Composition of natural antioxidants for the stabilization of polyunsaturated oils

The present invention provides for a composition of natural antioudants comprising tocopherol, ascorbic acid, citric acid and phospholepeds which are useful in oxidation of oils.

BACKGROUND OF INVENTION 
The present invention relates generally to the prevention of deterioration 
of food, cosmetic and pharmaceutical products which contain 
polyunsaturated fatty acids. More particularly, the present invention 
relates to a natural composition of antioxidants for stabilization of 
polyunsaturated oils comprising tocopherols, ascorbic acid, citric acid, 
and phospholipids. The phospholipids may be from soybean or egg. The 
former is usually called "soybean lecithin" commercially. Rosemary extract 
can also be added to the composition. 
Today, cosmetic and pharmaceutical products containing polyunsaturated 
fatty acids are manufactured at plants throughout the country, prepackaged 
for sale, and distributed to supermarkets and convenience stores across 
the country. Because of the nature of such products and the transportation 
of such products around the country, these products require a long 
shelf-life. In order to increase the shelf-life, it is necessary to 
prevent the deterioration of the quality of the product. One cause of 
deterioration is oxidation. Oxidation particularly occurs with 
fat-containing products. For example, oils and fats containing 
polyunsaturated fatty acids, such as fish oils which contain 
eicosapentaenoic acid and decosahexaenoic acid, as well as vegetable oils 
which contain linoleic and/or linolenic acid, are susceptible to oxidation 
by oxygen in the air to form peroxides. Peroxides decompose to produce 
volatile compounds with objectionable odors and flavors. For example, fish 
oil, such as menhaden oil, can quickly develop a green, grassy and fishy 
odor and flavor. Soybean oil is another product which can also easily 
oxidize to produce the classical reversion odor and flavor. In addition, 
such oxidation products may be harmful to human health 
Even when fish oil, such as menhaden oil, is highly purified to an odorless 
and flavorless oil, such as that according to the teachings of Chang et 
al. (U.S. Pat. No. 4,874,629), the oil can still redevelop the green and 
fishy odor and flavor when it is exposed to even a trace amount of air or 
oxygen. It has been reported that fish oil, even when packaged in gelatin 
capsules, can develop relatively high peroxide values during storage. 
Accordingly, to use such oils in food, or as a dietary supplement, they 
must be stabilized to prevent or to retard the development of 
objectionable odors and flavors, as well as to protect the health of 
consumers. 
Many different antioxidants and antioxidant compositions have been 
developed over the years. Many of these antioxidants, such as BHA and BHT, 
are synthetic. Today, people are more health oriented and prefer natural 
products which are considered safe for human consumption. In addition, 
synthetic compounds have recently come under heavy scrutiny by the FDA. 
The natural antioxidant compositions, which have been developed, also 
suffer from problems which limit their usefulness. For example, EP 0 326 
829 (Lollger et al.) discloses a natural mixture of tocopherol, ascorbic 
acid, and lecithin to protect lipids against oxidation. The mixture, 
however, may produce a red color in the oil due to the combination of 
ascorbic acid and lecithin. 
Accordingly, it is object of the present invention to provide a composition 
of natural antioxidants that will retard the oxidation of fats and oils 
and thus the deterioration of food products. Further, it will have 
improved antioxidant activity over prior compounds so as to provide better 
prevention of oxidation and the resulting food deterioration. In addition, 
the present invention will significantly decrease the undesirable color 
that results from the combination of ascorbic acid and lecithin in the 
oils or their products. 
SUMMARY OF THE INVENTION 
The present invention provides a composition of natural antioxidants 
comprising tocopherols, ascorbic acid, citric acid and phospholipids. The 
composition of the antioxidants of the present invention comprises from 
about 10% to about 62.5% by weight of tocopherols, from about -.5% to 
about 20% by weight of ascorbic acid, from about 1.5% to about 20% by 
weight of citric acid, and from about 26% to about 85% by weight of 
phospholipids. 
The composition preferably comprises about 29.4% tocopherols, about 5.9% 
ascorbic acid, about 5.9% citric acid, and about 58.8% phospholipids, all 
by weight. 
The composition can further comprise the addition of rosemary extract as 
described in U.S. Pat. No. 3,950,266 to the other antioxidants listed 
above. With rosemary extract, the composition of the present invention 
comprises from about 6.5% to about 54% by weight of tocopherols, from 
about 1.2% to about 16% by weight of ascorbic acid, from about 1.2% to 
about 16% by weight of citric acid, from about 17% to about 77% by weight 
of phospholipids, and from about 6.5% to about 54% by weight of rosemary 
extract. Preferably, the composition comprises about 22.7% tocopherols, 
about 4.5% ascorbic acid, about 4.5% citric acid, about 45.5% 
phospholipids, and about 22.7% rosemary extract, all by weight. 
The present invention also provides a composition of natural antioxidants 
for oils rich in tocopherols comprising ascorbic acid, citric acid, and 
phospholipids. The composition comprises from about 2% to about 27% by 
weight ascorbic acid, from about 2% to about 27% by weight citric acid, 
and from about 56% to about 95% by weight phospholipids. Preferably, the 
composition comprises about 8.3% ascorbic acid, 8.3% citric acid and 83.4% 
phospholipids, all by weight. The composition can further comprise the 
addition of rosemary extract to the other items listed above. With 
rosemary extract, the composition comprises from about 1.8% to about 23% 
by weight of ascorbic acid, from about 1.8% to about 23% by weight of 
citric acid, from about 35% to about 90% by weight of phospholipids, and 
from about 5% to about 45% by weight of rosemary extract. Preferably, the 
composition comprises about 6.9% of ascorbic acid, about 6.9% of citric 
acid, about 70% of phospholipids and about 17.2% of rosemary extract, all 
by weight. 
The composition of the antioxidants of the present invention in a fish oil 
comprises the following percentages with relation to the oil, from about 
0.05% to about 0.2% by weight of tocopherols, from about 0.01% to about 
0.04% by weight of ascorbic acid, from about 0.01% to about 0.04% by 
weight of citric acid, and from about 0.1% to about 0.4% by weight of 
de-oiled soybean phospholipids. The composition can further comprise 
rosemary extract in an amount of from about 0.05% to about 0.2% by weight. 
Preferably, the composition in the fish oil comprises about 0.1% 
tocopherols, about 0.02% ascorbic acid, about 0.02% citric acid, about 
0.2% de-oiled soybean phospholipids and about 0.1% rosemary extract, all 
by weight. 
The composition of the antioxidants of the present invention in a 
tocopherols rich vegetable oil comprises the following percentages with 
relation to the oil from about 0.01% to about 0.04% by weight of ascorbic 
acid, from about 0.01% to about 0.04% by weight of citric acid, and from 
about 0.1% to about 0.4% by weight of de-oiled soybean phospholipids. The 
composition can further comprise from about 0.025% to about 0.1% by weight 
of rosemary extract. Preferably, the composition in the vegetable oils 
comprises about 0.02% ascorbic acid, about 0.02% citric acid, about 0.2% 
de-oiled soybean phospholipids, and about 0.05% rosemary extract, all by 
weight. 
The compositions of the present invention may be added to products 
containing polyunsaturated fatty acids or oils at many different 
concentrations, depending upon the use to which the products are to be put 
and the economics of the product. It has been found that the use of from 
about 0.10 percent to about 0.6 percent by weight, based upon the weight 
of the unsaturated oils produces useful results, but other concentrations 
may be used. In a vegetable oil that is not rich in tocopherols, a 
composition of tocopherol, ascorbic acid, citric acid, phospholipids and 
possibly rosemary extract could be used. 
DESCRIPTION OF THE PREFERRED EMBODIMENT 
The present invention is concerned with a combination of natural 
antioxidants that together through a synergistic effect retard oxidation 
and the development of a green and fishy odor and flavor that results from 
the oxidation of polyunsaturated oils such as deodorized fish oils. A 
composition comprising tocopherols, which is usually a mixture of several 
tocopherol isomers, ascorbic acid, citric acid, and phospholipids has been 
found to possess an unexpectantly effective antioxidant property. The 
phospholipids can be from soybean or egg. Soybean phospholipids are 
available commercially in various forms and purities and can be used 
accordingly. A preferred phospholipid is de-oiled soybean phospholipid. 
The addition of rosemary extract to the composition further enhances the 
composition's antioxidant property. 
No single natural antioxidant, even when used at an amount equal to the 
total amount of the composition of the present invention, will have the 
same effect of antioxidant activity as that of the present composition. 
Further, a composition lacking any of the components of the present 
invention will also not have the same antioxidant activity that is 
achieved with the present composition. 
A preferred embodiment of the composition of the present invention, 
especially effective for deodorized and purified fish oil such as menhaden 
oil, is as follows by weight: 
______________________________________ 
Tocopherols 29.4% 
Ascorbic acid 5.9% 
Citric acid 5.9% 
De-oiled soybean phospholipids 
58.8% 
______________________________________ 
The preferred amount of the above embodiment for the addition to the 
menhaden oil is 0.34%. The addition of 0.1% of rosemary extract by weight 
of the oil can further improve the effectiveness of the antioxidant 
activity. 
Since vegetable oils are usually rich in tocopherols naturally, an example 
of the composition, especially effective for soybean oil is as follows by 
weight: 
______________________________________ 
Ascorbic Acid 8.3% 
Citric Acid 8.3% 
De-oiled soybean phospholipids 
83.4% 
______________________________________ 
The preferred amount of the above composition for the addition to soybean 
oil is 0.24% The addition of 0.05% of rosemary extract by weight of the 
oil can further improve the effectiveness of the antioxidant activity. 
The compositions of the present invention can also be used with all omega-3 
fatty acids containing oils such as menhaden oil, sardine oil, herring 
oil, anchovy oil, Pilchard oil, and other such oils. Other possible oils 
in which the present composition can retard oxidation include vegetable 
oils, which contain a significant amount of polyunsaturated fatty acid, 
such as sunflower seed oil, rapeseed oil, canola oil, corn oil, cottonseed 
oil, and other similar oils. Most vegetable oils already contain a 
sufficient amount of tocopherols naturally. Therefore, it is not necessary 
to add any additional tocopherols but rather to only add the other three 
components (and possibly rosemary extract) to achieve the synergistic 
effect of the present invention. Furthermore, animal fats such as lard, 
beef tallow, and butter can benefit by use of the composition of the 
present invention. Finally, other foods, cosmetic, and pharmaceutical 
products which contain polyunsaturated fatty acids can also have their 
oxidation and deterioration retarded by use of the compositions of the 
present invention.

EXAMPLES OF THE PRESENT INVENTION 
The following examples will demonstrate that the compositions of the 
present invention are clearly superior in the prevention of the 
deterioration of products containing menhaden oil or vegetable oil than 
prior compositions or synthetic antioxidants. 
In all of the examples, the effectiveness of the antioxidant composition is 
based on a determination of A0M hours (official method of American Oil 
Chemists' Society, Cd 12-57) using a recently developed instrument, the 
Rancimat (Model 617). The Rancimat was used to determine the induction 
period in hours at various temperatures, and at an air flow rate of 20 
liters per hour. 
The materials used were as follows: 
Menhaden Oil: A refined and double bleached menhaden oil, supplied under 
the trade name of SPMO by Zapata Haynie Corporation was further deodorized 
at 100.degree. C. and purified by passing through a silica gel column 
according to the teaching of Chang, et al. in U.S. Pat. No. 4,879,629. 
Soybean Oil: A refined, bleached and deodorized soybean oil supplied by 
Central Soya Company Inc. 
Tocopherols: Natural mixed tocopherols under the trade name of Covi-Ox T70 
supplied by the Henkel Corporation. 
De-oiled Soybean Phospholipids: Granular soybean lecithin containing 96% of 
phospholipids, under the trade name of Centrolex R, supplied by Central 
Soya Company, Inc. 
Rosemary Extract: Standard oleoresin extract supplied by Kalsec Inc., under 
trade name of Herbalox.RTM. O. 
EXAMPLE 1 
100 g of menhaden oil was used as the control (Sample A in Table 1). Sample 
B was produced through the addition of 0.1 g of tocopherols dissolved in 
hexane, 0.02g of ascorbic acid dissolved in anhydrous ethanol, 0.02g of 
citric acid dissolved in anhydrous ethanol and 0.2g of soybean 
phospholipids dissolved in hexane, to 100 g of menhaden oil. After mixing 
well, the solvents were removed with the use of a rotoevaporator under a 
vacuum and at a temperature below 80.degree. C. Sample C was made through 
the addition of 0.1 g of rosemary extract, dissolved in a mixture of 
anhydrous ethanol and hexane (9:1 v/v), to the same formula as was 
previously prepared in sample B. The rosemary extract was added before the 
solvents were removed through the use of the rotoevaporator. The induction 
period for each sample was measured by the use of the rancimat. In 
addition, the induction period for the menhaden oil with the addition of 
synthetic antioxidants, BHA and BHT and for the control was also measured. 
TABLE 1a 
______________________________________ 
Antioxidant Composition Added 
Induction Period 
Sample (% by weight of oil) (Hours at 90.degree. C.) 
______________________________________ 
A None 0.9 
B Tocopherols 0.10% 25.2 
Ascorbic Acid 0.02% 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
C Tocopherols 0.10% 26.4 
Ascorbic Acid 0.02% 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
Rosemary Extract 
0.10% 
D BHA 0.02% 2.1 
E BHT 0.02% 1.7 
______________________________________ 
Table 1a clearly shows that the induction period for the compositions of 
the present invention is much higher than that for Sample A which had no 
antioxidant added. Further, the synthetic antioxidants, at the maximum 
amount allowed by the FDA, have a very low induction period, not much 
higher than the induction period of Sample A, and considerably lower than 
the induction period for Samples B and C. In order to further demonstrate 
the antioxidant activity of the compositions, samples A, B, C, and D of 
Example 1 were aged at 45.degree. for one week and for two weeks. The 
peroxide values of the samples, after aging is shown in Table 1b. 
TABLE 1b 
______________________________________ 
Peroxide Value 
(meq./k.) (after 
aging at 45.degree. C. 
for 7 or 14 
Antioxidant Added days) 
Sample (% by weight of oil) 
7 days 14 days 
______________________________________ 
A None 16.8 24.0 
B Tocopherols 0.10% 0.9 7.9 
Ascorbic Acid 0.02% 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
C Tocopherols 0.10% 1.5 6.0 
Ascorbic Acid 0.02% 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
Rosemary Extract 
0.10% 
D BHA 0.02% 14.3 23.0 
______________________________________ 
As in the samples in Table 1a, no antioxidant has been added to Sample A, 
the antioxidant compositions of the present invention have been added to 
Samples B and C, and the synthetic antioxidant, BHA has been added to 
Sample D. Peroxides being the compounds which decompose to produce 
volatile compounds with objectionable odors and flavors, it is desirable 
to have a low peroxide value. Note, that Samples B and C of the present 
invention have a much lower peroxide value than that of the Samples A or 
D. Accordingly, the results of this example clearly show that the 
compositions of the present invention significantly retard the oxidation 
and the resulting deterioration of oil and do so much more effectively 
than a synthetic antioxidant. 
EXAMPLE 2 
Five samples of menhaden oil with antioxidants added were prepared in the 
same manner as in Example 1. The composition of Sample C of Example 1 was 
used as the "standard" for this Example. Samples 1 through 5 were produced 
from the same composition as the "Standard", except that one of the five 
components of the composition (Sample C of Example 1) was eliminated. The 
induction period for each sample was then measured and compared to a 
composition having all five components (Standard). 
TABLE 2 
______________________________________ 
Induction Period 
Sample Antioxidant Added (Hours at 90.degree. C.) 
______________________________________ 
Control 
None 0.9 
Standard 
Sample C of Example 1 
26.4 
1 Elimination of Rosemary Extract 
25.2 
2 Elimination of Tocopherols 
11.8 
3 Elimination of Ascorbic Acid 
10.5 
4 Elimination of Citric Acid 
24.1 
5 Elimination of Soybean 
15.6 
Phospholipids 
______________________________________ 
Table 2 clearly demonstrates that the compositions of the present 
invention, as represented in the Standard Sample and Sample 1, have a much 
higher induction period than any of the compositions having one of the 
components eliminated. Citric acid, as shown in Table 2, does not have a 
strong effect on antioxidant activity. However, it is important in the 
prevention of the development of an off-color. 
EXAMPLE 3 
The composition of Sample C of Example 1, with all five components, was 
used as the standard. Five samples of menhaden oil were also prepared in 
the same manner as in Example 1. In each sample, one of the components of 
the composition of the present invention (Standard) was added at a 
concentration of 0.44%. The induction period of each of the samples was 
measured. 
TABLE 3 
______________________________________ 
Antioxidant Added 
Induction Period 
Sample (% by weight of oil) 
(Hours at 90.degree. C.) 
______________________________________ 
Control None 0.9 
Standard Sample C of Example 1 
26.4 
1 Tocopherols, 0.44% 
2.3 
2 Ascorbic Acid, 0.44% 
1.4 
3 Citric Acid, 0.44% 
1.0 
4 De-oiled soybean 
1.3 
phospholipids 0.44% 
5 Rosemary extract, 0.44% 
6.9 
______________________________________ 
Table 3 shows that each of the five components of the composition of the 
present invention, when added singularly, even at a concentration higher 
than the total amount of the five components in the Standard, does not 
produce an effective antioxidant activity. Thus indicating clearly that 
the composition of the present invention has an unusual strong antioxidant 
activity due to synergism. 
EXAMPLE 4 
The composition of the present invention has another novel advantage. The 
amount of phospholipids used in the present invention should be sufficient 
to cause the amount of ascorbic acid used in the present invention to be 
soluble in the oil. This makes the ascorbic acid, which is otherwise 
insoluble in oil, more evenly distributed into the oil and hence makes the 
antioxidant activity of the ascorbic acid more effective. 
The unexpected but distinctive effect of phospholipids on the solubility of 
ascorbic acid in oils can be clearly demonstrated by the following simple 
example. Ten grams of ascorbic acid were dissolved in one liter of 
anhydrous ethanol at 60.degree. C. and 100 grams of de-oiled soybean 
phospholipids [Centrolex R]were dissolved in 250 ml of hexane. The two 
solutions were thoroughly mixed and the solvents were then removed with 
the use of a rotoevaporator, under vacuum, at a temperature below 
60.degree. C. A hexane-soluble, brownish-yellow powder was obtained. It 
should be noticed that the ascorbic acid was originally insoluble in 
hexane, but after it was combined with the soybean phospholipids, the 
brownish-yellow powder obtained was completely soluble in hexane. This 
hexane solution can then be easily added into an oil such as a fish oil or 
vegetable oil. After the solvent is removed, a clear oil solution of 
ascorbic acid is obtained. 
A commercial product, ascorbyl palmitate, manufactured by Hoffmann La Roche 
Inc. has a better oil solubility than ascorbic acid. However, the ascorbyl 
palmitate still cannot directly dissolve in oil. It has to be dissolved in 
a solvent, such as ethanol, and then dissolve the solution in oil. The 
ethanol will have to be removed in order to obtain a clear solution of the 
ascorbyl palmitate in the oil. Further, the loss of one hydroxyl group 
from the ascorbic acid molecule by the reaction with the palmitic acid 
makes the ascorbyl palmitate less effective as an antioxidant. 
In order to demonstrate the above mentioned novel advantage of the present 
invention, another set of samples was prepared in the same manner as that 
described in Example 1. Samples A, B, C and D were exactly the same as 
described in Example 1. However, an additional sample B-PA was added. This 
sample (BPA) was the same as Sample B except that the ascorbic acid was 
replaced by ascorbyl palmitate. Since ascorbyl palmitate has a larger 
molecular weight than ascorbic acid and in order for it to be equivalent 
to 0.02% of ascorbic acid in moles, 0.04% of ascorbyl palmitate was used. 
The results of the induction period of the above mentioned samples, as 
shown in Table 4, clearly indicates that ascorbic acid is more effective 
than ascorbyl palmitate in the invented antioxidant composition. 
TABLE 4 
______________________________________ 
Antioxidant Added Induction Period 
Sample (% by weight of oil) (Hours at 90.degree. C.) 
______________________________________ 
A None 0.9 
B Ascorbic Acid 0.02% 25.2 
Tocopherols 0.10% 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
B-AP Ascorbyl Palmitate 
0.04% 18.8 
Tocopherols 0.10% 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
C BHA 0.02% 2.1 
D BHT 0.02% 1.7 
______________________________________ 
EXAMPLE 5 
The present invention is equally effective when applied to vegetable oils, 
such as refined, bleached, and deodorized soybean oil. Since vegetable 
oils are generally rich in tocopherols, no additional tocopherols were 
added. The samples were prepared in the same manner as those in Example 1 
except that menhaden oil was replaced by refined, bleached and deodorized 
soybean oil. 
TABLE 5 
______________________________________ 
Antioxidant Added Induction Period 
Sample (by weight of oil) (hours at 110.degree. C.) 
______________________________________ 
A None 6.50 
B Ascorbic Acid 0.02% 13.15 
Citric Acid 0.02% 
Soybean Phospholipids 
0.20% 
C BHA 0.02% 6.50 
D BHT 0.02% 6.60 
______________________________________ 
Table 5 shows the induction period of these samples. The sample of the 
composition of the present invention (Sample B) has a much greater 
induction period than the synthetic antioxidants (Sample C and D) or the 
sample with no antioxidant (Sample A). 
EXAMPLE 6 
The unusual antioxidant activity of the composition of the present 
invention, when used in soybean oil, is demonstrated, in a manner similar 
to that used for menhaden oil (in Example 2), by the following results. 
TABLE 6 
______________________________________ 
Antioxidant Added (%)* 
De-oiled 
Induction 
Soybean 
Period 
Rosemary Ascorbic Citric 
Phospho- 
(Hours at 
Sample Extract Acid Acid lipids 100.degree. C.) 
______________________________________ 
Control 0.00 0.00 0.00 0.00 14.6 
Standard** 
0.05 0.02 0.02 0.20 28.8 
1 0.00 0.02 0.02 0.20 25.0 
2 0.05 0.00 0.02 0.20 21.3 
3 0.05 0.02 0.00 0.20 27.4 
4 0.05 0.02 0.02 0.00 24.6 
______________________________________ 
*By weight of the oil. 
**A composition of the present invention. 
EXAMPLE 7 
This example was intended to show the superiority of the composition of the 
present invention over the three component composition of the prior art. 
The three component composition of the Lollger patent contained 0.1% 
tocopherol, 0.02% ascorbic acid, and 0.2% lecithin. The antioxidants from 
each composition were added to refined and bleached menhaden oil. In the 
four component composition of the present invention, 0.02% by weight 
citric acid was added to the components of the three component system of 
Lollger . 
TABLE 7 
______________________________________ 
ANTIOXIDANTS ADDED* Lovibond Color 
to (51/4" cell) 
Menhaden Oil (refined and bleached) 
Red Yellow 
______________________________________ 
None 0.6 10.4 
Ternary System as 
Tocopherol 0.10% 3.7 27.7 
Lollger's Patent 
Ascorbic Acid 
0.02% 
Lecithin 0.20% 
Four Component 
Tocopherol 0.10% 1.1 17.7 
composition of the 
Ascorbic Acid 
0.02% 
present invention 
Lecithin 0.20% 
Citric Acid 0.02% 
______________________________________ 
*(% by weight of oil) 
Table 7 shows the difference in color between the three component 
composition of Lollger's patent and the four component composition of the 
present invention. Lollger's composition gives a much greater red color, 
which is undesirable, than the color resulting from the utilization of the 
present invention. The avoidance of the red color is considered of great 
importance to the quality of the oil. A difference in one unit of Lovibond 
color is significant. Accordingly, the compositions of the present 
invention, through the addition of citric acid (and rosemary extract in 
the five component composition), have at least three advantages over the 
prior art: 
(1) Significantly decreases the undesirable color developed by the 
combination of ascorbic acid and lecithin; 
(2) Has improved antioxidant activity as shown in Table 2 of Example 2, the 
elimination of citric acid decreases the induction period of the four 
component system from 26.4 to 24.1 hours; and 
(3) Uses a much lower amount of "Lecithin". In all the examples of 
Lollger's patent, 1% of "Lecithin" was used. Such a high amount of 
"Lecithin" will impart an undesirable odor and flavor to the product. 
The scope of the invention herein shown and described is to be considered 
only as illustrative. It will be apparent to those skilled in the art that 
numerous modifications may be made therein without departure from the 
spirit of the invention or the scope of the appended claims.