Chemistry and biochemistry of 4-hydroxynonenal, malonaldehyde and related aldehydes.

Biological effects of essential oils - A review

Publisher Summary This chapter describes the malondialdehyde (MDA) as index of lipid peroxidation. The determination of malondialdehyde (MDA) has attracted widespread interest, because it appears to offer a facile means of assessing lipid peroxidation in biological materials. Malondialdehyde occurs in biological materials in free state and in various covalently bound forms. Urine also contains small amounts of MDA adducts with guanine, the phospholipid bases serine and ethanolamine, and other unidentified reactants. Free MDA is a minor and variable excretory product. It is apparent from the occurrence of these derivatives in urine that MDA forms adducts with proteins, nucleic acids, and other substances in vivo, and this compromises the assessment of lipid peroxidation in the tissues based on the determination of free MDA. The pH required for maximum yield of MDA varies among biological materials depending on the nature of the derivatives present. MDA may be generated during hydrolysis by the oxidation of polyunsaturated fatty acids (PUFA) in the sample and by the degradation of preexisting oxidation products. Pigments present in the sample, or generated during hydrolysis, also can interfere in the colorimetric assessment of MDA. These problems, and possibilities for their resolution, are discussed in the chapter.

Malondialdehyde determination as index of lipid peroxidation

Malondialdehyde and thiobarbituric acid-reactivity as diagnostic indices of lipid peroxidation and peroxidative tissue injury.

The term pesticide covers a wide range of compounds including insecticides, fungicides, herbicides, rodenticides, molluscicides, nematicides, plant growth regulators and others. Among these, organochlorine (OC) insecticides, used successfully in controlling a number of diseases, such as malaria and typhus, were banned or restricted after the 1960s in most of the technologically advanced countries. The introduction of other synthetic insecticides – organophosphate (OP) insecticides in the 1960s, carbamates in 1970s and pyrethroids in 1980s and the introduction of herbicides and fungicides in the 1970s–1980s contributed greatly to pest control and agricultural output. Ideally a pesticide must be lethal to the targeted pests, but not to non-target species, including man. Unfortunately, this is not the case, so the controversy of use and abuse of pesticides has surfaced. The rampant use of these chemicals, under the adage, “if little is good, a lot more will be better” has played havoc with human and other life forms.

Production and usage of pesticides in India
The production of pesticides started in India in 1952 with the establishment of a plant for the production of BHC near Calcutta, and India is now the second largest manufacturer of pesticides in Asia after China and ranks twelfth globally (Mathur, 1999). There has been a steady growth in the production of technical grade pesticides in India, from 5,000 metric tons in 1958 to 102,240 metric tons in 1998. In 1996–97 the demand for pesticides in terms of value was estimated to be around Rs. 22 billion (USD 0.5 billion), which is about 2% of the total world market.

The pattern of pesticide usage in India is different from that for the world in general. As can be seen in Figure 1, in India 76% of the pesticide used is insecticide, as against 44% globally (Mathur, 1999). The use of herbicides and fungicides is correspondingly less heavy. The main use of pesticides in India is for cotton crops (45%), followed by paddy and wheat.



Figure 1

Consumption pattern of pesticides.





Benefits of pesticides
The primary benefits are the consequences of the pesticides' effects – the direct gains expected from their use. For example the effect of killing caterpillars feeding on the crop brings the primary benefit of higher yields and better quality of cabbage. The three main effects result in 26 primary benefits ranging from protection of recreational turf to saved human lives. The secondary benefits are the less immediate or less obvious benefits that result from the primary benefits. They may be subtle, less intuitively obvious, or of longer term. It follows that for secondary benefits it is therefore more difficult to establish cause and effect, but nevertheless they can be powerful justifications for pesticide use. For example the higher cabbage yield might bring additional revenue that could be put towards children's education or medical care, leading to a healthier, better educated population. There are various secondary benefits identified, ranging from fitter people to conserved biodiversity.

Improving productivity
Tremendous benefits have been derived from the use of pesticides in forestry, public health and the domestic sphere – and, of course, in agriculture, a sector upon which the Indian economy is largely dependent. Food grain production, which stood at a mere 50 million tons in 1948–49, had increased almost fourfold to 198 million tons by the end of 1996–97 from an estimated 169 million hectares of permanently cropped land. This result has been achieved by the use of high-yield varieties of seeds, advanced irrigation technologies and agricultural chemicals (Employment Information: Indian Labour Statistics, 1994). Similarly outputs and productivity have increased dramatically in most countries, for example wheat yields in the United Kingdom, corn yields in the USA. Increases in productivity have been due to several factors including use of fertiliser, better varieties and use of machinery. Pesticides have been an integral part of the process by reducing losses from the weeds, diseases and insect pests that can markedly reduce the amount of harvestable produce. Warren (1998) also drew attention to the spectacular increases in crop yields in the United States in the twentieth century. Webster et al. (1999) stated that “considerable economic losses” would be suffered without pesticide use and quantified the significant increases in yield and economic margin that result from pesticide use. Moreover, in the environment most pesticides undergo photochemical transformation to produce metabolites which are relatively non-toxic to both human beings and the environment (Kole et al., 1999).

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Impact of pesticides use in agriculture: their benefits and hazards.

Identification of volatile components in basil Ocimum basilicum L and thyme leaves Thymus vulgaris L and their antioxidant properties

Recently, research on natural antioxidants has become increasingly active in various fields. Accordingly, numerous articles on natural antioxidants, including polyphenols, flavonoids, vitamins, and volatile chemicals, have been published. Assays developed to evaluate the antioxidant activity of plants and food constituents vary. Therefore, to investigate the antioxidant activity of chemical(s), choosing an adequate assay based on the chemical(s) of interest is critical. There are two general types of assays widely used for different antioxidant studies. One is an assay associated with lipid peroxidations, including the thiobarbituric acid assay (TBA), malonaldehyde/high-performance liquid chromatography (MA/HPLC) assay, malonaldehyde/gas chromatography (MA/GC) assay, β-carotene bleaching assay, and conjugated diene assay. Other assays are associated with electron or radical scavenging, including the 2,2-diphenyl-1-picrylhydrazyl (DPPH) assay, 2,2′-azinobis(3-ethylbenzothiazoline-6-sulfonic acid) (ABTS) as...

Antioxidant assays for plant and food components.

Antioxidant property of aroma extract isolated from clove buds [Syzygium aromaticum (L.) Merr. et Perry]

Thirteen essential oils were examined for their antioxidant activity using three different assay systems. Jasmine, parsley seed, rose, and ylang-ylang oils inhibited hexanal oxidation by over 95% after 40 days at a level of 500 microg/mL in the aldehyde/carboxylic acid assay. Scavenging abilities of the oils for the 1,1-diphenyl-2-picrylhydrazyl (DPPH) radical ranged from 39% for angelica seed oil to 90% for jasmine oil at a level of 200 microg/mL. The greatest inhibitory activity toward malonaldehyde (MA) formation from squalene upon UV-irradiation was obtained from parsley seed oil (inhibitory effect, 67%), followed by rose oil (46%), and celery seed oil (23%) at the level of 500 microg/mL. The main compounds of oils showing high antioxidant activity were limonene (composition, 74.6%) in celery seed, benzyl acetate (22.9%) in jasmine, alpha-pinene (33.7%) in juniper berry, myristicin (44%) in parsley seed, patchouli alcohol (28.8%) in patchouli, citronellol (34.2%) in rose, and germacrene (19.1%) in ylang-ylang.

Antioxidant activities and volatile constituents of various essential oils.

Antioxidant activities of volatile extracts isolated from thyme, basil, rosemary, chamomile, lavender, and cinnamon were evaluated by two independent assays: the aldehyde/carboxylic acid assay and the conjugated diene assay. The volatile extracts were prepared from dried herbs and spices using liquid-liquid continuous extraction following steam distillation under reduced pressure (55 degrees C and 95 mmHg). The antioxidant activities of the extracts decreased in the following order in both of the lipophilic assay systems: thyme > basil > rosemary > chamomile > lavender and cinnamon. Thyme and basil extracts inhibited the oxidation of hexanal for 40 days at the levels of 10 microg/mL and 50 microg/mL, respectively. The extracts of thyme and basil were effective in retarding methyl linoleate deterioration at 40 degrees C, with activity increasing with concentration in the range 10-200 microg/mL. At a concentration of 50 microg/mL, thyme extract was similar in antioxidant activity to BHT and alpha-tocopherol in the conjugated diene assay. The antioxidant potentials of the volatile extracts used in this study were accurately measured by the lipophilic systems, such as the aldehyde/carboxylic acid assay and the conjugated diene assay.

Takayuki Shibamoto

Papers

Identification of volatile components in basil Ocimum basilicum L and thyme leaves Thymus vulgaris L and their antioxidant properties

Antioxidant assays for plant and food components.

Antioxidant property of aroma extract isolated from clove buds [Syzygium aromaticum (L.) Merr. et Perry]

Antioxidant activities and volatile constituents of various essential oils.

Determination of antioxidant potential of volatile extracts isolated from various herbs and spices