3 Chapters

Peel waste are highly perishable and seasonal, is a problem to the processing industries and pollution monitoring agencies. There is always an increased attention in bringing useful products from waste materials and citrus wastes are no exceptions. Suitable methods have to be adopted to utilize them for the conversion into value-added products [Nand, (1998)]. Pectin exists in varying amounts in fruit cell walls and has important nutritional and technological properties, mainly because of its ability to form gels (Westerlund etal, 1991).

Pectin is a polysaccharide having properties such as gelation and emulsion stabilization which make it useful in the manufacture of food, cosmetics, and medicine. It is a normal constituent of food and may therefore be safely ingested. Citrus peel, a by-product of the citrus processing industry, is a suitable source of pectin (Sakai and Okushima 1980). Pectin is a naturally occurring substance present in all plant tissue, calcium pectin being present between the cell walls and serving as a strengthening or building agent.

The traditional use of pectin has been as a gelling agent, and this has largely dictated the types of fruit from which commercial grades can be manufactured. A major consideration is the availability of fruit by-products in sufficient quantity and quality. Before the development of a distinct pectin industry it was often the practice for jam makers to make a simple pectin extract from waste fruit material such as apple cores or surplus orange pith, but commercial production demands large quantities of available raw material.

The history of the industry up to 1950 is described by Kertesz. Since that date, there has been a geographical shift of the production of pectin, driven to a large extent by difficulties with water supply and more especially effluent disposal in areas such as southern California, so that the major US plants producing citrus pectin, who had come to dominate that market, have been closed down by the companies concerned. The largest pectin plants today are either in Europe or in Latin America, and the expectation is that more of the industry may move to citrus-producing areas in future.

Pectin is very susceptible to degradation either by enzymes in the wet peel or by heat during drying and subsequent processing, and such loss of quality must always be controlled as far as possible. Pectin producers devote considerable resources to ensuring both the availability and quality of raw materials, and quality has a major effect on the types of pectin which can be economically produced. Because of the arising demand in producing pectin from fruits, the researcher will conduct a study on extraction of pectin from palapat fruit peels utilizing the waste material for its possible benefit in cosmetic industry.

Statement of the Problem This study aims to utilize the used of waste materials by extracting pectin from palapat fruit peels for the formulation of hair gel. Specifically, it seeks to answer the following questions. 1. Is it possible to extract pectin from dried palapat peels? 2. Is it feasible to produce hair gel out of the extracted pectin? 3. Between the given formulations (6:3:1, 7:2:1 ratio of extracted pectin, distilled water, 95% ethyl alcohol), which is the most comparable to commercial hair gel? Significance of the Study

This study will be focus on utilizing waste material by means of extracting pectin from palapat fruit peels for the formulation of hair gel. If the result of this study is permissing, it will benefit the future researchers. The results obtained from this study can initiate further studies on the other uses of palapat fruit. The success of this study will also be a great help for the people because the use of extracted pectin for the formulation of hair gel will make deflation on the cost of the hair gel’s production Scope and Limitation of the Study

This study deals with utilization of fruit waste by means of extracting pectin from the palapat fruit peels. The percent yield of the extracted pectin and physico-chemical properties will be determined. Formulation of hair gel will be conducted. Statistical treatment will be applied in order to compare the significant difference between the formulated hair gel and the commercially produced hair gel. The convenience of the researcher in gathering the sample in Masantol, Pampanga was also considered. CHAPTER II THEORETICAL FRAMEWORK Review of Related Literature Palapat (Sonneratia caseolaris (L. English names : Apple Mangrove, Crabapple Mangrove. Uses The heavy wood (800 kg/m3) is used for boatbuilding, construction, piles, and posts. Sour young fruits, used in or for vinegar, are widely used in Oriental chutnies and curries. Ripe fruits, said to taste like cheese, are eaten raw or cooked. A clear jelly can be prepared from the pectinaceous fruits. Pneumatophores cut up and used as corks or floats for fishing nets. The pulp is suitable for kraft paper production. Flowers, in anthesis, contain abundant honey (Backer and van Steenis, 1951). Folk Medicine

Reported to be hemostat, crabapple mangrove is a folk remedy for sprains, swellings, and worms (Duke and Wain, 1981). Burmese use the fruits for poultices, Indochinese poultice crushed leaves with salt onto cuts and bruises. Malayans use old fruit walls for worms, half-ripe fruits for coughs, and pounded leaves for hematuria and smallpox (Perry, 1980). Chemistry Fruits yield 11% pectin (ZMB). Wood yields 52. 7% brown pulp (8. 5% lignin, 17. 6% pentosan). Emodin and chrysophanic acid may be the coloring matter in the crude drug (Perry, 1980). Bark from Africa assayed at 17. 1% tannin, of the pyrogallol class.

Indian stem bark assayed 9–17%, twig bark 11-12%. Wood yields two coloring principles, archin (C15H10O5) and archinin (C15H14O12 ) (C. S. I. R. , 1948–1976). Description Evergreen tree 5–15(–20) m high without buttresses or stilt roots, with rather open spreading crown, glabrous throughout. Pneumatophores 50–90 cm high, to 7 cm in diameter. Bark gray, coarsely flaky. Leaves opposite, without stipules, nearly sessile, elliptical, oblong or ovate, 5–13 cm long, 2–5 cm wide, with broad or tapering base and blunt or rounded tip, entire, with 8–12 widely spreading fine side veins on each side, leathery.

Flowers 1–3 at end of drooping twigs malodorous, nocturnal. Hypanthium with 6–8 calyx lobes; petals 6–8, 2–3. 5 cm long, 1. 5–3. 5 mm wide, dark or blood-red, stamens numerous, with threadlike filaments 2. 5–3. 5 cm long, pistil with 16–21-celled ovary with many ovules; style long, stout (Little, 1983). Germplasm Reported from the Australia, Indonesia-Indochina, and Hindustani Centers of Diversity, crabapple mangrove, or cvs thereof, is reported to tolerate coral, disease, insects pests, salt, and waterlogging (NAS, 1980; Little, 1983). (2n = 24 in other Sonneratia). Studies

Antimicrobial / Cytotoxicity: Study isolated nine compounds from the fruits of S caseolaris. Screened against a rat glioma C-6 cell line, compounds 1, 2 and 6 were found to show moderate cytotoxic activity and suggests a potential foundation for further chemotaxonomic studies. Flavonoids / Antioxidant: Study yielded two flavonoids, luteolin and luteolin 7-O-B-glucoside. Both compounds showed to possess antioxidant activity. Distribution Sri Lanka to Malay Peninsula and northern Australia. Also Sumatra, Java, Borneo, Celebes, Philippines, Moluccas, Timor, New Guinea, Solomon Islands, New Hebrides.

Not widely introduced (Little, 1983). In the Philippines, the Crabapple Mangrove is commonly known as palapat. Palapat is the fruit of those living on river banks such as Macabebe, Sasmuan, Masantol, and Minalin, Pampanga. They are delectable to eat especially if they are perfectly ripe. And yet unripe and very small young fruit are also ingredient in a stew and saute sardines . It can also make sauce with fried fish, Jam for bread and desert. Pectins Pectins, also known as pectic polysaccharides, are rich in galacturonic acid.

Several distinct polysaccharides have been identified and characterised within the pectic group. In nature, around 80 percent of carboxyl groups of galacturonic acid are esterified with methanol. This proportion is decreased to a varying degree during pectin extraction. The ratio of esterified to non-esterified galacturonic acid determines the behavior of pectin in food applications. This is why pectins are classified as high- vs. low-ester pectins (short HM vs. LM-pectins), with more or less than half of all the galacturonic acid esterified.

The non-esterified galacturonic acid units can be either free acids (carboxyl groups) or salts with sodium, potassium, or calcium. The salts of partially esterified pectins are called pectinates, if the degree of esterification is below 5 percent the salts are called pectates, the insoluble acid form, pectic acid. Some plants such as sugar beet, potatoes and pears contain pectins with acetylated galacturonic acid in addition to methyl esters. Acetylation prevents gel-formation but increases the stabilising and emulsifying effects of pectin.

Apples, guavas, quince, plums, gooseberries, oranges and other citrus fruits, contain large amounts of pectin, while soft fruits like cherries, grapes and strawberries contain small amounts of pectin. The main raw-materials for pectin production are dried citrus peel or apple pomace, both by-products of juice production. Pomace from sugar-beet is also used to a small extent. From these materials, pectin is extracted by adding hot dilute acid at pH-values from 1. 5 – 3. 5. During several hours of extraction, the protopectin loses some of its branching and chain-length and goes into solution.

After filtering, the extract is concentrated in vacuum and the pectin then precipitated by adding ethanol or isopropanol. An old technique of precipitating pectin with aluminium salts is no longer used (apart from alcohols and polyvalent cations; pectin also precipitates with proteins and detergents). The main use for pectin (vegetable agglutinate) is as a gelling agent, thickening agent and stabilizer in food. The classical application is giving the jelly-like consistency to jams or marmalades, which would otherwise be sweet juices.

Pectin also reduces syneresis in jams and marmalades and increases the gel strength of low calorie jams. For household use, pectin is an ingredient in gelling sugar (also known as “jam sugar”) where it is diluted to the right concentration with sugar and some citric acid to adjust pH. In some countries, pectin is also available as a solution or an extract, or as a blended powder, for home jam making. For conventional jams and marmalades that contain above 60% sugar and soluble fruit solids, high-ester pectins are used. With low-ester pectins and amidated pectins less sugar is needed, so that diet products can be made.

Recently, ERRC chemist LinShu Liu developed a material from natural crop polymers, including pectin, which can be used in biomedical materials, such as those used in human tissue regeneration. The new, pectin-based material forms three-dimensional structures with better physical and mechanical properties than the tissue replacer in current use. Other potential medical applications of these novel pectin materials include prosthetic medical devices and scaffolding for bone or cartilage repair, since pectin and other polysaccharides have properties that allow human cells to bind to them and grow.

A patent application has been filed, and ARS has signed a cooperative research and development agreement with a private company to further develop the materials. Liu has combined pectin and zein—the main storage protein in corn seeds—and found that the combination can be used in a colon-specific drug-delivery system. It doesn’t degrade until it reaches the large intestine, allowing for controlled release. In another human health application, plant physiologist Arland T. Hotchkiss and cooperators demonstrated for the first time that pectin fragments from orange peel have prebiotic properties.

Prebiotics are nondigestible food ingredients that increase growth of beneficial probiotic bacteria in the large intestine. Probiotic bacteria stimulate health and help prevent growth of foodborne pathogens. Orange pectin prebiotics are also being evaluated by collaborators as animal-feed ingredients. This may allow reduction or elimination of antibiotics that are often added to feed. Extraction of Pectin from Arecanut (Areca catechu Linn. ) Peels and Husks for the production Hair Gel by Jaime (2001).

The author undergone pectin extraction using diluted HCl as solvent and then undergone alcohol precipitation method using the dried and fresh arecanut peels and husks. The extracted pectin was subjected to identification test and physico- chemical test. The extracted pectin was formulated into hair gel and was compared to the commercial hair gel. The study cited deals with the extraction of pectin and formulation of hair gel, likewise, this paper had conducted the same method for the formulation of hair gel using pectin extract from palapat fruit peels-utilizing waste material.

Research Hypotheses From the problem posted by the researcher, the following hypotheses were derived: 1. It is possible to extract pectin from dried palapat peels. 2. It is feasible to produce hair gel out of the extracted pectin. 3. The ratio of 7:2:1 (extracted pectin: distilled water: 95% ethyl alcohol) is the most comparable formulation to commercial hair gel. Research Paradigm Collection and preparation of samples Palapat fruit peels Extraction of pectin Percent yield of extracted pectin Physico-chemical test for pectin Solubility test Methoxyl content

Color determination Moisture content Formulation of hair gel 6:3:1 7:2:1 Comparative test on the effectivity of the best formulated hair gel to commercial hair gel Statistical treatment Definition of Terms To make the reader understand this paper fully, the following terms are defined: Initial titer is the amount of alkali required to remove or react with methoxyl group present in the pectin sample (Keenan, 1976) Saponification is the hydrolysis especially by alkali of an ester into the corresponding alcohol and acid or salt of the acid. (Redmore, 1988)

Methoxy is the methyl group present in pectin that can be easily removed by enzyme, acid, and alkali (Mule, 1972) Pectin consists of a linear backbone of randomly connected (1- 4)-linked a-d-galacturonyl units partially esterified with methanol. Hair Styling Gel is designed to help hold hair in a fixed shape. It is a clear product that is smoothed through the hair, coating it, and setting up a rigid film that inhibits movement Gel suspension in water medium of insoluble substance in hydrated form wherein the particle size approach on attains colloidal dimensions (Redmorem, 1980)

CHAPTER III METHODOLOGY This study deals with the hair formulation of hair gel using pectin extract from palapat fruit peels-utilizing waste material. The methods will be divided into 8 parts namely: Collection and Preparation of Samples, Extraction of Pectin, % Yield of the Extracted Pectin, Identification Test for Pectin, Physico-Chemical Test for Pectin, Formulation of Hair Gel, Comparative Test on the Effectiveness of the Formulated Hair Gel to Commercial Hair Gel and Statistical Analysis. Collection of Raw Material The palapat fruit will be collected in Cambasi, Masantol, Pampanga.

The fruit was authenticated by the Botany Division of National Museum. Wash and peel the palapat fruit. Peels will be used for the extraction of pectin. Extraction of Pectin Place 500 grams of fresh sample in a beaker and dry to constant weight in a constant temperature in an oven at 100 C. the moisture content of the sample is the difference between the weight before and after drying. Pectin will be extracted using dilute HCL (1:4) for the dried sample for the temperature between 60 C and 100 C for about 30 to 60 minutes with pH of 1. 2 to 3.

After extraction, cool and strain the extract to remove the waste solid from liquid. Precipitate the filtered pectin liquor with 95 % ethyl alcohol. Two volumes of alcohol will be used every one volume of pectin liquor then stir and set aside overnight to allow colloidal particles to form into flocs of jellies. Filter the formed flocs. Wash the precipitate with 95 % ethanol until precipitation is complete. The pectin will be air-dried for several hours. After the pectin was completely dried, it will be powdered then weigh and store for physic-chemical analysis.

Determination of the percent yield of pectin The percent yield of the pectin will be determined by dividing the weight of the powdered pectin over the weight of the sample used then multiply it to 100 %. Identification Test for Pectin Heat two grams of extracted pectin with 18 ml distilled water on a water bath until the solution forms. Add 10 ml of the 1% solution, equal volume of ethanol then observe. To another 5 ml of the 1% solution, add 1 ml of potassium hydroxide and allow to stand for 15 minutes at room temperature. Acidify the gel formed with 3N HCl. Physico-Chemical Test

Measurement of Methoxyl Content A known weight of sample (approximately 5g) will be stirred for 10 minutes with mixture of 5 ml of HCl and 100 ml of 60% ethyl alcohol. Filter and wash several times until the filtrate is free from chloride. One-tent (1/10) of the dried chloride- free pectin will be moistened with 2 ml of alcohol. Then it will be homogenized with 100 ml CO2 free water. Add five drops of phenolphthalein and titrate the mixture with 0. 5 NaOH. The result will be recorded as the initial titer (V1). The sample will be saponified by the addition of the equivalent amount of 0. 5 NaOH.

Shake the solution until the faint pink color disappeared. Add three drops of phenolphthalein and titrate with 0. 5 NaOH, then shake vigorously until faint pink color persists. Record the volume of NaOH (in ml) required in titration as the saponification titer (V2). Note that for every 1 ml of NaOH used titration, saponification titer is equivalent to 15. 25 mg of methoxyl content. Solubility Test The 0. 5 g of pectin powder will be dissolved in a certain amount of distilled water. Record the volume of the distilled water required to dissolve the precipitate (V3) then compute the % solubility.

Moisture Content Keep three grams of extracted pectin in an oven at 105 C and dry to constant weight. The moisture content is the difference between the weight before and the weight after drying. Powder Color Determination Spread a sufficient amount of extracted pectin over the entire top of a flat-bottomed petridish with white background then note the color of the pectin powder. Formulation of Hair Gel. Pectin has a jellying power that is why hair gel can be formulated using the extracted pectin out of the sample. Two formulations will be conducted to produce the best formulated hair gel. he first formulation is 6 g of powdered pectin, 3 ml of distilled water, and 1 ml of 95% ethyl alcohol. The second formulation is 7 g of powdered pectin, 2 ml of distilled water, and 1 ml of 95 % ethyl alcohol. From the formulations presented, dissolve the extracted pectin with distilled water, warm slightly to hasten the solution then slowly add the 95 % ethyl alcohol to the solution to form a jelly-like substance and filter to remove the alcohol. Comparative Test on the Effectivity of the Best Formulated Hair Gel to Commercial Hair Gel.

This will be done to determine if there is a significant difference on the two different formulations. 10 respondents will be asked to use the best formulated hair gel and allow them to apply it on their own same thing with commercial hair gel. The respondents must be ranging 20-30 years old with short hair cut. An evaluation sheet will be given to evaluate the effectiveness of both hair gels. The respondents will be asked if there is significant difference in terms of odor, texture, holding hair in place, and means of washing off.

Statistical Treatment ANOVA will be used to determine if there is a significant difference between the two formulations through the evaluation sheets that will be answered by the respondents. Formulation of Hair Gel Using Pectin Extract from Palapat (Sonneratia caseolaris (L. ) Fruit Peels-Utilizing Waste Material. A thesis presented to The College of Science Pamantasan ng Lungsod ng Maynila Intramuros, Manila In Partial Fulfillment Of the Requirements for the Degree of Bachelor of Science in Chemistry By Jessica V. Balingit 2013