have definite energies, only light of the proper wavelengths can excite electrons. If the appropriate wavelength for exciting electrons is in the visible portion of the electromagnetic spectrum, the substance will appear colored.
9 Chemistry at work HOMO (highest occupied molecular orbital) and LUMO (lowest unoccupied molecular orbital) The HOMO is the molecular orbital of highest energy that has electrons in it. The LUMO is the molecular orbital of lowest energy that does not have electrons it it. The energy difference between the HOMO and the LUMO is related to the minimum energy needed to excite an electron in the molecule. Colorless or white substances usually have such a large difference that visible light is not energetic enough to excite an electron to the higher level. Anthocyanin molecules contain conjugated p bonds that lower the energy difference between the HOMO and LUMO.

16

16.3

pH Indicator

A colored substance which changes color in an acid or base environment. Anthocyanins are pH indicators

16

16.3

pH meter

A device which measures the pH of a solution, using electrochemistry

Anthocyanins

How the Morning Glory Changes its Petals1

Blue morning glory flowers start out with pink buds. A single pigment called Heavenly Blue Anthocyanin (HBA) is responsible for the color change, depending on the pH of the environment. Laboratory experiments have shown that when HBA is exposed to CO2 gas the acidic environment (pH 6.6) causes the protonated pigment to reflect a pink-red color. When exposed to Oxygen, the increase in pH (7.7) causes the pigment to become deprotonated, and the pigment reflects a blue color. In a natural setting, the pigments in the bud are wrapped up unexposed to oxygen, and are pink. When the flower begins to open, it is exposed to atmospheric oxygen, and undergoes a color change to blue.

Heavenly Blue Morning Glory

 

Modification of Anthocyanins

Anthocyanins are modified in plant cells by glycosylation, acylation and methylation. The modifications effect flower and fruit color in the plant. Acylation is particularly important in stabilizing pigments, and generally makes the color more blue. The enzyme Hydrocinnamoyl-CoA acylates anthocyanins with hydroxycinnamic acids.

Move Over Vitamin E….2

A recent study of 14 anthocyanins showed that all the anthocyanins had anti-oxidant potency equivalent to Trolox, a common Vitamin E supplement, and some had antioxidant activity 3.5 times as high as Trolox. The anti-oxidant abilities of the anthocyanins may account for some of the beneficial effects of eating fruits and vegetables.

Anthocyanins as Sunscreens3

Solar radiation is a source of light for photosynthesis, but also DNA-damaging Ultra-Violet light. Maintaining DNA structure is of great importance to organisms, plants and animals alike. UV-B and UV-C rays can cause cyclobutane pyrimidine dimers in plant DNA. DNA damage effects the plant’s ability to grow and reproduce properly. The top tissue layers of the plants absorb 95-99% of UV light, flavinoid compounds and cuticle waxes are believed to be the major agents of UV absorption. A recent study with purple maize showed that when an extracted Anthocyanin was placed between plant DNA and an UV-B light source, the anthocyanin protects the DNA from Pyrimidine Dimer formation. When sections of purple and green leaf tissue are irradiated with UV light, the purple anthocyanin containing tissue showed less DNA damage than the green tissue.

More Flower Chemistry4

Beets change from red to purplish in very basic solution.

Blackberries, black currants, and black raspberries change from red in acids to dark blue or violet in basic solution.

Blue and red grapes contain several different pH-sensitive anthocyanins. For example, blue grapes are colored by a monoglucoside of malvinidin that changes from deep red in acidic solutions to violet in basic solution.

Red wines naturally contain these same pigments.

Blueberries change from blue (around pH 2.8-3.2) to red in a strongly acidic solution.

Cherries and cherry juice is bright red in acidic solution but purple to blue in basic solution.

Curry powder and tumeric are spices that contain a bright yellow pigment called curcumin (which is not an anthocyanin). It turns from yellow at pH 7.4 to red at pH 8.6.

Delphinium petals contain an anthocyanin called delphinin, which changes from bluish red in acid to blue to violet in basic solution.

Geranium petals contain pelargonin, an anthocyanin which changes from orange-red in acid solution to bluish in basic solution.

Horsechestnut leaves can be ground with alcohol to extract esculin, a fluorescent dye. Esculin changes from colorless at pH 1.5 to fluorescent blue at pH 2. Shine a black (ultraviolet) light on the indicator to get the full effect.

Morning glories contain an anthocyanin called "heavenly blue anthocyanin" which changes from purplish red at pH 6.6 to blue at pH 7.7. 

Onion is an olfactory indicator. The onion odor isn't detectable in strongly basic solutions. Red onion can act as a visual indicator at the same time. It changes from pale red in acid solution to green in basic solution.

Petunia petals contain petunin, an anthocyanin that changes from reddish purple in acid to violet in basic solution. 

Purple peonies contain peonin, which changes from reddish purple or magenta in acid solution to deep purple in basic solution.

Red cabbage contains a mixture of anthocyanins and other pigments that indicate a wide range of pH. The photograph at right shows how red cabbage juice changes from deep red at pH 1 to purple at pH 7 to to green at pH 12. At higher pH (13-14) it turns yellow.

Rose petals contain the oxonium salt of cyanin, and they turn blue in basic solution. (The potassium or calcium salt of the same pigment makes cornflowers blue!)

Vanilla extract, like onion, is an olfactory indicator. The vanilla odor isn't detectable in strongly basic solution because vanillin exists in ionic form at high pH.

References:

  1. http:/ /www.chem-inst-can.org/ncw/wonder.html
  2. Hong,W., Guohua, C & Prior.R. Anthocyanins: Natural Colorants with Potent Antioxidant Properties
  3. Stapleton,Anne & Walbot,Virginia. Anthocyanins protect DNA from UV Damage Maize Genetics Corporation Newsletter, http://www.agron.missouri.edu/mnl/66/169stapleton.html

4. http://antoine.fsu.umd.edu/chem/senese/101/acidbase/faq/household-indicators.shtml