Division for Chemistry Department of Analytical Chemistry Zeki Altun New Techniques for Sample Preparation in Analytical Chemistry Karlstad University Studies 2005:24 ฀ ฀฀ ฀฀ ฀ ฀฀ ฀฀฀฀฀฀฀฀฀ ฀ ฀฀฀ ฀ ฀ ฀฀ ฀ ฀฀ ฀฀ ฀฀฀ ฀฀฀฀ ฀฀฀฀ 06 6 6 + +. -+ 0.+ 0 * 0+. 4+4+ 7 +6 4 8 + +0 +. ++0 7+. 06 6 6 + 0 +* 7+ - +6+ .+0 + + # +6 7+ + 0+ 06 6 6 + 0 7#+76 4 8 .+06 6 6 + - + + # + 8 +0+769/: 7+0+769;/:- +6 + < + 6 7 915: 4+ #6 < + 951: 8 0 = - .+0 15 66+< 0 !07+.+- 0 +7 7 7 9!# :6706 6 6 + 6 + 6 - 1 + +. 8 4+ - 0 + +.+ 0 6006 715+ # 4 / 00 6 +0 9#:15+ + +06 4. +0 #6+. 06 +++ 0 + +.6006 0 67+.+- +- .+-+! < + - .+ 4 . 0+. 4+4+ 06 6 6 + +76*+ + 6+- 6 6 64 6 4 67+.6++6+0 0+ + 06 +- 4 + + 4 %'#4 6 /##2 ++ 0 60 4 06 4 0+ - %'#6 4 4+0 3 / + & =+- +-+ *5 + * 6+6 & & / 1 /$ ? /!$ ? / / , 6 /1/ /6 1 ++0+76 , , +< -+ 1;, 1 ;+, 0 1 1 +6+ = + ;/ ;/+0+76 ; ; , , 0 ) A + B+ / 8 /+0+76 1 8 # 8 1< + 15 +1< + 5 7 ?C + 6 +0 # * 06 +0 5, 5+ 0 +< A A -+ A5#/ A #5 8 /+0+76 &1 &+- 1< + 5,1 + #5 , 0 1< + 51 + #5 1< + 51 + #5 + < + A A + + + 7 A + * 0 A + * 0 A D D + 4 ! " !# $%& " ' # ("#""# ) * ! ! " !+, " " $ +0 - #A 0 ;&+0- 7 "% 9:!$$#!%" - *, "# ./%# # $%& " 0# # ! ("#""# ) % ! 1% %%$ +0 - #A 0 ;&+0- 7 $!"9:!%#!" "# ,! !) # ! !# #" # 23%, .4 23% 5 ### $ ;&+0- 7 +0 - #A 0-0 + 9: 5 ,# ! + + ( !!06 5 6 + ( !!!+ #5 1< + 951: ( !!!!06 5+ 7 51$ !!!/+06+ A + 51% !* 06 5 6 + ! !" + < + 5 7 915: !! ! & 5++5+0 + + ! ! 8 /+0+769/:! !'6 +0 9:!" !(06 ! !(!+ ! !(A++ ?+0+ !' * 0+.* 2+!( "A , + !$ "!15/+ + !$ " +, +60 956 :!$ "!* +- !% "* 2 7+ ""* 1 + + " ""/#+ "C 706 *+76 7+ + 5 * 6956 : "!* 5 6 + +.5++5+0 + + " +.5+9;#1;,#&:+ + .+5 6 * 6 "06 7' "' ( /+ + % +4 7 0 " A . "! 6 6 6$6"# 4 +. 6 +06 <0 +..+ <06 + 0 +- ++7 + 7 06 + - .+ + + + 0 * 06 6 6 + - +0 06+ 6 6+ 06 6 6 + +. 6 8 + .+006 +.+0 - .+ * . 6+ - + 0+ 8 4 - +06 * 6+ 0- 7 6+ - 4 + 66 - ++. 06 6 6 + 0 ++ + 0 00 0- +. 4+ 7 6- + - + 0 . - + +0 E!FB 0- +.06 7+4 7#+76 . +0 8 - +0 8 /+00+ 06 6 6 + 0 + 8 # 8 < + 91:+ #6 < + 951: + #6 0 + < + 951: 6$6$6 # %! 8 #+ < + + +. + #6 < + 951: 0 + .++ + + + +.7 7+ 66+51 + 0++00+ 06 6 6 + 0 + 0 +. 0 7 + 0 60 66 + EF514 +6 +06 0 + 6 0 .+ 1+0 6+- 0 +1 -+ .. + +0 + 0 7 +0 +. 7#6 + E#F * . 66 + +.51 + - +.0 +4 7 !%EF 7 + 6 4 !#!7+.7 -+ & + +7 0 06 <4 6 + ? +A E'F* 46 .+0 .+ 0 + +. + ++ 4 +60 +.51+ 4 4.+0 46 4 .. 0 E"F* 7 .+0 + 0+6+6 .+0EF6 + + +. 7 +4 B 7 ! 7 Figure 1. Schematic diagram showing a typical SPE cartridge. * + +. +6 7 - + 7+- 6 - 4 . 51 7 - = + 7.+0"07+! 7+.+- 4 !07+07+- 7 0+4 * 0++00+ 6 70 #- 4 0 -+ 0 7+# 6+0 # - = 6+0 B + 0 +.0 0+ .. 51 7 + + .+ +- +- 6 +. +48 6$6$6$6"# 6 + #6 < + + .+6+ 7 6B 7 . 6 +- + + 4 "#- +0 +.+ + 0+ 06 6+ - + +. * + 6 66 + +. 06 + + +7 < + * 6 .++4 - 7 7+. +- .+0 . 4 ++ 7 B +. .+0 +- 7+ 7+ E(F 8 Figure 2. The four processing steps in the operation of SPE experiment. * 60 - 7 6+ 7 6 51 + 7+ + 6 6 +. 8 +0+769/:E"(F 6$6$6$4 " ' 51 6 + - + - + +. - 4 + 6 70 8 0+- 6 * .. 51 . + +. - + 6 +. - + 66 < + EF* +0 7 #6 51 C + 6 6 4 0 -+ . + 7+6+ + . /!$ +0 -/$ + < * 6 70 /9 !: 51 - 0 < 6 6 7 51++7 + 4 .+4+7 +- -7 -.+8 + + +06 7 0 +00+ 06+ * + +. + + +- 6 0 ++6+- + *+ .+0 +- + #6++ B+ 7 4 + + + < 7 51 - * + 0 0 6 0 - + + + - 4 7 7 . + 7+6+ . +. +- *+ +. + + 76C = . + 7+6+. +- + = 7 + + 4 7 + 7 + +06+ 9 6$4, "# A 06 6 6 + .++ +4+0 = 6+ 06 +76 +- + # +6 06 6 6 + + + 0E(#!F * . 06+0 = 6+ 6+ 706 +764 + 4 + + +. 4.+051 E!!F6 6 6E!!#!F+0 4 7 0E!"#!'F 0 #4 6 E!(FB 0 = + +60 +. 4 0 + < + 8 +0 <06 +. 0 7 7 4 8 4 - 7 + #6 0 + < + 951: 6 0++00+ 0 + < + 8 E!$#!F 51. # . - + + + 4 66+6 + 6 .+06 72 + 6 6 + 4 06 0 <6 + 7+. - 4 6 6 * . - 6 +. ;/ G +.+ +- + * < + .. +.51 6 + 0- +..+ < + 0 7 + 06 6C + + 06 51 - < + 6 # + + +. .+07 + 8 + 06 + #6 0 < + 95,1: 8 4 = +.7 7 7 .+06 7E#"F* 4+. + 4 6+ 0 +< 95,: !H -+ + 6 * 0 06 7 6 .+0 -6 7 6 7 . < +0 +. 06 .+ 66+6 0- +. 0 * +- + - +6 + +;/ G + * 8 - .+ 6+ 8 06 + 8 + < .+0 8 06 - +6 < + 9&1:E#F07 -+ 4 5, + 6 .+06 7& 06 6+ + 4 -.+ 0 - 6 06 7- .+ 0 +6 + * < + 6 6 +. 8 515,1 &1 = 0 < + 0 05,- 0+ .. &1 + 0 0+ +- 51EF + + 0 7 7 4 8 7 0- +. + # +- - +6 ++06 +0 +. 4-+. - 0 7+0 - +6 + +.- E!F 10 6$7 + < + 6 7 915: 406 6 6 + 8 7 7 7 < + E'#(F 15 +- 0 -+!07 + 7 - 67 4 6+ . + -+ +- 4 7 - B 7 " Figure 3. Schematic picture of microextraction in packed syringe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igure 4. Schematic setup of an LC system. 1. Pump, 2. Mobile Phase Mixer, 3. Injector Valve, 4. Column and 5. Detector. * 06 + + +6+. +0 - G +* 6069: .+4+.0+- 6 +7 +0 * 0+ 4 .. +7 +0 + . + .+0 +0 * 7 4 0 7 6 + . + +. 0 6 + 6 + .. +. + + 6 * + <6 - + .+) t − t ´k = r 0 9!: t0 4 + 0 .+ + 0 .+ 6$3 " 6 +0 9:4 + - 6 JJ*+0+ 9!$'# !%:E"F ++ +. 0+ 06+ 0 .+ 0+ * - 0 6+ + +. + 6 + +. + + 7+ 0#+#7 90K=: + 0E"'FB+006 08 4 8 .+0 + - +- /+0- 7/ 0 4 4+ P 0 7 Q E"(F/+6 + 6 4 +6 0 & +. .. 0- 4 7 7 4+ 0 + +0 7 + 0+ 0- 6+ 7 0- . + 76 * + = + 8 4 +6 + = + 91: +6 6+ + 0+ * + .+0 /46 + 7 6 - + +.4 6+ 6+ 9"#D:466 * . + + +- 6+ = +6+.. +6 *+ 77 +7 9 :.+4 + 7 6+ 6 & .+ 7 06 +0 6+- 13 +6 6 +7 7 0- 4 + 6+ +6 7 0 +6 7 0 7 .