Application Of Novel In-tube Microextraction For Analysis Aldehyde Ketone Biomarkers In Liver Cancer

The current lack of accurate biomarkers is the main cause of the delayed treatment,and the complex matrix such as human serum,blood,urine,has great interference which directly affect the accuracy of detection.Therefore,developing the more accurate pretreatment method and providing the potential alternative biomarkers for early non-invasive diagnosis of liver cancer disease is a desirable goal.In-tube SPME has got great progress in recent years,researchers applied poly-tetrafluoroethylene(PTFE)tube for the new adsorbent carrier,which solved the shortcomings of the commen materials.Thus,the key of this paper is:to make some improvement for In-tube SPME which solves the problem that the monolith materials were synthesized inside the PTFE tube intricately;to develop new adsorption materials,which simplifies the pretreatment steps;to confirm new biomarkers of liver cancer,which improves the detection sensitivity to a great extent.Hence,this article has carried on the experiment contents as follows.(1)Magnetic mesoporous material(C8-Fe3O4@mSiO2)was synthetized,which can be attracted into the PTFE tube with a magnet,to save the step that adsorbent was bonded into tube.With in-situ derivatization,the hydrophobic mesoporous material adsorpted small molecular aldehyde ketone derivatives to the mesoporous channels through size exclusion and hydrophobic interaction,on the contrary,the proteins were excluded out of channels.The derivative and extraction conditions were optimized,the detection limit for 2-butanone and hexanal was 1.214,1.031 nmol L-1 respectively,RSD was lower than 7.874%.This method was successfully used for detect the aldehyde ketone targets in patients were significantly higher than normal levels in the volunteers,2-butanone and hexanal can confirm as potential biomarkers for liver cancer.(2)Based on our previous work,novel magnetic mesoporous material(C8/C18-Fe3O4@mSiO2)was fabricated via sol-gel method.Making hydrophobic modification of C8-Fe3O4@mSiO2 through adding C18 functional group into the mesoporous channels increased hydrophobic adsorption between the adsorbent and hydrophobic aldehyde ketone targets.With on need to move out proteins because of the mesoporous modification,the adsorbent was attracted into the PTFE tube with a magnet to simplify pretreatment process.Under the optimum conditions,the detection limit for 2-butanone and hexanal was 1.043,1.027 nmol L-1 respectively,RSD was lower than 6.975%,the method was applied to the real serum samples and received the same experiment conclusion as our previous paper.(3)The novel materials(PD/DAS/CHI)was synthetised into PTFE tube,which was used PD to functionalize the surface of PTFE tube,then dialdehyde starch/chitosan(DAS/CHI)was chemically bonded with its surface,to enhance the overall stability of material.The mesoporous material can adsorpt targets with hydrophobic and hydrogen bonding interaction,and can be used in complex matrix,such as serum samples.Under the best conditions,the detection limit for 2-butanone and hexanal was 1.590,1.398 nmol L-1 respectively,RSD was lower than 7.215%,and getted the experimental result that was consistent with our previous work,2-butanone and hexanal can serve as potential biomarkers for liver cancer.