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一、 飼料與養(yǎng)殖現(xiàn)狀
據(jù)統(tǒng)計(jì), 全球有73%的飼料樣品霉菌毒素超標(biāo)。中國(guó)現(xiàn)有飼料加工企業(yè)12000多家, 飼料產(chǎn)量不低于2億噸。大部分地區(qū), 特別是長(zhǎng)江以南地區(qū), 夏季高溫潮濕，飼料霉變及受霉菌毒素污染的現(xiàn)象非常普遍，其危害已是大問(wèn)題。常見(jiàn)的有:曲霉菌屬(主要分泌黃曲霉毒素、赭曲霉毒素等)、青霉菌屬(主要分泌桔霉素等)、麥角菌屬(主要分泌麥角毒素)、梭菌屬(主要分泌嘔吐毒素、玉米赤霉烯酮、T- 2毒素、Fumonisin毒素等)。
由于環(huán)境應(yīng)激, 霉菌毒素之間的聯(lián)合作用及飼料營(yíng)養(yǎng)不平衡等因素的存在, 飼料中低含量的霉菌毒素即可對(duì)動(dòng)物造成危害。例如， 當(dāng)飼料中黃曲霉毒素含量為 14 . 0 g/ kg ( 低于美國(guó)雞飼料黃曲霉毒素允許量 20 g/ kg 的衛(wèi)生標(biāo)準(zhǔn)) 時(shí)即可對(duì)肉仔雞生產(chǎn)性能造成嚴(yán)重影響。
二、 蒙脫石的作用
蒙脫石的名稱(chēng)來(lái)源于法國(guó)，法國(guó)做過(guò)一項(xiàng)動(dòng)物研究，家兔回腸感染大腸桿菌后，服用蒙脫石可以減輕胃腸黏膜損傷，重建水電解質(zhì)吸收，促進(jìn)絨毛恢復(fù)正常形態(tài)，促進(jìn)受損小腸黏膜上皮細(xì)胞的再生與修復(fù)。
霉菌毒素及各種細(xì)菌對(duì)Caco－2細(xì)胞均有不同程度的黏附作用，從而傷害胃腸黏膜，而蒙脫石能夠阻斷這種黏附，并且對(duì)病原菌黏附Caco－2細(xì)胞的阻斷作用，要明顯大于其對(duì)益生菌的阻斷效果。例如，對(duì)大腸桿菌鼠傷寒沙門(mén)氏菌、嗜水氣單胞菌 、副溶血弧菌黏附的阻斷率，分別為54.22％ 48．41％ 60．53％ 50．64％， 而對(duì)兩歧雙歧桿菌、嗜酸乳桿菌黏附的阻斷率，分別為25．64％和21．49％。結(jié)果顯示：蒙脫石可有效阻斷病原菌黏附胃腸道，從而防治腸道細(xì)菌感染和細(xì)菌移位，進(jìn)而可以預(yù)防和治療腹瀉的發(fā)生。
牛業(yè)來(lái)等應(yīng)用十六角蒙脫石治療消化性潰瘍及上消化道出血，病例30例皆取得滿(mǎn)意療效。由于蒙脫石可吸附各種病毒細(xì)菌及其他各種霉菌毒素，治療斷奶仔豬腹瀉綜合癥總有效率為94.74%，治愈率為42.11%，高于氟哌酸(氟哌酸治療總有效率為66.67%，治愈率27.77%)。
蒙脫石對(duì)豬，對(duì)人，對(duì)雞鴨牛羊兔等動(dòng)物的腹瀉也有很好的療效。在獺兔幼兔日糧中添加400g／t喹乙醇，與添3kg／t納米蒙脫石，均有效減少了獺兔幼兔的腹瀉次數(shù)，降低了腹瀉率，效果上添加納米蒙脫石組更明顯。
三、 蒙脫石的作用機(jī)理
1、概念
粘土礦中蒙脫石含量大于80%就稱(chēng)為蒙脫石，蒙脫石為高純度的膨潤(rùn)土，是膨潤(rùn)土的主要成分。這類(lèi)礦物包括鈉基蒙脫石、鈣基蒙脫石 、鎂基蒙脫石、鐵基蒙脫石、鋰基蒙脫石以及鋁蒙脫石等。
蒙脫石硬度為2～2．5，相對(duì)密度2～2．7，甚柔軟，有滑感。在電子顯微鏡下可見(jiàn)片狀晶體，層與層之間可以滑動(dòng)打開(kāi)，層與層之間并不散亂分離，在水介質(zhì)中可分散呈膠體狀態(tài)，屬酸性膠基，對(duì)強(qiáng)酸強(qiáng)堿具有一定的緩沖能力，因此能保持體系pH相對(duì)穩(wěn)定。例如：蒙脫石在消化道延展，可形成連續(xù)的保護(hù)膜，與消化道黏液蛋白靜電結(jié)合，可顯著提高黏液的內(nèi)聚力和彈性。( Girardeau，1987; Albengres等，1985) 。
2、結(jié)構(gòu)
蒙脫石 ontmorillonite ，是天然硅鋁酸鹽，由二層共頂聯(lián)接的硅氧四面體片，夾一層共棱聯(lián)接的鋁鎂氧氫氧八面體片，構(gòu)成2∶1型結(jié)構(gòu)。晶層表面都是氧原子，沒(méi)有氫氧原子組，晶層間沒(méi)有氫鍵結(jié)合力，晶層間距為0. 96 ~ 2 . 14 nm，水分子和交換性陽(yáng)離子可以進(jìn)入層間，使晶格底面間距增大，蒙脫石體積膨大。例如：美國(guó)西部的鈉基蒙脫石類(lèi)粘土，其甲基藍(lán)吸附能力 (僅表示陽(yáng)離子交換能力 )可以高達(dá) 15 0 meq，遇水膨脹系數(shù)可以達(dá)到其遇水前體積的2 0倍。
在蒙脫石形成過(guò)程中，蒙脫石分子硅氧四面體中的S i4+可被 Al3+替換，鋁氧八面體片中的 Al3+可被 Mg2+或Fe2 +替換。這種置換，經(jīng)常造成八面體畸變，進(jìn)而迫使四面體片作出旋轉(zhuǎn)、伸長(zhǎng)、歪扭等形式，來(lái)予以調(diào)正，直至出現(xiàn)斷鍵，使多面體核心陽(yáng)離子裸露，使晶層間產(chǎn)生永久性負(fù)電荷，為了平衡電荷，蒙脫石必須吸附環(huán)境中的陽(yáng)離子到層間，而發(fā)生我們看到的離子交換作用，主要陽(yáng)離子如Na+、Ca2+、K+、Mg2+、Li+、H+、Al3+等(楊獻(xiàn)忠等，2003) 。正是這種離子交換特性大大增強(qiáng)了蒙脫石吸附霉菌毒素的功能。
3、負(fù)電吸附特性
蒙脫石晶層間的永久性負(fù)電荷，產(chǎn)生靜電引力和非穩(wěn)態(tài)電位固定效應(yīng)，使蒙脫石吸附具有選擇性，即有效吸附各種霉菌毒素，而吸附弱極性的營(yíng)養(yǎng)成分甚微。許多霉菌毒素, 如黃曲霉毒素、 玉米赤霉稀酮等的分子結(jié)構(gòu)中含有極性基團(tuán)，如: O H, C O,N H2，或含有可極化的基團(tuán)，如: C C , C6H5 等，能被蒙脫石優(yōu)先吸附。例如：呈剛性平面分子結(jié)構(gòu)的黃曲霉毒素，能進(jìn)入蒙脫石的內(nèi)表面，與晶層間可交換性陽(yáng)離子產(chǎn)生強(qiáng)烈的相互作用，并且不易解吸，表現(xiàn)出較高的吸附效率和吸附穩(wěn)定性。吸附量隨黃曲霉毒素含量的增加而增加，兩者呈直線(xiàn)相關(guān)。當(dāng)吸附反應(yīng)體系中賴(lài)氨酸含量為0．2％—0．4％時(shí)，不影響蒙脫石對(duì)黃曲霉毒素的吸附。
蒙脫石礦物層間區(qū)域具有層間交換、 層間吸附、 層間催化、 層間聚合、 層間柱撐等特性。霉菌毒素分子在蒙脫石礦物層間區(qū)域可發(fā)生分子吸附、 氫鍵吸附、 不可逆交換吸附、 質(zhì)子化吸附及吸附分解模式。例如，蒙脫石邊面上未完全配位的鋁離子能與黃曲霉毒素上的 - 羰基進(jìn)行化學(xué)吸附而形成穩(wěn)定復(fù)合物，因而降低了黃曲霉毒素的生物有效性。
并且，透射電鏡分析表明吸附原毒素前后蒙脫石的粒徑?jīng)]有明顯改變，XRD分析證實(shí)，吸附原毒素后蒙脫石層間距沒(méi)有發(fā)生變化。“車(chē)廂式”結(jié)構(gòu)的蒙脫石，將毒素固定到蒙脫石分子的“車(chē)廂”中，從而使毒素在體內(nèi)失活。
4、表面吸附力
蒙脫石顆粒細(xì)小，0．2～1 m，顆粒表面積巨大，顆粒遇液體分散后引起有效表面積進(jìn)一步增大，蒙脫石每克粉劑可覆蓋100～110m2消化道表面，由于層間域的存在，不僅具有巨大的外表面積，也有巨大的內(nèi)表面積，其比表面積可達(dá) 600 ~800 m，2/ g。所以蒙脫石比表面積大，表面能很高，表面吸附力超強(qiáng)。蒙 脫石 的 吸 附 機(jī)理 說(shuō) 明 圖：
其中左 A 是未膨脹的蒙脫石礦物示意圖。右 B 是集合顆粒遇液體后單個(gè)片狀體之間膨脹而引起有效表面積增大，吸附示意圖。
四、總結(jié)
蒙脫石所具有的層紋片狀結(jié)構(gòu)，非均勻性電荷分布，巨大的表面積和陽(yáng)離子交換能力等特點(diǎn)，使其即有色散力又有靜電力，色散力易吸附非極性分子, 靜電力易吸附極性、不飽和及易極化的分子，從而對(duì)飼料中的霉菌毒素有較好的吸附能力。浙江大學(xué)飼料科學(xué)研究所測(cè)試,納米蒙脫石對(duì)霉菌毒素吸附力(%) 如下: 黃曲霉毒素,100%; 玉米赤霉烯酮,87%;赭曲霉毒素,70%;麥角毒素,100%;串珠鐮孢菌毒素,91%。
蒙脫石能增加消化道黏液的質(zhì)和量，加強(qiáng)黏膜的屏障作用，保護(hù)和修復(fù)消化道黏膜；能吸附并固定消化道黏膜上的病原微生物于分子內(nèi)，使其破裂脫水以至滅活；同時(shí)能在胃腸道中吸附其所產(chǎn)生的毒素，隨糞便排出體外。從而抵抗外來(lái)制病因子的侵入，防止腹瀉。
蒙脫石脫毒量大，作用力強(qiáng)，穩(wěn)定性好，主要取決于它的吸附性能和膠凝特性。
五、 參考文獻(xiàn)
1 齊德生，劉凡，于炎湖． 蒙脫石對(duì)黃曲霉毒素B1的吸附作用［J］礦物學(xué)報(bào)，2004，24( 4) :341～346．
2 胡秀榮，呂光烈，陳林深，等． 天然蒙脫石與細(xì)菌相互作用機(jī)理的研究［J］． 藥學(xué)學(xué)報(bào)，2002，37( 9) :718～720．
3 胡彩虹，夏枚生，熊莉，等． 蒙脫石對(duì)細(xì)菌黏附Caco-2細(xì)胞的影響［J］． 細(xì)胞生物學(xué)雜志，2006，28( 1) :76～78．
4 夏枚生，胡彩虹，趙文艷． 載銅蒙脫石的抗菌機(jī)理研究［J］． 微生物學(xué)報(bào)，2006，46( 3) :432～435．
5 韓秀山，呂大豐，黃周可，等． 蒙脫石對(duì)細(xì)菌的吸附作用［J］． 吉林畜牧獸醫(yī)，2007，28( 1) :23～24．
6 姬洪張如柏． 納米級(jí)的軸長(zhǎng)1．8nm蒙脫石藥理作用的礦物學(xué)解釋J ． 礦物巖石2002 .22 .3 .98－100．
7 翟永功左明雪．藥用礦物蒙脫石的紅外光譜分析J ．中草藥2001 9 837－838．
8 陳況陳淑潔姒健敏等． 不同產(chǎn)地的天然蒙脫石對(duì)大鼠慢性萎縮性胃炎治療作用的比較J ．中國(guó)新藥雜志2007. 16. 4. 296－299．
9 胡秀榮呂光烈陳林深等． 天然蒙脫石與細(xì)菌相互作用機(jī)理的研究J ． 藥學(xué)學(xué)報(bào)2002 .3.9 .718－720．
10 周學(xué)永陳守文吳新世等． 蘇云金芽胞桿菌原毒素在蒙脫石上的吸附特性研究J ． 農(nóng)業(yè)環(huán)境科學(xué)學(xué)報(bào)2006 .25. 4 .992－996．
11 陳奕王佩吳洪海等． 蒙脫石止瀉作用的實(shí)驗(yàn)研究J ．中國(guó)新藥與臨床雜志1999 .18 .4 .230－232．
12 劉海軍李兆申許國(guó)銘等． 十六角蒙脫石對(duì)大鼠急性胃粘膜損傷的預(yù)防和治療作用 J ． 中國(guó)新藥與臨床雜志1996.15. 5. 260－263．
13 牛業(yè)來(lái)龐輝李玉杰． 十六角蒙脫石治療消化性潰瘍并上消化道出血30例J ． 中國(guó)基層醫(yī)藥2001. 8. 1. 82．
14 孟玉良許家亮．蒙脫石的藥用機(jī)理及毒理性J ．山東畜牧獸醫(yī)2010 .4 .77－78．
15 林飛宏． 蒙脫石防治仔豬腹瀉的效果及其機(jī)理探索D．重慶西南大學(xué)2007．
16 粘土礦物燈霉菌毒素吸附劑及其主要區(qū)別.周慧堂
The English version
A, feed and breeding
According to statistics, 73% of the world's excess sample feed mycotoxins. More than 12000 Chinese existing feed processing enterprises, not less than 200 million tons of feed production. Most of the region, especially the area south of the Yangtze river, summer heat and damp, feed mildew and contaminated with mycotoxins phenomenon is very common, the harm is big problem. Common are: aspergillus species (mainly secreted aflatoxin, ochre and aspergillus toxin, etc.) and penicillium (mainly secreted citrinin, etc.), claviceps (mainly secreted ergot toxins), fusobacterium (mainly secreted vomiting toxins, corn gibberellic ketene, T 2 toxin, Fumonisin toxin, etc.).
Due to environmental stress, mycotoxin combination and feed nutrition imbalance between the existence of factors such as feed low levels of mycotoxin can cause harm to animals. For example, when the aflatoxin content in the feed for 14. 0 g/kg (below the chicken feed aflatoxin allowances the hygiene standards of 20 g/kg) is activated when a serious effects production performance of broiler chickens.
Second, the action of montmorillonite
Montmorillonite name comes from France, France made a animal study, rabbit ileum after infected with e. coli, taking montmorillonite can reduce gastric mucosa damage, reconstruction of water electrolyte absorption, promote hair returned to normal forms, promote the regeneration of the damaged small intestinal mucosa epithelial cells and repair.
Mycotoxin and optimization of various bacteria on Caco - 2 cells have different levels of adhesion, which damage the gastrointestinal mucosa, and montmorillonite can block the adhesion, and optimization of pathogenic bacteria adhesion Caco - 2 cells blocking effect, significantly greater than the blocking effect of probiotics. , for example, e. coli, salmonella typhimurium, moisture, deputy hemolytic bacterium vibrio adhesion blocking rate, 54.22% 60.53% 54.22% and 48.41%, respectively, and the discrepancy of bifidobacterium and lactobacillus acidophilus adhesion blocking rate, at 25.64% and 21.49% respectively. Results show that montmorillonite can effectively block the pathogenic bacteria adhesion of gastrointestinal tract, and prevention and treatment of intestinal bacteria infection and bacterial translocation, which can prevent and treat diarrhea.
Industry applications such as ten hexagonal montmorillonite treatment of peptic ulcer and upper gastrointestinal bleeding, 30 cases were satisfactory curative effect. Because of montmorillonite is adsorption various virus, bacteria, and other various mycotoxins, treatment of weaned piglets diarrhea syndrome, the total effective rate was 94.74%, the cure rate was 42.11%, higher than that of gatifloxacin (norfloxacin treatment the total effective rate was 66.67%, the cure rate 27.77%).
Montmorillonite to pigs, to people, cattle and sheep to chickens and ducks diarrhea also has a good curative effect of rabbits and other animals. In rabbit immature rabbit diet can add 400 g/t olaquindox, and add 3 kg/t nano montmorillonite, are effectively reduced the immature rabbit saw the number of diarrhea of otter, reduce the diarrhea rate, effect on adding nanometer montmorillonite group is more obvious.
Third, the mechanism of the montmorillonite
1, concept,
Clay minerals in the montmorillonite content greater than 80% is called montmorillonite, montmorillonite is highly purified bentonite, bentonite is the main component. Such minerals including sodium based montmorillonite, calcium montmorillonite, magnesium based montmorillonite, iron-based montmorillonite, lithium montmorillonite and aluminum montmorillonite, etc.
Montmorillonite hardness is 2 ~ 2.5, the relative density of 2 ~ 2.7, very soft, slippery feeling. By electron microscopy in crystal plate, can slide open between layer and layer, are not scattered between layer and layer separation, in colloidal state can be dispersed in water medium, belongs to the acid base glue, have certain buffering capacity to acid alkali, thus to maintain a system of pH is relatively stable. For example: montmorillonite in the digestive tract, can form the protective film of continuous, combine with the digestive tract mucous protein electrostatic, can significantly increase the cohesion of mucus and elasticity. (Girardeau, 1987; Albengres etc., 1985).
2, structure,
Montmorillonite ontmorillonite, is the natural sialic acid salt, by the top connection of the silicon oxygen tetrahedron on the second floor, a layer of common edge clamp connection of the aluminum magnesium hydroxide oxygen octahedron, constitute a 2:1 type structure. Crystal layer surface are oxygen, no hydrogen atomic groups, no hydrogen bond between crystal layer binding force, crystal layer spacing of 0. 96 ~ 2. 14 nm, water molecules and may enter the interlayer exchangeable cations, make lattice floor spacing increases, the volume of montmorillonite). In the western United States, for example, sodium based montmorillonite clay, the methylene blue adsorption capacity (said only cation exchange capacity) can be as high as 15 0 meq, encounter water expansion coefficient can reach its encounter water volume 2 0 times before.
In the process of montmorillonite to form, montmorillonite molecules in the silicon oxygen tetrahedron i2 + S can be replaced by Al3 +, aluminium oxide octahedron of Al3 + can be replaced by magnesium 2 + and Fe2 +. The displacement, often cause octahedral distortion, forcing tetrahedron pieces to rotate, elongation, crooked and form, to be reset, until a broken key, make solid core cationic naked, make the crystal layer between produces permanent negative charge, in order to balance charge, montmorillonite must of cation adsorption environment to the interlayer, and the ion exchange, we see the main cations such as Na +, Ca2 +, K +, magnesium 2 +, Li +, H +, Al3 + (xian-zhong Yang, etc., 2003). It is this ion exchange properties greatly enhances the montmorillonite adsorption function of mycotoxin.
3, negatively charged adsorption properties
Montmorillonite crystal layer between the permanent negative charge, produce electrostatic attraction and unsteady potential fixed effects, make the montmorillonite selective adsorption, namely effective mycotoxin, adsorption and adsorption little nutrition ingredient of weak polarity. Many mycotoxins such as aflatoxin, corn gibberellic is contained in the molecular structure of the dilute acetone etc polar groups, such as: O, H, O, C N H2, or contains polarizable groups, such as C, C C6H5, etc., can be montmorillonite preferential adsorption. For example: the molecular structure of rigid plane of aflatoxin, can enter the inner surface of montmorillonite, the interchangeability between the crystal layer and cationic produce strong interaction, and not easy desorption, showed higher adsorption efficiency and stability. Adsorption quantity increases with the increase of content of aflatoxin, both in a straight line. When the adsorption in the reaction system of lysine content is 0.2%, 0.4%, do not affect montmorillonite adsorption of aflatoxin.
Interlayer montmorillonite mineral area has interlayer, interlayer exchange adsorption, catalysis, between layer character such as polymerization, interlayer between column brace. Mycotoxin molecules in the layer of montmorillonite mineral area can occur between molecular absorption, hydrogen bond exchange adsorption, adsorption and irreversible proton adsorption and adsorption decomposition model. Montmorillonite edge, for example, can not completely ligand on the surface of aluminum ions and aflatoxin - carbonyl chemical adsorption and form stable complexes, and thus reduce the biological effectiveness of aflatoxin.
And transmission electron microscopy (sem) analysis showed that adsorption of montmorillonite before and after the original toxin size there is no obvious change, XRD analysis confirmed that the adsorption of the original toxins after the montmorillonite layer spacing has not changed. "CheXiangShi" structure of montmorillonite, toxins will be fixed to the montmorillonite molecules "car", so that the toxins in the body.
4, surface adsorption
Montmorillonite particles small, 0.2 ~ 1 m, particle surface area is huge, particles in the liquid dispersion caused by effective surface area increases further, montmorillonite powder covering 100 ~ 110 m2 per gram surface of the digestive tract, as a result of the existence of interlayer domain, not only has large surface area, there are large internal surface area, the specific surface area of up to 600 ~ 800 m, 2 / g. So the montmorillonite is greater than surface area, high surface energy, surface strong adsorption force. The adsorption mechanism of montmorillonite Ming said:
Which left A is not the expansion of the montmorillonite mineral diagram. B is right after the collection of particles in the liquid between individual lamellar body expansion caused by the effective surface area increases, adsorption.
Four,
Montmorillonite layer lines of lamellar structure, heterogeneity, charge distribution, large surface area and cation exchange capacity, etc, make its have the dispersion force and electrostatic force, dispersion force is easy to adsorb nonpolar molecules, electrostatic force easily adsorption polarity, unsaturated and polarized molecules, thus mycotoxins in feed has good adsorption capacity. Test feed science research institute, zhejiang university, nanometer montmorillonite on the mycotoxin adsorption force (%) as follows: yellow aspergillus toxin, 100%; Corn gibberellic ketene, 87%; Ochre and aspergillus toxin, 70%; Ergot toxin, 100%; Fusarium toxins, beaded 91%.
Montmorillonite can increase the quantity and quality of the digestive tract mucous, strengthen the mucous membrane barrier function, protect and restore gastrointestinal mucous membrane; Can adsorption and fixed on the digestive tract mucosa of pathogenic microorganisms in the molecule, the broken dehydration and inactivated; At the same time can be adsorbed in the gastrointestinal tract the toxin, produced by the faeces. To resist the invasion of the foreign system of disease factor, prevent the diarrhoea.
Large amount of montmorillonite detoxification, strong force, good stability, mainly depends on its adsorption performance and gelling properties.
Five, the references
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