Speciation Analysis And The Bioavailability Of Manganese In Special Herbs From Hainan Island And Their Herbal Pairs

Manganese is an essential trace element, plays an important role in cellular processes such as participating in many enzymes synthesis and activated, promoting fat oxidation in cells, reducing the fat in the liver, speeding up the synthesis content of protein, vitamin B and C, promoting hematopoiesis function. Also manganese is one part of several metal enzymes which can regulate endocrine system and improve immune function. Though manganese is essential for life, it is also potentially more toxic than other trace elements. Manganese concentration in body tissues must be tightly regulated because deficient in manganese leads to stunt and infertility, and excessive manganese causes rickets, manic or depressive psychosis.The contents, primary speciation, secondary-level speciation and bioavailability of Mn, which contained in seven Chinese herbs(Areca catectu L., Aquilaria sinensis(Lour.)Gilg, Salvia miltiorrhiza Bge., Morinda officinalis How, Zanthoxylum schinifolium Sieb.et Zucc, Amomum longiligulare T.L.Wu, Pogostemon cabl in(Blanco) Benth) and four herbal pairs (Areca catectu L-Aquilaria sinensis(Lour.) herbal pair (1:1mass ratio), Areca catectu L-Salvia miltiorrhiza Bge. herbal pair (2:3mass ratio), Morinda officinalis How-Zanthoxylum schinifolium Sieb.et Zucc. herbal pair (1:1mass ratio), Amomum longiligulare T.L.Wu-Pogos-temo cablin(Blanco) Benth. herbal pair (1:1mass ratio))was studied for the first time. In vitro digestion and dialysismethod was adopted to study the bioavailability of Mn. To forecast Mn bioaccessibility for risk assessment of Chinese medicines containing cinnabar.The FAAS with pressurized sample digestion and microwave digestion were applied to determine the contents of Mn in thirty-eight Chinese herbs (Areca catectu L.; Aquilaria sinensis(Lour.)Gilg; Salvia miltiorrhiza Bge.; Morinda officinalis How; Zanthoxylum schinifolium Sieb.et Zucc; Amomum longiligulare T.L.Wu; Pogostemon cablin(Blanco) Benth; Mimosa pudica L.; Cordyline fruticosa (Linn.)A. Cheval.; Eupatorium odoratum L.; Artocarpus heterophyllus Lam.; Portulaca oleracea L.; Aloe vera Linn. Var. chinensis (Haw.) Berger; Melia azedarach L.; Mangifera indica L.; Murraya paniculata (L.) Jack.; Paederia scandens (Lour.) Merr.; Cleome gynandra L.; Centella asiatica (L.) Urban,; Bryophyllum pinnatum (Linn.f.) Oken,; Psidium guajava L.; Clausena lansium (Lour.) Skeels; Basella alba L.; Plumeria rubra L.cv.Acutifolia, Perilla frutescens (L.) Britt. Var. crispa Decne.; Anisomeles indica (L.) O.Ktze.; Impatiens chinensis L.; Gentiana loureirii (G. Don) Griseb.; Sonerila hainanensis Merr.; Scoparia dulcis L.; Verbena officinalis L.; Clerodendrum cyrtophyllum Turcz.; Phyllanthus urinaria L.; Plant ago asiatica L.; Physalis angulata L.; Mirabilis jalapa L.; Cardiospermum halicacabum L.). The results show that the content of manganese (Mn) is abundant in all the above Chinese herbs, the highest content of Mn is Pogostemon cablin(Blanco) Benth., The relationship of contents with pressurized sample digestion-FAAS is Pogostemon cablin(Blanco) Benth.(1278μg·g-1)> Morinda officinalis How (604.8μg·g-1)> Amomum longiligulare T.L.Wu (313.3μg·g-1)>Aquilaria sinensis (Lour.)Gilg (238.5μg·g-1)> Zanthoxylum schinifolium Sieb.et Zucc.(84.74ug·g-1)> Areca catectu L.(40.22μg—g-1)> Salvia miltiorrhiza Bge.(34.48μg·g-1). The contents of Mn in other31Chinese herbs is between9.25μg·g-1-788.4μg·g-1, the contents of Mn is the highest of Gentiana loureirii (G. Don) Griseb.(788.4μg·g-1) among all Chinese herbs, Clerodendrum cyrtophyllum Turcz.(496.7μg·g-1) is next; the recovery rate is between98.32%-103.5%; RSD is between0.92%-1.76%(n=6).Primary speciation of Mn in seven Chinese medicines and four herbal pairs were studied. The contents of sample of primary speciation obtained from primary analytical flow was determined by atomic absorption spectrometry, species distributions of the primary speciation analysis, such as extractive rate, immerse-residue ratio et al. were also calculated. That extractive rate of Mn was different in each medicine: Areca catectu L.(72.58%), Salvia miltiorrhiza Bge.(46.52%), Areca catectu L-Salvia miltiorrhiza Bge. herbal pair (2:3mass ratio)(46.25%) was more than single herbal’s average of extractive rate. The extraction rate of Mn in herbal and herbal pairs is different. There may be some interaction between the different two drug compatibility, result in nutrition, health or efficacy of Mn changed. With the Dietary Reference in takes, NRV%of Mn also different in seven medicines and four herbal pairs. NRV%of Mn larger than100%inAmomum longiligulare T.L.Wu-Pogostemon cablin(Blanco) Benth. herbal pair, NRV%of Mn close100%in Pogostemon cablin(Blanco) Benth. It’s show that long term use of these tow herbs, may be affect health.Secondary-level speciation of Mn was studied on the base of the analysis of primary speciation. The result of secondary-level speciation were obtained by using the n-C8H17OH-warter extraction system, CHC13-warter extraction system and cation-exchange resin. It proved that Kow value of Mn is influenced by different pH Values in the n-CgH17OH-water extraction system. In the different acidity of stomach and intestine, only Aquilariasinensis(Lour.)Gilg and Areca catectu L.-Aquilaria sinensis(Lour.)Gilg herbal pairs of manganese in alcohol water distribution coefficient (Kow) are greater than1, the rest medicinal materials of manganese are less than1. The Kow are different of single drug and herbal pairs. As in pH=1.3, the Kow value of manganese are0.07in Areca catectu L., the Kow value of manganese are0.17in Aquilaria sinensis(Lour)Gilg, the Kow value of manganese are0.37in Areca catectu L.-Aquilaria sinensis(Lour.)Gilg herbal pairs, the Kow value of manganese in the herbal pairs was higher than the single drug, It proved that Kow value of Mn in the herbal pairs was improve biological activity.The chloroform-water distribution system will dissolve into organic and inorganic state, the results showed that:Mainly state of manganese is inorganic (quality score>50%), every medicine organic and inorganic state of Mn’s contents are different with herbal pairs. With strong acid cation exchange resin will soluble state into the free ions and non free ions, the result shows:the main state of manganese (quality score>90%) is free ions, the percentage of manganese in free ions content of herbal pairs are higher than the average of the two single herbals.On the basis of the study in the primary and secondary forms, using the method of in vitro digestion-dialysis to study the bioavailability of Mn in seven kinds of Chinese medicines and herbal pairs. In the gastric compartment, bioaccessibility of Mn from seven Chinese medicines and herbal pairs in decoction ranged from0.45%～8.74%. Bioaccessibility of Mn from seven Chinese medicines and herbal pairs in soluble state ranged from0.40%～9.49%. Bioaccessibility of Mn from seven Chinese medicines and herbal pairs in inorganic ranged from0.68%～9.19%. Bioaccessibility of Mn from seven Chinese medicines and herbal pairs in non free ions ranged from0.04%～2.73%. Bioaccessibility of Mn from seven Chinese medicines and herbal pairs in free ions ranged from1.08%～8.47%. The bioaccessibility of Mn are different in different speciations with seven medicines and four herbal pairs. The bioaccessibility of Mn in herbal and herbal pairs is different. It is result that there is intention with each other. The bioaccessibility of Mn is very low in seven medicines and four herbal pairs, So, there is no health risks for long term use these medicines with Mn.