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Regarding the second method (Figure 3), it¡¯s necessary to realize a chlorine-iodine exchange before executing the quaternarization, with the reaction of chlorine derivative being very low: in 5 days the efficiency is only 10%, where as with the iodine derivative, the reaction is quantitative. These series of reactions require extreme precaution: the solvent should be strictly anhydrous, very little amount of water will hydrolyze the methoxy group into silanol.

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In the reduction of salt pyridinium 2 or 6 by sodium dithionite in basic medium, it produces probably a light material degradation , as shown by the light decrease of nitrogen content. We have realized the reduction of salt pyridinium in phosphate buffer at pH7, and also noticed a partial stall of grafting reaction.

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The content of silica 3 and silica 7 in dihydro-1,4 nicotinamide pattern is 0.7 milliequivalent (mEq) per gram and 0.8 mEq per gram, respectively.

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The graft 5 is then obtained from 10g of 4 (0.034 mol) and 4.5 g (0.034 mol) of nicotinamide dissolved in 50mL anhydrous acetonitrile. The solution is then brought to reflux for 72 hours with light stir. After cooling, we observe the precipitation of pyridinium salt. This precipitation is filtered with argon and rinsed with anhydrous acetonitrile. The solid is then recristallized in 50 mL anhydrous acetonitrile. We obtain 13.6 g (95% rate) of pyridinium salt 5 F-158.5C.

5ºÅ¼Þ½ÓÎʵÑéƬ£©¿ÉÒÔÓÉ´Ë·½·¨»ñµÃ£º½«10¿Ë4ºÅ£¨ÊµÑéƬ£©£¨0.034mol£©ºÍ4.5¿ËÑ̼îÈܽâÔÚ50ºÁÉýÍÑË®Ç軯¼×ÍéÖУ¬È»ºó½«´ËÈÜÒº´øµ½»ØÁ÷×°ÖÃÖзÅÖÃ72Сʱ£¬Çá΢µÄ½Á¶¯Ò»·¬£¬ÔÚÀäÈ´ºó£¬ÎÒÃÇ»á¹Û²ìµ½ßÁà¤ÑεijÁµí¡£½«´Ë³ÁµíÎïÓÃë²Æø¹ýÂË£¬ÔÙÓÃÍÑË®Ç軯¼×ÍéÏ´¾»£¬¾Í¿ÉÒԵõ½13.6¿ËµÄ5ºÅßÁà¤ÑΣ¨×ª»¯ÂÊ95%£©¡£´ËʵÑéζÈÊÇ158.5¶È¡£

The graft of silica can be realized in this way: in a ball, introduce 10g of silica, 3g of graft 5 and 60mL of DMF. Take the whole thing into 115C for 12 hours. The cooled suspension is filtered with particular precaution, the solid is obtained with 50mL of toluene and the water is eliminated with azeotropic distillation. After cooling, the filica is filtered and washed multiple times with methanol and toluene. The solid is then treated in Kumagawa extractor for 12 hours with methanol, then dried with heat gun, at 80C for 3 days. Then silica 6 is obtained.

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